Isothermal decompression history in the “Western Granulite” terrain, central Tanzania: Evidence from reaction textures and trapped fluids in metapelites

The Mozambique Belt (MB) of the East Africa Orogen contains large areas of granulite-facies migmatitic gneisses with Archaean and Palaeoproterozoic protolith ages and that were recycled during the Neoproterozoic Pan-African orogeny. The study area is situated along the Great Ruaha River and within the Mikumi National Park in central Tanzania where migmatitic gneisses and mafic to intermediate granulites are interlayered with Neoproterozoic granulite-facies migmatitic metapelites. Mineral textures suggest isothermal decompression, with the peak mineral assemblage comprising Grt–Bt–Ky–Kfs–Pl–Qtz ± Phn ± Ti-Oxide ± melt and amphibolite-facies retrograde assemblage Grt–Bt–Sil–Ms–Kfs–Pl–Qtz ± Fe–Ti-Oxide. The near isothermal retrograde overprint is seen in well-developed formation of pseudomorphs after garnet. The HP granulite-facies assemblages record P–T conditions of 13–14 kbar at 760–800 °C. Retrogression and the release of fluids from crystallizing melts occurred at 7 kbar and 650–700 °C. A fluid inclusion study shows three types of fluid inclusion consisting of nearly pure CO₂, as well as H₂O–NaCl and H₂O–CO₂ mixtures. We suggest that a immiscible CO₂-bearing brine represents the fluid composition during high-grade peak metamorphism, and that the fluid inclusions containing H₂O–NaCl or nearly pure CO₂ represent trapped fluids from in situ crystallised melt. The results suggest strong isothermal decompression, which is probably related to a fast exhumation after crustal thickening in the central part of the Mozambique Belt in Tanzania.     

Solubility behavior of alkali aluminosilicate components in aqueous fluids and silicate melts at high pressure and temperature

The solubility behavior of K₂O, Na₂O, Al₂O₃, and SiO₂ in silicate-saturated aqueous fluid and coexisting H₂O-saturated silicate melts in the systems K₂O-Al₂O₃-SiO₂-H₂O and Na₂O-Al₂O₃-SiO₂-H₂O has been examined in the 1- to 2-GPa pressure range at 1100°C. Glasses of Na- and K-tetrasilicate compositions with 0, 3, and 6 mol% Al₂O₃ were used as starting materials. In both systems, the oxides dissolve incongruently in aqueous fluid and silicate melt. When recalculated to an anhydrous basis, the aqueous fluids are enriched in alkalis and depleted in silica and alumina relative to their proportions in the starting materials. The extent of incongruency is more pronounced in the Na₂O-Al₂O₃-SiO₂-H₂O system than in the K₂O-Al₂O₃-SiO₂-H₂O system.The partition coefficients of the oxides, D_oxide^fluid/melt, are linear and positive functions of the oxide concentration in the fluid for each composition. There is a slight dependence of the partition coefficients on bulk composition. No effect of pressure could be discerned. For alkali metals, the fluid/melt partition coefficients range from 0.06 to 0.8. For Al₂O₃ this range is 0.01 to 0.2, and for SiO₂, it is 0.01 to 0.32. For all compositions, D_K2O^fluid/melt∼D_Na2O^fluid/melt>D_SiO2^fluid/melt>D_Al2O3^fluid/melt for the same oxide concentration in the fluid. D_K2O^fluid/melt, D_Na2O^fluid/melt, and D_SiO2^fluid/melt correlate negatively with the Al₂O₃ content of the systems. This correlation is consistent with a solubility model of alkalis that involve associated KOH°, NaOH°, silicate, and aluminate complexes.     

