Geochemistry of spinel-hosted amphibole inclusions in abyssal peridotite: insight into secondary melt formation in melt–peridotite reaction

Spinel-hosted hydrous silicate mineral inclusions are often observed in dunite and troctolite as well as chromitite. Their origin has been expected as products associated with melt–peridotite reaction, based on the host rock origin. However, the systematics in mineralogical and geochemical features are not yet investigated totally. In this study, we report geochemical variations of the spinel-hosted pargasite inclusions in reacted harzburgite and olivine-rich troctolite collected from Atlantis Massif, an oceanic core complex, in the Mid-Atlantic Ridge. The studied samples are a good example to examine geochemical variations in the inclusions because the origin and geological background of the host rocks have been well constrained, such as the reaction between MORB melt and depleted residual harzburgite beneath the mid-ocean ridge spreading center. The trace-element compositions of the pargasite inclusions are characterized by not only high abundance of incompatible elements but also the LREE and HFSE enrichments. Distinctive trace-element partitioning between the pargasite inclusion and the host-rock clinopyroxene supports that the secondary melt instantaneously formed by the reaction is trapped in spinel and produces inclusion minerals. While the pargasite geochemical features can be interpreted by modal change reaction of residual harzburgite, such as combination of orthopyroxene decomposition and olivine precipitation, degree of the LREE enrichment as well as variation of HREE abundance is controlled by melt/rock ratio in the reaction. The spinel-hosted hydrous inclusion could be embedded evidence indicating melt–peridotite reaction even if reaction signatures in the host rock were hidden by other consequent reactions.     

Experiments on melt–rock reaction in the shallow mantle wedge

This experimental study simulates the interaction of hotter, deeper hydrous mantle melts with shallower, cooler depleted mantle, a process that is expected to occur in the upper part of the mantle wedge. Hydrous reaction experiments (~6 wt% H₂O in the melt) were conducted on three different ratios of a 1.6 GPa mantle melt and an overlying 1.2 GPa harzburgite from 1060 to 1260 °C. Reaction coefficients were calculated for each experiment to determine the effect of temperature and starting bulk composition on final melt compositions and crystallizing assemblages. The experiments used to construct the melt–wall rock model closely approached equilibrium and experienced <5% Fe loss or gain. Experiments that experienced higher extents of Fe loss were used to critically evaluate the practice of “correcting” for Fe loss by adding iron. At low ratios of melt/mantle (20:80 and 5:95), the crystallizing assemblages are dunites, harzburgites, and lherzolites (as a function of temperature). When the ratio of deeper melt to overlying mantle is 70:30, the crystallizing assemblage is a wehrlite. This shows that wehrlites, which are observed in ophiolites and mantle xenoliths, can be formed by large amounts of deeper melt fluxing though the mantle wedge during ascent. In all cases, orthopyroxene dissolves in the melt, and olivine crystallizes along with pyroxenes and spinel. The amount of reaction between deeper melts and overlying mantle, simulated here by the three starting compositions, imposes a strong influence on final melt compositions, particularly in terms of depletion. At the lowest melt/mantle ratios, the resulting melt is an extremely depleted Al-poor, high-Si andesite. As the fraction of melt to mantle increases, final melts resemble primitive basaltic andesites found in arcs globally. An important element ratio in mantle lherzolite composition, the Ca/Al ratio, can be significantly elevated through shallow mantle melt–wall rock reaction. Wall rock temperature is a key variable; over a span of <80 °C, reaction with deeper melt creates the entire range of mantle lithologies from a depleted dunite to a harzburgite to a refertilized lherzolite. Together, the experimental phase equilibria, melt compositions, and reaction coefficients provide a framework for understanding how melt–wall rock reaction occurs in the natural system during melt ascent in the mantle wedge.     

Experimental testing of olivine–melt equilibrium models at high temperatures

Data are presented on the equilibrium compositions of olivine and melts in the products of 101 experiments performed at 1300–1600°C, atmospheric pressure, and controlled oxygen fugacity by means of new equipment at the Vernadsky Institute. It was shown that the available models of the olivine–melt equilibrium describe with insufficient adequacy the natural systems at temperatures over 1400°C. The most adequate is the model by Ford et al. (1983). However, this model overestimates systematically the equilibrium temperature with underestimating by 20–40°C at 1450–1600°C. These data point to the need for developing a new, improved quantitative model of the olivine–melt equilibrium for high-temperature magnesian melts, as well as to the possibility of these studies on the basis of the equipment presented.     

