Chemical diffusion of fluorine in melts in the system Na2OAl2O3SiO2

The volatilization of fluorine from three melts in the system Na2OAl2O3SiO2 has been investigated at 1 atm pressure and 1200–1400°C. The melts chosen have base compositions corresponding to albite, jadeite and a peraluminous melt with 75 mole % SiO2. Melt spheres were suspended from platinum loops in a vertical tube furnace in a flow of oxygen gas, then quenched, sectioned and analysed by electron microprobe. The microprobe scans indicate that transport of fluorine to the melt-vapor interface is by binary, concentration-independent interdiffusion of fluorine and oxygen. FO interdiffusivity increases in the order albite < peraluminous < jadeite. There is no simple reciprocal relationship between FO interdiffusivity and melt viscosity. Comparison with data on high-pressure interdiffusivity of fluorine and oxygen in jadeite melt indicates that FO interdiffusivity increases with pressure from 0.001 to 10 kbar while the activation energy remains unchanged. Fluorine chemical diffusivity in albite melt is substantially lower than H2O chemical diffusivity in obsidian melts suggesting that different diffusive mechanisms are responsible for the transport of F and H2O in igneous melts. Fluorine diffuses in albite melt via an anionic exchange with oxygen whereas water probably diffuses in obsidian melt via an alkali exchange mechanism

Effects of water and fluorine on the viscosity of albite melt at high pressure: a preliminary investigation

The viscosities of fluorine- and water-bearing melts based on albite composition have been determined at 7.5, 15 and 22.5 kbar by the falling-sphere method. All melt viscosities decrease isothermally with increasing pressure. At 1200°C the viscosity of the fluorine-bearing melt (albite + 5.8 wt.% fluorine substituted for oxygen, denoted AbF2O−1) decreases from5000 ± 750P at7.5kbar to1600 ± 240P at22.5kbar. At 1400°C the viscosity of this melt decreases from1300 ± 200P at7.5kbar to430 ± 65P at22.5kbar. At 1400°C the viscosity of albite + 2.79 wt.% water (denoted AbH2O) decreases from650 ± 100P at7.5kbar to400 ± 60P at22.5kbar. Fluorine (as F2O−1) and water strongly decrease the viscosity of albite melt over the entire range of investigated pressures. The ratio of the effects of 5.8 wt.% fluorine [F/(F + O)molar = 0.10] and 2.79 wt.% water [OH/(OH + O)molar = 0.10] on the log of melt viscosity [Δ log η(AbF2O−1)/Δ log η(AbH2O)] equals0.90 ± 0.05, 0.84 ± 0.05and0.97 ± 0.05at7.5, 15and22.5kbar, respectively. Comparison with available data on the high-pressure viscosity of albite melt indicates that both F2O−1 and H2O maintain their viscosity-reducing roles to lower crustal pressures. The difference between the viscosities of melts of albite, AbF2O−1 and AbH2O, may be explained in terms of the relatively depolymerized structures of AbF2O−1 and AbH2O melts. The depolymerization of albite melt by the addition of water results from the formation of SiOH bonds. The depolymerization of albite melt by F2O−1 substitution results from the formation of non-bridging oxygens associated with network-modifying aluminum cations that are formed upon fluorine solution. The strong viscosity-reducing effects of water and fluorine in albite melt at pressures corresponding to the mid- to lower continental crust indicate that these two components will strongly influence the dynamic behavior of anatectic melts during initial magma coalescence and restite-melt segregation

Primary carbonatite melt from deeply subducted oceanic crust

Partial melting in the Earth's mantle plays an important part in generating the geochemical and isotopic diversity observed in volcanic rocks at the surface. Identifying the composition of these primary melts in the mantle is crucial for establishing links between mantle geochemical 'reservoirs' and fundamental geodynamic processes. Mineral inclusions in natural diamonds have provided a unique window into such deep mantle processes. Here we provide experimental and geochemical evidence that silicate mineral inclusions in diamonds from Juina, Brazil, crystallized from primary and evolved carbonatite melts in the mantle transition zone and deep upper mantle. The incompatible trace element abundances calculated for a melt coexisting with a calcium-titanium-silicate perovskite inclusion indicate deep melting of carbonated oceanic crust, probably at transition-zone depths. Further to perovskite, calcic-majorite garnet inclusions record crystallization in the deep upper mantle from an evolved melt that closely resembles estimates of primitive carbonatite on the basis of volcanic rocks. Small-degree melts of subducted crust can be viewed as agents of chemical mass-transfer in the upper mantle and transition zone, leaving a chemical imprint of ocean crust that can possibly endure for billions of years.4 page(s