Fluid geochemistry in the Ivigtut cryolite deposit, South Greenland

The 1.27 Ga old Ivigtut (Ivittuut) intrusion in South Greenland is world-famous for its hydrothermal cryolite deposit [Na₃AlF₆] situated within a strongly metasomatised A-type granite stock. This detailed fluid inclusion study characterises the fluid present during the formation of the cryolite deposit and thermodynamic modelling allows to constrain its formation conditions.Microthermometry revealed three different types of inclusions: (1) pure CO₂, (2) aqueous-carbonic and (3) saline-aqueous inclusions. Melting temperatures range between − 23 and − 15 °C for type 2 and from − 15 to − 10 °C for type 3 inclusions. Most inclusions homogenise between 110 and 150 °C into the liquid.Stable isotope compositions of CO₂ and H₂O were measured from crushed inclusions in quartz, cryolite, fluorite and siderite. The δ¹³C values of about − 5‰ PDB are typical of mantle-derived magmas. The differences between δ¹⁸O of CO₂ (+ 21 to + 42‰ VSMOW) and δ¹⁸O of H₂O (− 1 to − 21.7‰ VSMOW) suggest low-temperature isotope exchange. δD (H₂O) ranges from − 19 to − 144‰ VSMOW. The isotopic composition of inclusion water closely follows the meteoric water line and is comparable to Canadian Shield brines. Ion chromatography revealed the fluid's predominance in Na, Cl and F. Cl/Br ratios range between 56 and 110 and may imply intensive fluid–rock interaction with the host granite.Isochores deduced from microthermometry in conjunction with estimates for the solidification of the Ivigtut granite suggest a formation pressure of approximately 1–1.5 kbar for the fluid inclusions. Formation temperatures of different types of fluid inclusions vary between 100 and 400 °C. Thermodynamic modelling of phase assemblages and the extraordinary high concentration in F (and Na) may indicate that the cryolite body and its associated fluid inclusions could have formed during the continuous transition from a volatile-rich melt to a solute-rich fluid.     

Interaction between sulphide and H2O in silicate melts

Reaction between dissolved water and sulphide was experimentally investigated in soda-lime-silicate (NCS) and sodium trisilicate (NS3) melts at temperatures from 1000 to 1200 °C and pressures of 100 or 200 MPa in internally heated gas pressure vessels. Diffusion couple experiments were conducted at water-undersaturated conditions with one half of the couple being doped with sulphide (added as FeS or Na₂S; 1500-2000 ppm S by weight) and the other with H₂O (∼3.0 wt.%). Additionally, two experiments were performed using a dry NCS glass cylinder and a free H₂O fluid. Here, the melt was water-saturated at least at the melt/fluid interface. Profiling by electron microprobe (sulphur) and infrared microscopy (H₂O) demonstrate that H₂O diffusion in the melts is faster by 1.5-2.3 orders of magnitude than sulphur diffusion and, hence, H₂O can be considered as a rapidly diffusing oxidant while sulphur is quasi immobile in these experiments.In Raman spectra a band at 2576 cm⁻¹ appears in the sulphide - H₂O transition zone which is attributed to fundamental S-H stretching vibrations. Formation of new IR absorption bands at 5025 cm⁻¹ (on expense of the combination band of molecular H₂O at 5225 cm⁻¹) and at 3400 cm⁻¹ was observed at the front of the in-diffusing water in the sulphide bearing melt. The appearance and intensity of these two IR bands is correlated with systematic changes in S K-edge XANES spectra. A pre-edge excitation at 2466.5 eV grows with increasing H₂O concentration while the sulphide peak at 2474.0 eV decreases in intensity relative to the peak at 2477.0 eV and the feature at 2472.3 eV becomes more pronounced (all energies are relative to the sulphate excitation, calibrated to 2482.5 eV). The observations by Raman, IR and XANES spectroscopy indicate a well coordinated S²⁻ - H₂O complex which was probably formed in the glasses during cooling at the glass transition. No oxidation of sulphide was observed in any of the diffusion couple experiments. On the contrary, XANES spectra from experiments conducted with a free H₂O fluid show complete transformation of sulphide to sulphate near the melt surface and coexistence of sulphate and sulphide in the center of the melt. This can be explained by a lower H₂O activity in the diffusion couple experiments or by the need of a sink for hydrogen (e.g., a fluid which can dissolve high concentration of hydrogen) to promote oxidation of sulphide by H₂O via the reaction S²⁻ + 4H₂O = SO₄²⁻ + 4H₂. Sulphite could not be detected in any of the XANES spectra implying that this species, if it exists in the melt, it is a subordinate or transient species only.     

