The influence of water on melting of mantle peridotite

This experimental study examines the effects of variable concentrations of dissolved H₂O on the compositions of silicate melts and their coexisting mineral assemblage of olivine + orthopyroxene ± clinopyroxene ± spinel ± garnet. Experiments were performed at pressures of 1.2 to 2.0 GPa and temperatures of 1100 to 1345 °C, with up to ∼12 wt% H₂O dissolved in the liquid. The effects of increasing the concentration of dissolved H₂O on the major element compositions of melts in equilibrium with a spinel lherzolite mineral assemblage are to decrease the concentrations of SiO₂, FeO, MgO, and CaO. The concentration of Al₂O₃ is unaffected. The lower SiO₂ contents of the hydrous melts result from an increase in the activity coefficient for SiO₂ with increasing dissolved H₂O. The lower concentrations of FeO and MgO result from the lower temperatures at which H₂O-bearing melts coexist with mantle minerals as compared to anhydrous melts. These compositional changes produce an elevated SiO₂/(MgO + FeO) ratio in hydrous peridotite partial melts, making them relatively SiO₂ rich when compared to anhydrous melts on a volatile-free basis. Hydrous peridotite melting reactions are affected primarily by the lowered mantle solidus. Temperature-induced compositional variations in coexisting pyroxenes lower the proportion of clinopyroxene entering the melt relative to orthopyroxene. Isobaric batch melting calculations indicate that fluid-undersaturated peridotite melting is characterized by significantly lower melt productivity than anhydrous peridotite melting, and that the peridotite melting process in subduction zones is strongly influenced by the composition of the H₂O-rich component introduced into the mantle wedge from the subducted slab. Received: 7 April 1997 / Accepted: 9 January 1998     

Vesiculation of hydrous andesitic melt and transport of alkalies by separated vapor phase

Experiments have been carried out on the separation of H₂O-rich vapor phase from a hydrous andesite melt at pressures between 5 and 15 kbar at 1,150 ° C. The pressure at which the vapor phase separates from the melt by isothermal decompression depends on the H₂O content in the melt; for example, 14 kbar for 12wt.% and 8 kbar for 9wt.% H₂O. These values are lower than the solubility of H₂O in andesite melt previously estimated. Extensive decompression to near atmospheric pressure resulted in the formation of pumiceous glass.Vapor phase separated from the melt moves upward and transports significant amounts of alkalies (Na₂O and K₂O), resulting in the depletion of alkalies near the bottom and concentration of alkalies near the top of the container. The maximum concentration observed is 5.0 wt.% for Na₂O and 1.7% for K₂O, compared to the initial contents 3.3 and 1.3 wt.% respectively. The approximate viscosity of hydrous andesitic melt with 7.5–12 wt.% H₂O was roughly estimated to be less than 10 poise. The results of the present experiments imply that when H₂O-rich vapor separates from magma in a magma chamber (or in a conduit) and moves upward, the top of the chamber would be enriched in alkalies while the bottom would be depleted.     

Interaction of model peridotite with H2O-KCl fluid: Experiment at 1.9 GPa and its implications for upper mantle metasomatism

Mineralogical and geochemical data suggest that chloride components play an important role in the transformation and partial melting of upper mantle peridotites. The effect of KCl on the transformation of hydrous peridotite rich in Al₂O₃, CaO, and Na₂O was examined in experiments aimed at studying interaction between model NCMAS peridotite with H₂O-KCl fluid under a pressure of 1.9 GPa, temperatures of 900–1200°C, and various initial H₂O/KCl ratios. The experimental results indicate that KCl depresses the solidus temperature of the hydrous peridotite: this temperature is <900°C at 1.9 GPa, which is more than 100°C lower than the solidus temperature (1000–1025°C) of hydrous peridotite in equilibrium with KCl-free fluid. The reason for the decrease in the melting temperature is that the interaction of KCl with silicates prevails over the effect of chloride on the water activity in the fluid. Experimental data highlight the key role of Al₂O₃ as a component controlling the whole interaction process between peridotite and H₂O-KCl fluid. Garnet, spinel, and pargasite-edenite amphibole in association with aluminous orthopyroxene are unstable in the presence of H₂O-KCl fluid at a chloride concentration in the fluid as low as approximately 2 wt % and are replaced by Cl-bearing phlogopite (0.4–1.1 wt % Cl). Interaction with H₂O-KCl fluid does not, however, affect clinopyroxene and forsterite, which are the Al poorest phases of the system. Chlorine stabilizes phlogopite at relatively high temperatures in equilibrium with melt at temperatures much higher than the solidus (>1200°C). The compositional evolution of melt generated during the melting of model peridotite in the presence of H₂O-KCl fluid is controlled, on the one hand, by the solubility of the H₂O-KCl fluid in the melt and, on the other hand, by phlogopite stability above the solidus. At temperatures below 1050°C, at which phlogopite does not actively participate in melting reactions, fluid dissolution results in SiO₂-undersaturated (35–40 wt %) and MgO-enriched (up to 45 wt %) melts containing up to 4–5 wt % K₂O and 2–3 wt % Cl. At higher temperatures, active phlogopite dissolution and, perhaps, also the separation of immiscible aqueous chloride liquid give rise to melts containing >10 wt % K₂O and 0.3–0.5 wt % Cl. Our experimental results corroborate literature data on the transformation of upper mantle peridotites into phlogopite-bearing associations and the formation of ultrapotassic and highly magnesian melts.     

