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Melt inclusions in zircon represent time capsules, which provide deep insights into igneous rock formation including timing, physicochemical conditions, and the compositional evolution of cogenetic magmas with respect to major, trace, and volatile elements. However, their full potential as petrogenetic indicators, in particular their usability and consistency as geothermometers, is poorly investigated. Therefore, we present new mineralogical and chemical data for recrystallized and homogenized melt inclusions and host zircon from different mafic and felsic rocks of the Bushveld Complex (BC), South Africa. Samples include rutile-bearing cumulate rocks of the Marginal and Critical zones, as well as rutile-free, magnetite-ilmenite-titanite-bearing diorites and granites of the Upper Zone, Rashoop Granophyre and Lebowa Granite Suite. All melt inclusions, irrespective of rock type, have rhyolitic compositions with SiO2 contents ranging from 65 to 78 wt.%, and H2O from 1.6 to 4.0 wt.%, whereas trace element contents differ systematically between rock types. In rutile-bearing mafic rocks, melt inclusions commonly show higher Ti contents (>800 ppm), higher Th/U ratios (up to 38), and lower REE contents (ƩREE 150 ppm). Liquidus temperatures of melt inclusions obtained from normative Qz-Ab-Or and rhyolite-MELTS modelling indicate melt entrapment mostly at 930–850 °C (at 200 MPa), tailing down in some samples to 700 °C. For rutile-bearing rocks, these temperatures overlap with those obtained by TiO2-in-melt and Ti-in-zircon geothermometry. For all rutile-free mafic and felsic rocks, reduced TiO2 activities of aTiO2 ∼ 0.3 are required for Ti-in-zircon geothermometry, and TiO2rutile ∼ 30 wt.% for TiO2 saturation geothermometry, to match temperatures from other geothermometers. Furthermore, partition coefficients obtained from melt inclusion - host zircon pairs are within error identical for mafic and felsic rocks and also reveal no systematic dependency on melt inclusion size, composition and entrapment temperature. The results of this study demonstrate that melt inclusions in zircon are a powerful tool for geothermometry and to constrain magma compositions, H2O contents, and TiO2 activities, which are critical for the understanding of magmatic processes shaping Earth’s crust.

Single crystals of ABW-type CsAlTiO4 (CAT), CsFeTiO4 (CFT), CsGaTiO4 (CGT), and ANA-type CsTi1.1Si1.9O6.5 (CST) were grown and characterized by electron microprobe analyses, single-crystal X-ray diffraction, thermal analyses, and spindle-stage optical investigations to determine the electronic polarizability of 4-coordinated Ti4+, α([4]Ti4+). The crystal structure of CAT was confirmed to crystallize in the highest possible topological symmetry Imma (a = 8.9677(2) Å, b = 5.7322(1) Å, c = 9.9612(3) Å) with tetrahedrally coordinated Al and Ti equally distributed on Wyckoff position 8i. Twinning by reticular merohedry with a twin index of 2 was observed for most of the crystals resulting in a hexagonal twin lattice (a = 11.487(3) Å, c = 8.968(2) Å) with Laue symmetry 6/mmm. Refractive indices measured by immersion methods on an untwinned specimen are n x = 1.716(5), n y = 1.725(2), and n z = 1.727(1) with 2V z = 127.1(6)°. The diffraction patterns of CFT and CGT clearly showed superstructure reflections causing a symmetry lowering of index 4 with a transformation according to 2a, b, c from Imma to Pmab with a = 18.3054(7) Å, b = 5.8083(2) Å, c = 9.9938(4) Å for CFT, and a = 18.2921(6) Å, b = 5.7636(2) Å, c = 9.9210(3) Å for CGT. Refractive indices for CGT are n x = 1.750(3), n y = 1.772(3), and n z = 1.776(2) with 2V z = 132(1)°. The crystal structure of the ANA-type CsTi1.1Si1.9O6.5 was confirmed to crystallize in space group Ia 3 ¯ $\overline{3}$ d (a = 13.8333(4) Å). The extra 0.5 O atoms are needed for charge compensation and to allow the sum of electronic polarizabilities to give a total electronic polarizability calculated from the refractive index n = 1.718(4). The electronic polarizability of [4]Ti4+ was calculated from the difference between the observed total polarizabilities (derived from the mean refractive indices of CAT and CGT) and the sum of electronic polarizabilities of cations and anions omitting the polarizability of Ti resulting in α([4]Ti4+) = 5.15(5) Å3.

