Carbon isotopic fractionation between CO2 vapour,silicate and carbonate melts: an experimental study to 30 kbar

The carbon isotopic fractionation between CO₂ vapour and sodamelilite (NaCaAlSi₂O₇) melt over a range of pressures and temperatures has been investigated using solid-media piston-cylinder high pressure apparatus. Ag₂C₂O₄ was the source of CO₂ and experimental oxygen fugacity was buffered at hematite-magnetite by the double capsule technique. The abundance and isotopic composition of carbon dissolved in sodamelilite (SM) glass were determined by stepped heating and the ¹³C of coexisting vapour was determined directly by capsule piercing. CO₂ solubility in SM displays a complex behavior with temperature. At pressures up to 10 kbars CO₂ dissolves in SM to form carbonate ion complexes and the solubility data suggest slight negative temperature dependence. Above 20 kbars CO₂ reacts with SM to form immiscible Na-rich silicate and Ca-rich carbonate melts and CO₂ solubility in Na-enriched silicate melt rises with increasing temperature above the liquidus. Measured values for carbon isotopic fractionation between CO₂ vapour and carbonate ions dissoived in sodamelilite melt at 1200°–1400° C and 5–30 kbars average 2.4±0.2, favouring¹³C enrichment in CO₂ vapour. The results are maxima and are independent of pressure and temperature. Similar values of 2 are obtained for the carbon isotopic fractionation between CO₂ vapour and carbonate melts at 1300°–1400° C and 20–30 kbars.     

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.     

Partitioning of F between H2O and CO2 fluids and topaz rhyolite melt

Fluid/melt distribution coefficients for F have been determined in experiments conducted with peraluminous topaz rhyolite melts and fluids consisting of H₂O and H₂O+CO₂ at pressures of 0.5 to 5 kbar, temperatures of 775°–1000°C, and concentrations of F in the melt ranging from 0.5 to 6.9 wt%. The major element, F, and Cl concentrations of the starting material and run product glasses were determined by electron microprobe, and the concentration of F in the fluid was calculated by mass balance. The H₂O concentrations of some run product glasses were determined by ion microprobe (SIMS). The solubility of melt in the fluid phase increases with increasing F in the system; the solubility of H₂O in the melt is independent of the F concentration of the system with up to 6.3 wt% F in the melt. No evidence of immiscible silica- and fluoriderich liquids was detected in the hydrous but water-undersaturated starting material glasses (8.5 wt% F in melt) or in the water-saturated run product glasses. F concentrates in topaz rhyolite melts relative to coexisting fluids at most conditions studied; however, D_F (wt% F in fluid/wt% F in melt) increases strongly with increasing F in the system. Maximum values of D_F in this study are significantly larger than those previously reported in the literature. Linear extrapolation of the data suggests that D_F is greater than one for water-saturated, peraluminous granitic melts containing 8 wt% F at 800° C and 2 kbar. D_F increases as temperature and as (H₂O/H₂O+CO₂) of the fluid increase. For topaz rhyolite melts containing 1 wt% F and with H₂O-rich fluids, D_F is independent of changes in pressure from 2 to 5 kbar at 800° C; for melts containing 1 wt% F and in equilibrium with CO₂-bearing fluids the concentrations of F in fluid increases with increasing pressure. F-and lithophile element-enriched granites may evolve to compositions containing extreme concentrations of F during the final stages of crystallization. If F in the melt exceeds 8 wt%, D_F is greater than one and the associated magmatic-hydrothermal fluid contains >4 molal F. Such F-enriched fluids may be important in the mass transport of ore constituents, i.e., F, Mo, W, Sn, Li, Be, Rb, Cs, U, Th, Nb, Ta, and B, from the magma.     

Carbon in silicate liquids: the systems NaAlSi3O8-CO2, CaAl2Si2O8-CO2, and KAlSi3O8-CO2

