Bulk Melt Research Articles

Vapor-bubble growth in olivine-hosted melt inclusions

Abstract Melt inclusions record the depth of magmatic processes, magma degassing paths, and volatile budgets of magmas. Extracting this information is a major challenge. It requires determining melt volatile contents at the time of entrapment when working with melt inclusions that have suffered post-entrapment modifications. Several processes decrease internal melt inclusion pressure, resulting in nucleation and growth of a vapor bubble and, time permitting, diffusion of volatiles (especially CO2) into the vapor bubble. Previous studies have shown how this process may lead to most of the CO2 in the bulk melt inclusion being lost to the bubble. Without reconstruction, most of the melt inclusion data in the literature vastly underestimate the CO2 concentrations of magmas by measuring the glass phase only. Methods exist that attempt to reconstruct the entrapped CO2 contents, but they can be difficult to apply and do not always yield consistent results. Here, we explore bubble growth, evaluate CO2 reconstruction approaches, and develop improved experimental and computational approaches. Piston-cylinder experiments were conducted on olivine-hosted melt inclusions from Seguam (Alaska, U.S.A.) and Fuego (Guatemala) volcanoes at the following conditions: 500–800 MPa, 1140–1200 °C for Seguam and 1110–1140 °C for Fuego, 4–8 wt% H2O in the KBr brine filling the experimental capsules, and run durations of 10–120 min. Heated melt inclusions form well-defined S-CO2 trends consistent with degassing models. CO2 contents are enriched by a factor of ~2.5, on average, relative to those of the glasses in unheated melt inclusions, whereas S contents of heated and unheated melt inclusion glasses overlap, indicating that insignificant amounts of S partition into the vapor bubble. For naturally quenched melt inclusions, relatively low closure temperatures for CO2 diffusion enables some CO2 to enter vapor bubbles during quench, whereas higher closure temperatures for S diffusion limits its loss to vapor bubbles. We evaluate the timescales of post-entrapment processes and use the results to develop a new computational model to restore entrapped CO2 contents: melt inclusion modification corrections (MIMiC). Heated melt inclusion data are used as a benchmark to evaluate the results from MIMiC and other published methods of CO2 reconstruction. The methods perform variably well. Key advantages to our experimental technique are accurate measurements of CO2 contents and efficient rehomogenization of large quantities of melt inclusions. Our new computational model produces more accurate results than other computational methods, has similar accuracy to the Raman method of CO2 reconstruction in cases where Raman can be applied (i.e., no C-bearing phases in the bubble), and can be applied to the vast body of published melt inclusion data. To obtain the most robust data on bubble-bearing melt inclusions, we recommend taking both experimental- and MIMiC-based approaches.

Garnet fractionation, progressive melt loss and bulk composition variations in anatectic metabasites: Complications for interpreting the geodynamic significance of TTGs

Tonalite-trondhjemite-granodiorite (TTG) suites constitute a large proportion of the Archean geological record; however, the geodynamic processes that generated them, and Archean continental crust in general, remain a subject of debate. The concentrations and ratios of Sr, Y, La, Yb, Nb, and Ta in TTGs are commonly used to determine the depth of melting of their metabasic sources. The trace element composition of melt produced by metabasic source rocks during anatexis is strongly affected by the presence and abundance of pressure-sensitive minerals, such as plagioclase (Sr-bearing), garnet (Y- and HREE-bearing), and rutile (Nb- and Ta-bearing). Elevated Sr/Y and La/Yb ratios and low concentrations of Nb and Ta in TTGs are generally considered to indicate melting at high pressures (≥2.0 ​GPa). The depth of melting is a key factor in determining the origin of TTGs as this provides critical information on the tectonic setting of their generation. We use phase equilibrium and trace element modelling to explore the effects of three potential influences on TTG trace element compositions: fractionation of trace elements into peritectic garnet cores, progressive melt loss from the source, and source bulk composition. We model three different compositions of Archean basalts along thermal gradients of 500 ​°C/GPa, 750 ​°C/GPa, and 1000 ​°C/GPa. The models produce major and trace element melt compositions that are generally consistent with measured compositions of TTGs. Although Sr/Y, La/Yb, Nb, and Ta exhibit pressure-dependent behaviour, other factors also affect these values. Garnet fractionation causes Sr/Y and La/Yb to reach much greater values and in this scenario, the values also increase with increasing temperature. Source bulk composition has an effect in all scenarios and most strongly influences La/Yb, Nb, and Ta. Overall, these results show that Sr/Y, La/Yb, Nb, and Ta can reach values generally considered to be indicative of high pressure melting at a range of P–T conditions including P ​< ​2.0 ​GPa. Consequently, trace element compositions of TTGs alone may provide a misleading impression of the depth of melting of metabasites and the geodynamic environment of Archean crustal growth and reworking.