Fluid regime and diamond formation in the reduced mantle: Experimental constraints

The composition and potential diamond productivity of C–O–H fluids that could exist in the reduced regions of the Earth’s upper mantle and in the mantles of Uranus and Neptune were studied in experiments at 6.3 GPa and 1400–1600 °C and durations of 15–48 h. Hydrogen fugacity in the fluid phase was controlled by the Mo–MoO₂ or Fe–FeO buffers, using a specially modified double-capsule method. The oxygen fugacity in the samples was controlled by adding different amounts of water, stearic acid, anthracene, and docosane to a graphite charge. At high P–T conditions, the degree of decomposition of the heavy hydrocarbons added to the charge was 99.9%. The composition of the fluids coexisting with graphite/diamond in the buffered experiments varied from H₂O  H₂ > CH₄ (at fO₂ somewhat lower than the “water maximum”) to H₂ > CH₄ > (C₂H₄ + C₂H₆)>C₃H₈ (in C–H system). In the C–H system the maximum concentrations of major species in the synthesized fluid were: H₂ = 79 mol.% and CH₄ = 21 mol.%. The composition of the H₂-rich fluids, which were synthesized at 6.3 GPa and 1400–1600 °C for the first time, differs considerably from that of the ultra-reduced CH₄-rich fluids stable at 2.0–3.5 GPa and 1000–1300 °C. Thermodynamic calculations of the reduced C–O–H fluids at the P–T conditions of the experiments revealed CH₄-rich compositions (CH₄  H₂ > (C₂H₄ + C₂H₆)>C₃H₈), which however drastically differed from the synthesized compositions. The rates of diamond nucleation and growth in the experiments depended on the fluid composition. Diamond crystallization had a maximum intensity in the pure aqueous fluids, while in the H₂-rich fluids no diamond formation was observed. Only metastable graphite precipitated from the ultra-reduced fluids. The type of the initial hydrocarbon used for the fluid generation did not affect this process.     

The role of phosphorus in rhyolitic liquids as determined from the homogeneous iron redox equilibrium

The redox ratio of iron is used as an indicator of solution properties of silicate liquids in the system (SiO–Al₂O₃–K₂O–FeO–Fe₂O₃–P₂O₅). Glasses containing 80–85 mol% SiO₂ with 1 mol% Fe₂O₃ and compositions covering a range of K₂O/Al₂O₃ were synthesized at 1400°C in air (fixed fO₂). Variations in the ratio FeO/FeO_1.5 resulting from the addition of P₂O₅ are used to determine the solution behavior of phosphorus and its interactions with other cations in the silicate melt. In 80 mol% SiO₂ peralkaline melts the redox ratio, expressed as FeO/FeO_1.5, is unchanged relative to the reference curve with the addition of 3 mol% P₂O₅. Yet, the iron redox ratio in the 85 mol% SiO₂ potassium aluminosilicate melts is decreased relative to phosphorus-free liquids even for small amounts of P₂O₅ (0.5 mol%). The redox ratio in peraluminous melts is decreased relative to phosphorus- free liquids at P₂O₅ concentrations of 3 mol%. In peraluminous liquids, complexing of both Fe⁺³–O–P⁺⁵ and Al⁺³–O–P⁺⁵ occur. The activity coefficient of Fe⁺³ is decreased because more ferric iron can be accommodated than in phosphorus-free liquids. In peralkaline melts, there is no evidence that P⁺⁵ is removing K⁺ from either Al⁺³ or Fe⁺³ species. In chargebalanced melts with 3 mol% Fe₂O₃ and very high P₂O₅ concentrations, phosphorus removes K⁺ from K–O–Fe⁺³ complexes resulting in a redox increase. P₂O₅ should be accommodated easily in peraluminous rhyolitic liquids and phosphate saturation may be suppressed relative to metaluminous rhyolites. In peralkaline melts, phosphate solubility may increase as a result of phosphorus complexing with alkalis. The complexing stoichiometry may be variable, however, and the relative influence of peralkalinity versus temperature on phosphate solubility in rhyolitic melts deserves greater attention.     

Fluid inclusion characteristics of hematite-bearing quartz vein from the Daenam mine, Republic of Korea

The Daenam mine, which produced over 9250 tons of iron oxide ore from 1958 to 1962, is situated in the Early Cretaceous Yeongyang subbasin of the Gyeongsang basin. It consists of two lens-shaped, hematite-bearing quartz veins that occur along faults in Cretaceous leucocratic granite. The hematite-bearing quartz veins are mainly composed of massive and euhedral quartz and hematite with minor amounts of pyrite, pyrrhotite, mica, feldspar and chlorite.Fluid inclusions in quartz can be divided into three main types: CO₂-rich, CO₂–H₂O, and H₂O-rich. Hydrothermal fluids related to the formation of hematite are composed of either H₂O–CO₂–NaCl ± CH₄ (homogenization temperature: 262–455 °C, salinity <7 eq. wt.% NaCl) or H₂O–NaCl (homogenization temperature: 182–266 °C, and salinity <5.1 eq. wt.% NaCl), both of which evolved by mixing with deeply circulating meteoric water. Hematite from the quartz veins in the Daenam mine was mainly deposited by unmixing of H₂O–CO₂–NaCl ± CH₄ fluids with loss of the CO₂ + CH₄ vapor phase and mixing with downward percolating meteoric water providing oxidizing conditions.     