To further our knowledge of the effects of volatile components on phase relationships in aluminosilicate systems, we determined the vapor saturated solidi of albite, anorthite, and sanidine in the presence of CO₂ vapor. The depression of the temperature of the solidus of albite by CO₂ decreases from 30° C at 10 kbar, to 10° C at 20 kbar, to about 0 at 25 kbar, suggesting that the solubility of CO₂ in NaAlSi₃O₈ liquid in equilibrium with solid albite decreases with increasing pressure and temperature. In contrast, CO₂ lowers the temperature of the solidus of anorthite by 30° C at 14 kbar, and by 70dg C at 25 kbar. This contrasting behavior of albite and anorthite is also reflected in the behavior of melting in the absence of volatile components. Whereas albite melts congruently to a liquid of NaAl-Si₃O₈ composition to pressures of 35 kbar, anorthite melts congruently to only about 10 kbar and, at higher pressures, incongruently to corundum plus a liquid that is enriched in SiO₂ and CaO and depleted in Al₂O₃ relative to CaAl₂Si₂O₈.The tendency toward incongruent melting with increasing pressure in albite and anorthite produces an increase in the activity of SiO₂ component in the liquid ( ). We predict that this increases the ratio of molecular CO₂/CO ₃ ^2– in these liquids, but the experimental results from other workers are mutually contradictory. Because of the positive dP/dT of the albite solidus and the negative dP/dT of the anorthite solidus, we propose that a negative temperature derivative of the solubility of molecular CO₂ in plagioclase liquids may partly explain the decrease in solubility of carbon with increasing pressure in near-solidus NaAlSi₃O₈ liquids, which is in contrast to that in CaAl₂Si₂O₈ liquid. Also, reaction of CO₂ with NaAlSi₃O₈ liquid to form CO ₃ ^2– that is complexed with Na⁺ must be accompanied by a change in Al³⁺ from network-former to network-modifier, as Na⁺ is no longer abailable to charge-balance Al³⁺ in a network-forming role. However, when anorthite melts incongruently to corundum plus a CaO-rich liquid, the complexing of CO ₃ ^2– with the excess Ca²⁺ in the liquid does not require a change in the structural role of aluminum, and it may be more energetically favorable.The depression of the temperature of the solidus of sanidine resulting from the addition of CO₂ increases from 50° C at 5 kbar to 170° C at 15 kbar. In marked contrast to the plagioclase feldspars, sanidine melts incongruently to leucite plus a SiO₂-rich liquid up to the singular point at 15 kbar. Above this pressure, sanidine melts congruently, resulting in a decrease in the with increasing pressure in the interval up to 15 kbar. Above this pressure, the congruent melting of sanidine results in a lower and nearly constant relative to those of albite and anorthite, and CO₂ produces a nearly constant freezing-point depression of about 170° C. Because of the low at pressures above the singular point, we infer that most of the carbon dissolves as CO ₃ ^2– , resulting in a low CO₂/ CO ₃ ^2– , but a high total carbon content.The principles derived from the studies of phase equilibria in these chemically simple systems provide some information on the structural and thermal properties of magmas. We propose that the is an important parameter in controlling the speciation of carbon in these feldspathic liquids, but it certainly is not the only factor, and it may be relatively less significant in more complex compositions. In addition, our phase-equilibria approach does not provide direct thermal and structural information as do calorimetry and spectroscopy, but the latter have been used primarily on glasses (quenched liquids) and cannot be used in situ to derive direct information on liquids at elevated pressures, as can our method. Hopefully, the results of all of these approaches can be integrated to yield useful results.Institute of Geophysics and Planetary Physics, Contribution No. 2744     

CO2 solubility in Martian basalts and Martian atmospheric evolution

To understand possible volcanogenic fluxes of CO₂ to the Martian atmosphere, we investigated experimentally carbonate solubility in a synthetic melt based on the Adirondack-class Humphrey basalt at 1-2.5 GPa and 1400-1625 °C. Starting materials included both oxidized and reduced compositions, allowing a test of the effect of iron oxidation state on CO₂ solubility. CO₂ contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and Fe³⁺/Fe^T was measured by Mössbauer spectroscopy. The CO₂ contents of glasses show no dependence on Fe³⁺/Fe^T and range from 0.34 to 2.12 wt.%. For Humphrey basalt, analysis of glasses with gravimetrically-determined CO₂ contents allowed calibration of an integrated molar absorptivity of 81,500 ± 1500 L mol⁻¹ cm⁻² for the integrated area under the carbonate doublet at 1430 and 1520 cm⁻¹. The experimentally determined CO₂ solubilities allow calibration of the thermodynamic parameters governing dissolution of CO₂ vapor as carbonate in silicate melt, K_II, (Stolper and Holloway, 1988) as follows: , ΔV⁰ = 20.85 ± 0.91 cm³ mol⁻¹, and ΔH⁰ = −17.96 ± 10.2 kJ mol⁻¹. This relation, combined with the known thermodynamics of graphite oxidation, facilitates calculation of the CO₂ dissolved in magmas derived from graphite-saturated Martian basalt source regions as a function of P, T, and f_O2. For the source region for Humphrey, constrained by phase equilibria to be near 1350 °C and 1.2 GPa, the resulting CO₂ contents are 51 ppm at the iron-wüstite buffer (IW), and 510 ppm at one order of magnitude above IW (IW + 1). However, solubilities are expected to be greater for depolymerized partial melts similar to primitive shergottite Yamato 980459 (Y 980459). This, combined with hotter source temperatures (1540 °C and 1.2 GPa) could allow hot plume-like magmas similar to Y 980459 to dissolve 240 ppm CO₂ at IW and 0.24 wt.% of CO₂ at IW + 1. For expected magmatic fluxes over the last 4.5 Ga of Martian history, magmas similar to Humphrey would only produce 0.03 and 0.26 bars from sources at IW and IW + 1, respectively. On the other hand, more primitive magmas like Y 980459 could plausibly produce 0.12 and 1.2 bars at IW and IW + 1, respectively. Thus, if typical Martian volcanic activity was reduced and the melting conditions cool, then degassing of CO₂ to the atmosphere may not be sufficient to create greenhouse conditions required by observations of liquid surface water. However, if a significant fraction of Martian magmas derive from hot and primitive sources, as may have been true during the formation of Tharsis in the late Noachian, that are also slightly oxidized (IW + 1.2), then significant contribution of volcanogenic CO₂ to an early Martian greenhouse is plausible.     