Derivation of Jurassic HIMU-like intraplate basalts from mantle transition zone in South China: New geochemical constraints from olivine-hosted melt inclusion

The petrogenesis of high-μ (HIMU, μ = 238U/204Pb) basalt in a continental setting remains highly controversial. Here we present a comprehensive geochemical (including major and trace element and isotopic compositions of whole-rock, olivine and melt inclusion) data on Jurassic HIMU-like basalts from the interior (Antang) of South China. This study identified high-H2O (up to 5.0 wt%) olivine-hosted melt inclusions in these basalts. After stripping off the effects of degassing, post-entrapment crystallization and kinetic diffusion, the primary magma of the Antang basalts was estimated to contain ≥2.65 wt% H2O and the corresponding mantle source contains >1000 ppm H2O, which is much higher than the water content of convecting asthenosphere and lower mantle. In addition, the relative depletion of fluid-mobile elements and positive Nb-Ta anomalies in bulk rocks and melt inclusions, and the distance far away from the contemporaneous paleo-Pacific subduction zone, preclude an origin from a slab fluid-metasomatized mantle. The strong depletion of CaO in both olivine phenocrysts and whole-rock compositions further indicates that the basaltic magmas originated from an eclogitic or pyroxenitic mantle source. The combined geochemical data suggest that the Antang basalts were most likely derived from a hydrous source, which was composed mainly of ancient recycled oceanic crust that had stagnated in the mantle transition zone (MTZ) for more than one billion years. Our results therefore provide a new perspective on the MTZ origin of intracontinental basalts and imply that the hydrous MTZ can preserve recycled crustal components for long periods of time and form distinct mantle reservoirs for intraplate basalts.

Sensitivity Analysis of Unsteady Corium Solidification in an Initially Emptied Horizontal Turbulent Pipe Flow

Abstract In a reactor core meltdown under postulated severe accidents, the molten material called corium could be ejected or relocated through existing vessel penetrations. There exists, however, a potential for plugging of melt flow due to its complete solidification providing the availability of an adequate heat sink. Simulations of the melt flow in a horizontal tube were carried out to conduct a sensitivity study on the effect of key parameters on the melt penetration distance and bulk temperature distribution of the corium. The Reynolds number was varied from 10,000 to 20,000, inlet temperature was varied from 2600 K to 3000 K, the corium thermal conductivity was varied from 10 W/m·K to 20 W/m·K, and the pipe diameter was varied from 0.0095 m to 0.019 m. In addition, a comparison was made with an analytical model based on a modified Epstein's model and a previous numerical model. The study provided insight into the lower bound, which was found to be 98 mm, and the upper bound was 258 mm when predicting the potential penetration length of corium in horizontal pipes.

Varieties of Impactites and Impact Diamonds of the Kara Meteorite Crater (Pay-Khoy, Russia)