Intrinsic and scattering attenuation in western India from aftershocks of the 26 January, 2001 Kachchh earthquake

176 vertical-component, short period observations from aftershocks of the M_w 7.7, 26 January, 2001 Kachchh earthquake are used to estimate seismic wave attenuation in western India using uniform and two layer models. The magnitudes (M_w) of the earthquakes are less than 4.5, with depths less than 46 km and hypocentral distances up to 110 km. The studied frequencies are between 1 and 30 Hz. Two seismic wave attenuation factors, intrinsic absorption (Q_i^− 1) and scattering attenuation (Q_s^− 1) are estimated using the Multiple Lapse Time Window method which compares time integrated seismic wave energies with synthetic coda wave envelopes for a multiple isotropic scattering model. We first assume spatial uniformity of Q_i^− 1, Q_s^− 1 and S wave velocity (β). A second approach extends the multiple scattering hypothesis to media consisting of several layers characterized by vertically varying scattering coefficient (g), intrinsic absorption strength (h), density of the media (ρ) and shear wave velocity structure. The predicted coda envelopes are computed using Monte Carlo simulation. Results show that, under the assumption of spatial uniformity, scattering attenuation is greater than intrinsic absorption only for the lowest frequency band (1 to 2 Hz), whereas intrinsic absorption is predominant in the attenuation process at higher frequencies (2 to 30 Hz). The values of Q obtained range from Q_t = 118, Q_i = 246 and Q_s = 227 at 1.5 Hz to Q_t ≈ 4000, Q_i ≈ 4600 and Q_s ≈ 33,300 at 28 Hz center frequencies, being Q_t^− 1 a measure of total attenuation. Results also show that Q_i^− 1, Q_s^− 1 and Q_t^− 1 decrease proportional to f^−ν. Two rates of decay are clearly observed for the low (1 to 6 Hz) and high (6 to 30 Hz) frequency ranges. Values of ν are estimated as 2.07 ± 0.05 and 0.44 ± 0.09 for total attenuation, 1.52 ± 0.21 and 0.48 ± 0.09 for intrinsic absorption and 3.63 ± 0.07 and 0.06 ± 0.08 for scattering attenuation for the low and high frequency ranges, respectively. Despite the lower resolution in deriving the attenuation parameters for a two layered crust, we find that scattering attenuation is comparable to or smaller than the intrinsic absorption in the crust whereas intrinsic absorption dominates in the mantle. Also, for a crustal layer of thickness 42 km, intrinsic absorption and scattering estimates in the crust are lower and greater than those of the mantle, respectively.     

Fractionation of major elements between coexisting H2O-saturated silicate melt and silicate-saturated aqueous fluids in aluminosilicate systems at 1-2 GPa

From experimental data in the systems Na₂O-Al₂O₃-SiO₂-H₂O, K₂O-Al₂O₃-SiO₂-H₂O at 1100°C, and CaO-Al₂O₃-SiO₂-H₂O at 1200°C in the 1-2 GPa pressure range, the solution behavior of the individual oxides in coexisting H₂O-saturated silicate melts and silicate-saturated aqueous fluids appears to be incongruent. Recalculated on an anhydrous basis, in the CaO-Al₂O₃-SiO₂-H₂O system, CaO^fluid/CaO^melt < 1, whereas in the Na₂O-Al₂O₃-SiO₂-H₂O and K₂O-Al₂O₃-SiO₂-H₂O systems, K₂O^fluid/K₂O^melt and Na₂O^fluid/Na₂O^melt both are greater than 1. The aqueous fluids are depleted in alumina relative to silicate melt.In the Na₂O-Al₂O₃-SiO₂-H₂O, K₂O-Al₂O₃-SiO₂-H₂O, and CaO-Al₂O₃-SiO₂-H₂O systems, fluid/melt partition coefficients for the individual oxides range between ∼0.005 and 0.35 depending on oxide, bulk composition and pressure. The alkali partition coefficients are about an order of magnitude higher than that of CaO. Alumina and silica partition coefficient values in the CaO-Al₂O₃-SiO₂-H₂O system are 10-20% of the values for the same oxides in the Na₂O-Al₂O₃-SiO₂-H₂O and K₂O-Al₂O₃-SiO₂-H₂O systems.Positive correlations among individual partition coefficients and oxide concentrations in the aqueous fluids are consistent with complexing in the fluid that involves silicate polymers associated with alkalis and alkaline earths and aluminosilicate complexes where alkalis and alkaline earths may serve to charge-balance Al³⁺, which is, perhaps, in tetrahedral coordination. Alkali aluminosilicate complexes in aqueous fluid appear more stable than Ca-aluminosilicate complexes.     

