Presence Of Silicate Melt Research Articles

The presence of silicate melt may enhance rates of cation diffusion in olivine

Olivine is commonly used as a ‘crystal clock’ to extract timescales relevant to pre-eruptive perturbations within mafic magmatic systems. Diffusion chronometry applications require accurate calibrations for the rates at which Fe-Mg or other commonly measured elements like Ni, Mn, and Ca diffuse through the crystal lattice. In the past, these rates have been mainly characterized using solid-solid diffusion couple experiments involving olivine single crystals, thin films, or powder sources. Despite the presence of melt surrounding olivine in natural magmatic systems, very few experiments involving magma have been performed, largely because controlling interface reactions is difficult. For this study, we carried out olivine-melt diffusion experiments as a test of the diffusion chronometry method, and to determine whether the presence of melt influences the calculated timescales. To approximate a natural system, we incorporated small natural Kīlauea and San Carlos olivine seeds within a natural Kīlauea basalt and tracked diffusive re-equilibration through time. To better control interface reactions, after some equilibration period at an initial superliquidus temperature of 1290°C, the runs were rapidly cooled to form a rim and left to dwell at various final temperatures (1200, 1220, 1240, 1255°C) for 6–84 h. Concentration gradients for Fe-Mg, Mn, Ni, Ca were measured, and the step-wise nature of the core-rim transition was ascertained using slow diffusing elements like P or Al. When these gradients are modeled using published diffusivities, the timescales retrieved are typically 10 times longer than the actual experiment durations. Thus, measured diffusivities are an order of magnitude faster than those previously obtained in olivine-solid source experiments, but they are in excellent agreement with the only two other melt-olivine datasets. We explore reasons for why melt-bearing olivine diffusion experiments tend to yield faster rates. The possible effects of (1) growth during diffusion, (2) diffusion during any initial dissolution step, and (3) extended tube or planar defects at the interface on calculated diffusivities are all considered but found to be inconsequential. Instead, we argue that additional point defects (vacancies) are likely created at the interface by higher concentrations in elements like Al or H in the basalt melt compared to other solid couple diffusant sources. Future applications of diffusion chronometry in olivine may require a complete re-evaluation of published diffusivities using melt-bearing experimental configurations.

Transport of coexisting Ni-Cu sulfide liquid and silicate melt in partially molten peridotite

Transport of coexisting sulfide and silicate melts in partially molten peridotite contributes to the redistribution of chalcophile elements within the upper mantle as well as the genesis of magmatic Ni-Cu sulfide deposits, but has not been investigated systematically. Using laboratory experiments, theoretical calculations, and X-ray synchrotron microtomography, this study documents the topology and considers controls on the extraction of two immiscible liquids during partial melting of mantle peridotite. Under hydrostatic conditions, the measured dihedral angle at silicate melt-mineral-mineral junctions is 13.7–21.3°. Silicate melt is distributed along grain edges forming incompletely interconnected melt channels that disconnected by some dead ends at melt fractions ∼7–9 vol%. Application of theoretically predicted permeability (k∼10−14–10−16 m2) permits estimation of the extraction velocity of silicate melt of 0.7-11.1 μm/day within a single interconnected melt channel. In the absence of silicate melt, isolated sulfide droplets (3.77 vol%) show a sulfide-olivine-olivine dihedral angle of 91.5–101.3°. However, in the presence of silicate melt, sulfide droplets (average size ∼2.53 ± 2.14 μm, 1σ) are partially surrounded by silicate melt and stranded in triple junctions or melt pockets due to the limitation of the smallest dimension (0.3 μm) of melt channels. Thus, the extraction of sulfide liquid is highly restricted by these dead ends and the smallest dimension of melt channels during porous flow of silicate melt. In contrast, during large-strain shear deformation (strain ∼1.6–2.5), initially stranded sulfide droplets were elongated and extracted with silicate melt into liquid-rich sheets with a length of several hundred microns, constantly oriented at 14.3 ± 4.5° to the shear plane and antithetic to the shear direction. The angle is lower than that (18–30°) of those sheets containing sulfide liquid only, indicating that silicate melt dominates liquid-rich sheets. Driven by stress, silicate melt-dominated liquid-rich sheets open the appropriately oriented grain boundaries between silicate minerals, thus providing an efficient pathway for the extraction of sulfide liquid during deformation. When such sheet-like channels remain open, sulfide droplets (> millimeter-scale) can be potentially mobile through high strain domains of the upper mantle, contributing to the addition of chalcophile elements and the fertilization of the lithospheric mantle.

