Shock-induced devolatilization of calcite

The amounts of CO₂ and CO evolved upon shock compression and decompression of calcite to 18 GPa (180 kbar) have been determined using a new gas phase shock recovery technique and gas source mass spectrometry. The data demonstrate that from ～0.03 to 0.3 mole percent of calcite is devolatilized at shock pressures significantly lower than those predicted (30 GPa) for the onset of volatilization by continuum thermodynamic theory and are in qualitative agreement with release adiabat data for calcite and aragonite. Carbon and oxygen isotope ratios in the shock-released CO₂ are the same as those in the unshocked (hydrothermal) calcite, demonstrating that the CO₂ comes from the calcite rather than other potential sources.     

The phase diagram of CaCO3 in relation to shock compression and decomposition

The phase diagram for calcite (CaCO₃) is re-evaluated in relation to dynamic compression and following release from shock. Available shock compression data on Hugoniot dynamic measurements, analysis of recovered samples, and observation at terrestrial impact sites are compared with theoretically derived equations of state (EOS) for CaCO₃ and its decomposition products CaO and CO₂. The study results in a refined phase diagram for CaCO₃ in which the major change is the extension of the liquid field of CaCO₃. A general outcome of this analysis is that release of CO₂ from naturally shocked carbonates to the atmosphere is (grossly) overestimated if based on the calcite phase diagram constructed from thermodynamic equilibrium conditions.     

Evidence of an early alteration process driven by magmatic fluid in Mururoa volcano

Evidence for a deuteric alteration process induced by a magmatic fluid has been found in the feeder zone of the Mururoa volcano (French Polynesia). Within the dikes, where basaltic glass does not show any evidence of pervasive alteration, vesicles are filled with dioctahedral smectites and calcite, while olivine phenocrysts are replaced by dioctahedral smectites, ankerite and calcite.The ¹³C signature of carbonates, the carbon and H₂O content of the whole rocks and their impoverishment in deuterium are compatible with the presence of magmatic CO₂ during the crystallization of intruding lavas and exclude contamination by seawater. Mass balance calculations on selected thin sections photographs of partly filled up vesicles and replaced olivine crystals, constrain, assuming a closed system interaction, the chemical composition of the initial fluid and the respective amounts of the initial solid phases involved in the alteration process. Thermodynamic modelings using the EQ3/6 software package correctly predict the mineralogic, chemical and isotopic exchanges accompanying alteration, thus validating the closed system assumption. The model which allows prediction of the influence of CO₂ on the alteration products, shows that, above a 0.25 CO₂ mole fraction in the initial fluid, the alteration is entirely controlled by the chemical composition of the initial solid phases. The presence of CO₂ implies the precipitation of dioctahedral smectites and carbonates instead of the magnesian smectites commonly observed in CO₂-free systems.The Mururoa feeder zone shows alteration features typical of a closed system interaction between the basaltic rock and a magmatic fluid in which seawater did not take part.     

The join grossularite-calcite through the system CaO—Al2O3—SiO2—CO2 at 30 kilobars: Crystallization range of silicates and carbonates on the liquidus

At 30 kbar, calcite melts congruently at 1615°C, and grossularite melts incongruently to liquid + gehlenite (tentative identification) at 1535°C. The assemblage calcite + grossularite melts at 1450°C to produce liquid + vapor, with piercing point at about 49 wt.% CaCO₃. Vapor phase is present in all hypersolidus phase fields except for those with less than about 7% CaCO₃ or 8% Ca₃Al₂Si₃O₁₂. These results, together with known liquidus data for CaO—SiO₂—CO₂ and inferred results for CaO—Al₂O₃—CO₂ and Al₂O₃—SiO₂—CO₂, permit construction of the position of the CO₂- saturated liquidus surface in the quaternary system, and estimation of the positions of liquidus field boundaries separating some of the primary crystallization fields on this surface. The field of calcite is separated from those for grossularite and quartz by a field boundary with about 50% dissolved CaCO₃. Crystallization paths of silicate liquids in the range Ca₂SiO₄—Ca₃Al₂Si₃O₁₂—SiO₂, with some dissolved CO₂, will terminate at a quaternary eutectic on this field boundary, with the precipitation of calcite together with grossularite and quartz, at a temperature below 1450°C. Addition of Al₂O₃ to CaO—SiO₂—CO₂ in amounts sufficient to stabilize garnet thus causes little change in the general liquidus pattern as far as carbonates and silicates are concerned. With addition of MgO, we anticipate that silicate liquids with dissolved CO₂ will also follow liquidus paths to fields for the precipitation of carbonates; we conclude that similar paths link kimberlite and some carnbonatite magmas.     

