Electrical conductivity of hydrous basaltic melts: implications for partial melting in the upper mantle

The Earth’s uppermost asthenosphere is generally associated with low seismic wave velocity and high electrical conductivity. The electrical conductivity anomalies observed from magnetotelluric studies have been attributed to the hydration of mantle minerals, traces of carbonatite melt, or silicate melts. We report the electrical conductivity of both H₂O-bearing (0–6 wt% H₂O) and CO₂-bearing (0.5 wt% CO₂) basaltic melts at 2 GPa and 1,473–1,923 K measured using impedance spectroscopy in a piston-cylinder apparatus. CO₂ hardly affects conductivity at such a concentration level. The effect of water on the conductivity of basaltic melt is markedly larger than inferred from previous measurements on silicate melts of different composition. The conductivity of basaltic melts with more than 6 wt% of water approaches the values for carbonatites. Our data are reproduced within a factor of 1.1 by the equation log σ = 2.172 − (860.82 − 204.46 w ^0.5)/(T − 1146.8), where σ is the electrical conductivity in S/m, T is the temperature in K, and w is the H₂O content in wt%. We show that in a mantle with 125 ppm water and for a bulk water partition coefficient of 0.006 between minerals and melt, 2 vol% of melt will account for the observed electrical conductivity in the seismic low-velocity zone. However, for plausible higher water contents, stronger water partitioning into the melt or melt segregation in tube-like structures, even less than 1 vol% of hydrous melt, may be sufficient to produce the observed conductivity. We also show that ~1 vol% of hydrous melts are likely to be stable in the low-velocity zone, if the uncertainties in mantle water contents, in water partition coefficients, and in the effect of water on the melting point of peridotite are properly considered.     

The solubility of TiO2 in olivine: implications for the mantle wedge environment

One characteristic of many subduction-zone garnet peridotites is that they contain titanium-bearing phases not otherwise found in mantle rocks. In particular, titanoclinohumite and/or its breakdown assemblage consisting of symplectic intergrowths of olivine and ilmenite is common in many of these bodies. The Alpe Arami garnet lherzolite of the Swiss Alps, while lacking titanoclinohumite, displays instead large numbers of FeTiO₃ rod-shaped precipitates in the oldest generation of olivine, amounting to approximately 1% by volume, indicating that at some time in its past, the peridotite experienced conditions under which the solubility of TiO₂ in olivine was >0.6 wt.%. In order to test the hypothesis that the environment of very high solubility of TiO₂ in olivine is to be found at very high pressures, we have conducted experiments on lherzolite compositions with added ilmenite at pressures between 5 and 12 GPa and temperatures of 1350–1700 K. Our results on anhydrous compositions show that whereas solubility of TiO₂ was not detected in olivine at 5 GPa, 1400 K where it coexists with rutile, when rutile disappeared from the paragenesis, the solubility climbed to 0.4 wt.% at 8 GPa, 0.5 wt.% at 10 GPa and to >1.0 wt.% at 12 GPa, 1700 K. These results support our previous interpretations from titanate morphology and abundance that the Alpe Arami massif has surfaced from P=10 GPa but remove the need to suggest a deeper origin and possible precursor phase such as wadsleyite. They also support the hypothesis that garnet peridotites with unusual Ti-bearing phases reflect a unique mantle environment occurring in the mantle wedge overlying subduction zones.     

Phase equilibria for graphitic metapelite including solution of CO2 in melt and cordierite: implications for dehydration,partial melting and graphite precipitation

