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To provide new insights into the interaction of ultramafic alkaline melts with the subcontinental lithospheric mantle, we present results of a petrographical-mineralogical study of ilmenite-bearing mantle xenoliths from the Grib kimberlite, Archangelsk, Russia along with results from reaction experiments between harzburgite and Fe–Ti bearing carbonate–silicate melts similar to aillikite. The compositions of orthopyroxene, ilmenite and garnet from our mantle xenoliths are similar to compositions of minerals of the low-Cr megacryst suite from different kimberlite occurrences worldwide including the Grib kimberlite as well as minerals from sheared lherzolite xenoliths captured by the Grib kimberlite. This suggests that ilmenite-bearing xenoliths, megacrysts, and sheared lherzolite xenoliths could have a common origin and/or formed under similar conditions. The reaction experiments were performed at 4 GPa and 1200 °C with varying proportions of aillikite (0, 10, and 50 wt%) that reacted with harzburgite. The experimental runs with 10% and 50% aillikite resulted in two layers within the capsule, with an ilmenite-bearing reaction zone at the contact between aillikite and harzburgite, and an ilmenite-free zone characterized by higher garnet and clinopyroxene abundances. An increase of aillikite melt is directly correlated with increasing TiO2 and decreasing Cr2O3 contents and Mg# values in the mineral phases, most significantly for pyroxenes. Overall, the experiments produce a chemical gradation of minerals from Cr-rich (Fe–Ti-poor) to Cr-poor (Fe–Ti-rich) which is strikingly similar to the chemical gradation observed in minerals from natural mantle-derived xenoliths from kimberlites. In summary, comparison of our experimental data with natural samples indicates possible links between the generation of megacrysts and Ti-rich metasomatism of the lithospheric mantle by ultramafic alkaline (aillikite-related) melts and their possible evolution towards kimberlites. Our results illustrate the importance of melt-rock ratios in generating the mineralogical and chemical diversity in mantle xenolith suites.

Monazite and magnetite are sensitive indicators of local fluid chemistry, pressure, and temperature during metasomatism. In this study, the role of fluids, during the metamorphism of a granite to metagranite, (Jiao-Liao-Ji orogenic belt, North China Craton), is explored via monazite, magnetite, and pyrite microtextures and mineral chemistry coupled with zircon and monazite Th–U–Pb dating. CL bright zircon cores (2163 ± 17 Ma) record the crystallization age of the granite. BSE dark monazite cores (1876 ± 36 Ma) are characterized by high U and Ca and low Nd contents. The surrounding BSE bright mantle (1836 ± 14 Ma) is characterized by abundant fine-grained huttonite inclusions, a high porosity, a high Th and Si content, and a low P, La, Ce, and Y content. The monazites are surrounded by a three-layered concentric corona consisting of first fluorapatite, followed by allanite, and then epidote. TiO2 in the primary magmatic magnetite (Mag1–1) has been mobilized to form a series of compositionally and texturally distinct magnetites (Mag1–2, Mag2, Mag3, Mag4, and Mag5) associated with ilmenite, rutile, and titanite reaction textures. Combined, these results suggest that external NaCl and sulphate-bearing fluids derived from a local sulphate-bearing evaporate infiltrated the granite and induced the formation of pyrite and enriched the pre-existing monazite in S at around 1904 Ma. In situ δ34S values for pyrite range from 13.03 ‰ to 13.41 ‰, which is typical of metamorphic pyrite. Sporadic synchysite-(Y) inclusions in the pyrite indicate a local CO2-rich component in the fluid. The BSE bright mantle around monazite formed from later fluids from the same local evaporite deposit during the decompression stage of the Jiao-Liao-Ji orogenic belt at around ~ 1840 Ma, which overlaps with zircon dark rims at 1849 ± 12 Ma. This same Na-bearing fluid induced the albitization of the feldspars, formation of apatite–allanite–epidote coronas around monazite, and formation of rutile–titanite–epidote alteration textures associated with magnetite and ilmenite exsolved from the magnetite. During subsequent much later greenschist facies metamorphism, muscovite, chlorite, and Mag5 were precipitated along mineral grain boundaries, mineral cleavage, micropores, and fractures and pyrite experienced partial alteration to goethite.

Fe3+ and XFe3+, defined as Fe3+/(Fe2+ + Fe3+) on a molar basis, are now recognised as key parameters in phase equilibrium modelling. A hindrance is that it is only possible to routinely measure total Fe, and not Fe3+ and Fe2+, in minerals using the electron microprobe. Charge balance techniques can be used to estimate Fe3+ and Fe2+ for some minerals, but not for those that contain vacancies. Whilst other analytical techniques can determine XFe3+ in minerals, these are not commonly applied by metamorphic petrologists. Therefore, researchers must rely on estimates. This study collates wet chemical, Mossbauer spectroscopy, and X-ray absorption near edge structure (XANES) spectroscopy analyses of XFe3+ in metapelitic minerals and rocks from the literature. The resulting database of 77 studies contains 591 samples, of which 261 have XFe3+ determined for the whole rock. There are XFe3+ measurements for 483 biotites, 192 white micas, 78 chlorites, and 32 staurolites. Average (± 1σ) XFe3+ values in whole rock, biotite, white mica, chlorite, and staurolite are 0.23 ± 0.16, 0.11 ± 0.08, 0.55 ± 0.18, 0.08 ± 0.07, and 0.07 ± 0.06, respectively. The average (± 1σ) number of Fe3+ cations in biotite, white mica, chlorite, and staurolite is 0.28 ± 0.19 (22 O + Ti cations per formula unit, pfu), 0.17 ± 0.13 (22 O pfu), 0.31 ± 0.27 (28 O pfu), and 0.20 ± 0.17 (46 O pfu), respectively. The mean whole rock XFe3+ is similar for metapelites containing ilmenite and magnetite, as well as those that report no Fe-oxide, but is considerably higher for hematite-bearing rocks. Whilst there is little variation with pressure and temperature, there is an increase in the number of Fe3+ cations and XFe3+ of both white mica and biotite with the type of Fe-oxide present. Our observations are compared with the predictions of phase equilibrium modelling using thermodynamic dataset 6.2 (Holland and Powell, J Metamorph Geol 29:333–383, 2011) and the solution models of White et al. (J Metamorph Geol 32:261–286, 2014a) for Fe3+ and XFe3+ in these minerals. The predicted XFe3+ and number of Fe3+ cations in biotite, chlorite, and staurolite broadly match natural observations, but for white mica the predicted mean XFe3+ is underestimated by 0.2–0.4 and the number of Fe3+ cations by 0.05–0.2. Whilst modelling correctly predicted increases in the XFe3+ of white mica and biotite with whole rock XFe3+, it also predicted variations in mineral XFe3+ as a function of pressure and temperature which are not observed in the natural samples.

Replacement reactions occur during metamorphism and metasomatism in response to changes in pressure, temperature and bulk rock and fluid compositions. To interpret the changes in conditions, it is necessary to understand what phases have previously been present in the rocks. During fluid-mediated replacement, the crystallography of the replacement phases is often controlled by the parent reactant phase. However, excessive fluid fluxing can also lead to extreme element mobility. Titanium is not mobile under a wide range of fluid compositions and so titanium-bearing phases present an opportunity to interpret conditions from the most extreme alteration. We map orientation relationships between titanium-bearing phases from ore deposits using EBSD and use symmetry arguments and existing relationships to show that completely consumed phases can be inferred in ore deposits. An ilmenite single crystal from Junction gold deposit is replaced by titanite, rutile and dolomite. The rutile has the following well-documented orientation relationship to the ilmenite [0001]ilmenite // rutile and ilmenite // [001]rutile The anatase is a single crystal and shows a potential orientation relationship [0001]ilmenite = (0001)ilmenite // {211}anatase and ilmenite // anatase The single crystal orientation and lack of symmetrical equivalent variants suggest nucleation dominates the anatase production. Dolomite grew epitaxially on the ilmenite despite only sharing oxygen atoms suggesting the surface structure is important in dolomite nucleation. Titanite partially replaced ilmenite during metasomatism at Plutonic gold deposit. The titanite orientation is weakly related to the ilmenite orientation by the following relationship: [0001]ilmenite // titanite and { $$10{\bar{1}}0$$ }ilmenite // (001)titanite The prevalence of subgrain boundaries in the titanite suggests multiple nucleation points on an already deformed ilmenite needle leading to the formation of substructure in the absence of deformation. Existing known topotaxial replacement relationship can be used to infer completely replaced phases using the misorientation distributions of the replacement polycrystals. Orientation modelling for a cubic phase replaced by rutile in a sample from Productora tourmaline breccia complex shows misorientation distributions consistent with Rutile // cubic and Rutile // cubic Combining this with volume constraints and assuming Ti is immobile, the composition of the cubic phase is constrained as titanomagnetite with 85% ulvospinel. Complex microstructures with domanial preferred orientations can also be used to document the microstructure of replaced phases. An aggregate of rutile grains with two parts that share a common axis is interpreted as having replaced a twinned ilmenite grain. Modelling shows that the misorientation distribution for the aggregate is consistent with the above relationship replacing ilmenite with a { $$10{\bar{1}}2$$ } twin.