Melting of forsterite Mg2SiO4 up to 15 GPa

The melting curve of forsterite has been studied by static experiment up to a pressure of 15 GPa. Forsterite melts congruently at least up to 12.7 GPa. The congruent melting temperature is expressed by the Kraut-Kennedy equation in the following form: T_m(K)=2163 (1+3.0(V₀ ? V)/V₀), where the volume change with pressure was calculated by the Birch-Managhan equation of state with the isothermal bulk modulus K₀ = 125.4 GPa and its pressure derivative K′ = 5.33. The triple point of forsterite-β-Mg₂SiO₄-liquid will be located at about 2600°C and 20 GPa, assuming that congruent melting persists up to the limit of the stability field of forsterite. The extrapolation of the previous melting data on enstatite and periclase indicates that the eutectic composition of the forsterite-enstatite system should shift toward the forsterite component with increasing pressure, and there is a possibility of incongruent melting of forsterite into periclase and liquid at higher pressure, although no evidence on incongruent melting has been obtained in the present experiment.     

High-pressure partial melting of garnet pyroxenite: possible mafic lithologies in the source of ocean island basalts

Many ocean island basalts (OIB) that have isotopic ratios indicative of recycled crustal components in their source are silica-undersaturated and unlike silicic liquids produced from partial melting of recycled mid-ocean ridge basalt (MORB). However, experiments on a silica-deficient garnet pyroxenite, MIX1G, at 2.0-2.5 GPa show that some pyroxenite partial melts are strongly silica-undersaturated [M.M. Hirschmann et al., Geology 31 (2003) 481-484]. These low-pressure liquids are plausible parents of alkalic OIB, except that they are too aluminous. We present new partial melting experiments on MIX1G between 3.0 and 7.5 GPa. Partial melts at 5.0 GPa have low SiO₂ (<48 wt%), low Al₂O₃ (<12 wt%) and high CaO (>12 wt%) at moderate MgO (12-16 wt%), and are more similar to primitive OIB compositions than lower-pressure liquids of MIX1G or experimental partial melts of anhydrous or carbonated peridotite. Solidus temperatures at 5.0 and 7.5 GPa are 1625 and 1825°C, respectively, which are less than 50°C cooler than the anhydrous peridotite solidus. The liquidus temperature at 5.0 GPa is 1725°C, indicating a narrow melting interval (∼100°C). These melting relations suggest that OIB magmas can be produced by partial melting of a silica-deficient pyroxenite similar to MIX1G if its melting residue contains significant garnet and lacks olivine. Such silica-deficient pyroxenites could be produced by interaction between recycled subducted oceanic crust and mantle peridotite or could be remnants of ancient oceanic lower crust or delaminated lower continental crust. If such compositions are present in plumes ascending with potential temperatures of 1550°C, they will begin to melt at about 5.0 GPa and produce appropriate partial melts. However, such hot plumes may also generate partial melts of peridotite, which could dilute the pyroxenite-derived partial melts.     