Impact diamonds are technical material with valuable mechanical properties. Despite of a quite long story from their discovery and huge diamond storages at the Popigai astrobleme (Siberia, Russia) they were not involved into industrial production, first of all because of remoteness of objects, complexity of extraction and economically more favourable synthesis of technical diamonds in the seventies of the past century. However, due to the high hardness of impact diamonds and also to the high demand of new carbon materials, including nanomaterials, the interest towards this type of natural diamonds is significantly increased in the recent years. Although the mentioned Popigai astrobleme is situated in a remote part of Russia it has been studied in more details. At the same time, the less known Kara giant meteorite crater (Pay-Khoy, Russia) is situated essentially closer to the industrial infrastructure of the European part of Russia. This astrobleme, similarly to Popigai, is enriched in impact diamonds as well. But, till recent years it was not deeply studied using modern analytical methods. During our studies in 2015 and 2017 at the territory of the Kara meteorite crater we have distinguished and described 5 varieties of impactites – bulk melt impactites which form cover-like and thick dike bodies; melt ultrahigh-pressure vein bodies and at least 3 types of suevites formed after specific sedimentary target rocks. These varieties have typomorphic features regarding the crystallinity and mineral composition. It was found that all of them have high concentration of microdiamonds formed by high-pressure high temperature pyrolysis mechanism from precursor materials like coal and organic relicts. Using a set of modern mineralogical methods we have found two principal types of diamond morphologies within the Kara impactites – sugar-like after coal diamonds and diamond paramorphs after organic relicts. The Kara diamonds have several accompanying carbon substances including newly formed graphite, glass-like carbon and probably carbyne. The studied diamondiferous Kara impactites provide an essentially novel knowledge of impact processes in sedimentary targets.

Bulk Liquid for the Skaergaard Intrusion and Its PGE-Au Mineralization: Composition, Correlation, Liquid Line of Descent, and Timing of Sulphide Saturation and Silicate–Silicate Immiscibility

AbstractPreferred and modelled bulk composition of the Skaergaard intrusion are compared to coeval basaltic compositions in East Greenland and found to relate to the second evolved cycle of Geikie Plateau Formation lavas and coeval Skaergaard-like dikes in major and trace element (Mg# ∼45, Ce/Nb ∼2·5, (Dy/Yb)N ∼1·35), and precious metal composition (Pd/Pt ∼3, Au/Pt ∼2) as well as in age (∼56 Ma). Successful comparisons of precious metal compositions only occur with Skaergaard models based on mass balance. The bulk liquid of the intrusion evolved along the liquid line of descent to immiscibility between Si- and Fe-rich silicate liquids after ∼90% of crystallization (F = ∼0·10) in agreement with experimental constraints. Immiscibility led to accumulation and fractionation of the Fe-rich silicate melt in the mushy floor of the intrusion and continued accumulation of granophyre component in the remaining bulk liquid. The composition of plagioclase in the precious metal mineralized gabbro and modelling of Pd/Pt and Au/Pt in first formed droplets of sulphide melt suggest that sulphide saturation was reached in interstitial melts in crystal mushes in the floor and roof and in bulk liquid with a composition equivalent to that of the bulk liquid at lower UZa times and after crystallization of 82–85% of the bulk liquid (F = 0·19–0·16). Prior to sulphide saturation in UZa type melt, the precious metals ratios of the bulk liquid were controlled by the loss of Pt relative to Pd and Au in agreement with the low empirical and experimental solubility of Pt of ∼9ppb compared to a much higher value for Pd and Au. The relative timing between sulphide saturation (F = ∼0·18) and immiscibility between silicate melts (F = ∼0·10) and modelled precious metal ratios underpin the proposed multi-stage model for the mineralization, advocating initial accumulation in the mushy floor of the magma chamber controlled by sulphide saturation in mush melts rather than bulk melt, followed by redistribution of precious metals in a macro-rhythmic succession of gabbroic layers of the upward migrating crystallization zone.

Elemental Distributions and Mineral Parageneses of the Skaergaard PGE–Au Mineralization: Consequences of Accumulation, Redistribution, and Equilibration in an Upward-Migrating Mush Zone