When graphite is present, carbon‐bearing species dissolve in the C‐O‐H fluid and lower the activity of water (). Accordingly, metamorphic reactions that involve water, namely dehydration and partial melting reactions, adjust their P–T positions to accommodate the change of . In this modelling study, pseudosections are calculated for graphite‐bearing systems that are either closed or that progressively lose fluid and/or melt. The diagrams incorporate a new model of CO₂ solubility in felsic melts that we derived to be compatible with a recently published melt model. As the result of the lowered in the carbon‐bearing systems, the temperature displacements of the solidus can be as large as 50 °C at low pressures in cordierite‐bearing zones (<4 kbar), but are smaller than 15 °C at mid‐pressure P–T conditions (4–9 kbar). In the supersolidus region, the phase relations among silicate minerals + melt are very close to those in carbon‐free systems. The fluid CO₂ content increases as temperature increases in the supersolidus assemblages. The CO₂‐rich fluid can be stable in granulite facies conditions in an oxidized system. In graphitic systems, melt and/or cordierite dominate the CO₂ budget of high‐grade rocks. During cooling, the fluid that exsolves from such crystalizing melt is CO₂‐rich. In addition to the phase relations, the pseudosections presented in this study enable researchers to quantitatively investigate the evolution of phase modes, including graphite, along specific metamorphic P–T paths. At low pressures in the cordierite stability field, graphite is predicted to precipitate as the pressure increases or temperature decreases in the subsolidus assemblages, or temperature increases in the region of melt + fluid coexistence. On the other hand, the graphite abundance remains nearly constant along the mid‐pressure P–T series, but the graphite mode in the supersolidus region may increase due to residual enrichment if the melt is extracted. The modelling results show that metamorphic processes in closed systems lead to only small changes in graphite mode (a few tenths of a per cent). This strongly suggests that open‐system behaviours are required for large amounts of graphite deposition, including fluid infiltration and mixing or residual enrichment processes in high‐grade rocks. In addition to P–T pseudosections, P/T–X_O diagrams (X_O = O/(H + O) in the fluid) illustrate the thermodynamic features of internal buffering from another perspective, and explore the dependence of phase relations on the externally imposed redox state. If the system is equilibrated with CO₂ or CH₄‐rich infiltrating fluid, the temperature displacements of metamorphic reactions can be larger than 50 °C, compared with carbon‐free systems.     

A high pressure-high temperature study of TiO2 solubility in Mg-rich phlogopite: implications to phlogopite chemistry

The solubility of Tio₂ in phlogopites has been experimentally determined in the system K₂Mg₆Al₂Si₆O₂₀(OH)₄-K₂Mg₄TiAl₂Si₆O₂₀(OH)₄-K₂Mg₅TiAl₄Si₄O₂₀(OH)₄ between 825–1300°C and 10–30 kbar under vapour absent conditions. Starting compositions lie along the join K₂Mg₆Al₂Si₆O₂₀(OH)₄-K₂Mg_4.5TiAl₃Si₅O₂₀(OH)₄ which represents a combination of the Mg^[VI]2Si^[IV] = Ti^[VI]2Al^[VI] and $\text{2Mg}{}^{\mathrm{[VI]}}\text{=}\text{Ti}{}^{\mathrm{[VI]}}\text{□}{}^{\mathrm{[VI]}}$ substitution mechanisms for Ti in phlogopites. The results of the experiments indicate a systematic increase in solubility of Ti with increasing temperature and decreasing pressure for given bulk Tio₂ content. Under isobaric conditions high temperature Ti-saturated phlogopite breaks down to Ti-deficient phlogopite + rutile + vapour. Mass balance calculations suggest that the vapour phase may contain K₂O dissolved in H₂O and that the reaction is controlled by the vapour phase. Analyses of phlogopites coexisting with rutile and vapour can be represented in terms of the end-member components phlogopite [K₂Mg₆Al₂Si₆O₂₀(OH)₄], eastonite [K₂Mg₅Al₄Si₅O₂₀(OH)₄], an octahedral site deficient Ti-phlogopite (Ti-OSD) of composition K₂(Mg₄Ti□)Al₂Si₆)O₂₀(OH)₄, and Ti-eastonite [K₂Mg₅TiAl₄Si₄O₂₀(OH)₄]. With decreasing amounts of Ti in these phlogopites there is a decrease in the Ti-eastonite component and increase in the eastonite component.The general equation for the breakdown of Ti-phlogopite solid solution to Ti-free phlogopite + rutile + vapour is: 14 Ti-eastonite + 7 Ti-OSD ? 16 eastonite + 3 phlogopite + 21 rutile + 4 H₂O + 2 K₂O. Lack of knowledge of H₂O and K₂O activities in the vapour phase does not permit evaluation of thermodynamic constants for this reaction. The Ti solubility in phlogopites and hence its potential as a geothermobarometer under lower crustal to upper mantle conditions is likely controlled by common mantle minerals such as forsterite.     