Liquidus thermobarometer for chromite–melt equilibrium modeling: Development and verification

Liquidus chromite–silicate melt thermobarometer has been calculated by multiple linear regression of 234 experimental chromite–mafic melt equilibriums. Equations with low error reproduce the experimental compositions in a wide range of the compositions of mafic rocks, temperature, and pressure. Verification of the thermobarometers showed that the maximum error of the reproduction of the liquidus temperature is less than ±12°C. The formation equation of the cumulative chromites in the vertical section of the Burakovskii pluton was predicted with an error of ±50 m.     

Compositional dependence of REE partitioning between diopside and melt at 1 atmosphere

The effects of composition on pyroxene-melt partitioning of several REE (rare earth elements), Y, and Sr were experimentally evaluated. Using the synthetic model systems anorthite–diopside, diopside–titanite and anorthite–diopside–titanite different diopsides were grown at atmospheric conditions in a double-ellipsoid mirror furnace. The single samples were melted and crystallised in a Pt/Au crucible with compositions corresponding to the invariant points of these systems. Rotational motion with approximately 25 rpm around the longitudinal axis of the crucible increases the prevailing convection flows. By this means, the exclusively diffusional transport of assembly groups onto the growing crystals is avoided. Quenching is achieved by dropping the crucible into water. Crystals up to 2 mm were obtained and analysed by electron microprobe. No inhomogeneities or compositional zonation, either in the diopsides or in the coexisting melts, were observed within the analytical uncertainty of the electron microprobe. The crystallised diopsides occur as both euhedral single crystals and large symplectitic lamellar intergrowths with anorthite or titanite. The chemical homogeneity and the texture indicate near-equilibrium conditions. The analyses show strong positive correlations between D_REE and tetrahedrally coordinated Al in diopside but are not affected by octahedral Al or Ti-concentration. By means of correlations and mass balances the incorporation of REE can be described by 2 different coupled substitutions:

Fe–S melt as a likely solvent of diamond under mantle conditions

The first results of experimental study of diamond dissolution in a S-bearing Fe melt at high P–T parameters are reported and the morphology of partially dissolved crystals is compared with that of natural diamonds. Our results show that under the experimental conditions (4 GPa, 1400°C), flat-faced octahedral diamond crystals are transformed into curve-faced octahedroids with morphological features similar to those of natural diamonds.     

Experimental peridotite–melt reaction at one atmosphere: a textural and chemical study

Sieve-textured clinopyroxene and spinel are common in mantle xenoliths and have been interpreted to be the result of partial melting, mantle metasomatism and host magma–xenolith reaction during transport. In this paper, we test the latter hypothesis with a series of reduced and oxidized experiments at 1,200 and 1,156°C at one atmosphere using a synthetic leucitite melt and discs of natural peridotite. Our results show that sieve texture development on clinopyroxene and spinel in mantle xenoliths is the result of a multistage reaction process. In the first step, orthopyroxene undergoes incongruent dissolution to produce a silica and alkali-rich melt together with olivine. As this melt migrates along grain boundaries it causes incongruent dissolution of clinopyroxene and spinel. The incongruent dissolution mechanism involves complete dissolution of the clinopyroxene or spinel followed by nucleation and growth of a secondary clinopyroxene or spinel once the reacting melt is saturated. The reaction of orthopyroxene, clinopyroxene and spinel with infiltrated host magma results in a range of melt compositions that are very similar to those interpreted to be due to very small degrees of partial melting. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A micro-scale investigation of melt production and extraction in the upper mantle based on silicate melt pockets in ultramafic xenoliths from the Bakony–Balaton Highland Volcanic Field (Western Hungary)