CO2 solubility and speciation in intermediate (andesitic) melts: the role of H2O and composition

We determined total CO₂ solubilities in andesite melts with a range of compositions. Melts were equilibrated with excess C-O(-H) fluid at 1 GPa and 1300°C then quenched to glasses. Samples were analyzed using an electron microprobe for major elements, ion microprobe for C-O-H volatiles, and Fourier transform infrared spectroscopy for molecular H₂O, OH⁻, molecular CO₂, and CO₃²⁻. CO₂ solubility was determined in hydrous andesite glasses and we found that H₂O content has a strong influence on C-O speciation and total CO₂ solubility. In anhydrous andesite melts with ∼60 wt.% SiO₂, total CO₂ solubility is ∼0.3 wt.% at 1300°C and 1 GPa and total CO₂ solubility increases by about 0.06 wt.% per wt.% of total H₂O. As total H₂O increases from ∼0 to ∼3.4 wt.%, molecular CO₂ decreases (from 0.07 ± 0.01 wt.% to ∼0.01 wt.%) and CO₃²⁻ increases (from 0.24 ± 0.04 wt.% to 0.57 ± 0.09 wt.%). Molecular CO₂ increases as the calculated mole fraction of CO₂ in the fluid increases, showing Henrian behavior. In contrast, CO₃²⁻ decreases as the calculated mole fraction of CO₂ in the fluid increases, indicating that CO₃²⁻ solubility is strongly dependent on the availability of reactive oxygens in the melt. These findings have implications for CO₂ degassing. If substantial H₂O is present, total CO₂ solubility is higher and CO₂ will degas at relatively shallow levels compared to a drier melt. Total CO₂ solubility was also examined in andesitic glasses with additional Ca, K, or Mg and low H₂O contents (<1 wt.%). We found that total CO₂ solubility is negatively correlated with (Si + Al) cation mole fraction and positively correlated with cations with large Gibbs free energy of decarbonation or high charge-to-radius ratios (e.g., Ca). Combining our andesite data with data from the literature, we find that molecular CO₂ is more abundant in highly polymerized melts with high ionic porosities (>∼48.3%), and low nonbridging oxygen/tetrahedral oxygen (<∼0.3). Carbonate dominates most silicate melts and is most abundant in depolymerized melts with low ionic porosities, high nonbridging oxygen/tetrahedral oxygen (>∼0.3), and abundant cations with large Gibbs free energy of decarbonation or high charge-to-radius ratio. In natural silicate melt, the oxygens in the carbonate are likely associated with tetrahedral and network-modifying cations (including Ca, H, or H-bonds) or a combinations of those cations.     

Deep carbon cycle and geodynamics: the role of the core and carbonatite melts in the lower mantle

Carbon, though being abundant in the Solar system, barely exceeds 0.01 wt.% in the silicate mantle, whereas it is ~ 3.6 wt.% in primitive chondritic meteorites that most likely formed our planet. This deficit may be due to redistribution of carbon in the liquid metal phase and then in the core at the stage of magma ocean fractionation, because carbon is much more soluble in Fe–Ni ± S melt than in silicate melts. The terrestrial heat and mass transfer are controlled mainly by layered convection and periodic peaks of plume activity as fast mantle jets that rise from the core. Plumes carry significant amounts of CO₂, H₂O, and K₂O (most probably in the form of carbonatite or hydrous carbonatite melts) released by the degassing core on its interaction with oxidized silicate material. There are two mechanisms that may maintain fast plume ascent: (1) local melting at the plume front as a result of doping with volatiles (H₂O, CO₂) as in a gas burner (rise rate 60–110 cm/yr) or (2) flow controlled by diffusion transport of silicate components in carbonatite melt (rise rate ~ 100 cm/yr).     