The diffusive exchange of 30 trace elements during the interaction of natural mafic and silicic alkaline melts was experimentally studied at conditions relevant to shallow magmatic systems. In detail, a set of 12 diffusion couple experiments have been performed between natural shoshonitic and rhyolitic melts from the Vulcano Island (Aeolian archipelago, Italy) at a temperature of 1200 {\deg}C, pressures from 50 to 500 MPa, and water contents ranging from nominally dry to ca. 2 wt. %. Concentration-distance profiles, measured by Laser Ablation ICP-MS, highlight different behaviours, and trace elements were divided into two groups: (1) elements with normal diffusion profiles (13 elements, mainly low field strength and transition elements), and (2) elements showing uphill diffusion (17 elements including Y, Zr, Nb, Pb and rare earth elements, except Eu). For the elements showing normal diffusion profiles, chemical diffusion coefficients were estimated using a concentration-dependent evaluation method, and values are given at four intermediate compositions (SiO2 equal to 58, 62, 66 and 70 wt. %, respectively). A general coupling of diffusion coefficients to silica diffusivity is observed, and variations in systematics are observed between mafic and silicic compositions. Results show that water plays a decisive role on diffusive rates in the studied conditions, producing an enhancement between 0.4 and 0.7 log units per 1 wt.% of added H2O. Particularly notable is the behaviour of the trivalent-only REEs (La to Nd and Gd to Lu), with strong uphill diffusion minima, diminishing from light to heavy REEs. Modelling of REE profiles by a modified effective binary diffusion model indicates that activity gradients induced by the SiO2 concentration contrast are responsible for their development, inducing a transient partitioning of REEs towards the shoshonitic melt., Comment: 57 pages, 12 figures, 5 tables

Cumulate rocks of the Upper Main Zone and Upper Zone (UUMZ) of the Bushveld Complex, South Africa, contain the world's major resources of Fe-Ti-V ±, hosted in Ti-magnetite and apatite, and are commonly considered as having crystallized from the last major injection of magma into the magma chamber. In this study, we present the petrography, modal proportions, whole-rock major element chemistry (260 samples), electron microprobe data (∼10 000 analyses for plagioclase, olivine, and pyroxene), and compiled analyses of Cr in magnetite (239 samples) for the UUMZ sampled over 2.1 km of the Bierkraal drill cores in the western limb of the Complex. The UUMZ section exhibits a broad normal fractionation trend upwards, but a series of reversals to more primitive anorthite contents in plagioclase, Mg# in pyroxenes and olivine, Cr in whole-rocks and Cr in magnetite separates are observed, accompanied by the appearance or disappearance of various minerals. Anorthosite or leucogabbro layers are closely linked to these reversals; the reversals in An % of plagioclase are used as boundaries to divide the UUMZ into 18 cycles. These cycles are interpreted as indications of magma chamber replenishment by plagioclase-laden magmas (up to 20 vol. % plagioclase) and are also marked by spikes in Cr content. In addition, abundant Fe-Ti oxide-bearing plagioclase-rich rocks are identified in the lower half of the UUMZ. These have crystallized from a hybrid melt produced by the mixing of a new plagioclase-bearing magma batch and the resident magma. Further crystallization of this hybrid liquid may lead to the formation of magnetite layers in the lower part of the UUMZ. The Bushveld UUMZ therefore grew by multiple emplacements of crystal-laden magmas coming from deep-seated chambers. Slow cooling in a shallow chamber explains the systematic bottom-up compositional evolution in the cumulate pile within individual cycles. The residual melt reached silicate liquid immiscibility soon after the saturation of apatite. Thereafter, segregation of conjugate Fe-rich and Si-rich melts and crystallization of the paired melts produces cumulates with a smooth upward decrease in Fe-Ti oxides, whereas plagioclase mode increases in each apatite-bearing cycle. A comparison of systematic geochemical analyses and a detailed lithological stratigraphy between the Bushveld limbs demonstrates the possible connectivity between the western and eastern Upper Zone but indicates notable differences from the Bellevue section of the northern limb.