A computer simulation study of natural silicate melts. Part II: High pressure properties

The thermodynamic, structural and transport properties of natural silicate melts under pressure are investigated by molecular dynamics simulation with the help of a force field recently introduced by us [Guillot B. and Sator N. (2007) A computer simulation study of natural silicate melts. Part I: low pressure properties. Geochim. Cosmochim. Acta71, 1249-1265]. It is shown that the simulation reproduces accurately the bulk moduli of a large variety of silicate liquids as evaluated from ultrasonic studies. The equations of state (EOS) of the simulated melts are in good agreement with the density data on mid-ocean ridge basalt, komatiite, peridotite and fayalite as obtained either by sink/float experiments or by shock-wave compression. From the structural point of view it is shown that the population of ^[5]Al and ^[6]Al species increases rapidly upon initial compression (0-50 kbar) whereas for Si these highly coordinated species are found in a significant abundance (>5%) only above ∼50 kbar for ^[5]Si and ∼100-150 kbar for ^[6]Si. This increase of the coordination of network formers is not the only response of the melt structure to the densification: there is also a large redistribution of the T-O-T (T = Si, Al) bond angles with the pressure and noticeably upon initial compression in rhyolitic and basaltic liquids. Furthermore, a detailed analysis of the population of bridging oxygens (BO) and nonbridging oxygens (NBO) points out that the polymerization of the melt generally increases when the pressure increases, the magnitude of this polymerization enhancement being all the more important that the melt is depolymerized at low pressure. The role of triclusters (threefold coordinated oxygens to network former cations) is particularly emphasized in acidic and basaltic liquids. The pressure-induced redistribution of the oxygen atoms through the melt structure is also stressed. Finally, the simulation predicts a nonmonotonic behavior of the diffusivity of network former ions when the pressure increases, a feature with depends on the melt composition. This could have a counterpart in the electrical conductivity at sufficiently high temperature when the viscosity of the liquid is low.     

Solution behavior of reduced COH volatiles in silicate melts at high pressure and temperature

The solubility and solution mechanisms of reduced COH volatiles in Na₂OSiO₂ melts in equilibrium with a (H₂ + CH₄) fluid at the hydrogen fugacity defined by the iron-wüstite + H₂O buffer [f_H2(IW)] have been determined as a function of pressure (1-2.5 GPa) and silicate melt polymerization (NBO/Si: nonbridging oxygen per silicon) at 1400 °C. The solubility, calculated as CH₄, increases from ∼0.2 wt% to ∼0.5 wt% in the melt NBO/Si-range ∼0.4 to ∼1.0. The solubility is not significantly pressure-dependent, probably because f_H2(IW) in the 1-2.5 GPa range does not vary greatly with pressure. Carbon isotope fractionation between methane-saturated melts and (H₂ + CH₄) fluid varied by ∼14‰ in the NBO/Si-range of these melts.The (C..H) and (O..H) speciation in the quenched melts was determined with Raman and ¹H MAS NMR spectroscopy. The dominant (C..H)-bearing complexes are molecular methane, CH₄, and a complex or functional group that includes entities with CCH bonding. Minor abundance of complexes that include SiOCH₃ bonding is tentatively identified in some melts. There is no spectroscopic evidence for SiC or SiCH₃. Raman spectra indicate silicate melt depolymerization (increasing NBO/Si). The [CH₄/CCH]^melt abundance ratio is positively correlated with NBO/Si, which is interpreted to suggest that the (CCH)-containing structural entity is bonded to the silicate melt network structure via its nonbridging oxygen. The ∼14‰ carbon isotope fractionation change between fluid and melt is because of the speciation changes of carbon in the melt.     

