We have performed an experimental study of the influence of varying size and charge on cation partitioning between wollastonite and silicate-carbonate melt in the system CaCO3-SiO2. The experimental conditions (3 GPa, 1420°C) lie close to the wollastonite II tc/I tc phase boundary. Results for 1+, 2+, 3+ and 4+ partitioning show parabolic dependence of partition coefficients on ionic radius, which can be fitted to the elastic strain model of Blundy and Wood (1994), wherein partitioning is described using three parameters: site radius (r0), site elasticity (apparent Young's Modulus) and the ‘strain-free’ partition coefficient (D0) for an element with radius r0. The apparent Young's Modulus of the Ca site in wollastonite, obtained from modelling the 2+ partitioning data, is 99±3 GPa, similar to the bulk-crystal value for the polymorph wollastonite I tc. r0 decreases with increasing charge on the substituent cation, while D0 also shows an approximately parabolic dependence on charge, with a maximum for 2+ cations. Partition coefficients for divalent cations Zn, Co, Fe, Cd, Mn and Pb are lower than would be predicted from their ionic radii alone, indicating a preference for the melt. This may be a consequence either of cation-carbonate complexation in the melt, or of the more distorted nature of cation co-ordination environments in melts.

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 clinopyroxenes kanoite and spodumene were studied by single-crystal X-ray diffraction in a diamond anvil cell (DAC) at room temperature. At the displacive phase transitions between the C2/c and P21/c polymorphs both phases coexist within the same crystal. In this two-phase region the pressure in the DAC remains constant. The experimental results demonstrate that pressure buffering at first-order phase transitions can occur in the DAC.

The Tertiary (22 Ma) carbonatite centre at Buru hill is located towards the eastern end of the Nyanza rift, western Kenya. As revealed by geochemistry and petrology of drill core samples, the Buru centre ranges in composition from surficial lateritized pyroclastic ferrocarbonatite to recrystallized ferruginous calciocarbonatite at depth.

Mineralogically the lateritic cover of the Buru carbonatite centre is characterized by goethite, hematite, psilomelane, baryte, fluorite with minor calcite, bastnäsite and significant amounts of monazite. A transitional middle zone consists of ferrocarbonatite grading into ferruginous calciocarbonatite containing siderite, baryte and fluorite, a greater proportion of bastnäsite replacing calcite, but lesser proportions of monazite. The lowermost zone consists of ferruginous calciocarbonatite containing intimate mixtures of siderite and calcite, with parisite and synchysite existing as major replacive components of calcite down to depths of 200 m. Synchysite appears to be the more stable form of lanthanide fluorcarbonate at depths below 150 m.

Oxygen isotope measurements on separated calcite concentrates from three of the Buru drill cores reveal significant deviations from primary igneous carbonatite values suggesting isotopic re-equilibration with meteoric water. Accepting that the African plate may have been stationery during the past 30 Ma, it is possible to use a modern sample of water from the Kenya rift to estimate the equilibration temperature at which Buru carbonatite in western Kenya has recrystallized. Temperatures of ∼60 to 90°C suggest that the hot-spring activity encouraged the formation of replacive lanthanide fluorcarbonate in ferruginous calciocarbonatite. Lanthanide enrichment also occurred closer to the surface within the pyroclastic ferrocarbonatite at temperatures of ∼40 to 60°C corresponding to waning stages of hot-spring activity. Further lanthanide enrichment redistribution and oxide formation occurred at surface supergene temperatures of ∼20 to 30°C forming the lateritized top of the carbonatite.

The wider implications from these carbonatite studies are the recognition that lanthanide enrichment can be preserved in volcanic-subvolcanic centres, and that lanthanide fluorcarbonates can replace calcite in response to circulating hot-spring waters. From a classification point of view, ferrocarbonatites should be seen as products of meteoric hydrothermal systems unrelated to carbonatite magmatic processes

Analytical precision is vital in the interpretation of stable isotope data collected by secondary ion mass spectrometry (SIMS) given the small analysis volumes and the small magnitude of natural isotopic variations. The observed precision of a set of measurements is represented by the standard deviation(precision of an individual measurement) or the standard error of the mean (precision of the mean value). The SIMS data show both systematic variations with time and random Poisson variability, but the former largely cancel out when data for two different isotopes are expressed as a ratio. The precision of a SIMS isotope ratio routinely matches that predicted by Poisson counting statistics and can approach that of conventional bulk analysis techniques for counting times of several hours. All sample analyse must be calibrated for instrumental mass fractionation using SIMS analyses of a standard material. There is often a gradual drift in the mass fractionation with time, but this can be modelled by least-squares regression of the standard isotope ratios. Drift in the sample analyses is eliminated by using the relevant point on this regression line to calibrate each sample. The final precision of a corrected isotope ratio must take into account the scatter in both the sample and the standard data.