The Fe–Mg and Fe–Mn interdiffusion coefficients for ilmenite have been determined as a function of temperature and crystallographic orientation. Diffusion annealing experiments were conducted at 1.5 GPa between 800 and 1100 $$^{\circ }\hbox {C}$$ . For Fe–Mg interdiffusion, each diffusion couple consisted of an ilmenite polycrystal and an oriented single crystal of geikielite. The activation energy (Q) and pre-exponential factor ( $$D_0$$ ) for Fe–Mg diffusion in the ilmenite polycrystal were found to be Q = $$188 \pm 15\hbox { kJ mol}^{-1}$$ and $${\text {log}} D_0$$ = $$-6.0 \pm 0.6\hbox { m}^2\hbox { s}^{-1}$$ . For the geikielite single crystal, Fe–Mg interdiffusion has $$Q = 220 \pm 16\hbox { kJ mol}^{-1}$$ and $${\text {log}} D_0 = -4.6 \pm 0.7\hbox { m}^2\hbox { s}^{-1}$$ . Our results indicate that crystallographic orientation did not significantly affect diffusion rates. For Fe–Mn interdiffusion, each diffusion couple consisted of one ilmenite polycrystal and one Mn-bearing ilmenite polycrystal. For Fe–Mn interdiffusion, Q = $$264 \pm 30\hbox { kJ mol}^{-1}$$ and $${\text {log}} D_0$$ = $$-2.9 \pm 1.3\hbox { m}^2\hbox { s}^{-1}$$ in the ilmenite. We did not find a significant concentration dependence for the Fe–Mg and Fe–Mn interdiffusion coefficients. In comparing our experimental results for cation diffusion in ilmenite with those previously reported for hematite, we have determined that cation diffusion is faster in ilmenite than in hematite at temperatures

Numerous analyses of multiple ilmenite, titanomagnetite, sanidine, plagioclase, biotite, orthopyroxene, and clinopyroxene crystals (when present) in each of 24 single-clast pumices from the Bishop Tuff (BT), CA are presented, together with whole-rock compositions on the same single clasts. Data from multiple Fe–Ti oxide grains in each sample, coupled with an assessment of analytical uncertainty, show that there is a single population of ilmenite and titanomagnetite in each of 20 samples and no more than two populations of ilmenite and/or titanomagnetite in the remaining four. A statistical evaluation of microprobe uncertainty (for beam conditions of 15 kV and 10 nA) constrains the minimum number of ilmenite (≥ 21) and titanomagnetite (≥ 56) analyses required to obtain Fe–Ti two-oxide temperatures with propagated uncertainties ≤ ± 10 °C. Thermometry results confirm a continuous range (~ 700–800 °C) across the BT deposit. Plagioclase displays a bimodal compositional pattern, where a predominantly sodic (An14–15) vs. calcic (An22–23) population is found in single clasts where pyroxene is absent vs. present; the latter coincides with geochemical evidence for mixing between high-SiO2 rhyolite and less differentiated melts as previously documented in the literature. When sanidine rims are paired with plagioclase, calculated two-feldspar temperatures (~ 690–780 °C) are strongly correlated (R2 = 0.94) with Fe–Ti two-oxide temperatures. Application of plagioclase–liquid hygrometry reveals a systematic decrease in melt water content (~ 7.2–4.1 wt%) with increasing temperature across the BT deposit, consistent with experiments from the literature that show cotectic crystallization of quartz–sanidine–plagioclase in rhyolite melt requires a concomitant decrease of ~ 3 wt% H2O between 700 and 800 °C at 200 MPa. Single-clast, whole-rock concentrations of some elements (e.g., Rb) correlate strongly with Fe–Ti oxide temperature (R2 = 0.95). The Mg# in biotite also correlates strongly with temperature (R2 = 0.97), as do the Mg# values in orthopyroxene and clinopyroxene with whole-rock Mg# (R2 = 0.6 and 0.8, respectively) and melt water content (R2 = 0.7 for both). Evidence points to biotite crystallization in all BT samples from high-SiO2 rhyolite melt, which was already continuously zoned in composition and temperature prior to mixing with less differentiated melts, as previously noted in the literature. In contrast, several lines of evidence, including hydrous phase-equilibrium experiments on rhyolites from the literature, show that both pyroxenes in BT pumices co-crystallized with calcic plagioclase (~ An21–29), in equilibrium with both titanomagnetite and ilmenite, after mixing between less differentiated melt(s) and relatively hot (≥ 755 °C) high-SiO2 rhyolite.

In April 2015, an unpredicted rapid-onset eruption occurred at Calbuco Volcano, Southern Andes of Chile. This event consisted of two, sub-Plinian eruptions separated by a few hours. By analysis of Fe–Ti exchange between ilmenite and titanomagnetite crystals in samples of erupted material, we determine timescales of pre-eruptive heating experienced at the partially solidified chamber base and constrain the magma residence time for the bulk of the carrier magma. Analysis of the Fe–Ti oxide pairs from a sample retrieved from a pyroclastic density current deposit (Cal-160) shows that it was affected by a significant heating event (recording 70–220 °C of heating), while other collected samples did not record this late heating. This sample is interpreted to represent a piece of crystal mush located at the bottom of a prolate, ellipsoidal mush reservoir, mobilised

Titanite textures and chemistry have been investigated from the Roxby Downs Granite, host to the Olympic Dam Cu–U–Au–Ag deposit, South Australia. Three textural subtypes of titanite are documented: primary magmatic (cores and rims); deuteric; and hydrothermal (low T recrystallisation). Magmatic cores are defined by enrichment in LREE (~ 3 wt%), Nb (up to 1 wt%) and Zr relative to rims, which typically contain

Lunar mare basalts are a product of partial melting of the lunar mantle under more reducing conditions when compared to those expected for the Earth’s upper mantle. Alongside Fe, Ti can be a major redox sensitive element in lunar magmas, and it can be enriched by up to a factor of ten in lunar basaltic glasses when compared to their terrestrial counterparts. Therefore, to better constrain the oxidation state of Ti and its coordination chemistry during lunar magmatic processes, we report new X-ray absorption near edge structure (XANES) spectroscopy measurements for a wide range of minerals (pyroxene, olivine, Fe–Ti oxides) and basaltic melt compositions involved in partial melting of the lunar mantle. Experiments were conducted in 1 bar gas-mixing furnaces at temperatures between 1100 and 1300 °C and oxygen fugacities (fO2) that ranged from air to two orders of magnitude below the Fe–FeO redox equilibrium. Run products were analysed via electron microprobe and XANES Ti K-edge. Typical run products had large (> 100 µm) crystals in equilibrium with quenched silicate glass. Ti K-edge XANES spectra show a clear shift in energy of the absorption edge features from oxidizing to reducing conditions and yield an average valence for Fe–Ti oxides (armalcolite and ilmenite) of 3.6, i.e., a 40% of the overall Ti is Ti3+ under fO2 conditions relevant to lunar magmatism (IW − 1.5 to − 1.8). Pyroxenes and olivine have average Ti valence of 3.75 (i.e., 25% of the overall Ti is trivalent), while in silicate glasses Ti is exclusively tetravalent. Pre-edge peak intensities also indicate that the coordination number of Ti varies from an average V-fold in silicate glass to VI-fold in the Fe–Ti oxides and a mixture between IV and VI-fold coordination in the pyroxenes and olivine, with up to 82% [IV]Ti4+ in the pyroxene. In addition, our results can help to better constrain the Ti3+/∑Ti of the lunar mantle phases during magmatic processes and are applied to provide first insights into the mechanisms that may control Ti mass-dependent equilibrium isotope fractionation in lunar mare basalts.