Carbon dioxide and argon diffusion in silicate melts: Insights into the CO2 speciation in magmas

To investigate the influence of temperature and composition on the diffusivities of dissolved carbon dioxide and argon in silicate melts, diffusion experiments were performed at magmatic pressure and temperature conditions in (a) albite melts with excess Na₂O (0-8.6 wt%) and a constant Si/Al ratio of 3, and (b) albite₇₀quartz₃₀ to jadeite melts with decreasing SiO₂ content and a constant Na/Al ratio of 1. We obtained diffusion coefficients at 500 MPa and 1323-1673 K. In the fully polymerized system Ab₇₀Qz₃₀ - Jd, the change in composition only has a weak effect on bulk CO₂ diffusivity, but Ar diffusivity increases clearly with decreasing SiO₂ content. In the system Ab + Na₂O, bulk CO₂ and Ar diffusivity increase significantly with gradual depolymerisation. The relatively small change in composition on molar basis in the depolymerized system leads to a significantly larger change in diffusivities compared to the fully polymerized Ab₇₀Qz₃₀-Jd join. Within error, activation energies for bulk CO₂ and Ar diffusion in both systems are identical with decreasing silica content (Ab + Na₂O: 159 ± 25 kJ mol⁻¹ for bulk CO₂ and 130 ± 8 kJ mol⁻¹ for Ar; Ab₇₀Qz₃₀-Jd: 163 ± 16 kJ mol⁻¹ for bulk CO₂ and 148 ± 15 kJ mol⁻¹ for Ar) even though this results in depolymerisation in one system and not the other.Although there is a variation in CO₂ speciation with changing composition as observed in quenched glasses, it has previously established that this is not a true representation of the species present in the melt, with the ratio of molecular CO₂ to carbonate decreasing during quenching. Thus, diffusion coefficients for the individual CO₂ species cannot be directly derived by measuring molecular CO₂ and CO₃^2- concentration-distance profiles in the glasses. To obtain diffusivities of individual CO₂ species, we have made two assumptions that (1) inert Ar can be used as a proxy for molecular CO₂ diffusion characteristics as shown by our previous work and (2) the diffusivity of CO₃²⁻ can be calculated assuming it is identical to network forming components (Si⁴⁺ and Al³⁺). This is derived from viscosity data (Eyring eqn.) and suggests that CO₃²⁻ diffusion would be several orders of magnitude slower than molecular CO₂ diffusion.The systematics of measured bulk CO₂ diffusivity rates and comparison with the Ar proxy all suggest that the faster molecular CO₂ species is much more dominant in melts than measurements on resulting quenched glasses would suggest. This study has confirmed an observation of surprisingly consistent bulk CO₂ diffusivity across a range of natural compositions were Ar diffusivity significantly increases. This is consistent with an actual increase in molecular CO₂ mobility (similar to Ar) that is combined with an increase in the proportion of the slower carbonate in the melt.These results demonstrate that the CO₂ diffusion and speciation model provides an insight into the transport processes in the melt and is promising and an alternative tool to in situ speciation measurements at magmatic conditions, which at the moment are technically extremely difficult. We present the first high pressure high temperature in situ MIR spectra of a CO₂ bearing albitic glass/melt suggesting that molecular CO₂ is a stable species at high temperature, which is qualitatively consistent with the modelled CO₂ speciation data.     

Diffusion in fluid-bearing and slightly-melted rocks: experimental and numerical approaches illustrated by iron transport in dunite