Composition of primary kimberlite melt in a garnet lherzolite mantle source: constraints from melting phase relations in anhydrous Udachnaya-East kimberlite with variable CO2 content at 6.5 GPa

The critical issue in the study of kimberlites, known as principal host rocks of diamonds, is the reconstruction of their primary melt composition, which is poorly constrained due to contamination by xenogenic materials, significant loss of volatiles during eruption, and post-magmatic alteration. It is generally accepted that the last equilibration of primary kimberlite melt with surrounding mantle (garnet lherzolite) occurred beneath cratons at 5–7 GPa (150–230 km depths). However, the subliquidus mineral assemblages obtained in kimberlite melting experiments at mantle pressures differ from lherzolite_, probably owing to unaccounted loss of CO₂. Here we present experiments at 6.5 GPa and 1200–1600 °C on unaltered kimberlite with an addition of 2–22 mol% CO₂ over its natural abundance in the rock (13 mol%), but keeping proportions of other components identical to those in an exceptionally fresh anhydrous kimberlite from Udachnaya-East pipe in Siberia. We found that the partial melt achieves equilibrium with garnet lherzolite at 1500 °C and 19–23 mol% CO₂ in the system. Under these conditions this melt contains (mol%): SiO₂ = 9, FeO = 6–7, MgO = 23–26, CaO = 16, Na₂O = 4, K₂O = 1, and CO₂ = 30–35. We propose, therefore, the alkali-rich carbonatitic composition of primary kimberlite melt and loss of 34–45 mol% (34–46 wt%) CO₂ during ascent of the kimberlite magma to the surface.     

High-precision analysis of carbon isotopic composition for individual CO2 inclusions via Raman spectroscopy to reveal the multiple-stages evolution of CO2- bearing fluids and melts

The carbon isotopic composition of CO₂ inclusions trapped in minerals reflects the origin and evolution of CO₂-bearing fluids and melts, and records the multiple-stages carbon geodynamic cycle, as CO₂ took part in various geological processes widely. However, the practical method for determination isotope composition of individual CO₂ inclusion is still lacking. Developing a microanalytical technique with spatial resolution in micrometers to precisely determinate the δ¹³C value of individual CO₂ inclusion, will make it possible to analyze a tiny portion of a zoning mineral crystal, distinguish the differences in micro-scale, and possible to find many useful information that could not be obtained with the bulk extraction and analysis techniques. In this study, we systematically collected Raman spectra of CO₂ standards with different δ¹³C values (?34.9 ‰ to 3.58 ‰) at 32.0 °C and from ～7.0 MPa to 120.0 MPa, and developed a new procedure to precisely determinate the δ¹³C value of individual CO₂ inclusion. We investigated the relationship among the Raman peak intensity ratio, δ¹³C value, and CO₂ density, and established a calibration model with high accuracy (0.5 ‰?1.5 ‰), sufficient for geological application to distinguish different source of CO₂ with varying δ¹³CO₂. As a demonstration, we measured the δ¹³C values and the density of CO₂ inclusions in the growth zones of alkali basalt-hosted corundum megacrysts from Changle, Shandong Province. We found the significant differences of density and δ¹³C between the CO₂ inclusions in the core of corundum and those inclusions in the outer growth zones, the δ¹³C value decreases from core to rim with decreasing density: δ¹³C values are from ?7.5 ‰ to ?9.2 ‰ for the inclusions in the core, indicating the corundum core was crystallized from mantle-derived magmas; from ?13.5 ‰ to ?18.5 ‰ for CO₂ inclusions in zone 1 and from ?16.5 ‰ to –22.0 ‰ for inclusions in zone 2, indicating the outer zones of corundum grew in a low δ¹³C value environment, resulted from an infilling of low δ¹³C value fluid and/or degassing of the ascending basaltic magma.     