Mantle xenoliths in Neogene alkali basalts of the Bakony–Balaton Highland Volcanic Field (Western Hungary) frequently have melt pockets that contain silicate minerals, glass, and often carbonate globules. Textural, geochemical and thermobarometric data indicate that the melt pockets formed at relatively high pressure through breakdown of mainly amphibole as a result of temperature increases accompanied, in most cases, by the influx of external metasomatic agents. New elemental and Sr–Nd–Pb isotope data show that in several xenoliths the external agent was either a LIL-enriched aqueous fluid or a CO₂-rich fluid, whereas in other xenoliths the melt pockets were additionally enriched in LREE and sometimes HFSE, suggesting metasomatism by a silicate melt. The compositional character of the external agents might have been inherited by melting of a hydrated and probably carbonated deeper lithospheric component, which itself was metasomatized by melts with significant slab-derived components. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Structurally-controlled melt accumulation: Himalayan migmatites and related deformation — Dhauli Ganga valley, Garhwal Himalaya

In the uppermost parts of the Higher Himalayan Crystallines (HHC) of the Great Himalaya, widespread in situ partial melting of sillimanite+K-feldspar gneiss resulted in the formation of migmatite and resultant melt accumulation near the South Tibetan Detachment System (STDS) during various deformation events along the Dhauli Ganga valley in Garhwal. The oldest migmatite phase, designated as the Me1, parallels the main foliation S_m as the stromatite layers and concordant leucogranite bands. Younger melt phases Me2, Me3 and Me5 are recorded along small-scale ductile thrusts, extensional fabric and structureless patches, respectively. It is only the Me4 melting phase that is evidenced by large-scale melt migration along cross-cutting irregular veins. These were possible conduits for migration and accumulation of melt into larger leucogranite bodies like the Malari granite (19.0± 0.5 Ma).     

Formation by silicate–fluoride + phosphate melt immiscibility of REE-rich globular segregations within aplite dikes

Aplite dikes intruding the Proterozoic 1.42(±?3) Ga Longs Peak-St. Vrain Silver Plume-type peraluminous granite near Jamestown, Colorado, contain F, P, and rare earth element (REE)-rich globular segregations, with 40–46% REE, 3.7–4.8 wt% P₂O₅, and 5–8 wt% F. A combination of textural features and geochemical data suggest that the aplite and REE-rich globular segregations co-existed as two co-genetic liquids prior to their crystallization, and we propose that they are formed by silicate–fluoride?+?phosphate (+?S?+?CO₂) melt immiscibility following ascent, cooling, and decompression of what was initially a single homogeneous magma that intruded the granite. The REE distribution coefficients between the silica-rich aplites and REE-rich segregations are in good agreement with experimentally determined distribution coefficients for immiscible silicate–fluoride?+?phosphate melts. Although monazite-(Ce) and uraninite U–Th–Pb microprobe ages for the segregations yield 1.420(±?25) and 1.442(±?8) Ga, respectively, thus suggesting a co-genetic relationship with their host granite, ε_Nd1.42Ga values for the granites and related granitic pegmatites range from ??3.3 to ??4.7 (average ??3.9), and differ from the values for both the aplites and REE-rich segregations, which range from ??1.0 to ??2.2 (average ??1.6). Furthermore, the granites and pegmatites have (La/Yb)_N <50 with significant negative Eu anomalies, which contrast with higher (La/Yb)_N >100 and absence of an Eu anomaly in both the aplites and segregations. These data are consistent with the aplite dikes and the REE-rich segregations they contain being co-genetic, but derived from a source different from that of the granite. The higher ε_Nd1.42Ga values for the aplites and REE-rich segregations suggest that the magma from which they separated had a more mafic and deeper, dryer and hotter source in the lower crust or upper mantle compared to the quartzo-feldspathic upper crustal source proposed for the Longs Peak-St. Vrain granite.     

Diffusive reequilibration of quartz-hosted silicate melt and fluid inclusions: Are all metal concentrations unmodified?