A Fe–Ti-rich garnet, clinopyroxene, and quartz eclogite sample from the 1.0 Ga Sveconorwegian orogen, SW Sweden, contains abundant quartz, rutile, and zircon in distinct micro-textural sites: garnet core, garnet rim, and matrix, constituting an ideal case for investigation of the behavior of Zr-in-rutile and Ti-in-quartz at high-pressure and temperature. A P–T path, peaking at 16.5–19 kbar and 850–900 °C, has been constrained independently for the same rock by pseudosection modelling; input pressures from this model were used for trace element geothermometry of each garnet micro-textural domain. Trace element thermo(baro)metry, based on in situ Secondary Ion Mass Spectrometry analyses of Ti contents in quartz and Zr contents in rutile, yields P–T estimates of progressive crystallization of quartz and rutile along the prograde metamorphic path. For inclusions in the garnet cores, Zr-in-rutile geothermometry yields 700–715 °C and Ti-in-quartz 620–640 °C at 7 kbar. For inclusions in the garnet rims, temperature estimates are 760–790 °C (Zr-in-rutile) and 740–920 °C (Ti-in-quartz) at 12–18 kbar. Finally, matrix rutile records 775–800 °C and locally ~ 900 °C, and quartz records temperatures up to 900 °C at 18 kbar. Ti-in-quartz estimates for the metamorphic peak (inclusions in the garnet rims and matrix) conform to the pseudosection, but appear too low for the early prograde stage (garnet cores), possibly due to lack of equilibrium at T

A detailed petrological study is presented for six phenocryst-poor obsidian samples (73–75 wt% SiO2) erupted as small volume, monogenetic domes in the Mexican and Cascade arcs. Despite low phenocryst (+microphenocryst) abundances (2–6 %), these rhyolites are each multiply saturated with five to eight mineral phases (plagioclase + orthopyroxene + titanomagnetite + ilmenite + apatite ± zircon ± hornblende ± clinopyroxene ± sanidine ± pyrrhotite). Plagioclase and orthopyroxene phenocrysts (identified using phase-equilibrium constraints) span ≤30 mol % An and ≤15 % Mg#, respectively. Eruptive temperatures (±1σ), on the basis of Fe–Ti two oxide thermometry, range from 779 (±25) to 940 (±18) °C. Oxygen fugacities (±1σ) range from −0.4 to 1.4 (±0.1) log units relative to those along the Ni–NiO buffer. With temperature known, the plagioclase-liquid hygrometer was applied; maximum water concentrations calculated for the most calcic plagioclase phenocryst in each sample range from 2.6 to 6.5 wt%. This requires that the rhyolites were fluid-saturated at depths ≥2–7 km. It is proposed that the wide compositional range in plagioclase and orthopyroxene phenocrysts, despite their low abundance, can be attributed to changing melt water concentrations owing to degassing during magma ascent. Phase-equilibrium experiments from the literature show that higher dissolved water concentrations lead to more Fe-rich orthopyroxene, as well as more calcic plagioclase. Loss of dissolved water leads to a progressive increase in melt viscosity, and phenocrysts often display diffusion-limited growth textures (e.g., dendritic and vermiform), consistent with large undercoolings caused by degassing. A kinetic barrier to microlite crystallization occurred at viscosities from 4.5 to 5.0 log10 Pa s for these rhyolites, presumably because the rate at which melt viscosity changed was high owing to rapid loss of dissolved water during magma ascent.

A method is described for estimating the activity of titania (TiO2) in a magmatic liquid from the compositions of coexisting cubic oxide (spinel) and rhombohedral oxide (ilmenite). These estimates are derived from the thermodynamic models of Ghiorso and Evans (Am J Sci 308:957–1039, 2008; see also Sack and Ghiorso in Contrib Mineral Petrol 106:474–505, 1991a; Am Mineral 76:827-847, 1991b) and may be computed self consistently along with temperature and oxygen fugacity for an assumed pressure. The method is applied to a collection of 729 naturally occurring oxide pairs from rhyolites and dacites. For this suite of oxides, values of titania activity relative to rutile saturation range from 0.3 to 0.9. Genetically related groups of oxide pairs display activity–temperature trends with negative slopes at higher activities (0.6–0.9) or positive slopes at lower activities (0.3–0.7). Thermodynamic analysis supports the assumption of two-oxide, liquid equilibrium for the former group, but suggests that such an interpretation for oxide sequences with positive activity–temperature trends may be problematic. Application of the estimation method to oxide pairs from the Shiveluch Volcano and the Bishop Tuff reveals that the former are consistent with having equilibrated with known matrix glass compositions, whereas the latter pairs are inconsistent with equilibration with pre-eruptive liquids trapped in quartz inclusions.

Optical microscopy, secondary electron microscopy and analytical electron microscopy were used to characterize crystallographic orientation relationships between oriented mineral inclusions and clinopyroxene (Cpx) host from the Hujialing garnet clinopyroxenite within the Sulu ultrahigh-pressure (UHP) terrane, eastern China. One garnet clinopyroxenite sample (2HJ-2C) and one megacrystic garnet-bearing garnet clinopyroxenite (RZ-11D) were studied. Porphyroblastic clinopyroxene from sample 2HJ-2C contains oriented inclusions of ilmenite (Ilm), spinel (Spl), magnetite and garnet, whereas clinopyroxene inclusions within megacrystic garnet from sample RZ-11D contain oriented inclusions of ilmenite and amphibole. Specific crystallographic relationships were observed between ilmenite/spinel plates and host clinopyroxene in sample 2HJ-2C and between ilmenite plates and host clinopyroxene in sample RZ-11D, i.e. [\( 1\bar{1}00 \)]Ilm//[\( 0\bar{1}0 \)]Cpx (0001)Ilm//(100)Cpx; and [110]Spl//[\( 0\bar{1}0 \)]Cpx (\( \bar{1}11 \))Spl//(100)Cpx. These inclusions are suggested to be primary precipitates via solid-state exsolutions. Most of the needle-like magnetite/spinel inclusions generally occur at the rims or along fractures of clinopyroxene within sample 2HJ-2C. Despite the epitaxial relation with host clinopyroxene, these magnetite/spinel needles would have resulted from fluid/melt infiltrations. Non-epitaxial garnet lamellae in clinopyroxene of sample 2HJ-2C were formed via fluid infiltration-deposition primarily along (010) and subordinately along (100) partings. Epitaxial amphibole plates (with a thickness

Kimberlite sills emplaced in granite located near the town of Wemindji (Quebec, Canada) range from 2 cm to 1.2 m in thickness. The sills exhibit a wide variation in macroscopic appearance from fine-grained aphanitic dolomitic hypabyssal kimberlite to ilmenite/garnet macrocrystal hypabyssal kimberlite. Diatreme or crater facies rocks are not present. Multiple intrusions are present within the sills, and graded bedding and erosional features such as cross-bedding are common. The sills exhibit a wide range in their modal mineralogy with respect to the abundances of spinel, apatite, phlogopite and dolomite. Olivine is the dominant macrocryst, with an average composition of Fo90. Garnet macrocrysts are low chrome (2–3 wt. %) pyrope (G1/G9 garnet). Ilmenite occurs as rounded macrocrysts (7–13 wt. % MgO). Phlogopite microphenocrysts are Ti-poor and represent a solid solution between phlogopite and kinoshitalite end members. Spinel compositions mainly represent the Cr-poor members of the qandilite–ulvospinel–magnetite series. The principle carbonate comprising the groundmass is dolomite, with lesser later-forming calcite. Accessory minerals include apatite, Sr-rich calcite, Nb-rich rutile, baddeleyite, monazite-(Ce) and barite. While some of these accessory minerals are atypical of kimberlites in general, it is expected that differentiation products of an evolved carbonate-rich kimberlite magma will crystallize these phases. The Wemindji kimberlites offer insight into the process of crystal fractionation and differentiation in evolved kimberlite magmas. The macroscopic textural features observed in the Wemindji sills are interpreted to represent flow differentiation of a mantle-derived, very fluid, low viscosity carbonate-rich kimberlite. The diverse modes and textural features result entirely from flow differentiation and multiple intrusions of different batches of genetically related kimberlite magma. The mineralogy of the Wemindji kimberlites has some similarities to that of the Wesselton and Benfontein calcite kimberlite sills but differs in detail with respect to dominant carbonate (i.e. dolomite versus calcite), and the character of the rare earth-bearing accessory minerals (i.e. monazite-(Ce) versus rare earth fluorocarbonates).