Spatial distribution of melt-bearing structures in anatectic rocks from Southern Brittany, France: implications for melt transfer at grain- to orogen-scale

In this study, we present quantitative spatial information on the one- and two-dimensional distribution of inferred melt-bearing structures in anatectic supracrustal rocks of the Southern Brittany Migmatite Belt, south of the transcurrent South Armorican Shear Zone (SASZ); based on these data, we infer the mechanism of melt extraction from partially molten crust. Former melt-bearing structures include foliation-parallel leucosomes and cross-cutting granitic leucosomes that infill inter-boudin partitions and extensional shear surfaces, as well as discordant dykes of granite. Petrographic (i.e., mineralogical and microstructural) continuity of granite from structure to structure suggests that they once formed a continuous melt-bearing network. Measurements along one-dimensional line traverses perpendicular to layering of stromatic migmatite exposed in clean, sub-horizontal outcrop surfaces provide information about thickness and spacing distributions of foliation-parallel leucosomes. Most leucosome thicknesses fall in the range of 1–10 mm, with upper limits around 20–30 mm. The number of thicker layers decreases abruptly with increasing thickness, which is inconsistent with scale-invariance. This suggests that leucosome formation was controlled by short-range melt movement along grain boundaries to form melt-rich layers constrained by pre-existing compositional layering. Spacing distributions also are not scale-invariant; however, the large percentage of leucosomes (40–60%) in these line traverses suggests that spacing distributions may be controlled in part by impingement of leucosomes, making it difficult to derive genetic information from these data. Qualitative observation of inferred melt-bearing structures in mutually perpendicular two-dimensional exposures from the same outcrop reveals anisotropy of the leucosome network related to a well-developed sub-horizontal quartz–feldspar lineation reflecting stretching associated with transcurrent movement along the SASZ. Analysis of these two-dimensional distributions using the box-counting method corroborates the observed anisotropy, but indicates that leucosome morphology (and perhaps distribution) is not scale-invariant. The applicability of the box-counting method, or of fractal analysis, to understanding melt movement in migmatites is discussed in light of these results. Based on the anisotropy of melt-bearing structures, we infer that melt-movement in structures now represented by layer-parallel leucosomes was primarily sub-horizontal. These layers fed steeply dipping structures now represented by cross-cutting leucosomes, in particular those developed at inter-boudin partitions, and granite dykes. The formation and orientation of these steeply dipping structures was in part controlled by far-field stresses related to dextral displacement along the SASZ. Melt extraction is inferred to have occurred along these steeply dipping structures; extracted melt accumulated in plutons at higher crustal levels, such as the Quiberon, Sarzeau, and Guérande granites.     

Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases

The stoichiometry and stability of arsenic gaseous complexes were determined in the system As-H₂O ± NaCl ± HCl ± H₂S at temperatures up to 500°C and pressures up to 600 bar, from both measurements of As^(III) and As^(V) vapor-liquid and vapor-solid partitioning, and X-ray absorption fine structure (XAFS) spectroscopic study of As^(III)-bearing aqueous fluids. Vapor-aqueous solution partitioning for As^(III) was measured from 250 to 450°C at the saturated vapor pressure of the system (P_sat) with a special titanium reactor that allows in situ sampling of the vapor phase. The values of partition coefficients for arsenious acid (H₃AsO₃) between an aqueous solution (pure H₂O) and its saturated vapor (K = mAs_vapor /mAs_liquid) were found to be independent of As^(III) solution concentrations (up to ∼1 to 2 mol As/kg) and equal to 0.012 ± 0.003, 0.063 ± 0.023, and 0.145 ± 0.020 at 250, 300, and 350°C, respectively. These results are interpreted by the formation, in the vapor phase, of As(OH)₃(gas), similar to the aqueous As hydroxide complex dominant in the liquid phase. Arsenic chloride or sulfide gaseous complexes were found to be negligible in the presence of HCl or H₂S (up to ∼0.5 mol/kg of vapor). XAFS spectroscopic measurements carried out on As^(III)-H₂O (±NaCl) solutions up to 500°C demonstrate that the As(OH)₃ complex dominates As speciation both in dense H₂O-NaCl fluids and low-density supercritical vapor. Vapor-liquid partition coefficients for As^(III) measured in the H₂O-NaCl system up to 450°C are consistent with the As speciation derived from these spectroscopic measurements and can be described by a simple relationship as a function of the vapor-to-liquid density ratio and temperature. Arsenic^(III) partitioning between vapor and As-concentrated solutions (>2 mol As/kg) or As₂O₃ solid is consistent with the formation, in the vapor phase, of both As₄O₆ and As(OH)₃. Arsenic^(V) (arsenic acid, H₃AsO₄) vapor-liquid partitioning at 350°C for dilute aqueous solution was interpreted by the formation of AsO(OH)₃ in the vapor phase.The results obtained were combined with the corresponding properties for the aqueous As(III) hydroxide species to generate As(OH)₃(gas) thermodynamic parameters. Equilibrium calculations carried out by using these data indicate that As(OH)₃(gas) is by far the most dominant As complex in both volcanic gases and boiling hydrothermal systems. This species is likely to be responsible for the preferential partition of arsenic into the vapor phase as observed in fluid inclusions from high-temperature (400 to 700°C) Au-Cu (-Sn, -W) magmatic-hydrothermal ore deposits. The results of this study imply that hydrolysis and hydration could be also important for other metals and metalloids in the H₂O-vapor phase. These processes should be taken into account to accurately model element fractionation and chemical equilibria during magma degassing and fluid boiling.     

Annual variation of temperature sensitivity of soil organic carbon decomposition in North peatlands: implications for thermal responses of carbon cycling to global warming

Temperature sensitivities of microbial respiration and dissolved organic carbon (DOC) production were investigated by using a novel method, thermal gradient (2–20°C) temperature bar, in two typical peatlands (bog and fen) in North Wales, UK over 12 months. The study indicated that temperature sensitivity of soil organic carbon decomposition in North peatlands was regulated not only by temperature but soil water content, dry–rewet event and phenologies. Potential decreases of Q₁₀ (CO₂) with increasing soil temperature were confirmed in both peatlands, but Q₁₀ (DOC) increase with increasing soil temperature in both bog and fen sites. These results imply, if other factors such as the so-called CO₂ fertilization effect are simultaneously taken into account, that the feedback of global warming induced CO₂ release from peatlands to climate change may be overestimated in current biogeochemical models. However, global warming might have been nonlinearly accelerating DOC thermal production, and therefore it helps explaining the causes of remarkable increase of DOC in surface water in the Northern Hemisphere during last several decades.     

CO<Subscript>2</Subscript> content of andesitic melts at graphite-saturated upper mantle conditions with implications for redox state of oceanic basalt source regions and remobilization of reduced carbon from subducted eclogite

We have performed experiments to determine the effects of pressure, temperature and oxygen fugacity on the CO₂ contents in nominally anhydrous andesitic melts at graphite saturation. The andesite composition was specifically chosen to match a low-degree partial melt composition that is generated from MORB-like eclogite in the convective, oceanic upper mantle. Experiments were performed at 1–3 GPa, 1375–1550?°C, and fO₂ of FMQ ?3.2 to FMQ ?2.3 and the resulting experimental glasses were analyzed for CO₂ and H₂O contents using FTIR and SIMS. Experimental results were used to develop a thermodynamic model to predict CO₂ content of nominally anhydrous andesitic melts at graphite saturation. Fitting of experimental data returned thermodynamic parameters for dissolution of CO₂ as molecular CO₂: ln(K ⁰) = ?21.79?±?0.04, ΔV ⁰?=?32.91?±?0.65 cm³mol^?1, ΔH ⁰?=?107?±?21 kJ mol^?1, and dissolution of CO₂ as CO₃ ^2?: ln(K ⁰ ) = ?21.38?±?0.08, ΔV ⁰?=?30.66?±?1.33 cm³ mol^?1, ΔH ⁰?=?42?±?37 kJ mol^?1, where K ⁰ is the equilibrium constant at some reference pressure and temperature, ΔV ⁰ is the volume change of reaction, and ΔH ⁰ is the enthalpy change of reaction. The thermodynamic model was used along with trace element partition coefficients to calculate the CO₂ contents and CO₂/Nb ratios resulting from the mixing of a depleted MORB and the partial melt of a graphite-saturated eclogite. Comparison with natural MORB and OIB data suggests that the CO₂ contents and CO₂/Nb ratios of CO₂-enriched oceanic basalts cannot be produced by mixing with partial melts of graphite-saturated eclogite. Instead, they must be produced by melting of a source containing carbonate. This result places a lower bound on the oxygen fugacity for the source region of these CO₂-enriched basalts, and suggests that fO₂ measurements made on cratonic xenoliths may not be applicable to the convecting upper mantle. CO₂-depleted basalts, on the other hand, are consistent with mixing between depleted MORB and partial melts of a graphite-saturated eclogite. Furthermore, calculations suggest that eclogite can remain saturated in graphite in the convecting upper mantle, acting as a reservoir for C.     