Bulk diffusion of iron in synthetic dunites containing 1–6 vol.% fluid or melt at 10 kbar (1 GPa) and 900°–1300° C was examined by encapsulating the samples in platinum, which served as a sink for iron. The rate of iron loss from the dunite was found to depend strongly upon the identity of the fluid, which was varied from CO₂ and H₂O to melts of basaltic and sodium carbonate composition. Carbon dioxide in amounts up to 4 vol.% has no effect upon bulk iron diffusion because it exists in the dunite are isolated pores. The interconnected nature of H₂O, basaltic melt, and carbonate melt, on the other hand, results in marked enhancement of bulk-rock Fe diffusion that is correlated with the diffusivity and solubility of olivine components in the fluid. At 1300° C, 4–5 vol.% of either water or basaltic melt increases the effective bulk diffusivity from the fluidabsent value of 10^-10 cm²/s to 10^-8 cm²/s. A single experiment involving a similar volume fraction of carbonate melt yielded a minimum bulk diffusivity of 10^-7–10^-6 cm²/s. This remarkably high value is attributable to the concurrent high diffusivity and high solubility of olivine components in molten carbonate H₂O has a high diffusivity, estimated at 10^-4 cm²/s in this study, and basaltic melt can dissolve large amounts of olivine, but neither possesses these two qualities in combination. Bulk transport of Fe in dunite containing <2 vol.% of pure H₂O is independent of olivine grain size for samples having an average grain diameter of <10 m to 60 m. This is probably because bulk diffusion specifically in these H₂O-bearing samples is ratelimited by the flux (which is proportional to concentration) of olivine components in the fluid. Given a constant fluid volume fraction, the effect of reducing the grain size is to increase the number of fluid-filled channels, but at the same time to decrease their average aperture, thus keeping constant the cross-sectional area through which the diffusional flux occurs. (Independence of bulk diffusivity from grain size is not anticipated for rocks containing melt, in which the silicate components are much more soluble.) In numerical (finite difference) simulations of selected laboratory experiments, the bulk Fe transport process was modeled as diffusion in fluid-filled tubules of triangular cross-section that are supplied by volume diffusion from contacting olivine grains with which they are in surface equilibrium. Applying a tortuosity factor of 1.7 brings the numerically computed diffusional loss profiles for experiments containing basaltic melt into near-coincidence with the experimentally-determined curves. This success in reproducing the experimental results lends credence to the interpretation of the bulk diffusional loss profiles as composites of gradients due to volume, grain-boundary and fluid-phase diffusion.     

Solubility of carbon dioxide in melts of andesite,tholeiite, and olivine nephelinite composition to 30 kbar pressure

Carbon dioxide solubilities in H₂O-free hydrous silicate melts of natural andesite (CA), tholeiite (K 1921), and olivine nephelinite (OM1) compositions have been determined employing carbon-14 beta-track mapping techniques. The CO₂ solubility increases with increasing pressure, temperature, and degree of silica-undersaturation of the silicate melt. At 1650° C, CO₂ solubility in CA increases from 1.48±0.05 wt % at 15 kbar to 1.95±0.03 wt % at 30 kbar. The respective solubilities in OM1 are 3.41±0.08 wt % and 7.11±0.10 wt %. The CO₂ solubility in K1921 is intermediate between those of CA and OM1 compositions. At lower temperatures, the CO₂ contents of these silicate melts are lower, and the pressure dependence of the solubility is less pronounced. The presence of H₂O also affects the CO₂ solubility (20–30% more CO₂ dissolves in hydrous than in H₂O-free silicate melts); the solubility curves pass through an isothermal, isobaric maximum at an intermediate CO₂/(CO₂+H₂O) composition of the volatile phase. Under conditions within the upper mantle where carbonate minerals are not stable and CO₂ and H₂O are present a vapor phase must exist. Because the solubility of CO₂ in silicate melts is lower than that of H₂O, volatiles must fractionate between the melt and vapor during partial melting of peridotite. Initial low-temperature melts will be more H₂O-rich than later high-temperature melts, provided vapor is present during the melting. Published phase equilibrium data indicate that the compositional sequence of melts from peridotite +H₂O+CO₂ parent will be andesite-tholeiite-nephelinite with increasing temperature at a pressure of about 20 kbar. Examples of this sequence may be found in the Lesser Antilles and in the Indonesian Island Arcs.     

Experimental constraints on the mobility of Rhenium in silicate liquids

The volatization of Rhenium (Re) from melts of natural basalt, dacite and a synthetic composition in the CaO-MgO-Al₂O₃-SiO₂ system has been investigated at 0.1 MPa and 1250-1350 °C over a range of fO₂ conditions from log fO₂ = −10 to −0.68. Experiments were conducted using open top Pt crucibles doped with Re and Yb. Analysis of quenched glasses by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) normal to the melt/gas interface showed concentration profiles for Re, to which a semi-infinite one-dimensional diffusion model could be applied to extract diffusion coefficients (D). The results show Re diffusivity in basalt at 1300 °C in air is log D_Re = −7.2 ± 0.3 cm²/s and increases to log D_Re = −6.6 ± 0.3 cm²/s when trace amounts of Cl were added to the starting material. At fO₂ conditions below the nickel-nickel oxide (NNO) buffer Re diffusivity decreases to and to in dacitic melt. In the CMAS composition, . The diffusivity of Re is comparable to Ar and CO₂ in basalt at 500 MPa favoring its release as a volatile. Our results support the contention that subaerial degassing is the cause of lower Re concentrations in arc-type and ocean island basalts compared to mid-ocean ridge basalts.     