Spongy textures are observed in mantle peridotite xenoliths hosted in Cenozoic kamafugites from the Western Qinling, central China. These textures are mainly developed in clinopyroxenes and spinels, and occur as spongy rims consisting of low-Na clinopyroxene, ilmenite, and bubbles, enclosing nonspongy cores. The ilmenites and bubbles exhibit shapes and sizes that vary with the width of the spongy rims. The spongy-textured minerals preserve primary shapes and well-defined grain boundaries and do not show apparent interaction with contact minerals or observed melts except the subsequent melts forming melt pockets. The xenocrysts display reactive zoning textures with host magmas rather than spongy textures. Compositionally, the spongy rims are enriched in Ca, Ti, and most trace elements, have high Cr#, and are depleted in Na, Al, Fe, AlVI, and AlIV/AlVI compared with the cores. These observations suggest that melts/host magmas did not play any significant role in the formation of the spongy textures. We therefore propose that spongy-textured clinopyroxenes and spinels in Western Qinling peridotite xenoliths developed from a decompression-induced partial melting event prior to formation of melt pockets and xenolith entrainment in host magmas.

Analyses of trace elements in the mineral phases of granulites provide important information about the trace element distribution in the lower crust. Since granulites are often considered residues of partial melting processes, trace element characteristics of their mineral phases may record mineral/melt equilibria thus giving an opportunity to understand the nature and composition of melts in the lower continental crust. This study provides an extensive set of mineral trace element data obtained by LA-ICP-MS analyses of mafic and intermediate granulites from Central Finland. Mass balance calculations using the analytical data indicate a pronounced contribution of the accessory minerals apatite for the REE and ilmenite for the HFSE. Coherent mineral/mineral ratios between samples point to a close approach to equilibrium except for minerals intergrown with garnet porphyroblasts. Mineral trace element data were used for the formulation of a set of D mineral/melt partition coefficients that is applicable for trace element modelling under lower crustal conditions. D mineral/melt were derived by the application of predictive models and using observed constant mineral/mineral ratios. The comparison of the calculated D mineral/melt with experimental data as well as the relationship between mineral trace element contents and a leucosome with a composition close to an equilibrium melt provides additional constraints on mineral/melt partitioning. The D values derived in this study are broadly similar to magmatic partition coefficients for intermediate melt compositions. They provide a first coherent set of D values for Sc, V, Cr and Ni between clinopyroxene, amphibole, garnet, orthopyroxene, ilmenite and melt. In addition, they emphasize the strong impact that ilmenite exerts on the distribution of Nb and Ta.

Ilmenite in coronitic gabbros from the Bamble and Kongsberg sectors, southern Norway, is surrounded by zircons ranging in diameters from a fraction of a micrometer to 10 μm across. The zircons are inert during subsequent metamorphism (amphibolite- to pumpellyite–prehnite facies) and metasomatism (scapolitization and albitization) and can be found as trails in silicates (phlogopite, talc, chlorite, amphibole, albite, and tourmaline) in the altered rocks. The trails link up to form polygons outlining the former oxide grain boundary. This 3-dimensional framework of zircons is used to (a) recognize metasomatic origin of rocks, (b) quantify the mobility of elements during mineral replacement, (c) establish the growth direction of reaction fronts and to identify the reaction mechanism as dissolution–reprecipitation. Zircon coronas on Fe–Ti oxides have been described from a number of terrains and appear to be common in mafic rocks (gabbros and granulites) providing a tool for a better understanding of metasomatic and metamorphic reactions.

Abundant Fe–Ti oxide inclusions in cumulus olivine (Fo77–81) from the Panzhihua and Hongge intrusions, Emeishan large igneous province, SW China, document the first evidence for early crystallization of Fe–Ti oxides in ferrobasaltic systems in nature. The intrusions also contain significant stratiform Fe–Ti–V oxide ores. The oxide inclusions are sub-rounded or irregular, range from ∼5 to 50 μm in diameter, and are dominated by either titanomagnetite or ilmenite. The fact that the inclusions are either titanomagnetite- or ilmenite-dominant suggests that they are trapped crystals, instead of immiscible oxide melt, formed during growth of the host olivine. The absence of other silicate phases in the inclusion-bearing olivine is difficult to reconcile with a possible xenocrystic origin of the oxide inclusions. These oxide inclusions are thus interpreted to be cumulus minerals crystallized together and trapped in olivine from the same parental magma. In addition to Fe–Ti oxides, some inclusions contain amphibole + biotite ± fluorapatite that might have formed by reaction of trapped hydrous liquid with the host olivine. Numerical modeling of high-Ti Emeishan basalts using the MELTS program successfully simulates early crystallization of olivine (∼Fo81) and Fe–Ti spinel in the presence of a moderate amount of H2O (∼1.5 wt%) under pressure and fO2 conditions generally pertinent to the Panzhihua and Hongge intrusions. The modal mineralogy of the oxide inclusions is in good agreement with the bulk compositions of the ore, as inferred from whole-rock data, in a given intrusion. This is consistent with the interpretation that the stratiform oxide ores in the intrusions formed by accumulation of Fe–Ti oxide crystals that appeared on the liquidus with olivine and clinopyroxene.

The microtextures of stishovite and coesite in shocked non-porous lithic clasts from suevite of the Ries impact structure were studied in transmitted light and under the scanning electron microscope. Both high-pressure silica phases were identified in situ by laser-Raman spectroscopy. They formed from silica melt as well as by solid-state transformation. In weakly shocked rocks (stage I), fine-grained stishovite (≤1.8 μm) occurs in thin pseudotachylite veins of quartz-rich rocks, where it obviously nucleated from high-pressure frictional melts. Generally no stishovite was found in planar deformation features (PDFs) within grains of rock-forming quartz. The single exception is a highly shocked quartz grain, trapped between a pseudotachylite vein and a large ilmenite grain, in which stishovite occurs within two sets of lamellae. It is assumed that in this case the small stishovite grains formed by the interplay of conductive heating and shock reverberation. In strongly shocked rocks (stages Ib–III, above ∼30 GPa), grains of former quartz typically contain abundant and variably sized stishovite (

Major and trace element XRF and in situ LA-ICP-MS analyses of ilmenite in the Tellnes ilmenite deposit, Rogaland Anorthosite Province, SW Norway, constrains a two stage fractional crystallization model of a ferrodioritic Fe-Ti-P rich melt. Stage 1 is characterized by ilmenite-plagioclase cumulates, partly stored in the lower part of the ore body (Lower Central Zone, LCZ), and stage 2 by ilmenite-plagioclase-orthopyroxene-olivine cumulates (Upper Central Zone, UCZ). The concentration of V and Cr in ilmenite, corrected for the trapped liquid effect, (1) defines the cotectic proportion of ilmenite to be 17.5 wt% during stage 1, and (2) implies an increase of D V Ilm during stage 2, most likely related to a shift in fO2. The proportion of 17.5 wt% is lower than the modal proportion of ilmenite (ca. 50 wt%) in the ore body, implying accumulation of ilmenite and flotation of plagioclase. The fraction of residual liquid left after crystallization of Tellnes cumulates is estimated at 0.6 and the flotation of plagioclase at 26 wt% of the initial melt mass. The increasing content of intercumulus magnetite with stratigraphic height, from 0 to ca. 3 wt%, results from differentiation of the trapped liquid towards magnetite saturation. The MgO content of ilmenite (1.4–4.4 wt%) is much lower than the expected cumulus composition. It shows extensive postcumulus re-equilibration with trapped liquid and ferromagnesian silicates, correlated with distance to the host anorthosite. The Zr content of ilmenite, provided by in situ analyses, is low (