Reactive modelling of CO2 intrusion into freshwater aquifers: current requirements, approaches and limitations to account for temperature and pressure effects

The modelling of CO₂ intrusion into virtual freshwater aquifers after a leakage from CO₂ storage formations is a well-established approach for the identification of monitoring parameters and for the risk assessment. At presence, standard or close-to-standard conditions in terms of temperature (T), i.e. 25?°C and pressure (P), i.e. 1?C5?bar, are assumed. This approach neglects the fact that temperature and pressure conditions change with the depth of the freshwater aquifer. This study tests the accuracy of T?CP corrections of the geochemical constants in the system gaseous CO₂?Cwater?Cmineral which are performed by the simulators PhreeqC (Parkhurst and Appelo in User??s guide to phreeqc (version 2)??a computer program for speciation, batch reaction, one-dimensional transport, and inverse geochemical calculations. Technical report, US Department of the Interior, 1999) and TOUGHREACT (Xu et?al. in Toughreact user??s guide: a simulation program for non-isothermal multiphase reactive geochemical transport in variably saturated geologic media. Technical report, Lawrence Berkeley National Laboratory, 2004). It further identifies the impact of T and P variations on the predicted concentrations of the monitoring parameters pH and total inorganic carbon (TIC) and on the predicted concentration of the trace metal lead (Pb) in 3D multiphase-multicomponent simulations of virtual aquifers. The results reveal a strong imprecision in the correction of kinetic rates of mineral dissolution and a lack of corrections of sorption equilibrium states. The predicted pH and concentrations of TIC and lead depend strongly on the assumed T and P conditions. It is concluded that a neglect of T and P effects results in inaccurate predictions of groundwater chemistry. The impact assessment and monitoring strategies based on currently available modelling results consequently require strong improvements.     

Effects of fO2, fS2, temperature, and melt composition on Fe-Ni exchange between olivine and sulfide liquid: implications for natural olivine-sulfide assemblages

The apparent equilibrium constant for the exchange of Fe and Ni between coexisting olivine and sulfide liquid (K_D = (X_NiS/X_FeS)_liquid/(X_NiSi12O2/X_FeSi12O2)_olivine; X_i = mole fraction) has been measured at controlled oxygen and sulfur fugacities (fO₂ = 10^−8.1 to 10⁻¹⁰ and fS₂ = 10^−0.9 to 10^−1.7) over the temperature range 1200 to 1385°C, with 5 to 37 wt% Ni and 7 to 18 wt% Cu in the sulfide liquid. At log fO₂ of −8.7 ± 0.1, and log fS₂ of −0.9 to −1.7, K_D is relatively insensitive to sulfur fugacity, but comparison with previous results shows that K_D increases at very low sulfur fugacities. K_D values show an increase with the nickel content of the sulfide liquid, but this effect is more complex than found previously, and is greatest at log fO₂ of −8.1, lessens with decreasing fO₂, and K_D becomes independent of melt Ni content at log fO₂ ≤ −9.5. The origin of this variation in K_D with fO₂ and fS₂ is most likely the result of nonideal mixing of Fe and Ni species in the sulfide liquid. Such behavior causes activity coefficients to change with either melt oxygen content or metal/sulfur ratio, effects that are well documented for metal-rich sulfide melts.Application of these experimental results to natural samples shows that the relatively large dispersion that exists in K_D values from different olivine + sulfide-saturated rock suites can be interpreted as arising from variations in fO₂, fS₂, and the nickel content of the sulfide liquid. Estimates of fO₂ based on K_D and sulfide melt composition in natural samples yields a range from fayalite-magnetite-quartz (FMQ)-1 to FMQ-2 or lower, which is in good agreement with previous values determined for oceanic basalts that use glass ferric/ferrous ratios. Anomalously high K_D values recorded in some suites, such as Disko Island, probably reflect low fS₂ during sulfide saturation, which is consistent with indications of low fO₂ for those samples. It is concluded that the variation in K_D values from natural samples reflects olivine-sulfide melt equilibrium at conditions within the T-fO₂-fS₂ range of terrestrial mafic magmas.     