Fenites associated with carbonatite complexes : a review

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this record.Carbonatites and alkaline-silicate rocks are the most important sources of rare earth elements (REE) and niobium (Nb), both of which are metals imperative to technological advancement and associated with high risks of supply interruption. Cooling and crystallizing carbonatitic and alkaline melts expel multiple pulses of alkali-rich aqueous fluids which metasomatize the surrounding country rocks, forming fenites during a process called fenitization. These alkalis and volatiles are original constituents of the magma that are not recorded in the carbonatite rock, and therefore fenites should not be dismissed during the description of a carbonatite system. This paper reviews the existing literature, focusing on 17 worldwide carbonatite complexes whose attributes are used to discuss the main features and processes of fenitization. Although many attempts have been made in the literature to categorize and name fenites, it is recommended that the IUGS metamorphic nomenclature be used to describe predominant mineralogy and textures. Complexing anions greatly enhance the solubility of REE and Nb in these fenitizing fluids, mobilizing them into the surrounding country rock, and precipitating REE- and Nb-enriched micro-mineral assemblages. As such, fenites have significant potential to be used as an exploration tool to find mineralized intrusions in a similar way alteration patterns are used in other ore systems, such as porphyry copper deposits. Strong trends have been identified between the presence of more complex veining textures, mineralogy and brecciation in fenites with intermediate stage Nb-enriched and later stage REE enriched magmas. However, compiling this evidence has also highlighted large gaps in the literature relating to fenitization. These need to be addressed before fenite can be used as a comprehensive and effective exploration tool.This research has received funding from the European Union’s Horizon 2020 research and innovation programme under grant No 689909

Comparison of mantle lithosphere beneath early Triassic kimberlite fields in Siberian craton reconstructed from deep-seated xenocrysts

Mantle xenocrysts from Early Triassic kimberlite pipes from Kharamai, Ary Mastakh and Kuranakh fields in the Anabar shield of Siberia revealing similar compositional trends were studied to estimate the superplume influence on the SCLM. PT reconstructions using monomineral thermobarometry for 5 phases show division of the SCLM beneath the Kharamai field into 6 units: pyroxenitic Fe-rich (1-2 GPa) and Mg-rich (2-3 GPa) layers; middle with two levels of Gar -Sp pyroxenites at ∼3 and 4 -5 GPa; Ga- dunite –harzburgites ∼ 4.5-6.5 GPa subjected to Ilm-Px vein metasomatism, and a Mg-rich dunite lower part. In the Anabar shield (Ary Mastakh, Dyuken and Kuranakh fields) mantle lithosphere is composed of three large units divided into two parts: upper part with amphiboles and phlogopite; two levels of pyroxenites and eclogites at 3 and 4 GPa, and a lower part composed of refertilized dunites. Diagrams showing P- Fe#Gar clusters for garnets and omphacites illustrate the differences between SCLM of these localities. Differences of Triassic SCLM from Devonian SCLM are in simple layering; abundance of Na-Cr-amphiboles and metasomatism in the upper SCLM part, thick pyroxenite - eclogite layer and lower part depletion, heated from SCLM base to 5.0 GPa. Kharamai mantle clinopyroxenes represent three geochemical types: 1) harzburgitic with inclined linear REE, HFSE troughs and elevated Th, U; 2) lherzolitic or pyroxenitic with round TRE patterns and decreasing incompatible elements; 3) eclogitic with Eu troughs, Pb peak and high LILE content. Calculated parental melts for garnets with humped REE patterns suggest dissolution of former Cpx and depression means Cpx and garnets extraction. Clinopyroxenes from Ary Mastakh fields show less inclined REE patterns with HMREE troughs and an increase of incompatible elements. Clinopyroxenes from Kuranakh field show flatter spoon-like REE patterns and peaks in Ba, U, Pb and Sr, similar to those in ophiolitic harzburgites. The PT diagrams for the mantle sections show high temperature gradients in the uppermost SCLM accompanied by an increase of P-Fe#Ol upward and slightly reduced thickness of the mantle keel of the Siberian craton, resulting from the influence of the Permian -Triassic superplume, but with no signs of delamination