At fast-spreading mid-ocean ridges (MORs), the horizon between the axial melt lens (AML) and the overlying sheeted dikes is characterized by extensive anatectic processes. The heat flux of the AML in combination with hydrothermal fluids from above causes high-grade contact metamorphism, which may result in anatexis of the roof rocks above the AML. The products of this process are silica-rich anatectic melts that have the potential to contaminate MOR basalts and residual hornfels. Here, we simulate the complex igneous and metamorphic processes occurring at the AML roof by hydrous partial melting experiments and provide corresponding trace element partition coefficients between melt and residues, which are useful to quantify those processes. We present trace element patterns from experimental anatectic felsic melts and the related residue produced by hydrous partial melting of various types of AML roof rocks. The starting materials used are sheeted dikes and hornfelses from Hole 1256D drilled by the Integrated Ocean Drilling Program. Results are compared with directly-related natural lithologies (i.e., felsic veins and granoblastic hornfels) from the same site. The trace element contents generally overlap with natural examples and experimental melts produced at low water activity (aH2O

A crystal of BaCaBO3F was grown by the Czochralski method. It shows a phase transition at 242.7 °C upon cooling where the hexagonal high-temperature modification is transformed to a monoclinic low-temperature form (space group C2, a = 17.8779(8) A, b = 9.0596(4) A, c = 12.9735(5) A, β = 118.875(13)°, V = 1840.03(22) A3, Z = 18). The monoclinic phase has a symmetry lowered by an index of 18 relative to the hexagonal supergroup. This represents a higher symmetry than the rhombohedral model which has a symmetry of index 36 lower than the hexagonal form determined in a previous study (Li and Zeng, J. Cryst. Growth 2013, 382, 47). The monoclinic system is confirmed by optical investigations with a polarizing microscope showing biaxial negative character and refractive indices nx = 1.615(1), ny = 1.664(1), and nz = 1.665(1), 2Vx = 10.0(2)° as measured on a microrefractometer spindle stage in immersion liquids. Electron microprobe analysis yielded a slight excess of Ba resulting in the composition Ba1.04Ca0.96BO...

© 2016 Elsevier B.V.. The Bushveld Complex (South Africa) is the largest layered intrusion on Earth and plays a considerable role in our understanding of magmatic differentiation and ore-forming processes. In this study, we present new geochemical data for apatite-hosted multiphase inclusions in gabbroic cumulates from the Bushveld Upper Zone. Inclusions re-homogenized at high-temperature (1060-1100 °C) display a range of compositions in each rock sample, from iron-rich (35 wt.% FeOtot; 28 wt.% SiO2) to silica-rich (5 wt.% FeOtot; 65 wt.% SiO2). This trend is best explained by an immiscible process and trapping of contrasted melts in apatite crystals during progressive cooling along the binodal of a two-liquid field. The coexistence of both Si-rich and Fe-rich immiscible melts in single apatite grains is used to discuss the ability of immiscible melts to segregate from each other, and the implications for mineral and bulk cumulate compositions. We argue that complete separation of immiscible liquids did not occur, resulting in crystallization of similar phases from both melts but in different proportions. However, partial segregation in a crystal mush and the production of contrasting phase proportions from the Fe-rich melt and the Si-rich melt can be responsible for the cyclic evolution from melanocratic (Fe-Ti-P-rich) to leucocratic (plagioclase-rich) gabbros which is commonly observed in the Upper Zone of the Bushveld Complex where it occurs at a vertical scale of 50 to 200 m. ispartof: EARTH AND PLANETARY SCIENCE LETTERS vol:443 pages:108-117 status: published