AbstractThe Skaergaard PGE–Au mineralization, aka the Platinova Reef, is a syn-magmatic Platinum Group Element (PGE) and gold (Au) mineralization that formed after crystallization of ∼74% of the bulk melt of the intrusion. It is hosted in a more than 600 m deep and bowl-shaped succession of gabbroic macro-rhythmic layers in the upper 100 m of the Middle Zone. The precious metal mineralization comprises a series of concordant, but compositionally zoned, mineralization levels identified by distinct PGE, Au and Cu peaks. They formed due to local sulphide saturation in stratiform concentrations of interstitial and evolved mush melts in six MLs over &amp;gt; 2000 years. The PGE–Au mineralization is compared to a stack of gold-rimmed saucers of PGE-rich gabbro of upward decreasing size. Fundamentally different crystallization and mineralization scenarios have been proposed for the mineralization, including offset reef type models based on sulphide saturation in the melt from which the silicate host crystallized, and the here argued model which restricts the same processes to the melt of the inward migrating mush zone of the magma chamber. The latter is supported by: i) a 3 D summary of the parageneses of precious metal minerals and phases (&amp;gt; 4000 grains) from 32 samples across the mineralization; ii) a 3 D compilation of all bulk rock assay data; and iii) a principal component analysis (PCA) of PGE, Au, Cu, and selected major and trace elements. In the main PGE-mineralization level (Pd5 alias Pd-Zone) the precious metal mineral paragenesis varies across the intrusion with precious metal sulphides and Au-alloys at the W-margin to Precambrian basement, precious metal plumbide and Au- and Ag-alloys at the E-margin to flood basalts, and skaergaardite (PdCu) and intermetallic compounds and alloys of PGE–Au and Cu in the central parts of the mineralization. Precious metal parageneses are distinct for a given sector of the intrusion, i.e. drill core (local control), rather than for a given stratigraphic or temporal interval in the accumulated gabbros. The precious metal ‘grade times width’ number (average g/t x metres) for the mineralization at an upper and a lower cut off of 100 ppb PGE or Au increases from ∼20 to ∼45 g toward the centre of the mineralization due to ponding of precious metal bearing melt. A strong increase in (Pd+Pt+Au)/Cu and dominance of (PdCu) alloys in the lower and central parts of the mineralization demonstrate the partial dissolution of droplets of Cu-rich sulphide melt and fractionation of precious metal ratios. The precious metal parageneses, the distribution of precious metals in the mineralization, and the PCA support initial accumulation of precious metals in the melt of the mush in the floor, followed by equilibration, sulphide saturation, and reactions with residual and immiscible Fe-rich silicate melt in a series of macro-rhythmic layers in the stratified and upward migrating mush zone in the floor of the magma chamber. Syn-magmatic and upward redistribution of precious metals sets the Skaergaard PGE–Au Mineralization apart from conventional reef type and offset-reef type precious metal mineralizations, and characterize ‘Skaergaard type’ precious metal deposits.

Mid-infrared spectroscopy of laser-produced basalt melts for remote sensing application

We obtained mid-infrared spectra and major-element analyses of glasses produced in pulsed laser experiments of basalt. Materials from pits excavated in a basalt slab, as well as of a larger, separated melt droplet were studied. The results of this study show that these glasses exhibits spectral features clearly distinguishable from the unprocessed starting material. Spectra and chemistry show changes, which could be the result of not only melting but also vaporization.Christiansen Features (CF) for the melt glass in the laser-excavated pits are at 8.3–8.5 μm, and a dominating Reststrahlen Band (RB) at 10.1–10.5 μm in wavelength. The spectra of the powdered glass droplet has a CF at 8.8–8.9 μm and a RB at 10.3–10.5 μm. The spectra are clearly different from the spectra of the surrounding starting material, which shows CF between 8.0 and 8.3 μm, and ample RBs between 9.3 μm and 14.7 μm, typical olivine, plagioclase and pyroxene features.The results reflect the chemical composition, which shows significant losses of volatiles like K2O and Na2O, as well as of moderate volatiles like FeO, SiO2, and MgO. Refractories TiO2, Al2O3, and CaO tend to be enriched compared to the bulk starting composition. This indicates loss of material through evaporation.While the spectra of size fractions of the powdered bulk melt glass droplet follow this trend in general, but, because of contamination by the experimental set-up, CaO was found to be strongly enriched in contrast to the other refractories TiO2 and Al2O3.At least the composition of the glasses in the laser-excavated pits could serve as an ‘endmember’ for the sequence of glassy materials expected to be produced in high energy impact processes involving a basaltic target.Correlation of CF with SiO2 contents and the SCFM (SiO2/(SiO2 + CaO + FeO + MgO)) index show similar behaviour of the pit melts like found in earlier studies. However, when the position of the RB in the pit glass is correlated with the SiO2 content, the result shows a different trend compared with earlier studies. Consequently, the data presented in this study could help distinguishing between surface regions formed by volcanic processes and such modified by high-velocity impacts, where evaporation could play a central role.This is of high interest for remote sensing studies of Mercury, which, because of its proximity to the Sun, was probably affected by high-velocity impacts to a very high degree.