The speciation of water in silicate melts

Previous models of water solubility in silicate melts generally assume essentially complete reaction of water molecules to hydroxyl groups. In this paper a new model is proposed that is based on the hypothesis that the observed concentrations of molecular water and hydroxyl groups in hydrous silicate glasses reflect those of the melts from which they were quenched. The new model relates the proportions of molecular water and hydroxyl groups in melts via the following reaction describing the homogeneous equilibrium between melt species: H₂O_molecular (melt) + oxygen (melt) = 2OH (melt). An equilibrium constant has been formulated for this reaction and species are assumed to mix ideally. Given an equilibrium constant for this reaction of 0.1–0.3, the proposed model can account for variations in the concentrations of molecular water and hydroxyl groups in melts as functions of the total dissolved water content that are similar to those observed in glasses. The solubility of molecular water in melt is described by the following reaction: H₂O (vapor) = H₂O_molecular (melt).These reactions describing the homogeneous and heterogeneous equilibria of hydrous silicate melts can account for the following observations: the linearity between f_H2O and the square of the mole fraction of dissolved water at low total water contents and deviations from linearity at high total water contents; the difference between the partial molar volume of water in melts at low total water contents and at high total water contents; the similarity between water contents of vapor-saturated melts of significantly different compositions at high pressures versus the dependence on melt composition of water solubility in silicate melts at low pressures; and the variations of viscosity, electrical conductivity, the diffusivity of “water,” the diffusivity of cesium, and phase relationships with the total dissolved water contents of melts.This model is thus consistent with available observations on hydrous melt systems and available data on the species concentrations of hydrous glasses and is easily tested, since measurements of the concentrations of molecular water and hydroxyl groups in silicate glasses quenched from melts equilibrated over a range of conditions and total dissolved water contents are readily obtainable.     

Phase relations and melting of carbonated peridotite between 10 and 20 GPa: a proxy for alkali- and CO<Subscript>2</Subscript>-rich silicate melts in the deep mantle

We determined the melting phase relations, melt compositions, and melting reactions of carbonated peridotite on two carbonate-bearing peridotite compositions (ACP: alkali-rich peridotite + 5.0 wt % CO₂ and PERC: fertile peridotite + 2.5 wt % CO₂) at 10–20 GPa and 1,500–2,100 °C and constrain isopleths of the CO₂ contents in the silicate melts in the deep mantle. At 10–20 GPa, near-solidus (ACP: 1,400–1,630 °C) carbonatitic melts with < 10 wt % SiO₂ and > 40 wt % CO₂ gradually change to carbonated silicate melts with > 25 wt % SiO₂ and < 25 wt % CO₂ between 1,480 and 1,670 °C in the presence of residual majorite garnet, olivine/wadsleyite, and clinoenstatite/clinopyroxene. With increasing degrees of melting, the melt composition changes to an alkali- and CO₂-rich silicate melt (Mg# = 83.7–91.6; ~ 26–36 wt % MgO; ~ 24–43 wt % SiO₂; ~ 4–13 wt % CaO; ~ 0.6–3.1 wt % Na₂O; and ~ 0.5–3.2 wt % K₂O; ~ 6.4–38.4 wt % CO₂). The temperature of the first appearance of CO₂-rich silicate melt at 10–20 GPa is ~ 440–470 °C lower than the solidus of volatile-free peridotite. Garnet + wadsleyite + clinoenstatite + carbonatitic melt controls initial carbonated silicate melting at a pressure < 15 GPa, whereas garnet + wadsleyite/ringwoodite + carbonatitic melt dominates at pressure > 15 GPa. Similar to hydrous peridotite, majorite garnet is a liquidus phase in carbonated peridotites (ACP and PERC) at 10–20 GPa. The liquidus is likely to be at ~ 2,050 °C or higher at pressures of the present study, which gives a melting interval of more than 670 °C in carbonated peridotite systems. Alkali-rich carbonated silicate melts may thus be produced through partial melting of carbonated peridotite to 20 GPa at near mantle adiabat or even at plume temperature. These alkali- and CO₂-rich silicate melts can percolate upward and may react with volatile-rich materials accumulate at the top of transition zone near 410-km depth. If these refertilized domains migrate upward and convect out of the zone of metal saturation, CO₂ and H₂O flux melting can take place and kimberlite parental magmas can be generated. These mechanisms might be important for mantle dynamics and are potentially effective metasomatic processes in the deep mantle.     