Relationship between13C and18O fractionation and changes in major element composition in a recent calcite-depositing spring — A model of chemical variations with inorganic CaCO3 precipitation

A theoretical model is derived in which isotopic fractionations can be calculated as a function of variations in dissolved carbonate species on CO₂ degassing and calcite precipitation. This model is tested by application to a calcite-depositing spring system near Westerhof, Germany. In agreement with the model,¹³C of the dissolved carbonate species changes systematically along the flow path. The difference in δ values between the upper and lower part of the stream is about 1‰. The¹³C content of the precipitated calcite is different from that expected from the theoretical partitioning. The isotopic composition of the solid CaCO₃ is similar to that of the dissolved carbonate, though in theory it should be isotopically heavier by about 2.4‰. The¹⁸O composition of dissolved carbonate and H₂O is constant along the stream. Calculated calcite-water temperatures differ by about +5°C from the observed temperatures demonstrating isotopic disequilibrium between the water and precipitated solid. This is attributed to kinetic effects during CaCO₃ deposition from a highly supersaturated solution, in which precipitation is faster than equilibration with respect to isotopes.Plant populations in the water have virtually no influence on CO₂ degassing, calcite saturation and isotopic fractionation. Measurements of P_CO2, S_C and¹³C within a diurnal cycle demonstrate that metabolic effects are below the detection limit in a system with a high supply-rate of dissolved carbonate species. The observed variations are due to differences in CO₂ degassing and calcite precipitation, caused by continuously changing hydrodynamic conditions and carbonate nucleation rates.     

Shock and post-shock temperatures in an ice–quartz mixture: implications for melting during planetary impact events

Melting of H₂O ice during planetary impact events is a widespread phenomenon. On planetary surfaces, ice is often mixed with other materials; yet, at present, the partitioning of energy between the components of a shocked mixture is still an open question in the shock physics community. Knowledge of how much energy is partitioned into the ice component is necessary to predict and interpret a wide range of processes, including shock-induced melting and chemistry. In this work, we construct a conceptual framework for the thermodynamic pathways of the components in a shocked hydrodynamic mixture by defining three broad regimes based on the characteristic length scale of the mixture compared to the thickness of the shock front: (1) small length scale mixtures where pressure and temperature equilibrate immediately behind the shock front; (2) intermediate length scales where pressure but not thermal equilibration is achieved behind the shock front; and (3) long length scales where pressure equilibration requires multiple shock wave reflections. We conduct shock wave experiments, reaching pressures from 8 to 23 GPa, in an H₂O ice–SiO₂ quartz mixture in the intermediate length scale regime. In each experiment, all the parameters required to address the question of energy partitioning were determined: the shock velocity in the mixture, the shock front thickness, and the shock and post-shock temperatures of the H₂O component. The measured pressure is in agreement with the bulk compressibility of the mixture. The shock and post-shock temperatures of the H₂O component indicate that the ice was shocked close to the principal Hugoniot. Therefore, in the intermediate length scale regime, the partitioning of shock energy is defined initially by the Hugoniots of the components at the equilibrated pressure. We discuss energy partitioning in mixtures over the wide range of length and time scales encountered during planetary impact events and identify the current challenges in calculating the volume of melted ice. In some cases, the criteria for shock-induced melting of ice in a mixture are the same as for pure ice.     

Shock-induced CO2 loss from CaCO3; implications for early planetary atmospheres

We report new results of shock recovery experiments on single crystal calcite. Recovered samples are subjected to thermogravimetric analysis. This yields the maximum amount of post-shock CO₂, the decarbonization interval, ΔT, and the energy of association (or vaporization), ΔEV, for the removal of remaining CO₂ in shock-loaded calcite. Comparison of post-shock CO₂ with that initially present determines shock-induced CO₂ loss as a function of shock pressure. Incipient to complete CO₂ loss occurs over a pressure range of 10to 70GPa. The latter pressure should be considered a lower bound. Comparable to results on hydrous minerals, ΔT and ΔEV decrease systematically with increasing shock pressure. This indicates that shock loading leads to both the removal of structural volatiles and weakening of bonds between the volatile species and remainder of the crystal lattice.Optical and scanning electron microscopy (SEM) reveal structural changes, which are related to the shock-loading. Comparable to previous findings on shocked antigorite is the occurrence of dark, diffuse areas, which can be resolved as highly vesicular areas as observed with a scanning electron microscope. These areas are interpreted as representing quenched partial melts, into which shock-released CO₂ has been injected.The experimental results are used to place bonds on models of impact production of CO₂ during accretion of the terrestrial planets.     