Thiazolium as Single‐Group Bifunctional Catalyst for Selectively Bulk Melt ROP of Cyclic Esters

AbstractNovel single‐group bifunctional hydrogen‐bonding catalysts based on thiazolium were developed. The integration of hydrogen‐bonding donor and acceptor in a single thiazolium ring not only amplified synergetic effect, but also enhanced the stability and the controllability for catalysis, and hence prompt thiazolium an efficient metal‐free catalyst for melt ROP of cyclic esters. More interestingly, thiazolium may form a compacted active center with monomer and initiator (or propagating chain end), thus enabling it to selectively activate lower sterically encumbered substrates in ROP.

Improving the Modeling of Slag and Steel Bath Chemistry in an Electric Arc Furnace Process Model

An improvement to the thermochemical module of the electric arc furnace (EAF) process model developed by Meier based on the work of Logar, Dovžan, and Skrjanc is presented. Different models for the calculation of activities in melt and slag are implemented, and separate reaction zones are defined for the interaction of slag and melt, the injection of oxygen, and the injection of carbon. For each zone, equilibrium compositions and reaction rates are calculated. Furthermore, diffusion of species is considered as a rate-limiting factor in reactions between slag and melt, and diffusion rates are calculated from the bulk melt to the reaction zone where reactions with the slag take place. Oxygen and sulfur dissolved in the melt and CaS in the slag are added as new species not previously considered in the EAF model. The treatment of carbon is revised to reduce model complexity and improve accuracy. The improved model is validated using extensive data from an industrial EAF, and results are compared to measured data as well as results obtained with the unmodified model. The different models for the determination of thermodynamic activities and their impacts on the duration of the simulation as well as its results are evaluated.

Volumetric Reduction of the FeCl2–CaCl2 Melt by Calcium Dissolved in Calcium Chloride

The purpose of this study is to fabricate highly dispersed powder suitable for spheroidization with further application in additive technologies. The volumetric reduction of the FeCl2–CaCl2 melt by calcium dissolved in CaCl2 produced a fine iron powder. The process included three states, notably, the preparation of melts containing FeCl2 and Ca, their mixing, and high-temperature aging at 800°C for 1 h. Upon finishing the process, the solidified fusion cake is divided into top and bottom parts. The product from the top part has a specific surface of 7.60 m2/g, and that from the bottom part has a specific surface of 5.38 m2/g. The average particle size is 157 μm for the former and 124 μm for the latter. Ultrasonic dispersing is reduced to 26 μm and 71 μm, respectively. Quantitative X-ray phase analysis shows that the main phase of powder is metallic iron (more than 97 wt %). Thus, the originality of the research is due to the application of an intense volumetric reduction of iron from chloride melts by calcium dissolved in its chloride. The uniqueness of the study is due to its product, so far as the main part of reduced iron is arranged in the melt bulk in the form of linear aggregates 40–600 μm in length and 10–50 μm in diameter, which easily destruct by ultrasonic dispersal into separate crystals with an average size of 26 μm. The results of the study show the possibility of implementing the calcium-thermal production of fine iron powder.