Diffusive transport of water in porous feldspars from granitic saprolites: In situ experiments using FTIR spectroscopy

A novel experimental cell was developed for in situ measurements of transport phenomena in porous media using Fourier-Transform Infrared (FTIR) Spectroscopy. The technique was employed at ambient pressure in the temperatures range of 11–44 °C to study the H₂O → D₂O exchange between water-saturated weathered feldspars (bulk porosity of 5–19 vol% for feldspar) from granitic saprolites and a surrounding aqueous liquid. Such measurements are an important step for understanding internal weathering reactions of feldspars in soils and aquifers. Effective diffusion coefficients D_eff for water in water-saturated porous feldspars were determined assuming one-dimensional diffusion in a quasi-homogeneous medium. The values of D_eff vary from 7.2 × 10⁻¹⁰ to 1.9 × 10⁻¹¹ m²/s and are 1–2 orders of magnitude lower than the diffusion coefficients (D) of protons and molecular H₂O in liquid water. The activation energy for the H₂O → D₂O exchange process in porous feldspars ranges from 7.8 to 18.8 kJ/mol.The results imply that the effective diffusivity of water is mainly controlled by physical properties of the feldspars like porosity, pore connectivity, pore geometry and distribution. Perthitic feldspars with homogeneous pore distribution in the albitic lamellas have diffusional tortuosity factors X = D/D_eff between 3 and 10 while alkali feldspars with inhomogeneously distributed and disconnected pores have much higher X values up to 129. Diffusion anisotropy has been verified for a vein perthite with diffusion perpendicular to the lamellas being faster by 0.3–0.5 log units than within the lamellas. It has to be emphasized that the study is based only on few selected feldspars, including perthitic feldspar, and additional work on samples with different weathering stages is needed to test the importance of the different parameters controlling diffusive transport in the pore system.     

Evidence from olivine/melt element partitioning that nonbridging oxygen in silicate melts are not equivalent

Partitioning of Ca, Mn, Mg, and Fe²⁺ between olivine and melt has been used to examine the influence of energetically nonequivalent nonbridging oxygen in silicate melts. Partitioning experiments were conducted at ambient pressure in air and 1400°C with melts in equilibrium with forsterite-rich olivine (Fo >95 mol%). The main compositional variables of the melts were NBO/T and Na/(Na+Ca). In all melts, the main structural units were of Q⁴, Q³, and Q² type with nonbridging oxygen, therefore, in the Q³ and Q² units.For melts with high Q³/Q²-abundance ratio (corresponding to NBO/T near 1), increasing Na/(Na+Ca) [and Na/(Na+Ca+Mn+Mg+Fe²⁺)] results in a systematic decrease of the partition coefficients, K_Ca^ol/melt, K_Mn^ol/melt, K_Mg^ol/melt, and K_Fe2+^ol/melt, because of ordering of the network-modifying Ca, Mn, Mg, and Fe²⁺ among nonbridging oxygen in Q³ and Q² structural units. This decrease is more pronounced the smaller the ionic radius of the cation. With decreasing Q³/Q² abundance ratio (less-polymerized melts) this effect becomes less pronounced.Activity-composition relations among network-modifying cations in silicate melts are, therefore, governed by availability of energetically nonequivalent nonbridging oxygen in individual Qⁿ-species in the melt. As a result, any composition change that enhances abundance of highly depolymerized Qⁿ-species will cause partition coefficients to decrease.     