Rare earth partitioning between immiscible carbonate and silicate liquids and CO2 vapor: Results and implications for the formation of light rare earth-enriched rocks

Melting relations at 5 and 20 kbar on the composition join sanidine-potassium carbonate are dominated by a two-liquid region that covers over 60% of the join at 1,300 ° C. At this temperature, the silicate melt contains approximately 19 wt% carbonate component at 5 kbar and 32 wt% carbonate component at 20 kbar. The conjugate carbonate melt contains less than 5 wt% silicate component, and it varies less as a function of temperature than does the silicate melt.Partition coefficients for Ce, Sm, and Tm between the immiscible carbonate and silicate melts at 1,200 ° and 1,300 ° C at 5 and 20 kbar are in favor of the carbonate melt by a factor of 2–3 for light REE and 5–8 for heavy REE. The effect of pressure on partitioning cannot be evaluated independently because of complementary changes in melt compositions.Minimum REE partition coefficients for CO₂ vapor/carbonate melt and CO₂ vapor/silicate melt can be calculated from the carbonate melt/silicate melt partition coefficients, the known proportions of melt, and maximum estimates of the proportion of CO₂ vapor. The vapor phase is enriched in light REE relative to both melts at 20 kbar and enriched in all REE, especially the light elements, at 5 kbar. The enrichment of REE in CO₂ vapor relative to both melts is 3–4 orders of magnitude in excess of that in water vapor (Mysen, 1979) at 5 kbar and is approximately the same as that in water vapor at 20 kbar.Mantle metasomatism by a CO₂-rich vapor enriched in light REE, occurring as a precursor to magma genesis, may explain the enhanced REE contents and light REE enrichment of carbonatites, alkali-rich silicate melts, and kimberlites. Light REE enrichment in fenites and the granular suite of nodules from kimberlites attests to the mobility of REE in CO₂-rich fluids under both mantle and crustal conditions.     

The Effects of Small Amounts of H2O, CO2 and Na2O on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2 {+/-} H2O {+/-} CO2 {+/-} Na2O at 1{middle dot}1 GPa

The effects of small amounts of H₂O (<4 wt % in the melt)on the multiply saturated partial melting of spinel lherzolitein the system CaO–MgO–Al₂O₃–SiO₂ ±Na₂O ± CO₂ have been determined at 1·1 GPa inthe piston-cylinder apparatus. Electron microprobe analysisand Fourier transform infrared spectroscopy were used to analysethe experimental products. The effects of H₂O are to decreasethe melting temperature by 45°C per wt % H₂O in the melt,to increase the Al₂O₃ of the melts, decrease MgO and CaO, andleave SiO₂ approximately constant, with melts changing fromolivine- to quartz-normative. The effects of CO₂ are insignificantat zero H₂O, but become noticeable as H₂O increases, tendingto counteract the H₂O. The interaction between H₂O and CO₂ causesthe solubility of CO₂ at vapour saturation to increase withincreasing H₂O, for small amounts of H₂O. Neglect of the influenceof CO₂ in some previous studies on the hydrous partial meltingof natural peridotite may explain apparent inconsistencies betweenthe results. The effect of small amounts of H₂O on multiplysaturated melt compositions at 1·1 GPa is similar tothat of K₂O, i.e. increasing H₂O or K₂O leads to quartz-normativecompositions, but increasing Na₂O produces an almost oppositetrend, towards nepheline-normative compositions. KEY WORDS: H₂O; CO₂; FTIR; hydrous partial melting; mantle melting; spinel lherzolite; system CaO–MgO–Al₂O₃–SiO₂ ± H₂O ± CO₂ ± Na₂O     

Mineral/melt partitioning of trace elements during hydrous peridotite partial melting