Observation of dendrite growth velocity and microstructure transition in highly undercooled single phase alloys

Dendrite growth velocity as a function of initial bulk undercooling was systematically studied in situ using high speed thermal imaging of highly undercooled Ni90Cu10 and Ni95Cu5 single phase alloy melts. For these two non-dilute concentrated alloys, the dendrite growth velocity first increased continuously at small and mediate undercooling regimes and then discontinuously to a maximum value at the high undercooling range. A clear plateau appeared in the growth velocity-undercooling curve revealed a gradual transition from mainly solute-controlled growth to mainly thermal-controlled growth, which was very similar to the solidification characteristics of a dilute alloy. The discontinuity appeared in the growth velocity-undercooling relationship was suggested to be induced by the finite solute diffusion speed in the bulk melt ahead of the advancing solid-liquid interface. Microstructure, substructure and microtexture of the two undercooled alloys were characterized using EBSD technique, and the fundamental mechanism behind “spontaneous grain refinement” is elucidated. The microstructure evolution indicated two kinds of grain refinements: one was dendrite remelting induced grain refinement and the other was recrystallization induced grain refinement. It was found that the texture of the as-solidified microstructure was getting more and more random as the initial bulk undercooling increased, which was due to the increased stress and recrystallization in the as-solidified microstructure. New evidence of grain refinement was found in the as-solidified samples. We found that the samples undercooled beyond the critical undercooling had a grain refined microstructure and that this corresponded with a clear discontinuity in the dendrite growth velocity-undercooling curve. Microstructural data suggested that in Ni-Cu alloys grain refinement at a high undercooling was a consequence of a recrystallization process, which contrasted with conventional grain refined alloys where grain refinement appeared to be the result of remelting-induced dendritic fragmentation.

Impact of the Pendant Group on the Chain Conformation and Bulk Properties of Norbornene Imide-Based Polymers.

Three series of well-defined norbornene imide-based polymers with different pendant groups were synthesized to investigate the effect of the pendant group on the polymer conformation in solution and bulk melt properties. Each of these three series was examined by analyzing the polymers' bulk z-average radius of gyration via static light scattering and the polymers' melt viscoelastic properties via oscillatory measurements and differential scanning calorimetry. Sterically bulky pendant wedge groups modestly increase the rodlike conformation of the norbornene-imide polymer, however, the inherent rigidity of the polymer main-chain can still be observed with less bulky substituents. In stark contrast, the different side groups significantly impacted the bulk viscoelastic and thermal properties. By increasing the pendant group size, the chain diameter of the polymer increases and lowers the entanglement modulus. Finally, as the wedge pendant group size increases, the segmental relaxation time and the fragility index of these norbornene-based polymers are decreased.

A CFD Study Assisted with Experimental Confirmation for Liquid Shape Control of Electromagnetically Levitated Bulk Materials

Two types of optimized electromagnetic levitators were designed to achieve the free surface shape control of metallic melts as the combined results of the Lorentz force, sample gravity, and surface tension. The levitation behavior of bulk melts was investigated using computational fluid dynamics (CFD) modeling coupled with high-frequency electromagnetic field analysis and the arbitrary Lagrangian–Eulerian (ALE) method. The difference in the oscillation behavior between the solid and molten samples was explained by the damping of the electromagnetic induction and liquid viscosity. The motion of the mass center, melt shape, flow pattern, and Lorentz force in the levitated melt were determined within a wide excitation current range. With the increase in the applied current, the melt’s centroid position rose sharply in the area with low current but displayed a slow increase in the area with high current. Meanwhile, the stable shape of the bulk melt showed the typical transition from a long taper through a short taper and then into a rhombus. The internal flow pattern transformed from a simple double-loop structure to a complex configuration with three or four loops. The dependence of the deformation on the Bond number was analyzed in the two types of levitators. In addition, the stable shape and swing process of the bulk Al melt within the two types of electromagnetic levitation (EML) systems were quantitatively studied under protective inert gas conditions. The melt contour could be well described by the 10th Legendre polynomial function with a deviation of less than 0.5 pct.