A common origin for Thai/Cambodian rubies and blue and violet sapphires from Yogo Gulch, Montana, U.S.A.?

A wide number of genetic models have been proposed for volcanically transported ruby and sapphire deposits around the world. In this contribution we compare the trace element chemistry, mineral and melt inclusions, and oxygen isotope ratios in blue to reddish-violet sapphires from Yogo Gulch, Montana, U.S.A., with rubies from the Chantaburi-Trat region of Thailand and the Pailin region of Cambodia. The similarities between Thai/Cambodian rubies and Yogo sapphires suggest a common origin for gem corundum from both deposits. Specifically, we advance a model whereby sapphires and rubies formed through a peritectic melting reaction when the lamprophyre or basalts that transported the gem corundum to the surface partially melted Al-rich lower crustal rocks. Furthermore, we suggest the protolith of the rubies and sapphires was an anorthosite or, in the case of Thai/Cambodian rubies, an anorthosite subjected to higher pressures and converted into a garnet-clinopyroxenite. In this model the rubies and sapphires are rightfully considered to be xenocrysts in their host basalts or lamprophyre; however, in this scenario they are not accidental xenocrysts but their formation is intimately and directly linked to the magmas that transported them to the surface. The similarities in these gem corundum deposits suggests that the partial melting, non-accidental xenocryst model may be more wide-reaching and globally important than previously realized. Importantly, in both cases the gem corundum has an ostensibly metamorphic trace element signature, whereas the presence of silicate melt (or magma) inclusions shows they ought to be considered to be magmatic rubies and sapphires. This discrepancy suggests that existing trace element discriminant diagrams intended to separate metamorphic from magmatic gem corundum ought to be used with caution.

Defluidization in fluidized bed gasifiers using high-alkali content fuels

A major concern in thermal conversion of biomass encountered in fluidized beds is bed agglomeration, which may result in de-fluidization, leading to unscheduled downtime and additional costs. Biomass fuels, especially herbaceous plants, often contain significant amounts of silicon, potassium and calcium, which may form viscous melts that adhere on the surface of the colliding bed particles and bind them to form agglomerates. In this paper, studies were made to understand the behavior of inorganic elements (mainly K, Si and Ca) on agglomeration and de-fluidization of alkali rich bed-material samples under non-oxidizing conditions in a bench-scale fluidized bed reactor set up. The de-fluidization studies involved measurements with sand and pure potassium salts (KCl and K2CO3) as well as with bed material samples obtained from a 6 MW Low Temperature Circulating Fluidized Bed (LTCFB) gasifier using straw as a fuel. It was seen that in sand + KCl agglomerates, the sand particles were bound by KCl melts. Only very limited chemical reaction was observed between KCl and the sand particles and no presence of silicate melts in the agglomerates. For sand + K2CO3 mixtures and for LTCFB bed material samples, agglomeration could be attributed to viscous silicate melts formed from reaction of inorganic alkaline and alkali earth species with silica from the bed particles. A mathematical model that addresses the de-fluidization behavior of alkali-rich samples was developed based on the experiments performed in the bench-scale fluidized bed reactor as well as on results from literature. The model was then used to predict the de-fluidization behavior of alkali-rich bed material in a large-scale LTCFB gasifier.