The single-crystal X-ray structure of tungstenian wulfenite-I41/a containing 10 mol.% WO3 from the San Francisco mine, Sonora, Mexico, space group I41/a, a = 5.436(2), c = 12.068(8)Å and Z = 4, has been refined to R = 0.052. The Mo and W are disordered over special position 4a (0,0,0) in the lattice. Tungstenian wulfenite-I4̄ (‘chillagite’) from the Christmas Gift mine, Chillagoe, Queensland, Australia (Museum of Victoria specimen M16934), crystallizes in the closely related tetragonal space group I4̄, with a = 5.441(1), c = 12.068(6) Å and Z = 4. The structure was refined to R = 0.038. Refined site occupancy factors show that Mo and W are not distributed equally over the two crystallographically independent Mo/W positions, being 0.136(2) for Mo and 0.114(2) for W in special position 2a (0,0,0) and 0.184(2) for Mo and 0.066(2) for W in special position 2c (0,Ý,Ü). These give a composition corresponding to wulfenite64stolzite36, in agreement with analytical data. The Mo/W distributions in the unit cell provide one explanation for the origin of hemihedrism in the wulfenite-stolzite series.

Zircon commonly occurs as one of important accessory HFSE-bearing minerals in A-type granite. A detailed electron microprobe study was carried out on zircon from the Laoshan complex, Eastern China, which is composed of I- and A-type granites. Zircon from the I-type rocks is relatively poor in trace elements (HfO2<2 wt.%, UO2, ThO2 and Y2O3 <1 wt.%), but that from the A-type rocks is richer in Hf, U, Th and Y. Hafnian zircon with a HfO2 content of up to 12.37 wt.% was found in the arfvedsonite granite, which is considered the most evolved facies in the A-type suite. Enrichment in Hf is generally observed at the rims of zircon crystals relative to the cores. The Hf enrichment in zircon, and the association of exotic REE- and HFSE-bearing minerals are linked to hydrothermal activity, suggesting that during the last stage of crystallization of the A-type magma, fluids enriched in REE, HFSE, F−, CO32− and PO43− were released.

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.

In order to limit the range of possible differentiation mechanisms and the impact of these processes on the trace element signatures of igneous suites, it is important to be able to predict or model the compositional evolution of the primary and/or parental magmas. Part of the problem in understanding these relationships in basalts from ocean islands is the paucity of reliable trace element mineral/melt partition coefficients, particularly for undersaturated magmas. Consequently, we have measured mineral/groundmass partition coefficients for Rb, Sr, Y, Zr, Nb, Hf, Ta, Th and REE, in situ, in clinopyroxene, Fe-Ti oxides and olivine in primitive basalts from Rarotonga, Cook Islands using LAM-ICP-MS.

Analyses of these mafic rocks show high concentrations of most incompatible trace elements (e.g. Sr, Th, Y, REE, etc.) in pyroxenes relative to the other phases, suggesting that fractionation of pyroxenes was the dominant factor in the distribution of these trace elements during crystal fractionation. In such cases, the highly incompatible elements (D <0.01) are Ba, Cs and Nb. Elements that could also be classified as strongly incompatible (D <0.1) are Rb, Ta and Th. The remaining trace elements have bulk partition coefficient values that range from ∼.0.1 up to ∼.0.8 (Sr, Hf, Zr, Y and REE). Magnetites incorporate greater amounts of Nb and Ta than the titanaugites, and any significant fractionation of magnetite would have affected the bulk distribution of Nb and Ta. The LREE have lower Kd values than other REE, with the HREE having Kd values close to unity. Consequently, with the separation of titanaugite an overall enrichment of REE in the residual liquid with an increase in the La/Yb ratio is produced.

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.