Evaluation of the petrogenetic significance of melt inclusions in pegmatitic schorl-dravite from graphic tourmaline-quartz assemblages: Application of LA-ICP-QMS analyses and volume ratio calculations

The composition of melt inclusions in tourmaline was studied from graphic quartz-tourmaline intergrowth assemblages of common, muscovite – rare-element class pegmatites belonging to the lithium-caesium-tantalum family. This study applied laser ablation inductively coupled quadrupole mass spectrometry in combination with 2D and 3D microscopic volume calculation to analyse these unhomogenised melt inclusions. The determination of the analytical precision of the method is performed by repeated microscope-scanning and laser ablation analyses of tourmaline mineral inclusions in muscovite hosts for which the compositions have been independently measured by electron microprobe.The analysed melt inclusions are hosted in schorl-dravite series tourmaline from the early-Neoproterozoic pegmatite dykes of the Gatumba-Gitarama field in Rwanda. Multiple dykes have been studied, representing three regional pegmatite zones showing an increasing bulk regional degree of differentiation. The sampled graphic quartz-tourmaline assemblages are the only manifestation of an internal mineralogical zonation within these pegmatite dykes.The melt inclusions dominantly contain muscovite, quartz, dickite, feldspars, jeremejevite and childrenite minerals and variable amounts of Cs-rich, interstitial fluid. The major element composition of the ablated melt inclusions is variable but mainly plot on the low Ca-granitic compositional trend. The inclusions show, moreover, a significantly higher normative quartz content compared to bulk pegmatitic rock counterparts. The melt inclusions demonstrate a near-constant Rb concentration (100 up to 160 ppm) whereas Cs concentrations vary between 10 and 1000 ppm. Although Rb and Cs enrichment trends are accurate proxies to deduce pegmatite melt differentiation in general, both the Rb and Cs concentrations of the melt inclusions are remarkably unrelated to the regional degree of differentiation deduced from the constituent bulk rock and rock-forming minerals of the Gatumba-Gitarama pegmatites. A comparison of the alkali metal content of melt inclusions and cogenetic fluid inclusions with previously modelled bulk melt concentration indicates that this deviating Rb and Cs behaviour is caused by heterogeneous trapping of variable portions of the Cs-enriched aqueous fluid phase together with the residual melt and this during melt inclusion formation.The melt inclusions in tourmaline represent local and residual, hydrous boro-aluminosilicate melt compositions. The formation of graphic intergrowths inside the pegmatite dykes indicates rapid tourmaline growth rates causing in turn quartz saturation and nucleation in the surrounding residual melt. Fast tourmaline crystallisation contributed directly to the formation of these “melt pools” with distinct residual compositions. Our study shows that already for less-differentiated common pegmatites, melt inclusions from internal mineralogical zones represent closed melt subsystems that cannot be directly linked to the bulk system. These findings imply, moreover, that the use of tourmaline trace element compositions as an indirect geochemical proxy for the bulk melt composition of pegmatites and evolved granites, has to be considered with caution.

Fluid Force-Induced Detachment Criteria for Nonmetallic Inclusions Adhered to a Refractory/Molten Steel Interface

Since nonmetallic inclusions (NMIs) in steel cannot be completely avoided, a greater understanding of their development and evolution during the steelmaking process is required. In particular, this includes the adhesion of microinclusions to the refractory/steel interface in the flow control system between the tundish and the mold. This phenomenon, commonly referred to as clogging, causes losses in productivity and product quality. Inclusions transported from the bulk melt to the boundary layer may adhere to the refractory/steel interface due to formation of a fluid cavity. A detailed model was derived for the detachment of NMIs adhering to a nozzle wall and is based on the local hydrodynamic conditions combined with the specific interfacial properties in the system consisting of the inclusions, the refractories, and the steel. The model is evaluated for three different application-oriented cases. This study has been focused on providing a better understanding of fluid flow in the near-wall region in order to reduce clogging during steelmaking.

Bulk and Mush Melt Evolution in Agpaitic Intrusions: Insights from Compositional Zoning in Eudialyte, Ilímaussaq Complex, South Greenland

Bulk and Mush Melt Evolution in Agpaitic Intrusions: Insights from Compositional Zoning in Eudialyte, Ilímaussaq Complex, South Greenland

Densely Packed Semiflexible Macromolecules in a Rigid Spherical Capsule

The ordering of semiflexible polymers with persistence length lp and contour length L confined in a sphere of radius R is studied by molecular dynamics simulations of a coarse-grained model. Monomer densities are chosen where the corresponding bulk lyotropic solution or melt is a well-ordered nematic, and purely repulsive walls of the rigid confining sphere are considered. It is found that polymers close to the walls are bent according to the curvature of the confining spheres with all their monomers in a few layers parallel to the sphere surface, whereas the remaining macromolecules closer to the sphere center have one chain end and their center of mass far from the surface. The latter chains are responsible for the average nematic order of the system for sufficiently stiff chains. If L exceeds R, a single transition from isotropic to nematic states is found when lp increases. However, if R is close to an even multiple of L, a second transition occurs where chain ends are enriched near the equatorial plane (and two further planes parallel to it, if R ≈ 2L); i.e., the system develops a distorted smectic structure. The order in the surface shell then is characterized by topological defects.