Deformation of a crystalline olivine aggregate containing two immiscible liquids: Implications for early core–mantle differentiation

Deformation-assisted segregation of metallic and sulphidic liquid from a solid peridotitic matrix is a process that may contribute to the early differentiation of small planetesimals into a metallic core and a silicate mantle. Here we present results of an experimental study using a simplified system consisting of a polycrystalline Fo90-olivine matrix containing a small percentage of iron sulphide and a synthetic primitive MORB melt, in order to investigate whether the silicate melt enhances the interconnection and segregation of FeS liquid under deformation conditions at varying strain rates. The experiments have been performed at 2 GPa, 1450 °C and strain rates between 1×10−3 s−1 to 1×10−5 s−1. Our results show that the presence of silicate melt actually hinders the migration and segregation of sulphide liquid by reducing its interconnectivity. At low to moderate strain rates the sulphide liquid pockets preserved a roundish shape, showing the liquid behavior is governed mainly by surface tension rather than by differential stress. Even at the highest strain rates, insignificant FeS segregation and interconnection were observed. On the other hand the basaltic melt was very mobile during deformation, accommodating part of the strain, which led to its segregation from the matrix at high bulk strains leaving the sulphide liquid stranded in the olivine matrix. Hence, we conclude that deformation-induced percolation of sulphide liquid does not contribute to the formation of planetary cores after the silicate solidus is overstepped. A possible early deformation enhanced core–mantle differentiation after overstepping the Fe–S solidus is not possible between the initial formation of silicate melt and the formation of a widespread magma ocean.

Plume scar in the mantle lithosphere beneath the Seychelles revealed by seismic imaging

Continental flood basalts are commonly thought to form by direct melting of lithospheric mantle, either during rifting episodes or when a mantle plume impinges on the base of the lithosphere. If correct, then significant alteration of the chemical and physical properties of the lithospheric mantle should be observable beneath such provinces. To date, however, this hypothesis remains unproved through lack of direct evidence. Here we present the results from a seismic experiment conducted in the Seychelles, a region that separated from India at the time of the eruption of the Deccan Traps. The analysis shows a stratified upper mantle with exceptionally low S-wave velocities at depths between 50 and 190km. It is difficult to explain these anomalies without invoking the presence of melt. However, the depth extent of the low velocities rules out the presence of silicate melt. We argue that the most probable interpretation is that these layers contain sulphide melt trapped from earlier interactions of the lithosphere with episodes of continental-flood basalt generation. The presence of this melt over a depth interval of ∼130km suggests that it is stagnant, and has remained coupled with the Seychelles lithosphere.

Reply to ‘Comment on “The beginnings of hydrous mantle wedge melting” by Till et al.’ by Green, Rosenthal and Kovacs

The comment of Green et al. debates the interpretation of the temperature of the H2O-saturated peridotite solidus and presence of silicate melt in the experiments of Till et al. (Contrib Mineral Petrol 163:669–688, 2012) at <1,000 °C. The criticisms presented in their comment do not invalidate any of the most compelling observations of Till et al. (Contrib Mineral Petrol 163:669–688, 2012) as discussed in the following response, including the changing minor element and Mg# composition of the solid phases with increasing temperature in our experiments with 14.5 wt% H2O at 3.2 GPa, as well as the results of our chlorite peridotite melting experiments with 0.7 wt% H2O. The point remains that Till et al. (Contrib Mineral Petrol 163:669–688, 2012) present data that call into question the H2O-saturated peridotite solidus temperature preferred by Green (Tectonophysics 13(1–4):47–71, 1972; Earth Planet Sci Lett 19(1):37–53, 1973; Can Miner 14:255–268, 1976); Millhollen et al. (J Geol 82(5):575–587, 1974); Mengel and Green (Stability of amphibole and phlogopite in metasomatized peridotite under water-saturated and water-undersaturated conditions, Geological Society of Australia Special Publication, Blackwell, pp 571-581, 1989); Wallace and Green (Mineral Petrol 44:1–19, 1991) and Green et al. (Nature 467(7314):448–451, 2010).