Differentiation and crystallization conditions of basalts from the Kerguelen large igneous province: an experimental study

Phase relations of basalts from the Kerguelen large igneous province have been investigated experimentally to understand the effect of temperature, fO₂, and fugacity of volatiles (e.g., H₂O and CO₂) on the differentiation path of LIP basalts. The starting rock samples were a tholeiitic basalt from the Northern Kerguelen Plateau (ODP Leg 183 Site 1140) and mildly alkalic basalt evolved from the Kerguelen Archipelago (Mt. Crozier on the Courbet Peninsula), representing different differentiation stages of basalts related to the Kerguelen mantle plume. The influence of temperature, water and oxygen fugacity on phase stability and composition was investigated at 500 MPa and all experiments were fluid-saturated. Crystallization experiments were performed at temperatures between 900 and 1,160°C under oxidizing (log fO₂ ~ ΔQFM + 4) and reducing conditions (log fO₂ ~ QFM) in an internally heated gas-pressure vessel equipped with a rapid quench device and a Pt-Membrane for monitoring the fH₂. In all experiments, a significant influence of the fO₂ on the composition and stability of the Mg/Fe-bearing mineral phases could be observed. Under reducing conditions, the residual melts follow a tholeiitic differentiation trend. In contrast, melts have high Mg# [Mg²⁺/(Mg²⁺ + Fe²⁺)] and follow a calk-alkalic differentiation trend at oxidizing conditions. The comparison of the natural phenocryst assemblages with the experimental products allows us to constrain the differentiation and pre-eruptive conditions of these magmas. The pre-eruptive temperature of the alkalic basalt was about 950–1,050°C. The water content of the melt was below 2.5 wt% H₂O and strongly oxidizing conditions (log fO₂ ~ ΔQFM + 2) were prevailing in the magma chamber prior to eruption. The temperature of the tholeiitic melt was above 1,060°C, with a water content below 2 wt% H₂O and a log fO₂ ~ ΔQFM + 1. Early fractionation of clinopyroxene is a crucial step resulting in the generation of silica-poor and alkali-rich residual melts (e.g., alkali basalt). The enrichment of alkalis in residual melts is enhanced at high fO₂ and low aH₂O.     

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     

Adsorption of NO, SO2 and light hydrocarbons on activated Greek brown coals

Twenty-eight samples of peat, peaty lignites and lignites (of both matrix and xylite-rich lithotypes) and subbituminous coals have been physically activated by pyrolysis. The results show that the surface area of the activated coal samples increases substantially and the higher the carbon content of the samples the higher the surface area.The adsorption capacity of the activated coals for NO, SO₂, C₃H₆ and a mixture of light hydrocarbons (CH₄, C₂H₆, C₃H₈ and C₄H₁₀) at various temperatures was measured on selected samples. The result shows a positive correlation between the surface area and the gas adsorption. In contrast, the gas adsorption is inversely correlated with the temperature. The maximum recorded adsorption values are: NO = 8.22 × 10^− 5 mol/g at 35 °C; SO₂ = 38.65 × 10^− 5 mol/g at 60 °C; C₃H₆ = 38.9 × 10^− 5 mol/g at 35 °C; and light hydrocarbons = 19.24 × 10^− 5 mol/g at 35 °C. Adsorption of C₃H₆ cannot be correlated with either NO or SO₂. However, there is a significant positive correlation between NO and SO₂ adsorptions. The long chain hydrocarbons are preferentially adsorbed on activated lignites as compared to the short chain hydrocarbons.The results also suggest a positive correlation between surface area and the content of telohuminite maceral sub-group above the level of 45%.     

Zr-rich accessory minerals (titanite, perrierite, zirconolite, baddeleyite) record strong oxidation associated with magma mixing in the south Peruvian potassic province