International audience; We have studied glass-bearing leucocratic (granitic to Qz-monzonitic) crustal xenoliths from the Tindfjöll Pleistocene volcanic complex, SW Iceland. The xenoliths consist of strongly resorbed relicts of anorthitic plagioclase, K-rich feldspar and rounded quartz in colorless through pale to dark-brown interstitial glass. Spongy clinopyroxene and/or rounded or elongated crystals of orthopyroxene are in subordinate amount. Magnetite, ilmenite, zircon, apatite, allanite and/or chevkinite are accessory minerals. The xenoliths more likely are relicts of earlier-formed, partially melted Si-rich rocks or quartz–feldspar-rich crystal segregations, which suffered latter interaction with hotter and more primitive magma(s). Icelandic lavas are typically low in δ 18O compared to mantle-derived, “MORB”-like rocks (~5.6 ± 0.2 ‰), likely due to their interaction with, or contamination by, the upper-crustal rocks affected by rain and glacial melt waters. Surprisingly, many quartz and feldspar crystals and associated colorless to light-colored interstitial glasses of the studied xenoliths are not low but high in δ 18O (5.1–7.2 ‰, excluding three dark-brown glasses of 4–5 ‰). The xenoliths contain abundant, low- to high-δ 18O (2.4–6.3 ‰) young zircons (U–Pb age 0.2–0.27 ± 0.03 Ma; U–Th age 0.16 ± 0.07 Ma), most of them in oxygen isotope equilibrium with interstitial glasses. The δ 18O values >5.6 ‰ recorded in the coexisting zircon, quartz, feldspar and colorless interstitial glass suggest crystallization from melts produced by fusion of crustal rocks altered by seawater, also reflecting multiple melting and crystallization events. This suggests that “normal”-δ 18O silicic magmas may not be ultimately produced by crystallization of mafic, basaltic magmas. Instead, our new single-crystal laser fluorination and ion microprobe O-isotope data suggest addition of diverse partial crustal melts, probably originated from variously altered and preconditioned crust.

Zr-in-rutile thermometry on samples of blueschist from Sifnos, Greece, yields temperatures that reflect progressive crystallization of rutile from ca. 445 to 505°C with an analytical precision of + 18/−27 and ± 10°C using the electron microprobe and ± 1.5–3.5°C using the ion microprobe. Individual grains are generally homogeneous within analytical uncertainty. Different grains within a single sample record temperature differences as large 55°, although in most samples the range of temperatures is on the order of 25°. In several samples, Zr-in-rutile temperatures from grains within garnet are lower than temperatures from matrix grains, reflecting growth of rutile with increasing temperature of metamorphism. Although the specific rutile-producing reactions have not been identified, it is inferred that rutile grows from either continuous reaction involving the breakdown of lower grade phases (possibly ilmenite), or from pseudomorph reactions involving the breakdown of relic igneous precursors at blueschist-facies conditions. No systematic variation in rutile temperatures was observed across the blueschist belt of northern Sifnos, consistent with the belt having behaved as a coherent block during subduction.

Thirty-two peridotite xenoliths from kimberlitic pipes of the Kaapvaal craton were analysed for S and studied in reflected light microscopy and electron microprobe. Correlation between whole-rock S concentrations and sulphide modal abundances has been obscured by kimberlite-related sulphur within the mantle and by low-temperature contamination processes during emplacement. Mantle-derived base metal sulphides (BMS) occur as solitary inclusions (SI) and intergranular blebs. Unfractured SI encloses intergrowths of Ni-poor and Ni-rich monosulphide solid solution (Mss) phases, coexisting with pentlandite (Pn) and Cu-rich sulphides. Textural relationships between Mss phases and Cu-sulphides are consistent with fractional crystallization of Mss from a Cu–Fe–Ni sulphide melt. Pn-rich euhedral SI may have crystallized from a more metal-rich sulphide melt. However, the opaque mineral assemblages of both fractured sulphide inclusions and intergranular BMS point to a progressive desulphurization of Mss, yielding Pn-rich grains, often replaced by Fe-poor heazlewoodite and abundant magnetite, while Cu-sulphides are replaced by native copper. This trend is consistent with reducing conditions generated by low-temperature serpentinization. A residual origin cannot be ruled out for the Mss enclosed in the most refractory peridotites, although their Ni/Fe ratios are too low to be consistent with an equilibration with olivine at magmatic temperatures. Modal abundances of mantle-derived BMS increase in the Fe-enriched metasomatized peridotites. At least two BMS precipitation processes can be recognized: (1) precipitation of Fe–Cu-rich immiscible sulphide melts in phlogopite-(ilmenite–rutile) peridotites and (2) sulphidation reactions from an H2S-rich fluid phase in phlogopite-K richterite peridotites.

Chemical composition of rock-forming minerals in Appalachian Siluro-Devonian granitoid intrusions, southwestern New Brunswick, was systematically determined by electron microprobe. The mineral chemical data together with petrographic examination was used to test magmatic equilibration and to constrain crystallization conditions, volatile exsolution, and fluorine-chlorine activity of fluids associated with these intrusions. Mineralogical distinction between Late Silurian to Early Devonian granodioritic to monzogranitic series (GMS) and Late Devonian granitic series (GS) rocks is evident, although both are subsolvus I-type to evolved I-type granitoids. Oxidized to reduced GMS rocks consist of quartz, plagioclase (An>10), K-feldspar, biotite, apatite, titanite, zircon, monazite, ± hornblende, ± pyroxene, ± magnetite, ± ilmenite, and ± sulfide. GS rocks comprise quartz, K-feldspar, plagioclase (An

Rocks of the Cerro del Almirez ultramafic massif (Sierra Nevada, Betic Cordillera, S. Spain) record the high-pressure dehydration of antigorite–olivine serpentinite to form chlorite harzburgite (ol + opx + chl). In the field, these two rock types are separated by a well-defined isograd. Titanian clinohumite (TiCl) and olivine show textural and compositional differences depending on the rock type. OH–TiCl occurs in the serpentinite as disseminated grains and in veins. F–OH–TiCl is observed exclusively in the chlorite harzburgite, where it occurs as porphyroblastic grains and within prograde olivine as irregular and lamellar, planar intergrowths at microscopic and submicroscopic scales. Petrological evidence of partial to complete breakdown of TiCl to olivine + ilmenite is preserved in both rock types. Chlorite harzburgite is characterized by a brown pleochroic olivine with abundantally oriented microscopic to submicroscopic oxide particles. The mean Ti-content of the brown olivine is 144 ppm. The brown olivine preserves TiCl lamellae that sometimes grade into ghost lamellae outlined by the oxide trails. This observation suggests that some of the oxide inclusions in the brown olivine are derived from the breakdown of TiCl intergrowths. Thermodynamic modelling of selected Almirez bulk rock compositions indicates a temperature increase from 635°C to 695°C, at pressures ranging from 1.7 GPa to 2.0 GPa, as the cause for the compositional adjustment of TiCl between the Almirez antigorite serpentinite and chlorite harzburgite. These P–T estimates are in good agreement with the sequence of phase relations observed in the field. The computed phase diagrams in conjunction with the geothermal conditions envisaged for different subduction settings indicate that TiCl is stable in the vicinity of the antigorite serpentinite/chlorite harzburgite phase boundary in some subduction settings. In these circumstances, clinohumite–olivine intergrowths in chlorite harzburgite may act as a sink for high field strength elements, and probably other elements, that are present in the mantle–wedge fluids.