Evaluation of the carbon isotopic effects of NDIR and CRDS analyzers on atmospheric CO2 measurements

Non-dispersive infrared(NDIR) and cavity ring-down spectroscopy(CRDS) CO_2 analyzers use 12CO_2 isotopologue absorption lines and are insensitive to all or part of other CO_2-related isotopologues. This may produce biases in CO_2 mole fraction measurements of a sample if its carbon isotopic composition deviates from that of the standard gases being used. To evaluate and compare the effects of carbon isotopic composition on NDIR and CRDS CO_2 analyzers, we prepared three test sample air cylinders with varying carbon isotopic abundances and calibrated them against five standard cylinders with ambient carbon isotopic composition using CRDS and NDIR systems. We found that the CO_2 mole fractions of the sample cylinders measured by G1301(CRDS) were in good agreement with those measured by Lo Flo(NDIR). The CO_2 values measured by both instruments were higher than that of a CO_2 isotope measured by G2201i(CRDS) analyzer for a test cylinder with depleted carbon isotopic composition δ~(13)C =-36.828‰, whereas no obvious difference was found for other two test cylinders with δ~(13)C=-8.630‰ and δ~(13)C=-15.380‰, respectively. According to the theoretical and experimental results, we concluded that the total CO_2 mole fractions of samples with depleted isotopic compositions can be corrected on the basis of their 12CO_2 values calibrated by standard gases using Lo Flo and G1301 if the δ~(13)C and δ18O values are known.     

Natural gas leakage of Mizhi gas reservoir in Ordos Basin,recorded by natural gas fluid inclusion

Abundant natural gas inclusions were found in calcite veins filled in fractures of Central Fault Belt across the centre of Ordos Basin. Time of the calcite veins and characteristics of natural gas fluid inclusion were investigated by means of dating of thermolum luminescence (TL) and analyzing stable isotope of fluid inclusion. Results show that natural gas inclusion formed at 130–140°C with salinity of 5.5 wt%–6.0 wt% NaCl. It indicates that natural gas inclusion is a kind of thermal hydrocarbon fluid formed within the basin. Method of opening inclusion by heating was used to analyze composition of fluid inclusion online, of which the maximal hydrocarbon gas content of fluid inclusion contained in veins is 2.4219 m³/t rock and the maximal C₁/ΣC _i ratio is 91%. Laser Raman spectroscopy (LRS) was used to analyze chemistry of individual fluid inclusion in which the maximal hydrocarbon gas content is 91.6% compared with little inorganic composition. Isotope analysis results of calcite veins show that they were deposited in fresh water, in which the δ ¹³C_PDB of calcite veins is from ?5.75‰ to 15.23‰ and δ ¹⁸O_SMOW of calcite veins is from 21.33‰ to 21.67‰. Isotope results show that δ ¹³C_{1 PDB} of natural gas fluid inclusion is from ?21.36‰ to ?29.06‰ and δD_SMOW of that is from ?70.89‰ to ?111.03‰. It indicates that the gas of fluid inclusion formed from coal source rocks and it is the same as that of natural gas of Mizhi gas reservoir. Results of TL dating show that time of calcite vein is (32.4±3.42)×10⁴ a, which is thought to be formation time of gas inclusion. It indicated that natural gas inclusion contained in calcite veins recorded natural gas leakage from Mizhi gas reservoir through the Central Fault Belt due to Himalayan tectonic movement.     