Experiments were conducted to determine the extent and mechanism by which the composition of quartz-hosted silicate melt inclusions (SMI) and aqueous fluid inclusions (FI) can undergo post-entrapment modification via diffusion. Quartz slabs containing assemblages of SMI and FI were reacted with synthetic HCl bearing and metalliferous aqueous fluids at T = 500-720 °C and P = 150-200 MPa. SMI from the single inclusion assemblages were analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) and electron probe microanalysis (EPMA) before and after the experiments. Analyses revealed that rapid diffusion of the univalent cations Na⁺, Li⁺, Ag⁺, Cu⁺ and H⁺ occurred through the quartz from the surroundings, resulting in significant changes in the concentrations of these elements in the inclusions. Concentrations of other elements with an effective ionic radius larger than that of Ag⁺, or multiple valence states were not modified in the inclusions during the experiments. Our results warn inclusion‘‘ researchers that the interpretation of Na, Li, Cu and Ag concentrations from quartz-hosted SMI and FI should be treated critically.     

Ra-partitioning between phlogopite and silicate melt and 226Ra/Ba–230Th/Ba isochrons

In this study we experimentally determine phlogopite/melt partition coefficients of Ra and other trace elements in a lamproitic system. This work was achieved using an analytical technique (LA-ICP-MS) with low detection limits (~ 0.01 fg) permitting the measurement of the very low Ra concentrations feasible in experiments (~ 1 ppb). D_Ra^{phlogopite/melt} was determined to 2.28 ± 0.44 and 2.84 ± 0.47 in two experiments, the ratio D_Ra/D_Ba is around 1.6. The compatibility of Ra in phlogopite results from an ionic radius being close to the apex of the lattice strain parabola for earth alkalis in the large XII-coordinated interlayer site of phlogopite. A re-evaluation of D_Ra and D_Ra/D_Ba for magmatic minerals containing appreciable Ra, yields D_Ra^mineral/melt ranging from ~ 2.6 for phlogopite down to 2–3 ? 10^? 5 for pyroxenes, and D_Ra/D_Ba^mineral/melt from ~ 4 for leucite to 2 ? 10^? 2 for orthopyroxene. The influence of melt composition on D_Ra/D_Ba is less than 10%. All investigated minerals have different D_Ra/D_Ba, strongly fractionating Ra from Ba. Thus, for magmatic systems, (²²⁶Ra)/Ba in the various minerals is not constant, these minerals do not form a straight line in the (²²⁶Ra)/Ba–(²³⁰Th)/Ba system at the time of crystallization and thus, there is no (²²⁶Ra)/Ba–(²³⁰Th)/Ba isochron at t₀. ²²⁶Ra–²³⁰Th–Ba mineral dating is thus applicable only to model ages calculated from mineral–glass pairs with known D_Ra.     

Copper partitioning between granitic silicate melt and coexisting aqueous fluid at 850 °C and 100 MPa

Experiments on the partitioning of Cu between different granitic silicate melts and the respective coexisting aqueous fluids have been performed under conditions of 850 °C, 100 MPa and oxygen fugacity（f O₂） buffered at approaching Ni–Ni O（NNO）. Partition coefficients of Cu（DCu= cfluid/cmelt） were varied with different alumina/alkali mole ratios [Al₂O₃/（Na₂O·K₂O）, abbreviated as Al/Alk], Na/K mole ratios, and Si O₂ mole contents. The DCu increased from 1.28 ± 0.01 to 22.18 ± 0.22 with the increase of Al/Alk mole ratios（ranging from 0.64 to 1.20）and Na/K mole ratios（ranging from 0.58 to 2.56）. The experimental results also showed that DCuwas positively correlated with the HCl concentration of the starting fluid.The DCuwas independent of the Si O₂ mole content in the range of Si O₂ content considered. No DCuvalue was less than 1 in our experiments at 850 °C and 100 MPa, indicating that Cu preferred to enter the fluid phase rather than the coexisting melt phase under most conditions in the melt-fluid system, and thus a significant amount of Cu could be transported in the fluid phase in the magmatichydrothermal environment. The results indicated that Cu favored partitioning into the aqueous fluid rather than themelt phase if there was a high Na/K ratio, Na-rich, peraluminous granitic melt coexisting with the high Cl-fluid.     