Four samples of Fe-bearing prismatic sillimanite, containing ∼1 wt.% Fe2O3, were annealed experimentally at temperatures of 1465 and 1675°C, and pressures between 1 atm and 30 kbar. Transmission electron microscopy (TEM) and analytical TEM (ATEM) investigation of the samples reveal that the starting material partly transformed into mullite during the annealing, and that this process was assisted by partial melting. The exsolved partial melt (now a glass), observed at triple junctions and in the form of small precipitates (∼10–1000 nm in size) within the sillimanite matrix, contains >80 wt.% SiO2. It also contains ∼11 wt.% Al2O3, some FeO and detectable amounts of K2O and CaO. Dissociated c dislocations in sillimanite are preferential nucleation sites for SiO2-rich precipitates. The equilibrium compositions of residual sillimanite-mullite were measured with a 2 nm wide probe at the interface with the SiO2-rich glass in each sample after heat treatment. We used these equilibrium compositions to constrain the parameters of a point defect model for sillimanite mullitization proposed by Raterron et al. (1999). With the revised parameterization, it is now possible to calculate the position of the boundary between fields of mullite + melt and mullite in the SiO2–Al2O3 phase diagram, and to predict the effect of pressure on this boundary. However, to be used as a standard, this model still needs to be calibrated in the pure SiO2–Al2O3 system (without impurities such as iron).

Italian carbonatites form part of a suite with melilitites, normally an association characteristic of continental interiors; the perfect analogue of the Italian suite being the kamafugites (from the type area in SW Uganda, where the western branch of the East African Rift Zone cuts across the craton). The latter are commonly attributed to plume generation, whereas the Italian carbonatites, strung along the Appennine front, are usually linked to subduction. Evidently these two mechanisms are not essential, since neither can apply in both provinces. This conclusion is re-inforced by the related magmatism registered in both provinces in the Cretaceous. Phlogopite is ubiquitous in the mantle debris, and compositions from the two provinces overlap. Xenolithic phlogopites are distinct from cognate micas in the lavas, and from the carrier melt compositions, with similar distribution patterns in both suites. Kamafugitic magmas must be products of exceptional conditions, and added to the many near-identical magmatic features, the Italian and Ugandan volcanoes have sampled similar mantle conditions. Although the large scale geodynamic regimes are in total contrast, as are the deep mantle tomographic structures, the crucial common factor at the igneous province level is extensional tectonics. Extension, promoting release of volatiles (esp. CO2), is the vital trigger for this small volume, primary magmatism.

The crystal structure of synthetic shannonite, Pb2O(CO3), orthorhombic, P212121, a = 5.1465(7), b = 9.014(1), c = 9.315(1)Å, V = 432.12(10)Å3, Z = 4, has been solved by direct methods and refined to R = 0.054. There are two symmetrically distinct Pb2+ cations in irregular coordination polyhedra due to the effect of stereoactive s2 lone-electron pairs. The structure can be described as composed of chains of [OPb2] composition running parallel to [100] that are built by corner-sharing of OPb3 oxocentred triangles. The [OPb2] chains are surrounded by CO3 groups to form complex [OPb2](CO3) chains that are linked into a 3-dimensional framework by additional Pb–O bonds. The structure has channels that are parallel to [100] in which the lone-electron pairs of the Pb2+ cations are probably located.

The crystal structure of the rare secondary lead mineral georgiadesite has been solved from single-crystal X-ray diffraction data (R = 0.071). The structure can be visualized in terms of alternating puckered (100) layers of [Pbϕ6] octahedra and [Pbϕ8] bicapped trigonal prisms (ϕ = generic anion). Lead also occurs in irregular, lopsided polyhedra. This structural study shows unambiguously that arsenic occurs as As3+ and not as As5+. The chemical formula of georgiadesite has therefore been revised, on structural grounds, to Pb4(AsO3)Cl4(OH).

The crystal structure of synthetic ‘plumbonacrite’, Pb5O(OH)2(CO3)3, hexagonal, P63cm, a = 9.0921(7), c = 24.923(3)Å, V = 1784.3(3)Å3, Z = 6, has been solved by direct methods and refined to R = 0.049. There are six symmetrically independent Pb2+ positions in the structure, the coordination polyhedra of which are strongly distorted due to the effect of s2 lone-electron pairs on the Pb2+ cations. The Pb(6) position is disordered with a Pb–Pb distance of 1.24 Å . The structure of ‘plumbonacrite’ is built from complex Pb–O layers parallel to the (001) plane similar to those observed in polymorphs of Pb4(OH)2(SO4)(CO3)2. The structure of these layers can be described in terms of Pb–O,OH motifs and CO3 groups. The smallest structural subunit is the oxocentred [OPb4] tetrahedron that shares three of its Pb-Pb edges with three [(OH)Pb3] distorted triangles to form [O(OH)3Pb7] clusters. These clusters are surrounded by CO3 groups, forming more complex clusters. Due to the disorder in the Pb(6) site, the clusters comprising this site are linked with each other via OH(10) groups to give continuous sheets of Pb–O,OH bonds which are parallel to the (001) plane. The [O(OH)3Pb7] clusters in ‘plumbonacrite’ may be important in more complex Pb carbonate oxo/hydroxo complexes that may exist in aqueous environments.