Vadose CO2 gas drives dissolution at water tables in eogenetic karst aquifers more than mixing dissolution

Most models of cave formation in limestone that remains near its depositional environment and has not been deeply buried (i.e. eogenetic limestone) invoke dissolution from mixing of waters that have different ionic strengths or have equilibrated with calcite at different _pCO₂ values. In eogenetic karst aquifers lacking saline water, mixing of vadose and phreatic waters is thought to form caves. We show here calcite dissolution in a cave in eogenetic limestone occurred due to increases in vadose CO₂ gas concentrations and subsequent dissolution of CO₂ into groundwater, not by mixing dissolution. We collected high‐resolution time series measurements (1 year) of specific conductivity (SpC), temperature, meteorological data, and synoptic water chemical composition from a water table cave in central Florida (Briar Cave). We found SpC, _pCO₂ and calcite undersaturation increased through late summer, when Briar Cave experienced little ventilation by outside air, and decreased through winter, when increased ventilation lowered cave CO_2(g) concentrations. We hypothesize dissolution occurred when water flowed from aquifer regions with low _pCO₂ into the cave, which had elevated _pCO₂. Elevated _pCO₂ would be promoted by fractures connecting the soil to the water table. Simple geochemical models demonstrate that changes in _pCO₂ of less than 1% along flow paths are an order of magnitude more efficient at dissolving limestone than mixing of vadose and phreatic water. We conclude that spatially or temporally variable vadose CO_2(g) concentrations are responsible for cave formation because mixing is too slow to generate observed cave sizes in the time available for formation. While this study emphasized dissolution, gas exchange between the atmosphere and karst aquifer vadose zones that is facilitated by conduits likely exerts important controls on other geochemical processes in limestone critical zones by transporting oxygen deep into vadose zones, creating redox boundaries that would not exist in the absence of caves. Copyright © 2014 John Wiley & Sons, Ltd.     

The equation-of-states of Jilin ordinary chondrite and Nandan iron meteorite

Shock wave data for Jilin ordinary chondrite and Nandan iron meteorite are measured by electric-pin techniques on the dynamic high-pressure device equipped with a two-stage light gas gun, and then equation-of-states supposedly fit for describing theirP- V-E relations are chosen to evaluate the values of their parameters. Demonstrated from the comparison between P-V curves of equation-of-states and experimental data points, P-V relation of Jilin ordinary chondrite can be described by the universal equation-of-state, of which bulk modulus value of zero-pressure K_os = 48.10 GPa, its pressure derivativeK’ _os = 4.13. That of Nandan iron meteorite can be described by the three-term form of equation-of-state, of which the values of two matter parameters Q = 41.235 31 GPa, q = 12. 27179. The Hugoniot data and equation-of-states for Jilin ordinary chondrite and Nandan iron meteorite are first reported in this paper. The equation-of-state defined by Hugoniot data measurement provides strong empirical support for describing the compression of meteorites to high pressure. Project supported by the National Natural Science Foundation of China.     

Diffuse CO2 efflux from Iwojima volcano,Izu-Ogasawara arc,Japan

Iwojima volcano, located on the southernmost part of the Izu-Ogasawara arc, is characterized by the extrusion of trachyte or trachy andesite lavas and pyroclastic rocks of Holocene and surface thermal manifestations. Small phreatic explosions have been recorded frequently during the last 100 years with the most recent in 1999 and 2001. In order to elucidate the behavior of volcanic volatiles and to assess the potential activity of this volcano, diffuse CO₂ efflux, CO₂ content and δ¹³C–CO₂ in soil gas, and soil temperature at 30 cm depth were measured at 272 sites in March 2000, 112 sites in December 2000 and 40 sites in December 2001. We found that high CO₂ efflux values, of more than 100 g m⁻² day⁻¹, occurred at several locations on Motoyama volcano corresponding with high soil temperatures (more than 60 °C at 30 cm depth) region and with areas where CO₂ with magmatic δ¹³C was observed. Here, the magmatic δ¹³C determined for fumarolic CO₂ data ranged from −2‰ to +3‰, which is clearly higher than magmatic gas values (−8‰ to −2‰) typically found in island arc settings around the world. However, this can be explained in terms of carbon-isotope fractionation between calcite and CO₂ under subsurface temperature and pressure conditions at Iwojima. A total efflux of CO₂ for Iwojima volcano is estimated to be 760 t day⁻¹, with a magmatic contribution of about 450 t day⁻¹. This value is rather high compared with other volcanoes in island arc settings. Since Iwojima has no visible plume, almost all volcanic CO₂ is released as diffuse efflux through the volcanic edifice.     