The Oroscocha Quaternary volcano, in the Inner Arc Domain of the Andean Cordillera (southern Peru), emitted peraluminous rhyolites and trachydacites that entrained decimetric to millimetric lamprophyric blobs. These latter show kersantite modal compositions (equal proportion of groundmass plagioclase and K-feldspar) and potassic bulk-rock compositions (1<K₂O/Na₂O<2; 6.7–7.2 wt.% CaO). Kersantite blobs have shapes and microstructures consistent with an origin from a mixing process between mafic potassic melts and rhyolitic melts. Both melts did exchange their phenocrysts during the mixing process. In addition to index minerals of lamprophyres (Ba–Ti–phlogopite, F-rich apatite, andesine and Ca-rich sanidine), the groundmass of kersantite blobs displays essenite-rich diopside (up to 22 mol%), Ti-poor magnetite microlites, Ti-poor hematite microlites and a series of Ca–Ti–Zr- and REE-rich accessory minerals that have never been reported from lamprophyres. Titanite [up to 5.3 wt.% ZrO₂ and 5.2 wt.% (Y₂O₃ + REE₂O₃)] and Zr- and Ca-rich perrierite (up to 7.2 wt.% ZrO₂ and 10.8 wt.% CaO) predate LREE- and iron-rich zirconolite and Fe-, Ti-, Hf-, Nb- and Ce-rich baddeleyite (up to 5.3 wt.% Fe₂O₃, 3.2 wt.% TiO₂, 1.5 wt.% HfO₂, 1.2 wt.% Nb₂O₅, 0.25 wt.% CeO₂) in the crystallization order of the groundmass. Isomorphic substitutions suggest iron to occur as Fe³⁺ in all the accessory phases. This feature, the essenitic substitution in the clinopyroxene and the occurrence of hematite microlites, all indicate a drastic increase of the oxygen fugacity (from FMQ − 1 to FMQ + 5 log units) well above the HM synthetic buffer within a narrow temperature range (1100–1000 °C). Such a late-magmatic oxidation is ascribed to assimilation of water from the felsic melts during magma mixing, followed by rapid degassing and water dissociation during eruption of host felsic lavas. Thus, magma mixing involving felsic melt end-members provides a mechanism for mafic potassic melts to be oxidized beyond the HM synthetic buffer curve.     

Nature of fluids and regional implications for Lesser Himalayan carbonates and associated mineralization

Fluid inclusion data are presented for the successive stages of limestone, dolomite, magnesite and sulphide-bearing quartz veins in Proterozoic carbonate rocks of the Lesser Himalaya. Subsurface fluids were H₂O–NaCl–KCl ± MgCl₂ ± CaCl₂ and showed successive increase in salinity and temperature. The salinity of the pore fluid during limestone diagenesis was in the range of 7.5–15 eq wt.% NaCl and the magnesite-forming fluids had a salinity of about 9 to 19 eq wt.% NaCl. This progressive rise in salinity is attributed to a more saline fluid in the deeper zones. The inverse relation between homogenization temperatures and final melting temperatures suggests mixing of the fluids during diagenesis, and highly depleted δ¹⁸O values rule out participation of magmatic fluid in the mixing. A late stage carbonic fluid is linked with talc formation. The low temperature of sulphide-forming epigenetic solutions, as obtained from fluid inclusions, is also substantiated by the chemical data from these sulphides. δ³⁴S values in galena infer that magmatic sulphur was probably not involved, and the sulphur of the galena is derived from an isotopically heavy source.     

Structure of H2O-saturated peralkaline aluminosilicate melt and coexisting aluminosilicate-saturated aqueous fluid determined in-situ to 800 °C and ∼800 MPa

The structure of H₂O-saturated silicate melts and of silicate-saturated aqueous solutions, as well as that of supercritical silicate-rich aqueous liquids, has been characterized in-situ while the sample was at high temperature (to 800 °C) and pressure (up to 796 MPa). Structural information was obtained with confocal microRaman and with FTIR spectroscopy. Two Al-bearing glasses compositionally along the join Na₂O•4SiO₂-Na₂O•4(NaAl)O₂-H₂O (5 and 10 mol% Al₂O₃, denoted NA5 and NA10) were used as starting materials. Fluids and melts were examined along pressure-temperature trajectories of isochores of H₂O at nominal densities (from PVT properties of pure H₂O) of 0.85 g/cm³ (NA10 experiments) and 0.86 g/cm³ (NA5 experiments) with the aluminosilicate + H₂O sample contained in an externally-heated, Ir-gasketed hydrothermal diamond anvil cell.Molecular H₂O (H₂O°) and OH groups that form bonds with cations exist in all three phases. The OH/H₂O° ratio is positively correlated with temperature and pressure (and, therefore, fugacity of H₂O, f_H2O) with (OH/H₂O°)^melt > (OH/H₂O°)^fluid at all pressures and temperatures. Structural units of Q³, Q², Q¹, and Q⁰ type occur together in fluids, in melts, and, when outside the two-phase melt + fluid boundary, in single-phase liquids. The abundance of Q⁰ and Q¹ increases and Q² and Q³ decrease with f_H2O. Therefore, the NBO/T (nonbridging oxygen per tetrahedrally coordination cations), of melt is a positive function of f_H2O. The NBO/T of silicate in coexisting aqueous fluid, although greater than in melt, is less sensitive to f_H2O.The melt structural data are used to describe relationships between activity of H₂O and melting phase relations of silicate systems at high pressure and temperature. The data were also combined with available partial molar configurational heat capacity of Qⁿ-species in melts to illustrate how these quantities can be employed to estimate relationships between heat capacity of melts and their H₂O content.     