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.

An ultramafic lamprophyre dyke is described from the otherwise tholeiitic Ferrar magmatic province of Antarctica. We report an Ar-Ar age of 183 ± 2.2 Ma for the dyke, indistinguishable from those of the Ferrar tholeiites. However, the dyke has mineralogical and major and trace element compositions, and radiogenic isotopes ratios, very different from the Ferrar tholeiites. The sample consists of olivine and rare clinopyroxene phenocrysts with perovskite and spinel microphenocrysts in a groundmass of amphibole, nepheline and biotite. Carbonatitic globules contain calcite, dolomite, Fe-rich carbonate, nepheline, biotite, orthoclase, pyrite, clinopyroxene, apatite and silicate glass, and were formed by liquid immiscibility. The rock is mildly potassic and classifies as an ouachitite. It is strongly enriched in both moderately and highly incompatible trace elements and is the first high-Ti rock to be described from the Ferrar magmatic province. The rock has similar initial 143Nd/144Nd to OIB, notably Bouvet, Crozet and Réunion, but significantly higher initial 87Sr/86Sr. The lamprophyre magma is interpreted as having been generated by low-degree partial fusion of metasomatized lithospheric mantle as a result of heat conducted from an underlying Jurassic mantle plume. The same mantle plume was probably also responsible for generating one of the world’s largest layered gabbro bodies, the Dufek-Forrestal intrusions.

The crystal structure of a manganoan cummingtonite, composition [M4](Na0.13Ca0.41Mg0.46Mn1.00) [M1,2,3](Mg4.87Mn0.13)(Si8O22)(OH)2, (Z = 2), a = 9.5539(2) Å, b = 18.0293(3) Å, c = 5.2999(1) Å, β = 102.614(2)° from Talcville, New York, has been refined at high temperature using in situ neutron powder diffraction. The P21/m to C2/m phase transition, observed as spontaneous strains +ε1 = −ε2, occurs at ˜107°C. Long-range disordering between Mg2+ and Mn2+ on the M(4) and M(2) sites occurs above 550°C. Mn2+ occupies the M(4) and M(2) sites preferring M(4) with a site-preference energy of 24.6±1.5 kJ mol−1. Disordering induces an increase in XMnM2 and decrease in XMnM4 at elevated temperatures. Upon cooling, the ordered states of cation occupancy are ‘frozen in’ and strains in lattice parameters are maintained, suggesting that re-equilibration during cooling has not taken place.

The golden iridescence observed in orthoamphiboles from the Nuuk district, southern West Greenland has been shown by analytical transmission electron microscopy to be the result of the interference of light reflected from alternate, coherent gedrite and anthophyllite exsolution lamellae parallel to (010). The lamellae are periodic with an average spacing of ∼180 nm; lamellae with this spacing would give rise to yellow iridescence. It is concluded that the exsolution lamellae are the origin of the features previously seen on cleaved surfaces of the amphiboles in the atomic force microscope (AFM). The suggestion is that the 0.75° difference in the cleavage angle for the two phases produces corrugations that are imaged by AFM. The morphology of the lamellae is consistent with an origin by spinodal decomposition.

Pyrochlore group minerals have the general formula A16–xB16O48Z8–y·nH2O, with A mainly Na, Ca, Sr, REE, Th, U; B mainly Nb, Ta, Ti and Z being O, F, OH. In this study, pyrochlore specimens were examined from carbonatites at Argor, Carillon Dam, Chilwa Island, Fen, Lueshe, Oka, Mbeya, Meech Lake and Verity. Primary features include a background with little compositional variation, from core to rim, upon which are commonly superimposed narrow oscillatory zones, parallel to {111}. These zones are usually characterized by high Ta, in many cases coupled with U (here Argor, Meech Lake and Verity specimens), but Chilwa Island and Fen pyrochlores have little Ta and zonation is mainly by enrichment in Ce and Nb. Primary zonation may persist through high-temperature metamorphism (Meech Lake and Verity) and metamictization (Meech Lake). Oscillatory zones were generated by a disequilibrium system that cooled under tranquil conditions, signalling absence of magma turbulence and, in many cases, the end of crystal growth. Some fresh crystals (Oka, Fen) have no oscillatory zones, possibly the product of magma turbulence in space or time. Low-temperature effects may mimic those of primary high temperature and are especially characterized by replacement rims, pyrochlore-inpyrochlore veinlets and low A-ion totals (Carillon Dam, Lueshe, Myeba).