Effect of hydrogen on the melting temperature of FeS at high pressure: Implications for the core of Ganymede

We have carried out in situ X-ray diffraction experiments on the FeS–H system up to 16.5 GPa and 1723 K using a Kawai-type multianvil high-pressure apparatus employing synchrotron X-ray radiation. Hydrogen was supplied to FeS from the thermal decomposition of LiAlH₄, and FeSH_x was formed at high pressures and temperatures. The melting temperature and phase relationships of FeSH_x were determined based on in situ powder X-ray diffraction data. The melting temperature of FeSH_x was reduced by 150–250 K comparing with that of pure FeS. The hydrogen concentration in FeSH_x was determined to be x = 0.2–0.4 just before melting occurred between 3.0 and 16.5 GPa. It is considered that sulfur is the major light element in the core of Ganymede, one of the Galilean satellites of Jupiter. Although the interior of Ganymede is differentiated today, the silicate rock and the iron alloy mixed with H₂O, and the iron alloy could react with H₂O (as ice or water) or the hydrous silicate before the differentiation occurred in an early period, resulting in a formation of iron hydride. Therefore, Ganymede's core may be composed of an Fe–S–H system. According to our results, hydrogen dissolved in Ganymede's core lowers the melting temperature of the core composition, and so today, the core could have solid FeSH_x inner core and liquid FeH_x–FeSH_x outer core and the present core temperature is considered to be relatively low.     

Carbon isotopic compositions of Recent planktonic foraminifera of the Indian Ocean

Carbon and oxygen isotopic determinations have been made of 29 species of Recent Indian Ocean planktonic foraminifera. Fourteen core-top samples were used and as many as 18 species were chosen from a single core-top sample. The δ¹³C of the foraminifera was compared with that of total dissolved CO₂ (ΣCO₂) and of calcite precipitated in isotopic equilibrium with ΣCO₂. The foraminiferal calcite is always at least 1.2‰ less than the value estimated for equilibrium calcite. This carbon isotopic disequilibrium suggests the partial utilization of¹³C-depleted metabolic CO₂. The calcite tests of several species, however, have δ¹³C values which are similar to the δ¹³C of ΣCO₂ in seawater. This relationship suggests that important paleohydrographic information may be obtained from carbon isotope records based on analyses of several foraminiferal species from single deep-sea sediment samples.     

Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2 concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2 ]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.     

Melting of enstatite from 13 to 18 GPa under hydrous conditions

Experiments on MgSiO₃ enstatite were conducted in the pressure range from 13 to 18 GPa under hydrous conditions in order to clarify the effect of water on the melting phase relations of enstatite at pressures corresponding to the Earth’s mantle transition zone. In some previous experiments [Geol. Soc. Am. Bull. 79 (1968) 1685; Phys. Earth Planet. Inter. 85 (1994) 237], incongruent melting behavior to form Mg₂SiO₄ forsterite and SiO₂ enriched liquid up to 5 GPa was observed, and congruent melting behavior at pressures up to 12 GPa was observed. Under hydrous conditions, we found that the melting reaction changes from congruent to incongruent at around 13.5 GPa. Liquid formed above 13.5 GPa is enriched in MgO component relative to MgSiO₃ because it coexists with stishovite (SiO₂). Moreover, the solidus temperature decreases drastically at around 13.5 GPa, in unison with the change in the melting reaction. The solidus temperature is about 1400 °C at 13 GPa, but approximately 900 °C at 15 GPa. Our results show that the liquidus phase changes from clinoenstatite to stishovite with increasing pressure and water content above 13.5 GPa. MgSiO₃ enstatite is one of the major constituent minerals in the Earth’s mantle, and it is expected that MgO-enriched liquid will be generated in the transition zone if water is present.     