Platinum solubility and partitioning in a felsic melt-vapor-brine assemblage

The solubility and partitioning of Pt in a S-free vapor - brine - rhyolite melt - Pt metal assemblage has been quantified at 800 °C, f_O2=NNO and pressures of 100 and 140 MPa. Vapor and brine were sampled at run conditions by trapping these phases as glass-hosted fluid inclusions as the melt cooled through the glass transition temperature. The vapor and brine were in equilibrium with the melt at the time of trapping and, thus, represent fluids which were sampled at the termination of each experimental run. The microthermometrically determined salinities of vapor and brine are ∼2 and ∼63 wt.% NaCl eq. and ∼9 and ∼43 wt.% NaCl eq. at 100 and 140 MPa, respectively. Platinum solubilities in vapor, brine and glass (i.e., quenched melt) were quantified by using laser ablation - inductively coupled plasma - mass spectrometry (LA-ICP-MS). Equilibrium is discussed with reference to the major and trace element concentrations of glass-hosted fluid inclusions as well as the silicate melt over run times that varied from 110 to 377 h at 140 MPa and 159 to 564 h at 100 MPa. Platinum solubility values (±1σ) in H₂O-saturated felsic melt are 0.28 ± 0.13 μg/g and 0.38 ± 0.06 μg/g at 140 and 100 MPa, respectively. Platinum solubility values () at 140 and 100 MPa, respectively, in aqueous vapor are 0.91 ± 0.29 μg/g and 0.37 ± 0.17 μg/g and in are brine 16 ± 10 μg/g and 3.3 ± 1.0 μg/g. The measured solubility data were used to calculate Nernst-type partition coefficients for Pt between vapor/melt, brine/melt and vapor/brine. The partition coefficient values () for vapor/melt, brine/melt and vapor/brine at 140 MPa are 2.9 ± 1.0, 67 ± 27, and 0.13 ± 0.05 and at 100 MPa are 1.0 ± 0.2, 6.8 ± 2.4, and 0.15 ± 0.05. The partitioning data were used to model the Pt-scavenging capacity of vapor and brine during the crystallization-driven degassing (i.e., second boiling) of a felsic silicate melt over a depth range (i.e., 3-6 km) consistent with the evolution of magmatic-hydrothermal ore deposits. Model calculations suggest that aqueous vapor and brine can scavenge sufficient quantities of Pt, and by analogy other platinum group elements (PGE), to produce economically important PGE-rich magmatic-hydrothermal ore deposits in Earth’s upper continental crust.     

Water speciation and diffusion in haploandesitic melts at 743-873 K and 100 MPa

Water is an important volatile component in andesitic eruptions and deep-seated andesitic magma chambers. We report an investigation of H₂O speciation and diffusion by dehydrating haploandesitic melts containing ?2.5 wt.% water at 743-873 K and 100 MPa in cold-seal pressure vessels. FTIR microspectroscopy was utilized to measure species [molecular H₂O (H₂O_m) and hydroxyl group (OH)] and total H₂O (H₂O_t) concentration profiles on the quenched glasses from the dehydration experiments. The equilibrium constant of the H₂O speciation reaction H₂O_m+O?2OH, K = (X_OH)²/(X_H2OmX_O) where X means mole fraction on a single oxygen basis, in this Fe-free andesite varies with temperature as ln K = 1.547-2453/T where T is in K. Comparison with previous speciation data on rhyolitic and dacitic melts indicates that, for a given water concentration, Fe-free andesitic melt contains more hydroxyl groups. Water diffusivity at the experimental conditions increases rapidly with H₂O concentration, contrary to previous H₂O diffusion data in an andesitic melt at 1608-1848 K. The diffusion profiles are consistent with the model that molecular H₂O is the diffusion species. Based on the above speciation model, H₂O_m and H₂O_t diffusivity (in m²/s) in haploandesite at 743-873 K, 100 MPa, and H₂O_t ? 2.5 wt.% can be formulated as

     

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.     

Solubility and solution mechanisms of C-O-H volatiles in silicate melt with variable redox conditions and melt composition at upper mantle temperatures and pressures