This experimental study examines the mineral/melt partitioning of incompatible trace elements among high-Ca clinopyroxene, garnet, and hydrous silicate melt at upper mantle pressure and temperature conditions. Experiments were performed at pressures of 1.2 and 1.6 GPa and temperatures of 1,185 to 1,370 °C. Experimentally produced silicate melts contain up to 6.3 wt% dissolved H ₂O, and are saturated with an upper mantle peridotite mineral assemblage of olivine+orthopyroxene+clinopyroxene+spinel or garnet. Clinopyroxene/melt and garnet/melt partition coefficients were measured for Li, B, K, Sr, Y, Zr, Nb, and select rare earth elements by secondary ion mass spectrometry. A comparison of our experimental results for trivalent cations (REEs and Y) with the results from calculations carried out using the Wood-Blundy partitioning model indicates that H ₂O dissolved in the silicate melt has a discernible effect on trace element partitioning. Experiments carried out at 1.2 GPa, 1,315 °C and 1.6 GPa, 1,370 °C produced clinopyroxene containing 15.0 and 13.9 wt% CaO, respectively, coexisting with silicate melts containing ~1–2 wt% H ₂O. Partition coefficients measured in these experiments are consistent with the Wood-Blundy model. However, partition coefficients determined in an experiment carried out at 1.2 GPa and 1,185 °C, which produced clinopyroxene containing 19.3 wt% CaO coexisting with a high-H ₂O (6.26±0.10 wt%) silicate melt, are significantly smaller than predicted by the Wood-Blundy model. Accounting for the depolymerized structure of the H ₂O-rich melt eliminates the mismatch between experimental result and model prediction. Therefore, the increased Ca ²⁺ content of clinopyroxene at low-temperature, hydrous conditions does not enhance compatibility to the extent indicated by results from anhydrous experiments, and models used to predict mineral/melt partition coefficients during hydrous peridotite partial melting in the sub-arc mantle must take into account the effects of H ₂O on the structure of silicate melts.     

Experimental study of eclogite melting with participation of the H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript>-KCl fluid at 5 GPa

In order to model the processes of formation of the highly alkaline (potassic) melts during the partial melting of the eclogite nodules in kimberlites, experiments on the melting of the model and natural eclogites in presence of the H₂O-CO₂ and H₂O-CO₂-KCl fluids at 5 GPa and 1200 and 1300°C are performed. A comparative analysis of the phase relations in the systems with H₂O-CO₂ and H₂O-CO₂-KCl demonstrate that KCl in the fluid equilibrated with eclogites intensifies their melting. It is related to both high Cl concentration in the forming silicate melt (2.0–5.5 wt %) and its enrichment in K₂O owing to the K-Na exchange reactions with the immiscible chloride melt. Because of these reactions, the K₂O/Cl ratio in the melts increases with the KCl content in the system and reaches 2.5–3.5 in the silicate melts coexisting with the immiscible chloride liquid. However, the ratio KCl/(H₂O + CO₂ + KCl) in the fluid does not influence on the ratio K₂O/Cl in the melts. Thus, the solubility KCl in the melts, apparently, does not depend on presence of the H₂O-CO₂ fluid, at least, within the concentration range used in the experiments (up to 20 wt %). The experiments show that the deliberated chloride liquid is necessary to form the potassium-rich chlorine-bearing silicate melts during the eclogite melting. It corresponds to the KCl content in the system above 5 wt %.     

The origin and evolution of the parental magmas of frontal volcanoes in Kamchatka: Evidence from magmatic inclusions in olivine from Zhupanovsky volcano