Composition of a carbonatitic melt in equilibrium with lherzolite at 5.5–6.3 GPa and 1350°C

Generation of ultra-alkaline melts by the interaction of lherzolite with cardonatites of various genesis was simulated at the P–T parameters typical of the base of the subcratonic lithosphere. Experiments with a duration of 150 h were performed at 5.5 and 6.3 GPa and 1350°C. The concentrations of CaO and MgO in melts are buffered by the phases of peridotite, and the concentrations of alkalis and FeO depend on the composition of the starting carbonatite. Melts are characterized by a low (<7 wt %) concentration of SiO₂ and Ca# from 0.40 to 0.47. It is demonstrated that only high-Mg groups of carbonatitic inclusions in fibrous diamonds have a composition close to that of carbonatitic melts in equilibrium with lherzolite. Most likely, the formation of kimberlite-like melts relatively enriched in SiO₂ requires an additional source of heat from mantle plumes and probably H₂O fluid.     

Vanadium magnetite–melt oxybarometry of natural,silicic magmas: a comparison of various oxybarometers and thermometers

To test a recently developed oxybarometer for silicic magmas based on partitioning of vanadium between magnetite and silicate melt, a comprehensive oxybarometry and thermometry study on 22 natural rhyolites to dacites was conducted. Investigated samples were either vitrophyres or holocrystalline rocks in which part of the mineral and melt assemblage was preserved only as inclusions within phenocrysts. Utilized methods include vanadium magnetite–melt oxybarometry, Fe–Ti oxide thermometry and -oxybarometry, zircon saturation thermometry, and two-feldspar thermometry, with all analyses conducted by laser-ablation ICP–MS. Based on the number of analyses, the reproducibility of the results and the certainty of contemporaneity of the analyzed minerals and silicate melts the samples were grouped into three classes of reliability. In the most reliable (n = 5) and medium reliable (n = 10) samples, all fO₂ values determined via vanadium magnetite–melt oxybarometry agree within 0.5 log units with the fO₂ values determined via Fe–Ti oxide oxybarometry, except for two samples of the medium reliable group. In the least reliable samples (n = 7), most of which show evidence for magma mixing, calculated fO₂ values agree within 0.75 log units. Comparison of three different thermometers reveals that temperatures obtained via zircon saturation thermometry agree within the limits of uncertainty with those obtained via two-feldspar thermometry in most cases, whereas temperatures obtained via Fe–Ti oxide thermometry commonly deviate by ≥50 °C due to large uncertainties associated with the Fe–Ti oxide model at T-fO₂ conditions typical of most silicic magmas. Another outcome of this study is that magma mixing is a common but easily overlooked phenomenon in silicic volcanic rocks, which means that great care has to be taken in the application and interpretation of thermometers and oxybarometers.     

Constraining magma sources using primitive olivine-hosted melt inclusions from Puñalica and Sangay volcanoes (Ecuador)

Constraining arc magma sources at continental arc settings is a delicate task, because chemical signatures from crustal processes obscure the slab and mantle signatures. Here, we present major, trace, and volatile element compositions of olivine-hosted melt inclusions (Fo_82–89) selected from the most primitive lavas (Mg# >?60) from two Ecuadorian volcanoes (Puñalica and Sangay) situated at the southern termination of the Andean Northern Volcanic Zone. Melt inclusions (MI) from Puñalica are nepheline normative and have basaltic-to-basaltic-andesite compositions (45–56 wt% SiO₂) similar to peridotite-derived melts. Sangay MI is also nepheline normative, with high CaO (up to 16 wt% and CaO/Al₂O₃?<?1) and low silica contents (41.9–44.5 wt%) pointing out an amphibole-bearing clinopyroxenite source. Both volcanoes display volatile-rich compositions (up to 6100 ppm Cl, 2200 ppm F, and 6700 ppm S). These MI cannot be related to their host lavas by fractional crystallization, implying that they represent true primitive liquids. The source of Puñalica MI was metasomatized by slab-derived melts that imprints its low Ba/Th, Sr/Th, and high Th/La (average values of 66, 129, and 0.22, respectively). On the contrary, the slab component added to the source of Sangay MI has a higher Ba/Th, Sr/Th, and low Th/La (average values of 261, 517, and 0.11, respectively) which could suggest a relative contribution of aqueous fluids. This dichotomy is related to the presence of the Grijalva Fracture Zone that separates a younger and hotter oceanic crust to the north (below Puñalica) from a colder and older oceanic crust to the south (below Sangay).