Cr-poor and Cr-rich megacryst suites, both comprising of varying proportions of megacrysts of orthopyroxene, clinopyroxene, garnet, olivine, ilmenite and a number of subordinate phases, coexist in many kimberlites, with wide geographic distribution. In rare instances, the two suites occur together on the scale of individual megacryst hand specimens. Deformation textures are common to both suites, suggesting an origin related to the formation of the sheared peridotites that also occur in kimberlites. Textures and compositions of the latter are interpreted to reflect deformation and metasomatism within the thermal aureole surrounding the kimberlite magma in the mantle. The megacrysts crystallized in this thermal aureole in pegmatitic veins representing small volumes of liquids derived from the host kimberlite magma, which were injected into a surrounding fracture network prior to kimberlite eruption. Close similarities between compositions of Cr-rich megacryst phases and those in granular lherzolites are consistent with early crystallization from a primitive kimberlite liquid. The low-Cr megacryst suite subsequently crystallized from residual Cr-depleted liquids. However, the Cr-poor suite also reflects the imprint of contamination by liquids formed by melting of inhomogeneously distributed mantle phases with low melting temperatures, such as calcite and phlogopite, present within the thermal aureole surrounding the kimberlite magma reservoir. Such carbonate-rich melts migrated into, and mixed with some, but not all, of the kimberlite liquids injected into the mantle fracture network. Contamination by the carbonate-rich melts changed the Ca–Mg and Mg–Fe crystal–liquid distribution coefficient, resulting in the crystallization of relatively Fe-rich and Ca-poor phases. The implied higher crystal-melt Mg–Fe distribution coefficient for carbonate-rich magmas accounts for the generation of small volumes of Mg-rich liquids that are highly enriched in incompatible elements (i.e. primary kimberlite magmas). The inferred metasomatic origin for the sheared peridotites implies that this suite provides little or no information regarding vertical changes in the thermal, chemical and mechanical characteristics of the mantle.

The Fe 3+ /Fetot of all Fe-bearing minerals has been analysed by Mossbauer spectroscopy in a suite of biotite-rich to biotite-free graphitic metapelite xenoliths, proxies of an amphibolite-granulite transition through progressive biotite melting. Biotite contains 9 to 16% Fe 3+ /Fetot, whereas garnet, cordierite and ilmenite are virtually Fe 3+ -free (0-1% Fe 3+ /Fetot) in all samples, regardless of biotite presence. Under relatively reducing conditions (graphite-bearing assemblages), biotite is the only carrier of Fe 3+ during high-temperature metamor- phism; therefore, its disappearance by melting represents an important event of iron reduction during granulite formation, because haplogranitic melts usually incorpo- rate small amounts of ferric iron. Iron reduction is accompanied by the oxidation of carbon and the production of CO2, according to the redox reaction: 2Fe2O ðBtÞ 3 þ C ðGrÞ ) 4FeO ðCrd;Grt;Ilm;OpxÞ þ CO ðfluid;melt;CrdÞ 2 : Depending on the nature of the peritectic Fe-Mg mineral produced (garnet, cordierite, orthopyroxene), the CO2 can either be present as a free fluid component, or be completely stored within melt and cordierite. The oxi- dation of graphite by iron reduction can account for the in situ generation of CO2, implying a consequential ra- ther than causal role of CO2 in some granulites and migmatites. This genetic model is relevant to graphitic rocks more generally and may explain why CO2 is present in some granulites although it is not required for their formation.

Glassy orthopyroxene granodiorite-tonalite (named pincinite after type locality) was described from basaltic lapilli tuffs of the Pliocene maar near Pincina village in the Slovakian part of the Pannonian Basin. Two pincinite types exhibit a qualitatively similar mineral composition (quartz, An20–55 plagioclase, intergranular silicic glass with orthopyroxene and ilmenite, ±K-feldspar), but strongly different redox potential and formation PT conditions. Peraluminous pincinite is reduced (6–7% of total iron as Fe3+ in corundum-normative intergranular dacitic glass) and contains ilmenite with 8–10 mol% Fe2O3 and orthopyroxene dominated by ferrosilite. High-density (up to 0.85 g/cm3) primary CO2 inclusions with minor H2, CH4, H2S, CO and N2 ( 0.705–0.706, δ18O>9‰ V-SMOW) around alkali basalt reservoir in depths between 17 and 20 km, and around late stage derivatives of the basalt fractionation, intruding the crust up to depths of 10–11 km. Low water activity in the pincinite parental melt was caused by CO2-flux from the Tertiary basaltic reservoirs and intrusions. The anatexis leads to generation of a melt-depleted granulitic crust beneath the Pannonian Basin, and the pincinites are interpreted as equivalents of igneous charnockites and enderbites quenched at temperatures above solidus and unaffected by sub-solidus re-equilibration and metamorphic overprint.

This study has examined the ~300 MPa partial melting behaviour of four metapelites collected from the highest grade rocks occurring below the anatectic zone of the Mt. Stafford area, Arunta Inlier, central Australia. In this area, metasediments are interpreted to have undergone partial melting within the andalusite stability field; possibly as a result of a lowering of the metapelite solidus by the presence of boron in the rocks. Two of the samples were two mica metapelites (MTS70 and MTS71). These both contained significant quantities of tourmaline and were thus boron enriched. The other two samples are biotite metapelites. One of these rocks contains only a trace of tourmaline (MTS8) and the other is tourmaline free (MTS7). Despite expectations that muscovite in the two mica samples would break down via a subsolidus reaction, muscovite was stable to above 750°C due to the incorporation of Ti, phengitic and possibly F components into its structure. Between 750 and 800°C, muscovite melted out completely via a coupled muscovite + biotite fluid-absent incongruent reaction. Tourmaline was partially consumed in this reaction, with the elbaitic component being preferentially consumed. In the most mica-rich sample this reaction produced ~60% melt at 800°C. In the biotite metapelites, biotite melting began at a temperature below 800°C and was accompanied by very modest melt production at this low temperature. In contrast to the two mica metapelites, the main pulse of melt production in these samples occurred at a temperature between 850 and 950°C. In both these samples biotite + melt coexisted over a temperature range in excess of 150°C, and in MTS8, biotite was still in the run products at 950°C. The very refractory nature of these evolved biotite compositions is most likely a consequence of both the presence of a Ti buffering phase in the assemblage (ilmenite) and the essentially plagioclase-free nature of the starting compositions. Under the fluid-absent conditions of this study, tourmaline is clearly a reactant in the partial melting process, but does not appear to shift the fluid-absent incongruent melting reactions markedly. In the tourmaline-rich two mica metapelites, tourmaline only disappears from the run products at a temperature above 850°C, where it coexisted with a substantial melt proportion. This appears to coincide with the point of maximum boron concentration in the melts.

Lavas of the Biu and Jos Plateaus, Northern Cameroon Volcanic Line (CVL), contain abundant genetically related megacrysts of clinopyroxene, garnet and subordinately plagioclase, ilmenite and amphibole. P, T-estimates of crystallization for the primitive group of cpx and gnt megacrysts are 1.7–2.3 GPa and ~1,400 °C. Because crustal thickness in these areas is only ~30 km (~0.9 GPa), megacrysts must have formed within the lithospheric mantle. Primitive Biu and Jos lavas are isotopically heterogeneous in Sr-Nd isotope space (87Sr/86Sr=0.70285–0.70360 and eNd=7.5–4.6). Biu Plateau megacrysts overlap the range of Biu lavas in Sr-Nd isotope composition, indicating that crustal contamination of Biu lavas was minor. Jos Plateau lavas are isotopically more enriched than their associated megacrysts. Therefore an additional contamination of Jos lavas due to assimilation of continental crust (~5%) or enriched shallow lithospheric mantle is indicated. Lavas of Biu and Jos Plateau do not reflect simple fractionation or equilibrium crystallization products, but instead reflect mixing between primary melts and their fractionated derivatives.

New analytical and experimental data constrain the storage and equilibration conditions of the magmas erupted in 1912 from Novarupta in the 20th century's largest volcanic event. Phase relations at H2O+CO2 fluid saturation were determined for an andesite (58.7 wt% SiO2) and a dacite (67.7 wt%) from the compositional extremes of intermediate magmas erupted. The phase assemblages, matrix melt composition and modes of natural andesite were reproduced experimentally under H2O-saturated conditions (i.e., PH2O=PTOT) in a negatively sloping region in T–P space from 930 °C/100 MPa to 960 °C/75 MPa with fO2~NNO+1. The H2O-saturated equilibration conditions of the dacite are constrained to a T–P region from 850 °C/50 MPa to 880 °C/25 MPa. If H2O-saturated, these magmas equilibrated at (and above) the level where co-erupted rhyolite equilibrated (~100 MPa), suggesting that the andesite-dacite magma reservoir was displaced laterally rather than vertically from the rhyolite magma body. Natural mineral and melt compositions of intermediate magmas were also reproduced experimentally under saturation conditions with a mixed (H2O + CO2) fluid for the same range in PH2O. Thus, a storage model in which vertically stratified mafic to silicic intermediate magmas underlay H2O-saturated rhyolite is consistent with experimental findings only if the intermediates have XH2O fl=0.7 and 0.9 for the extreme compositions, respectively. Disequilibrium features in natural pumice and scoria include pristine minerals existing outside their stability fields, and compositional zoning of titanomagnetite in contact with ilmenite. Variable rates of chemical equilibration which would eliminate these features constrain the apparent thermal excursion and re-distribution of minerals to the time scale of days.