Mg isotope systematics during magmatic processes: Inter-mineral fractionation in mafic to ultramafic Hawaiian xenoliths

Observed differences in Mg isotope ratios between bulk magmatic rocks are small, often on a sub per mill level. Inter–mineral differences in the 26Mg/24Mg ratio (expressed as δ26Mg) in plutonic rocks are on a similar scale, and have mostly been attributed to equilibrium isotope fractionation at magmatic temperatures. Here we report Mg isotope data on minerals in spinel peridotite and garnet pyroxenite xenoliths from the rejuvenated stage of volcanism on Oahu and Kauai, Hawaii. The new data are compared to literature data and to theoretical predictions to investigate the processes responsible for inter–mineral Mg isotope fractionation at magmatic temperatures. Theory predicts up to per mill level differences in δ26Mg between olivine and spinel at magmatic temperatures and a general decrease in Δ26Mgolivine-spinel (=δ26Mgolivine – δ26Mgspinel) with increasing temperature, but also with increasing Cr# in spinel. For peridotites with a simple petrogenetic history by melt depletion, where increasing depletion relates to increasing melting temperatures, Δ26Mgolivine-spinel should thus systematically decrease with increasing Cr# in spinel. However, most natural peridotites, including the Hawaiian spinel peridotites investigated in this study, are overprinted by variable extents of melt-rock reaction, which disturb the systematic primary temperature and compositionally related olivine–spinel Mg isotope systematics. Diffusion, subsolidus re-equilibration, or surface alteration may further affect the observed olivine–spinel Mg isotope fractionation in peridotites, making Δ26Mgolivine-spinel in peridotites a difficult–to–apply geothermometer. The available Mg isotope data on clinopyroxene and garnet suggest that this mineral pair is a more promising geothermometer, but its application is restricted to garnet–bearing igneous (garnet pyroxenites) and metamorphic rocks (eclogites). Although the observed δ26Mg variation is on a sub per mill range in bulk magmatic rocks, the clearly resolvable inter–mineral Mg isotope differences imply that crystallization or preferential melting of isotopically distinct minerals such garnet, spinel, and clinopyroxene should cause Mg isotope fractionation between bulk melt and residue. Calculated Mg isotope variations during partial mantle melting indeed predict differences between melt and residue, but these are analytically resolvable only for melting of mafic lithologies, that is, garnet pyroxenites. Contributions from garnet pyroxenite melts may thus account for some of the isotopically light δ26Mg observed in ocean island basalts and trace lithological mantle heterogeneity. Consequently, applications for high-temperature Mg isotope fractionations are promising and diverse, and recent advances in analytical precision may allow the full petrogenetic potential inherent in the sub per mill variations in δ26Mg in magmatic rocks to be exploited.

Dynamical shift of NMR lines in nanostructured Ga–In–Sn melt

NMR spectrum and recovery of longitudinal nuclear magnetization after inverting pulses were measured for isotopes 69Ga and 71Ga in a liquid eutectic alloy Ga–In–Sn introduced in porous glasses having pores with the sizes of 25 and 7 nm. The measurements were conducted in the fields of 9.4, 11.7, and 17.6 T and compared with those for the bulk melt sample. Differences between the shape and position of the NMR lines in various fields and for different gallium isotopes were revealed in the melt introduced into the porous glass with the pores size of 7 nm. Data obtained for this sample were interpreted based on the theoretical model of dynamic quadrupolar shift, and correlation time of atomic motion was found within this model. Characteristics of the atomic motion calculated based on the dynamic shift model and from the spin relaxation data were shown to agree with each other.