The mixing of magmas is a fundamental process in the Earth system causing extreme compositional variations in igneous rocks. This process can develop with different intensities both in space and time, making the interpretation of compositional patterns in igneous rocks a petrological challenge. As a time-dependent process, magma mixing has been suggested to preserve information about the time elapsed between the injection of a new magma into sub-volcanic magma chambers and eruptions. This allowed the use of magma mixing as an additional volcanological tool to infer the mixing-to-eruption timescales. In spite of the potential of magma mixing processes to provide information about the timing of volcanic eruptions its statistical robustness is not yet established. This represents a prerequisite to apply reliably this conceptual model. Here, new chaotic magma mixing experiments were performed at different times using natural melts. The degree of reproducibility of experimental results was tested repeating one experiment at the same starting conditions and comparing the compositional variability. We further tested the robustness of the statistical analysis by randomly removing from the analysed dataset a progressively increasing number of samples. Results highlight the robustness of the method to derive empirical relationships linking the efficiency of chemical exchanges and mixing time. These empirical relationships remain valid by removing up to 80% of the analytical determinations. Experimental results were applied to constrain the homogenization time of chemical heterogeneities in natural magmatic system during mixing. The calculations show that, when the mixing dynamics generate millimetre thick filaments, homogenization timescales of the order of a few minutes are to be expected.

International audience; At oceanic spreading centers, interactions between magma and hydrothermal convecting systems trigger major physical, thermal, and chemical exchanges. The two-pyroxene hornfels recovered from the base of the sheeted dike sequence at Integrated Ocean Drilling Program (IODP) Site 1256 (equatorial Eastern Pacific) are interpreted as a conducting boundary layer between the underlying axial melt lens and the hydrothermally cooled sheeted dikes. They are cut by numerous small, felsic veins, which were recently interpreted as a product of hydrous partial melting of sheeted dikes. Here, we present trace element compositions of products (melts and residues) of hydrous partial melting experiments using basalts and hornfels from IODP Site 1256 as starting material. The experimental products generated between 910 °C and 970 °C match the natural lithologies from Site 1256 in terms of major and trace element compositions. The compositions of the anatectic melts correspond to the compositions of the felsic veins, while the residual minerals match the compositions of the two-pyroxene hornfels, evidencing that hydrous partial melting is an important magmatic process in the gabbro/dike transition of fast-spreading mid-oceanic ridges. Our results complement previous experimental studies on anatectic processes occurring at the roof of the magma chambers from fast-spreading mid-ocean ridges. Moreover, calculations of mixing and assimilation fractional crystallization using the experimental partial melts as contaminant/assimilant showed that anatectic melts can only be a minor contributor to the contamination process.

International audience; Replenished axial melt lenses at fast-spreading mid-oceanic ridges may move upward and intrude into the overlying hydrothermally altered sheeted dikes, resulting in high-grade contact metamorphism with the potential to trigger anatexis in the roof rocks. Assumed products of this process are anatectic melts of felsic composition and granoblastic, two-pyroxene hornfels, representing the residue after partial melting. Integrated Ocean Drilling Program Expeditions 309, 312, and 335 at Site 1256 (eastern equatorial Pacific) sampled such a fossilized oceanic magma chamber. In this study, we simulated magma chamber roof rock anatectic processes by performing partial melting experiments using six different protoliths from the Site 1256 sheeted dike complex, spanning a lithological range from poorly to strongly altered basalts to partially or fully recrystallized granoblastic hornfels. Results show that extensively altered starting material lacking primary magmatic minerals cannot reproduce the chemistry of natural felsic rocks recovered in ridge environments, especially elements sensitive to hydrothermal alteration (e.g., K, Cl). Natural geochemical trends are reproduced through partial melting of moderately altered basalts from the lower sheeted dikes. Two-pyroxene hornfels, the assumed residue, were reproduced only at low melting degrees (