The Rare Earth Elements: demand, global resources, and challenges for resourcing future generations

The rare earth elements (REE) have attracted much attention in recent years, being viewed as critical metals because of China’s domination of their supply chain. This is despite the fact that REE enrichments are known to exist in a wide range of settings, and have been the subject of much recent exploration. Although the REE are often referred to as a single group, in practice each individual element has a specific set of end-uses, and so demand varies between them. Future demand growth to 2026 is likely to be mainly linked to the use of NdFeB magnets, particularly in hybrid and electric vehicles and wind turbines, and in erbium-doped glass fiber for communications. Supply of lanthanum and cerium is forecast to exceed demand. There are several different types of natural (primary) REE resources, including those formed by high-temperature geological processes (carbonatites, alkaline rocks, vein and skarn deposits) and those formed by low-temperature processes (placers, laterites, bauxites and ion-adsorption clays). In this paper, we consider the balance of the individual REE in each deposit type and how that matches demand, and look at some of the issues associated with developing these deposits. This assessment and overview indicate that while each type of REE deposit has different advantages and disadvantages, light rare earth-enriched ion adsorption types appear to have the best match to future REE needs. Production of REE as by-products from, for example, bauxite or phosphate, is potentially the most rapid way to produce additional REE. There are still significant technical and economic challenges to be overcome to create substantial REE supply chains outside China

Peralkaline Felsic Magmatism of the Atlantic Islands

The oceanic-island magmatic systems of the Atlantic Ocean exhibit significant diversity in their respective sizes, ages, and the compositional ranges of their eruptive products. Nevertheless, almost all of the Atlantic islands and island groups have produced peralkaline felsic magmas, implying that similar petrogenetic regimes may be operating throughout the Atlantic Ocean, and arguably elsewhere. The origins of peralkaline magmas are frequently linked to low-degree partial melting of enriched mantle, followed by protracted differentiation in the shallow crust. However, additional petrogenetic processes such as magma mixing, crustal melting, and contamination have been identified at numerous peralkaline centers. The onset of peralkalinity leads to magma viscosities lower than those typical for metaluminous felsic magmas, which has profound implications for processes such as crystal settling. This study represents a compilation of published and original data which demonstrates trends that suggest that the peralkaline magmas of the Atlantic Ocean islands are generated primarily via extended (up to ∼ 95%), open system fractional crystallization of mantle-derived mafic magmas. Crustal assimilation is likely to become more significant as the system matures and fusible material accumulates in the crust. Magma mixing may occur between various compositional end-members and may be recognized via hybridized intermediate magmas. The peralkaline magmas are hydrous, and frequently zoned in composition, temperature, and/or water content. They are typically stored in shallow crustal magma reservoirs (∼ 2–5 km), maintained by mafic replenishment. Low melt viscosities (1 × 101.77 to 1 × 104.77 Pa s) facilitate two-phase flow, promoting the formation of alkali-feldspar crystal mush. This mush may then contribute melt to an overlying melt lens via filter pressing or partial melting. We utilize a three-stage model to account for the establishment, development, and termination of peralkaline magmatism in the ocean island magmatic systems of the Atlantic. We suggest that the overall control on peralkaline magmatism in the Atlantic is magma flux rate, which controls the stability of upper crustal magma reservoirs. The abundance of peralkaline magmas in the Atlantic suggests that their development must be a common, but not inevitable, stage in the evolution of ocean islands