Speciation of reduced C-O-H volatiles in coexisting fluids and silicate melts determined in-situ to ∼1.4 GPa and 800 °C

The structure of silicate melts in the system Na₂O·4SiO₂ saturated with reduced C-O-H volatile components and of coexisting silicate-saturated C-O-H solutions has been determined in a hydrothermal diamond anvil cell (HDAC) by using confocal microRaman and FTIR spectroscopy as structural probes. The experiments were conducted in-situ with the melt and fluid at high temperature (up to 800 °C) and pressure (up to 1435 MPa). Redox conditions in the HDAC were controlled with the reaction, Mo + H₂O = MoO₂ + H₂, which is slightly more reducing than the Fe + H₂O = FeO + H₂ buffer at 800 °C and less.The dominant species in the fluid are CH₄ + H₂O together with minor amounts of molecular H₂ and an undersaturated hydrocarbon species. In coexisting melt, CH₃ - groups linked to the silicate melt structure via Si-O-CH₃ bonding may dominate and possibly coexists with molecular CH₄. The abundance ratio of CH₃ - groups in melts relative to CH₄ in fluids increases from 0.01 to 0.07 between 500 and 800 °C. Carbon-bearing species in melts were not detected at temperatures and pressures below 400 °C and 730 MPa, respectively. A schematic solution mechanism is, Si-O-Si + CH₄?Si-O-CH₃+H-O-Si. This mechanism causes depolymerization of silicate melts. Solution of reduced (C-O-H) components will, therefore, affect melt properties in a manner resembling dissolved H₂O.     

The solution behavior of H2O in peralkaline aluminosilicate melts at high pressure with implications for properties of hydrous melts

Solubility and solution mechanisms of H₂O in depolymerized melts in the system Na₂O-Al₂O₃-SiO₂ were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na₂Si₄O₉-Na₂(NaAl)₄O₉] with Al/(Al+Si) = 0.00-0.25. The H₂O solubility was fitted to the expression, X_H2O=0.20+0.0020f_H2O-0.7X_Al+0.9(X_Al)², where X_H2O is the mole fraction of H₂O (calculated with O = 1), f_H2O the fugacity of H₂O, and X_Al = Al/(Al+Si). Partial molar volume of H₂O in the melts, , calculated from the H₂O-solulbility data assuming ideal mixing of melt-H₂O solutions, is 12.5 cm³/mol for Al-free melts and decreases linearly to 8.9 cm³/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H₂O, , increases with Al/(Al+Si).Solution mechanisms of H₂O were obtained by combining Raman and ²⁹Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H₂O content. The rate of NBO/T-change with H₂O is negatively correlated with H₂O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q⁴-species to form Q² species. Steric hindrance appears to restrict bonding of H⁺ with nonbridging oxygen in Q³ species. The presence of Al³⁺ does not affect the water solution mechanisms significantly.     

H2O diffusion models in rhyolitic melt with new high pressure data

Water diffusion in silicate melts is important for understanding bubble growth in magma, magma degassing and eruption dynamics of volcanos. Previous studies have made significant progress on water diffusion in silicate melts, especially rhyolitic melt. However, the pressure dependence of H₂O diffusion is not constrained satisfactorily. We investigated H₂O diffusion in rhyolitic melt at 0.95–1.9 GPa and 407–1629 °C, and 0.2–5.2 wt.% total water (H₂O_t) content with the diffusion-couple method in a piston-cylinder apparatus. Compared to previous data at 0.1–500 MPa, H₂O diffusivity is smaller at higher pressures, indicating a negative pressure effect. This pressure effect is more pronounced at low temperatures. Assuming H₂O diffusion in rhyolitic melt is controlled by the mobility of molecular H₂O (H₂O_m), the diffusivity of H₂O_m (D_H2Om) at H₂O_t ≤ 7.7 wt.%, 403–1629 °C, and ≤ 1.9 GPa is given by

D_H2Om=D₀exp(aX),