Evidence of denser MgSiO3glass above 133 gigapascal (GPa) and implications for remnants of ultradense silicate melt from a deep magma ocean

Ultralow velocity zones are the largest seismic anomalies in the mantle, with 10-30% seismic velocity reduction observed in thin layers less than 20-40 km thick, just above the Earth's core-mantle boundary (CMB). The presence of silicate melts, possibly a remnant of a deep magma ocean in the early Earth, have been proposed to explain ultralow velocity zones. It is, however, still an open question as to whether such silicate melts are gravitationally stable at the pressure conditions above the CMB. Fe enrichment is usually invoked to explain why melts would remain at the CMB, but this has not been substantiated experimentally. Here we report in situ high-pressure acoustic velocity measurements that suggest a new transformation to a denser structure of MgSiO(3) glass at pressures close to those of the CMB. The result suggests that MgSiO(3) melt is likely to become denser than crystalline MgSiO(3) above the CMB. The presence of negatively buoyant and gravitationally stable silicate melts at the bottom of the mantle, would provide a mechanism for observed ultralow seismic velocities above the CMB without enrichment of Fe in the melt. An ultradense melt phase and its geochemical inventory would be isolated from overlying convective flow over geologic time.

An experimental investigation into the metastable formation of phosphoran olivine and pyroxene

The formation of phosphoran olivine by crystallization from a melt was investigated experimentally using a one atmosphere furnace, using San Carlos olivine [(Mg,Fe) 2SiO 4] mixed with either iron phosphide (FeP) or magnesium pyrophosphate (Mg 2P 2O 7). Both dynamic crystallization and isothermal experiments produced phosphoran olivine as zoned single crystals and as overgrowths surrounding normal, phosphorus-free olivine grains. The crystallization pathways that form phosphoran olivine were traced and confirm that it is a metastable phase that can crystallize from a phosphorus-rich melt over timescales of hours to days. Removal of the P and equilibration of the olivine however requires weeks to months in the presence of silicate melt. Phosphoran olivine with up to 27 wt% P 2O 5 was generated and up to 69% of the Si tetrahedral sites were replaced by P. The substitution of Si by P into olivine was confirmed as 4 VIM +2 + 2 IVSi +4 ↔ 3 VIM +2 + 2 IVP +5 + VI[]. Phosphoran olivine compositions that vary from (Mg,Fe) 2SiO 4 to (Mg,Fe) 1.65[] 0.35Si 0.3P 0.7O 4 have been produced in these experiments. Phosphoran pyroxene was also generated in a few experiments and forms when phosphoran olivine reacts with either tridymite or melt. It has compositions compatible with protopyroxene, orthopyroxene, pigeonite and sub-calcic augite, and can contain up to 31.5 wt% P 2O 5. Like phosphoran olivine, it is also a metastable phase. Phosphorus replaces Si in pyroxene by the following substitution methods: 8 IVSi +4 ↔ 3 IVSi +4 + 4 IVP +5 + IV[] with Al entering the structure by the exchange 2 IVSi +4 ↔ IVAl +3 + IVP +5. Phosphoran pyroxene compositions vary from (Mg,Fe) 8Si 8O 24 to (Mg,Fe) 8Si 3P 4[]O 24.

Kinematic and rheological model of exhumation of high pressure granulites in the Variscan orogenic root: example of the Blanský les granulite, Bohemian Massif, Czech Republic

A large-scale relict domain of granulite facies deformation fabrics has been identified within the Blanský les granulite body. The granulite facies mylonitic fabric is discordant to the dominant amphibolite facies structures of the surrounding retrograde granulite. The complex geometry of retrograde amphibolite facies fabric indicates a large-scale fold-like structure, which is interpreted to be a result of either crustal-scale buckling of an already exhumed granulite sheet or active rotation of a rigid granulite facies ellipsoidal domain in kinematic continuity with the regional amphibolite facies deformation. We argue that both concepts allow similar restoration of the original granulite facies fabrics prior to the amphibolite facies deformation and “folding”. The geometry of the granulite facies foliations coincides with the earliest fabrics in the nearby mid-crustal units suggesting complete mechanical coupling between the deep lower crust and the mid-crustal levels during the vertical movements of crustal materials. Microstructures indicate grain-size sensitive flow enhanced by the presence of silicate melts at deep crustal levels and a beginning of an exhumation process of low viscosity granulites through a vertical channel. The amphibolite facies fabrics developed at middle crustal levels and their microstructures indicate significant hardening of feldspar-made rigid skeleton of the retrograde granulite. Increase in the strength of the granulite allowed an active buckling or a rigid body rotation of the granulite sheet, which acted as a strong layer inside the weaker metasediments.