Experimental determination of synthetic NdPO4 monazite end-member solubility in water from 21°C to 300°C: implications for rare earth element mobility in crustal fluids

The solubility of synthetic NdPO₄ monazite end-member has been determined experimentally from 21 to 300°C in aqueous solutions at pH = 2, and at 21°C and pH = 2 for GdPO₄. Measurements were performed in batch reactors, with regular solution sampling for pH measurement, rare earths and phosphorous analysis by inductively coupled plasma mass spectrometry (ICP-MS) coupled with a desolvation system. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were employed to check that no reprecipitation of secondary phases occurred and that the mineral surfaces remained those of a monazite. Coupled with speciation calculations, measured solution compositions permitted the determination of NdPO₄ and GdPO₄ solubility products which are in general agreement with previous experimental determination on rhabdophane at 25°C, but showing that monazite is more than two orders of magnitude less soluble than inferred on the basis of previous thermodynamic estimates. The temperature evolution from 21 to 300°C of the equilibrium constant (K) of the NdPO₄ monazite end-member dissolution reaction given by:

     

Melting of albite and dehydration of brucite in H2O–NaCl fluids to 9 kbars and 700–900°C: implications for partial melting and water activities during high pressure metamorphism

 The melting reaction: albite_(solid)+ H₂O_(fluid) =albite-H₂O_(melt) has been determined in the presence of H₂O–NaCl fluids at 5 and 9.2 kbar, and results compared with those obtained in presence of H₂O–CO₂ fluids. To a good approximation, albite melts congruently at 9 kbar, indicating that the melting temperature at constant pressure is principally determined by water activity. At 5 kbar, the temperature (T)- mole fraction (X _(H2O) ) melting relations in the two systems are almost coincident. By contrast, H₂O–NaCl mixing at 9 kbar is quite non-ideal; albite melts ∼70 ^°C higher in H₂O–NaCl brines than in H₂O–CO₂ fluids for X _(H2O) =0.8 and ∼100 ^°C higher for X _(H2O) =0.5. The melting temperature of albite in H₂O–NaCl fluids of X _(H2O)=0.8 is ∼100 ^°C higher than in pure water. The P–T curves for albite melting at constant H₂O–NaCl show a temperature minimum at about 5 kbar. Water activities in H₂O–NaCl fluids calculated from these results, from new experimental data on the dehydration of brucite in presence of H₂O–NaCl fluid at 9 kbar, and from previously published experimental data, indicate a large decrease with increasing fluid pressure at pressures up to 10 kbar. Aqueous brines with dissolved chloride salt contents comparable to those of real crustal fluids provide a mechanism for reducing water activities, buffering and limiting crustal melting, and generating anhydrous mineral assemblages during deep crustal metamorphism in the granulite facies and in subduction-related metamorphism. Low water activity in high pressure-temperature metamorphic mineral assemblages is not necessarily a criterion of fluid absence or melting, but may be due to the presence of low a _(H2O) brines. Received: 17 March 1995/Accepted: 9 April 1996