The paper presents data on naturally quenched melt inclusions in olivine (Fo 69–84) from Late Pleistocene pyroclastic rocks of Zhupanovsky volcano in the frontal zone of the Eastern Volcanic Belt of Kamchatka. The composition of the melt inclusions provides insight into the latest crystallization stages (∼70% crystallization) of the parental melt (∼46.4 wt % SiO₂, ∼2.5 wt % H₂O, ∼0.3 wt % S), which proceeded at decompression and started at a depth of approximately 10 km from the surface. The crystallization temperature was estimated at 1100 ± 20°C at an oxygen fugacity of ΔFMQ = 0.9–1.7. The melts evolved due to the simultaneous crystallization of olivine, plagioclase, pyroxene, chromite, and magnetite (Ol: Pl: Cpx: (Crt-Mt) ∼ 13: 54: 24: 4) along the tholeiite evolutionary trend and became progressively enriched in FeO, SiO₂, Na₂O, and K₂O and depleted in MgO, CaO, and Al₂O₃. Melt crystallization was associated with the segregation of fluid rich in S-bearing compounds and, to a lesser extent, in H₂O and Cl. The primary melt of Zhupanovsky volcano (whose composition was estimated from data on the most primitive melt inclusions) had a composition of low-Si (∼45 wt % SiO₂) picrobasalt (∼14 wt % MgO), as is typical of parental melts in Kamchatka and other island arcs, and was different from MORB. This primary melt could be derived by ∼8% melting of mantle peridotite of composition close to the MORB source, under pressures of 1.5 ± 0.2 GPa and temperatures 20–30°C lower than the solidus temperature of “dry” peridotite (1230–1240°C). Melting was induced by the interaction of the hot peridotite with a hydrous component that was brought to the mantle from the subducted slab and was also responsible for the enrichment of the Zhupanovsky magmas in LREE, LILE, B, Cl, Th, U, and Pb. The hydrous component in the magma source of Zhupanovsky volcano was produced by the partial slab melting under water-saturated conditions at temperatures of 760–810°C and pressures of ∼3.5 GPa. As the depth of the subducted slab beneath Kamchatkan volcanoes varies from 100 to 125 km, the composition of the hydrous component drastically changes from relatively low-temperature H₂O-rich fluid to higher temperature H₂O-bearing melt. The geothermal gradient at the surface of the slab within the depth range of 100–125 km beneath Kamchatka was estimated at 4°C/km.     

Behavior of molybdenum in alkali silicate melts: Effects of excess SiO2 and CO2

The effects of excess SiO₂ and CO₂ on the solubility of molybdenite in hydrous sodium disilicate melts were experimentally determined at 680 bars and 650°C. The molybdenite solubility decreases with increasing SiO₂ and CO₂. Under the experimental conditions, the MoS₂ content of the vapor-saturated liquid decreases from 10 wt.% to 2.5 wt.% at SiO₂ saturation. In the presence of CO₂, the solubility decreases to 4.6 wt.% MoS₂ and becomes negligible at high P_CO2. These results are explained as deriving from the increased polymerization and hence decreased NBO/Si ratio of the melt with increasing SiO₂ content and CO₂, respectively. Sulfur dissolves principally as SO₄^?2 at the relatively high fo₂ of the experiments. Consequently, the effect of sulfur is to lower the Mo solubility by effectively decreasing the NBO/Si ratio of the melt. Sulfur saturation is, therefore, likely to be a limiting factor in the Mo content of alkali silicate melts because of the chalcophile affinities of molybdenum.     

The effect of CO<Subscript>2</Subscript> on the solubility of aqueous chloride fluid in dacite,phonolite, and rhyolite melts

The solubility of H₂O–CO₂–Cl-containing fluids of various concentrations (0, 3, 10, and 23 wt % of HCl and from 0 to ~8–15 wt % of CO₂) in dacite, phonolite, and rhyolite melts at 1000°C and 200 MPa was studied in experiments. It was shown that the Cl concentration in the melt increased substantially from rhyolite to phonolite and dacite (up to 0.25, 0.85, and 1.2 wt %, respectively). The introduction of CO₂ into the system resulted in an increase in the Cl content in the melt composition by 20–25%. One may suppose that Cl reactivity in a fluid increases in the presence of CO₂ to cause growth of the Cl content in the melt. The introduction of CO₂ into the system considerably affects the content of H₂O in aluminosilicate melts as well. Thus, the addition of CO₂ decreases the H₂O content in the melt by ~0.5–1.0 wt %. The decrease in the H₂O content in an aluminosilicate melt is probably caused by fluid dilution with CO₂ resulting in a decrease in the H₂O mole fraction and fugacity in the fluid.     

The effect of alkalis and polymerization on the solubility of H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> in alkali-rich silicate melts

The effect of alkalis on the solubility of H₂O and CO₂ in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H₂O/(H₂O + CO₂) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H₂O solubility (melt equilibrated with pure H₂O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO₂ content in melts equilibrated with CO₂-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO₂ contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO₂ solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO₂ solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO₂ solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.     