Textural equilibria of iron sulfide liquids in partly molten silicate aggregates and their relevance to core formation scenarios

The influence of the coexistence of silicate and iron sulfide melts on the wetting of mantle olivine by iron sulfide melt is investigated. The dihedral angle between iron alloy and olivine is unaffected by the presence of silicate melt at 1.5 GPa and 1370–1410°C and is much greater than the maximum allowable dihedral angle for melt connectivity at low melt fractions. In experimental charges where silicate and sulfide melt occupy the same melt pocket, the sulfide melt adheres to olivine grain faces rather than forming discrete droplets. The relative interfacial energy between iron sulfide and basaltic silicate melt is lower than that of iron sulfide with olivine, but the contrast is not sufficient for basaltic silicate melt to wet FeS‐olivine grain boundaries. This result implies that very large silicate melt fractions are necessary to mobilize iron sulfide melts in partially molten silicate phase assemblages. Therefore segregation of Fe‐rich metallic melts by porous flow at low melt fraction is not a likely process for metal separation. The experiments also investigated the influence of the presence of a thermal gradient on sulfide melt migration. Although the sulfide melt can not migrate through the olivine network by porous flow, evidence in the experiments indicates mobility of sulfide through the interconnected silicate melt network. The sulfide melt pools in contact with silicate melt at the hot, top part of the experimental charges grow over time at the expense of the silicate melt pools in the cooler part of the charge. This points to a diffusive transport mechanism for local sulfide redistribution. We review literature data on metal‐olivine wetting angles and find that the metal composition has a dominant influence on the wetting behavior of a metallic liquid on an olivine matrix. Iron‐rich metallic liquid compositions are characterized by large dihedral angles (&gt;90°). The metal‐olivine dihedral angle decreases with increasing amounts of dissolved light element (S, C, O). For light element contents in excess of ∼59 at %, the dihedral angle approaches 60°, and the wetting behavior of a metallic liquid is similar to that of a silicate liquid.

The Effect of Temperature on the Partitioning of Nickel, Cobalt, Manganese, Chromium, and Vanadium at 9 GPa and Constraints on Formation of the Earth’s Core

The distribution of the elements Ni, Co, Mn, Cr, and V between liquid Fe-Ni-metal and magnesiowüstite solid solutions is investigated at 9 GPa in the temperature range 1800–2400°C. The variation of starting material enables the temperature effects to be determined at different redox conditions, although the buffering capacity of the sample plus high pressure assembly appears to be limited at temperatures above 2200°C. The observed metal-magnesiowüstite distribution coefficients (normalized to D Fe) for the elements Ni and Co show a weak decrease with increasing temperature while those of Mn, Cr, and V progressively increase. The increasingly siderophile behaviour of Mn, Cr, and V with increasing temperature at high pressure is consistent with their depletion in the Earth’s mantle being at least partly a consequence of core-mantle fractionation. The presence of silicate melt in some of the experiments also provides metal-silicate distribution coefficients as a function of temperature. The K DM met/sil values for Mn, Cr, and V also increase with temperature. The metal-silicate distribution coefficients for Cr and V are slightly higher than those for metal-oxide partitioning while the results for Mn show larger differences. Manganese partitions preferentially into silicate phases, while Cr and V partition into magnesiowüstite. Comparison of the new metal-oxide partitioning data with previous results suggests that the magnesiowüstite composition has a strong influence on Ni partitioning. The distribution coefficients are extrapolated to higher temperatures in order to test the homogenous accretion model of core formation. Constraints on the solubility of Si and O in liquid metal are also obtained at 9 GPa and appear to preclude either of these elements as major light components in the Earth’s core.