Solubility and solution mechanisms in silicate melts of oxidized and reduced C-bearing species in the C-O-H system have been determined experimentally at 1.5 GPa and 1400 °C with mass spectrometric, NMR, and Raman spectroscopic methods. The hydrogen fugacity, f_H2, was controlled in the range between that of the iron-wüstite-H₂O (IW) and the magnetite-hematite-H₂O (MH) buffers. The melt polymerization varied between those typical of tholeiitic and andesitic melts.The solubility of oxidized (on the order of 1-2 wt% as C) and reduced carbon (on the order of 0.15-0.35 wt% as C) is positively correlated with the NBO/Si (nonbridging oxygen per silicon) of the melt. At given NBO/Si-value, the solubility of oxidized carbon is 2-4 times greater than under reducing conditions. Oxidized carbon dioxide is dissolved as complexes, whereas the dominant reduced species in melts are CH₃-groups forming bonds with Si⁴⁺ together with molecular CH₄. Formation of complexes results in silicate melt polymerization (decreasing NBO/Si), whereas solution of reduced carbon results in depolymerization of melts (increasing NBO/Si).Redox melting in the Earth’s interior has been explained with the aid of the different solution mechanisms of oxidized and reduced carbon in silicate melts. Further, effects of oxidized and reduced carbon on melt viscosity and on element partitioning between melts and minerals have been evaluated from relationships between melt polymerization and dissolved carbon combined with existing experimental data that link melt properties and melt polymerization. With total carbon contents in the melts on the order of several mol%, mineral/melt element partition coefficients and melt viscosity can change by several tens to several hundred percent with variable redox conditions in the range of the Earth’s deep crust and upper mantle.     

CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids: Implications for modeling the solubility of CO2 in silicic melts

The solubility of CO₂ in dacitic melts equilibrated with H₂O-CO₂ fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO₂ is dissolved in dacitic glasses as molecular CO₂ and carbonate. The quantification of total CO₂ in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm⁻¹ can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO_2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO₂ species concentrations from the MIR spectra we have measured total CO₂ contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO₂ solubility in dacitic melts on x^fluid_CO2,total shows a strong positive deviation from linearity with almost constant CO₂ solubility at x_CO2fluid > 0.8 (maximum CO₂ solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO₂. A similar nonlinear variation of CO₂ solubility with x_CO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO₂ (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO₂ molecules.A thermodynamic model describing the dependence of the CO₂ solubility in hydrous rhyolitic and dacitic melts on T, P, f_CO2 and the mol fraction of water in the melt (x_water) has been developed. An exponential variation of the equilibrium constant K₁ with x_water is proposed to account for the nonlinear dependence of x_CO2,totalmelt on x_CO2fluid. The model reproduces the CO₂ solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low x_CO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO₂ at low pressures (a Henrian behavior of the CO₂ solubility is observed at low pressure and low H₂O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the x_CO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO₂ is much lower in rhyolitic melts (31.7 cm³/mol) than in dacitic melts (46.6 cm³/mol). The dissolution enthalpy for CO₂ in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO₂ solubility in silicic melts.     

Solubility of plutonium(VI) carbonate in saline solutions

Among the plutonium oxidation states found to form in the environment, mobile plutonium(VI) can exist under oxidizing conditions and in waters with high chloride content due to radiolysis effects. We are investigating the solubility and speciation of plutonium(VI) carbonate under conditions relevant to natural waters and brines such as those found near some geologic radioactive waste repositories. The solid Pu(VI) phase PuO₂CO₃(s) was prepared and its solubility was measured in NaCl and NaClO₄ solutions in a CO₂ atmosphere as a function of pH and ionic strength (0.1-5.6 m). The concentration of soluble plutonium in solution was calculated from spectroscopic data and liquid scintillation counting. Spectroscopic measurements also revealed the plutonium oxidation state. The apparent solubility product of PuO₂CO₃(s) was determined at selected electrolyte concentrations to be, log K_s,0 = −13.95 ± 0.07 (0.1 m NaCl), log K_s,0 = −14.07 ± 0.13 (5.6 m NaCl), and log K_s,0 = −15.26 ± 0.11 (5.6 m NaClO₄). Specific ion interaction theory was used to calculate the solubility product at zero ionic strength, .     

Redox equilibria of iron and silicate melt structure: Implications for olivine/melt element partitioning

Olivine/melt partitioning of ΣFe, Fe²⁺, Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺, and Ni²⁺ has been determined in the systems CaO-MgO-FeO-Fe₂O₃-SiO₂ (FD) and CaO-MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂ (FDA3) as a function of oxygen fugacity (f_O2) at 0.1 MPa pressure. Total iron oxide content of the starting materials was ∼20 wt%. The f_O2 was to used to control the Fe³⁺/ΣFe (ΣFe: total iron) of the melts. The Fe³⁺/ΣFe and structural roles of Fe²⁺ and Fe³⁺ were determined with ⁵⁷Fe resonant absorption Mössbauer spectroscopy. Changes in melt polymerization, NBO/T, as a function of f_O2 was estimated from the Mössbauer data and existing melt structure information. It varies by ∼100% in melts coexisting with olivine in the FDA3 system and by about 300% in the FD system in the Fe³⁺/ΣFe range of the experiments (0.805-0.092). The partition coefficients ( in olivine/wt% in melt) are systematic functions of f_O2 and, therefore, NBO/T of the melt. There is a -minimum in the FDA3 system at NBO/T-values corresponding to intermediate Fe³⁺/ΣFe (0.34-0.44). In the Al-free system, FD, where the NBO/T values of melts range between ∼1 and ∼2.9, the partition coefficients are positively correlated with NBO/T (decreasing Fe³⁺/ΣFe). These relationships are explained by consideration of solution behavior in the melts governed by Qⁿ-unit distribution and structural changes of the divalent cations in the melts (coordination number, complexing with Fe³⁺, and distortion of the polyhedra).     