A modified iterative sandwich method for determination of near-solidus partial melt compositions. II. Application to determination of near-solidus melt compositions of carbonated peridotite

We performed modified iterative sandwich experiments (MISE) to determine the composition of carbonatitic melt generated near the solidus of natural, fertile peridotite + CO₂ at 1,200–1,245°C and 6.6 GPa. Six iterations were performed with natural peridotite (MixKLB-1: Mg# = 89.7) and ∼10 wt% added carbonate to achieve the equilibrium carbonatite composition. Compositions of melts and coexisting minerals converged to a constant composition after the fourth iteration, with the silicate mineral compositions matching those expected at the solidus of carbonated peridotite at 6.6 GPa and 1,230°C, as determined from a sub-solidus experiment with MixKLB-1 peridotite. Partial melts expected from a carbonated lherzolite at a melt fraction of 0.01–0.05% at 6.6 GPa have the composition of sodic iron-bearing dolomitic carbonatite, with molar Ca/(Ca + Mg) of 0.413 ± 0.001, Ca# [100 × molar Ca/(Ca + Mg + Fe*)] of 37.1 ± 0.1, and Mg# of 83.7 ± 0.6. SiO₂, TiO₂ and Al₂O₃ concentrations are 4.1 ± 0.1, 1.0 ± 0.1, and 0.30 ± 0.02 wt%, whereas the Na₂O concentration is 4.0 ± 0.2 wt%. Comparison of our results with other iterative sandwich experiments at lower pressures indicate that near-solidus carbonatite derived from mantle lherzolite become less calcic with increasing pressure. Thus carbonatitic melt percolating through the deep mantle must dissolve cpx from surrounding peridotite and precipitate opx. Significant FeO* and Na₂O concentrations in near solidus carbonatitic partial melt likely account for the ∼150°C lower solidus temperature of natural carbonated peridotite compared to the solidus of synthetic peridotite in the system CMAS + CO₂. The experiments demonstrate that the MISE method can determine the composition of partial melts at very low melt fraction after a small number of iterations.     

Compositions of magmatic melts and evolution of mineral-forming fluids in the banska Stiavnica epithermal Au-Ag-Pb-Zn deposit, Slovakia: A study of inclusions in minerals

Melt and fluid inclusions were investigated in minerals from igneous rocks and ore (Au-Ag-Pb-Zn) veins of the Stiavnica ore field in Central Slovakia. High H₂O (7.1–12.0 wt %) and Cl (0.32–0.46 wt %) contents were found in silicate melt inclusions (65–69 wt % SiO₂ and 5.2–5.6 wt % K₂O) in plagioclase phenocrysts (An 68–36) from biotite-homblende andesites of the eastern part of the caldera. Similar high water contents are characteristic of magmatic melts (71–76 wt % SiO₂ and 3.7–5.1 wt % K₂O) forming the sanidine rhyolites of the Vyhne extrusive dome in the northwestern part of the Stiavnica caldera (up to 7.1 wt %) and the rhyolites of the Klotilda dike in the eastern part of the ore field (up to 11.5 wt %). The examination of primary inclusions in quartz and sanidine from the Vyhne rhyolites revealed high concentrations of N₂ and CO₂ in magmatic fluid (8.6 g/kg H₂O and 59 g/kg H₂O, respectively). Fluid pressure was estimated as 5.0 kbar on the basis of primary CO₂ fluid inclusions in plagioclase phenocrysts from the Kalvari basanites. This value corresponds to a depth of 18 km and may be indicative of a deep CO₂ source. Quartz from the granodiorites of the central part of the Stiavnica-Hodrusa complex crystallized from a melt with 4.2–6.1 wt % H₂O and 0.24–0.80 wt % Cl. Magmatic fluid cogenetic with this silicate melt was represented by a chloride brine with a salinity of no less than 77–80 wt % NaCl equiv. Secondary inclusions in quartz of the igneous rocks recorded a continuous trend of temperature, pressure, and solution salinity, from the parameters of magmatic fluids to the conditions of formation of ore veins. The gold mineralization of the Svyatozar vein system was formed from boiling low-salinity fluids (0.3–8.0 wt % NaCl equv.) at temperatures of 365–160°C and pressures of 160–60 bar. The Terezia, Bieber, Viliam, Spitaler, and Rozalia epithermal gold-silver-base metal veins were also formed from heterogeneous low-salinity fluids (0.3–12.1 wt %) at temperatures of 380–58°C and pressures of 240–10 bar. It was found that the salt components of the solutions were dominated by chlorides (high content of fluorine, up to 0.45 mol/kg H₂O, was also detected), and sulfate solutions appeared in the upper levels. The dissolved gas of ore-forming solutions was dominated by CO₂ (0.1–8.4 mol %, averaging 1.3 wt %) and contained minor nitrogen (0.00–0.85 mol %, averaging 0.05 mol %) and negligible methane admixtures (0.00–0.05 mol %, averaging 0.004 mol %). These data allowed us to conclude that the magmatic melts could be sources of H₂O, Cl, CO₂, and N₂. The formation of the epithermal mineralization of the Stiavnica ore field was associated with the mixing of magmatic fluid with low-concentration meteoric waters, and the fluid was in a heterogeneous state.     