Rare earth element systematics of hydrous liquids from partial melting of basaltic eclogite a re-evaluation

The origin of orogenic andesitic magmas is tested by calculations of REE fractionation in hydrous melts derived from partial melting of subducted ocean basalt in eclogite facies. New data on the subsolidus phase proportions of basaltic eclogite, the enrichment of LREE in altered ocean basalts, and experimentally determined REE partition coefficients (K_D's) between garnet and melt have been included in trace element fractionation equations. Non-modal melting of phases combined with variation inK_D's during melting is a unique feature of these calculations.Variation ofK_D, melting proportions, initial proportion of subsolidus phases, degree of melting, and initial REE concentrations yield a wide range of input parameters that produce REE profiles in partial melts of basaltic eclogite matching REE profiles of some orogenic andesites. The positive correlation of REE concentration with silica content for many andesitic suites can be accounted for by non-modal melting if quartz (or a similar phase with low REEK_D values) melts at a high melting proportion and garnet melts at a low melting proportion during the first stages of fusion. However, no mineralogic fractionation scheme can account for REE/silica systematics if REEK_D values are linearly decreasing with increasing melting. Earlier workers who have used similar calculations to discredit the eclogite fractionation model have set overly strict, and sometimes incorrect, constraints concerning the range in REEK_D values for garnet, the subsolidus proportions of phases in basaltic eclogite, and the relative concentrations of REE in subducted ocean crust undergoing partial melting.     

New insights into the spatial variability of the surface water carbon dioxide in varying sea ice conditions in the Arctic Ocean

In the summer of 2005, continuous surface water measurements of fugacity of CO₂ (fCO₂^sw), salinity and temperature were performed onboard the IB Oden along the Northwest Passage from Cape Farwell (South Greenland) to the Chukchi Sea. The aim was to investigate the importance of sea ice and river runoff on the spatial variability of fCO₂ and the sea–air CO₂ fluxes in the Arctic Ocean. Additional data was obtained from measurements of total alkalinity (A_T) by discrete surface water and water column sampling in the Canadian Arctic Archipelago (CAA), on the Mackenzie shelf, and in the Bering Strait. The linear relationship between A_T and salinity was used to evaluate and calculate the relative fractions of sea ice melt water and river runoff along the cruise track. High-frequency fCO₂^sw data showed rapid changes, due to variable sea ice conditions, freshwater addition, physical upwelling and biological processes. The fCO₂^sw varied between 102 and 678 μatm. Under the sea ice in the CAA and the northern Chukchi Sea, fCO₂^sw were largely CO₂ undersaturated of approximately 100 μatm lower than the atmospheric level. This suggested CO₂ uptake by biological production and limited sea–air CO₂ gas exchange due to the ice cover. In open areas, such as the relatively fresh water of the Mackenzie shelf and the Bering Strait, the fCO₂^sw values were close to the atmospheric CO₂ level. Upwelling of saline and relatively warm water at the Cape Bathurst caused a dramatic fCO₂^sw increase of about 100 μatm relative to the values in the CAA. At the southern part of the Chukchi Peninsula we found the highest fCO₂^sw values and the water was CO₂ supersaturated, likely due to upwelling. In the study area, the calculated sea–air CO₂ flux varied between an oceanic CO₂ sink of 140 mmol m⁻² d⁻¹ and an oceanic source of 18 mmol m⁻² d⁻¹. However, in the CAA and the northern Chukchi Sea, the sea ice cover prevented gas exchange, and the CO₂ fluxes were probably negligible at this time of the year. Assuming that the water was exposed to the atmosphere by total melting and gas exchange would be the only process, the CO₂ undersaturated water in the ice-covered areas will not have the time to reach the atmospheric CO₂ value, before the formation of new sea ice. This study highlights the value of using high-frequency measurements to gain increased insight into the variable and complex conditions, encountered on the shelves in the Arctic Ocean.