Carbon solubility in core melts in a shallow magma ocean environment and distribution of carbon between the Earth’s core and the mantle

The solubility of carbon in Fe and Fe-5.2 wt.% Ni melts, saturated with graphite, determined by electron microprobe analysis of quenched metal melts was 5.8 ± 0.1 wt.% at 2000 °C, 6.7 ± 0.2 wt.% at 2200 °C, and 7.4 ± 0.2 wt.% at 2410 °C at 2 GPa, conditions relevant for core/mantle differentiation in a shallow magma ocean. These solubilities are slightly lower than low-pressure literature values and significantly beneath calculated values for even higher pressures [e.g., Wood B. J. (1993) Carbon in the core. Earth Planet. Sci. Lett.117, 593-607]. The trend of C solubility versus temperature for Fe-5.2 wt.% Ni melt, within analytical uncertainties, is similar to or slightly lower (∼0.2-0.4 wt.%) than that of pure Fe. Carbon content of core melts and residual mantle silicates derived from equilibrium batch or fractional segregation of core liquids and their comparison with our solubility data and carbon content estimate of the present day mantle, respectively, constrain the partition coefficient of carbon between silicate and metallic melts, in a magma ocean. For the entire range of possible bulk Earth carbon content from chondritic to subchondritic values, of 10⁻⁴ to 1 is derived. But for ∼1000 ppm bulk Earth carbon, is between 10⁻² and 1. Using the complete range of possible for a magma ocean at ∼2200 °C, we predict maximum carbon content of the Earth’s core to be ∼6-7 wt.% and a preferred value of 0.25 ± 0.15 wt.% for a bulk Earth carbon concentration of ∼1000 ppm.     

Searching for parental kimberlite melt

Constraining the composition of primitive kimberlite magma is not trivial. This study reconstructs a kimberlite melt composition using vesicular, quenched kimberlite found at the contact of a thin hypabyssal dyke. We examined the 4 mm selvage of the dyke where the most elongate shapes of the smallest calcite laths suggest the strongest undercooling. The analyzed bulk compositions of several 0.09-1.1 mm² areas of the kimberlite free from macrocrysts were considered to be representative of the melt. The bulk analyses conducted with a new “chemical point-counting” technique were supplemented by modal estimates, studies of mineral compositions, and FTIR analysis of olivine phenocrysts. The melt was estimated to contain 26-29.5 wt% SiO₂, ∼7 wt% of FeO_T, 25.7-28.7 wt% MgO, 11.3-15 wt% CaO, 8.3-11.3 wt% CO₂, and 7.6-9.4 wt% H₂O. Like many other estimates of primitive kimberlite magma, the melt is too magnesian (Mg# = 0.87) to be in equilibrium with the mantle and thus cannot be primary. The observed dyke contact and the chemistry of the melt implies it is highly fluid (η = 10¹-10³ Pa s at 1100-1000 °C) and depolymerized (NBO/T = 2.3-3.2), but entrains with 40-50% of olivine crystals increasing its viscosity. The olivine phenocrysts contain 190-350 ppm of water suggesting crystallization from a low SiO₂ magma (a_SiO2 below the olivine-orthopyroxene equilibrium) at 30-50 kb. Crystallization continued until the final emplacement at depths of few hundred meters which led to progressively more Ca- and CO₂-rich residual liquids. The melt crystallised phlogopite (6-10%), monticellite (replaced by serpentine, ∼10%), calcite rich in Sr, Mg and Fe (19-27%), serpentine (29-31%) and minor amounts of apatite, ulvöspinel-magnetite, picroilmenite and perovskite. The observed content of H₂O can be fully dissolved in the primitive melt at pressures greater than 0.8-1.2 kbar, whereas the amount of primary CO₂ in the kimberlite exceeds CO₂ soluble in the primitive kimberlite melt. A mechanism for retaining CO₂ in the melt may require a separate fluid phase accompanying kimberlite ascent and later dissolution in residual carbonatitic melt. Deep fragmentation of the melt as a result of volatile supersaturation is not inevitable if kimberlite magma has an opportunity to evolve.