Stability of phlogopite-quartz and sanidine-quartz: A model for melting in the lower crust

The melting of phlogopite-quartz and sanidine-quartz under vapor-absent conditions and in the presence of H₂O-CO₂ vapor have been determined from 5–20 kbar. In the lower crust (P=6–10 kbar), phlogopite + quartz melts incongruently to enstatite + liquid at temperatures as low as 710° C in the presence of H₂O. When the activity of water is sufficiently reduced by addition of CO₂, phlogopite + quartz undergoes a dehydration reaction to enstatite + sanidine + vapor, for example at 790±10° C, 5 kbar, with \(X_{H_2 O}^V\) =0.35. In the absence of vapor, phlogopite + quartz is stable up to a maximum temperature of 900° C in the crust; at higher temperatures this assemblage melts incongruently to enstatite + sanidine + liquid. The melting of sanidine-quartz in the presence of H₂O-CO₂ vapor shows marked topological differences from melting in the system albite-H₂O-CO₂, and as a result, apparent activity coefficients for water calculated from sanidine-quartz H₂O-CO₂ are less than those calculated from albite-H₂O-CO₂ by up to a factor of five. These data shed light on anatexis in the lower crust, but uncertainties related to ordering of Al and Si in natural and synthetic micas forestall a more rigorous analysis. Nevertheless, maximum temperatures for some granulite terranes can be established.     

H<Subscript>2</Subscript>O solubility in basalt at upper mantle conditions

This study presents a new experimental approach for determining H₂O solubility in basaltic melt at upper mantle conditions. Traditional solubility experiments are limited to pressures of ~600 MPa or less because it is difficult to reliably quench silicate melts containing greater than ~10 wt% dissolved H₂O. To overcome this limitation, our approach relies on the use of secondary ion mass spectrometry to measure the concentration of H dissolved in olivine and on using the measured H in olivine as a proxy for the concentration of H₂O in the co-existing basaltic melt. The solubility of H₂O in the melt is determined by performing a series of experiments at a single pressure and temperature with increasing amounts of liquid H₂O added to each charge. The point at which the concentration of H in the olivine first becomes independent of the amount of initial H₂O content of the charge (added + adsorbed H₂O) indicates its solubility in the melt. Experiments were conducted by packing basalt powder into a capsule fabricated from San Carlos olivine, which was then pressure-sealed inside a Ni outer capsule. Our experimental results indicate that at 1000 MPa and 1200 °C, the solubility of H₂O in basaltic melt is 20.6 ± 0.9 wt% (2 × standard deviation). This concentration is considerably higher than predicted by most solubility models but defines a linear relationship between H₂O fugacity and the square of molar H₂O solubility when combined with solubility data from lower pressure experiments. Further, our solubility determination agrees with melting point depression determined experimentally by Grove et al. (2006) for the H₂O-saturated peridotite solidus at 1000 MPa. Melting point depression calculations were used to estimate H₂O solubility in basalt along the experimentally determined H₂O-saturated peridotite solidus. The results suggest that a linear relationship between H₂O fugacity and the square of molar solubility exists up to ~1300 MPa, where there is an inflection point and solubility begins to increase less strongly with increasing H₂O fugacity.     

Mechanism of water solubility in silicate melts of the albite-nepheline system

Water solubility and speciation have been studied in melts from the system albite-nepheline. Water solubility was determined at P_H2O = 200 MPa and T = 1200ºC using Karl Fischer titration (KFT) and weight loss methods. It increases from 5.8?±?0.1 wt. % in the albite melt to 7.25?±?0.25 % in the nepheline melt. The solubility dependence has a sigmoidal shape with a steep increase in the Ab40–Ab60 compositional range. The densities of the hydrous glasses have been measured using the thermal-gradient method. Infrared (IR) combination bands of molecular H₂O and hydroxyl groups in these glasses demonstrate a systematic shift to lower frequencies with increasing alkalinity. The data are consistent with the appearance of aluminate species (Al-O-Al fragments) appearing at 40–60 wt.% nepheline (Ab60–Ab40).