Kimberlite magmas from the Kimberley area of South Africa have sampled two main types of phlogopite-rich mafic xenoliths which represent deep mantle segregations from highly alkaline melts. The first group corresponds to the MARID rocks characterised by the mineral association mica (phlogopite)–amphibole (K-richterite)–rutile–ilmenite–clinopyroxene and the second group consists of the PIC rocks characterised by the mineral association mica (phlogopite)–ilmenite–clinopyroxene–minor rutile. The two groups are clearly distinguished from one another by their mineral paragenesis, by the major element composition of their phlogopite and ilmenite, by the trace element content of their clinopyroxene and by their clinopyroxene and whole rock Sr and Nd isotope ratios. The combined major and trace element variations are interpreted to indicate a genetic relationship between the PIC rocks and group I kimberlite magma, and between the MARID rocks and group II kimberlite magma. The two types of parental melts percolated through, and metasomatised, the upper mantle beneath the Kimberley area as indicated by the trace element characteristics of the clinopyroxenes of the studied phlogopite-bearing peridotites.

Thermodynamic models are vital tools to evaluate magma crystallization and storage conditions. Before their results can be used independently, however, they must be verified with controlled experimental data. Here, we use a set of hydrothermal experiments on the Late-erupted Bishop Tuff (LBT) magma to evaluate the rhyolite-MELTS thermodynamic model, a modified calibration of the original MELTS model optimized for crystallization of silicic magmas. Experimental results that are well captured by rhyolite-MELTS include a relatively narrow temperature range separating the crystallization of the first felsic mineral and the onset of the ternary minimum (quartz plus two feldspars), and extensive crystallization over a narrow temperature range once the ternary minimum is reached. The model overestimates temperatures by ~40 °C, a known limitation of rhyolite-MELTS. At pressures below 110 MPa, model and experiments differ in the first felsic phase, suggesting that caution should be exercised when applying the model to very low pressures. Our results indicate that for quartz, sanidine, plagioclase, magnetite, and ilmenite to crystallize in equilibrium from LBT magma, magma must have been stored at ≤740 °C, even when a substantial amount of CO2 occurs in the coexisting fluid. Such temperatures are in conflict with the hotter temperatures retrieved from magnetite–ilmenite compositions (~785 °C for the sample used in the experiments). Consistent with other recent studies, we suggest that the Fe–Ti oxide phases in the Late Bishop Tuff magma body are not in equilibrium with the other minerals and thus the retrieved temperature and oxygen fugacity do not reflect pre-eruptive storage conditions.

Alluvial diamonds from the Juina area in Mato Grosso, Brazil, have been characterized in terms of their morphology, syngenetic mineral inclusions, carbon isotopes and nitrogen contents. Morphologically, they are similar to other Brazilian diamonds, showing a strong predominance of rounded dodecahedral crystals. However, other characteristics of the Juina diamonds make them unique. The inclusion parageneses of Juina diamonds are dominated by ultra-high-pressure ("superdeep") phases that differ both from "traditional" syngenetic minerals associated with diamonds and, in detail, from most other superdeep assemblages. Ferropericlase is the dominant inclusion in the Juina diamonds. It coexists with ilmenite, Cr-Ti spinel, a phase with the major-element composition of olivine, and SiO2. CaSi-perovskite inclusions coexist with titanite (sphene), "olivine" and native Ni. MgSi-perovskite coexists with TAPP (tetragonal almandine-pyrope phase). Majoritic garnet occurs in one diamond, associated with CaTi-perovskite, Mn-ilmenite and an unidentified Si-Mg phase. Neither Cr-pyrope nor Mg-chromite was found as inclusions. The spinel inclusions are low in Cr and Mg, and high in Ti (Cr2O3 10 wt%). Most ilmenite inclusions have low MgO contents, and some have very high (up to 11.5 wt%) MnO contents. The rare "olivine" inclusions coexisting with ferropericlase have low Mg# (87–89), and higher Ca, Cr and Zn contents than typical diamond-inclusion olivines. They are interpreted as inverted from spinel-structured (Mg, Fe)2Si2O4. This suite of inclusions is consistent with derivation of most of the diamonds from depths near 670 km, and adds ilmenite and relatively low-Cr, high-Ti spinel to the known phases of the superdeep paragenesis. Diamonds from the Juina area are characterized by a narrow range of carbon isotopic composition (δ13C=–7.8 to –2.5‰), except for the one majorite-bearing diamond (δ13C=–11.4‰). There are high proportions of nitrogen-free and low-nitrogen diamonds, and the aggregated B center is predominant in nitrogen-containing diamonds. These observations have practical consequences for diamond exploration: Low-Mg olivine, low-Mg and high-Mn ilmenite, and low-Cr spinel should be included in the list of diamond indicator minerals, and the role of high-Cr, low-Ti spinel as the only spinel associated with diamond, and hence as a criterion of diamond grade in kimberlites, should be reconsidered.

Zircon-bearing veins in a harzburgite xenolith from kimberlite have imposed Ca-metasomatism on the harzburgite wall rock, in addition to adding K, Fe, Ti and OH. The zircon, previously dated to have an age similar to that of the xenolith-hosting kimberlite, shows higher Y, Nb, Ba, REE, Th and U contents than other mantle-derived zircons. Peripheral alteration of the zircon to baddeleyite and zirconolite, and alteration of vein ilmenite to perovskite suggest reaction with an evolving carbonatitic kimberlite melt. The high Cr2O3 content (0.77 wt%) of the zirconolite extends the compositional range of terrestrial zirconolite.

Rod-shaped ilmenite inclusions in olivine have been observed in numerous peridotite lenses of the Adula–Cima Lunga unit, Central Alps. The rods are elongated parallel to [010]ol and identical in size, shape and concentration to those reported from garnet peridotite at Alpe Arami (AA). TEM investigation of the rods at AA, Cima di Gagnone (CDG) and Monte Duria (MD) demonstrates that the titanate inclusions correspond to a Mg-bearing ilmenite with exclusively a trigonal crystal structure. No other FeTiO3 polymorphs have been identified. The shape of the ilmenite inclusions concurs with minimum topotactic misfits between the lattices of olivine and Mg-bearing ilmenite. Optical microscopy reveals that the ilmenite rods are not randomly distributed within olivine but have, at all localities, a preferred alignment parallel to (001)ol, forming palisades. TEM images of the ilmenite palisades at AA and CDG show that they are controlled by the presence of (001) planar defects in olivine along which the rods nucleated. The defects have been characterised by high-resolution TEM and identified as 4.4 A-wide humite-type layers, i.e. (Mg2SiO4)·Mg(OH,F)2, intergrown within olivine. In such layers substitution of up to 50 mol% MgH2 by Ti4+ is possible. Assuming Ti-saturated humite slabs, the maximum density of (001) faults observed at AA, approximately 1900 mm–1, can accommodate about 170 ppm TiO2 in olivine. This represents about half the values obtained by UV-laser ablation ICP-MS and EMPA analysis. Evidence for annealing of the defects, however, suggests that only parts of the defects are still preserved. The formation of ilmenite rods is considered to be a consequence of the breakdown of isolated humite layers in olivine. The apparent TiO2 content in olivine at AA, CDG and MD is regarded as a function of the Ti-humite defect density.

Oxygen fugacities have been estimated for a wide distribution of samples from the granulite facies terrane (region C) of the Bamble Sector, SE Norway using both the titaniferous magnetite–ilmenite and orthopyroxene–titaniferous magnetite–quartz oxygen barometers. These oxygen fugacities are estimated using temperatures calculated from the titaniferous magnetite–ilmenite thermometer of Ghiorso and Sack (1991) and are both internally consistent with each other as well with the thermometer. In samples for which the estimated temperature is high, the two oxygen barometers show good agreement whereas agreement is poor for low temperature samples. In these low temperature samples, oxygen fugacities estimated from titaniferous magnetite–ilmenite are considerably less than those estimated from orthopyroxene–titaniferous magnetite–quartz. An increase in this discrepancy with decrease in temperature appears to reflect preferential resetting of the hematite component in the ilmenite grains without significant alteration of the more numerous titaniferous magnetite grains. This is due, in part, to greater re-equilibration of the ilmenite grains during retrograde interoxide resetting between the ilmenite grains and the titaniferous magnetite grains. The mean temperature for the non-reset samples, 791 ± 17 °C (1σ), is in good agreement with temperatures obtained from garnet–orthopyroxene KD exchange thermometry in the same region, 785–795 °C (1σ) (Harlov 1992, 2000a). Most non-reset oxygen fugacities range from log10 f O2=−14 to −11.8 or approximately 0.5–1.5 log units above quartz–fayalite–magnetite at 7.5 kbar. Both these temperatures and the range of oxygen fugacities are in good agreement with those estimated using the titaniferous magnetite–ilmenite thermometer/oxygen barometer of Andersen et al. (1991). The QUIlP equilibrium (quartz–ulvospinel–ilmenite–pyroxene) is used to project self-consistent equilibrium temperatures and oxygen fugacities for samples reset due to hematite loss from the ilmenite grains. These projected temperatures and oxygen fugacities agree reasonably well with the non-reset samples. The mean projected QUIlP temperature is 823 ± 6 °C (1σ). This result supports the conclusion that low titaniferous magnetite–ilmenite temperatures (down to 489 °C) and accompanying low oxygen fugacities are the result of hematite loss from the ilmenite grains. Non-reset oxygen fugacities lie approximately 1.5 log10 units above the upper graphite stability curve indicating that the stable C–O–H fluid phase interacting with these gneisses, whether regionally or locally, was CO2. This is borne out by the presence of numerous CO2-rich fluid inclusions in these rocks.

The 150 m thick late Miocene Graveyard Point sill (GPS) is situated at the Idaho-Oregon border near the southwestern edge of the western Snake River Plain. It records from bottom to top continuous fractional crystallization of a tholeiitic parent magma (lower chilled border, FeO/(FeO+MgO) = 0.59, Ni = 90 ppm) towards granophyres (late pods and dikes, FeO/(FeO+MgO) = 0.98, 78 wt% SiO2 3.5 wt% K2O

Detailed phase relations have been determined within the systems Fe2O3-MgO-TiO2 and FeO-MgO-TiO2. Experiments were performed over the temperature interval 1173–1473 K by equilibrating pelletized, fine-grained oxide mixtures in either inert calcia-stabilized zirconia pots (Fe2O3-MgO-TiO2 system) or evacuated silica tubes (FeO-MgO-TiO2 system). Equilibrium phase assemblages were determined by combined optical microscope, X-ray diffraction and EMP examination. Phase relations in the Fe2O3-MgO-TiO2 ternary are dominated by the instability of the M2O3 solid solution relative to the phase assemblage M3O4 + M3O5. A miscibility gap along the M2O3 binary also gives rise to two, 3-phase fields (α-M2O3 + M3O5 + M3O4 and α′-M2O3 + M3O5 + M3O4) separated by the M3O4 + M3O5 phase field. Phase relations in the FeO-MgO-TiO2 ternary were divided into two sub-systems. For the FeTiO3-MgTiO3-TiO2 sub-ternary, there is complete solid solution along the M2O3 and M3O5 binary joins at high temperature. At low temperatures (T < 1373 K) the M3O5 pseudobrookite solid solution decomposes to M2O3 + TiO2. Increasing the concentration of MgO in M3O5 phase results in a decrease in the temperature at which M3O5 becomes unstable and compositional tie lines linking M2O3 and TiO2 fan out, before the appearance of a three-phase region where M2O3, M3O5, and TiO2 coexist. Within the expanded FeO-MgO-TiO2 system, at temperatures above ∼1273 K there is a continuous solid solution along the M3O4 binary. At low temperatures (T < 1273 K) the Mg2TiO4 end-member breaks down to MgO and MgTiO3. The M3O4 phase shows significant non-stoichiometry, down to at least 1173 K. Fe2+-Mg partitioning data were obtained for coexisting M2O3-M3O5 and M2O3-M3O4 pairs in the FeO-MgO-TiO2 ternary. Assuming a regular solution mixing model for all phases, the M2O3 and M3O4 solid solutions were both found to exhibit moderate positive deviations from ideality (∼2600 J/mol), whereas the data for the M3O5 binary suggest close to ideal behaviour.

The partitioning of Fe2+ and Mn2+ between (Fe, Mn)TiO3 and (Fe, Mn)2SiO4 solid solutions in the system FeO-MnO-TiO2-SiO2 has been experimentally investigated at 1100 ∘C and pressures of 1 bar and 25 kbar, over a wide range of Fe/Mn ratios, using electron microprobe analysis of quenched run products. The ilmenite solid solution in this system is within analytical uncertainty a simple binary between FeTiO3 and MnTiO3, but the olivine solid solution appears to contain up to 2.5 wt% TiO2. The Fe-Mn partitioning results constrain precisely the difference in the thermodynamic mixing properties of the two solid solutions. If the mixing properties of (Fe, Mn)2SiO4 solid solutions are assumed to be ideal, as experimentally determined by Schwerdtfeger and Muan (1966), then the ilmenite is a regular, symmetric solution with W ilm Fe-Mn=1.8±0.1 kJ mol−1. The quoted uncertainty does not include the contribution from the uncertainty in the mixing properties of the olivine solution, which is estimated to be ±1.8 kJ mol−1, and which therefore dominates the uncertainty in the present results. Nevertheless, this result is in good agreement with the previous experimental study of O'Neill et al. (1989), who obtained W ilm Fe-Mn=2.2±0.3 kJ mol−1 from an independent method. The results provide another item of empirical evidence supporting the proposition that solid solutions between isostructural end-members, in which order-disorder effects are not important, generally have simple thermodynamic mixing properties, with little asymmetry, modest excess entropies, and excess enthalpies approximately proportional to the difference in the molar volumes of the end-members.

Fe-rich tholeiitic liquids are preserved as chilled pillows and as the chilled base of a 27 meter thick macrorhythmic layer in the Pleasant Bay mafic-silicic layered intrusion. The compositions of olivine (Fo1) and plagioclase (An13−8) in these extremely fine grained rocks suggest that they represent nearly end stage liquids that formed by fractionation of tholeiitic basalt. Their major element compositions (∼17.5 wt% FeOT and 54 wt%SiO2) closely resemble highly evolved glasses in the Loch Ba ring dike and some recent estimates of end-stage liquids related to the Skaergaard layered intrusion, and are consistent with recent experimental studies of tholeiite fractionation. Their trace element compositions are consistent with extensive earlier fractionation of plagioclase, olivine, clinopyroxene, ilmenite, magnetite and apatite. The mineral assemblage of the chilled rocks (olivine, clinopyroxene, quartz, ilmenite and magnetite), apatite saturation temperatures, and very low Fe3+/Fe2+indicate conditions of crystallization at temperatures of about 950 °C and fO2 about two log units below FMQ. Cumulates that lie about 3 meters above the chilled base of the macrorhythmic layer contain cumulus plagioclase, olivine, clinopyroxene, ilmenite, apatite and zircon. This mineral assemblage and the Fe-Mg ratio in clinopyroxene cores suggest that this cumulate was in equilibrium with a liquid having a composition identical to that of the chilled margin which lies directly beneath it. The high FeOT and low SiO2 concentrations of this cumulate (23.3 and 45.8 wt%, respectively) are comparable to those in late stage cumulates of the Skaergaard and Kiglapait intrusions. This association of a chilled liquid and cumulate in the Pleasant Bay intrusion suggests that late stage liquids in tholeiitic layered intrusions may have been more SiO2-rich than field-based models suggest and lends support to recent experimental studies of tholeiite fractionation at low fO2 which indicate that saturation of an Fe-Ti oxide phase should cause FeOT to decrease in the remaining liquid.