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 relationships in CaO-CO2 and MgO-CO2 to 36 kilobars with comments on CO2 in the mantle

The melting curves of CaCO₃ and MgCO₃ have been extended to pressures of 36 kb by experiments in piston-cylinder apparatus. At 30 kb, the melting temperatures of calcite and magnesite are 1610°C and 1585°C, respectively. New data for the magnesite dissociation reaction permit the location of an invariant point for the assemblage magnesite + periclase + liquid + vapor near 26 kb-1550°C. New data are also presented for the calcite-aragonite transition at 800°C, 950°C and 1100°C. At pressures above 36–50 kb, calcite and magnesite melt at temperatures lower than the solidus of dry mantle peridotite. Natural and experimental evidence suggests that carbon dioxide in the Earth's mantle could be present in a variety of forms: (a) a free vapor phase, (b) vapor dissolved in silicate magma, (c) crystalline carbonate, (d) carbonatite liquid, (e) carbon-bearing silicate analogs, or (f) carbonato-silicates (such as scapolite, spurrite, tilleyite, and related compounds).     

Correlations between13C and ΣCO2 in surface waters and atmospheric CO2

¹³C and ΣCO₂ data from the North and South Atlantic, the Antarctic, and the North and South Pacific are given. The δ¹³C of the ΣCO₂ in the deep water (～3000m) decreases from 1.7‰ in the North Atlantic to ?0.10‰ in the North Pacific. This change is attributed to the addition of about 158 μmoles of CO₂ per kg of seawater. The in-situ oxidation of organic matter accounts for 83% of this increase in ΣCO₂, while the remainder is attributed to dissolution of calcium carbonate.The δ¹³C of the dissolved CO₂ in mid-latitude surface water samples is controlled by a quasi-steady-state equilibrium with atmospheric CO₂ at a mean temperature of 16°C. The δ¹³C and ΣCO₂ values of Antarctic surface water samples suggest that these waters are derived from a mixture of North Atlantic deep water and equilibrated surface water.     

Compression and phase behavior of solid CO2 to half a megabar

CO₂ has been investigated up to 514 kbar at23 ± 2°C by both optical and in situ X-ray diffraction studies using a diamond-anvil pressure cell. CO₂ solidifies in an unknown structure in the pressure range 5 to 23 kbar, and transforms to ordinary dry-ice structure above 23 kbar at room temperature. Isothermal compression data for dry ice have been obtained above about 24 kbar. These appear to be the first data at room temperature known in the literature. The data fitted to the Birch equation of state yieldK₀ = 29.3 ± 1.0kbar andK₀^′ = 7.8 assuming the volume of the hypothetical dry ice at zero-pressure and room temperature is 31.4 ± 0.2 cm³/mole. The isothermal bulk modulus(K₀) thus derived is consistent with the compression data and compressibilities for dry ice obtained at low temperatures using dilatometry and ultrasonic techniques, respectively, reported in the literature. By comparing shock-wave data for relevant materials, it is suggested that CO₂ is not likely to transform to one of the crystalline forms of SiO₂ which is otherwise expected from empirical grounds, but may instead decompose into C (diamond) + O₂, at high pressures.     

Geochemical features of the geothermal CO2-watercarbonate rock system and analysis on its CO2 sources

Taking Huanglong Ravine and Kangding, Sichuan, and Xiage, Zhongdian, Yunnan, as examples, the authors summarize the hydrogeochemical and carbon stable isotopic features of the geothermal CO₂-water-carbonate rock system and analyze the CO₂ sources of the system. It was found that the hydrogeochemical and carbon stable isotopic features of such a system are different from those of shallow CO₂-water-carbonate rock system, which is strongly influenced by biosphere. The former has higher CO₂ partial pressure, and is rich in heavy carbon stable isotope. In addition, such a geothermal system is also different from that developed in igneous rock. The water in the latter system lacks Ca²⁺, and thus, there are few tufa deposits on ground surface, but it is rich in light carbon stable isotope. Further analysis shows that CO₂ of the geothermal CO₂-water-carbonate rock system is a mixture of metamorphic CO₂ and magmatic CO₂.     

CO2/CaCl2 solution interfacial tensions under CO2 geological storage conditions: Influence of cation valence on interfacial tension

The effectiveness of CO₂ storage in deep saline aquifers and hydrocarbon reservoirs is governed, among other factors, by the interfacial tension between the injected CO₂ and formation water (brine). Experimental data on CO₂/water and CO₂/NaCl solution have revealed that the interfacial tension depends on the pressure, temperature and water salinity. However, there is still a lack of data for other salts (such as MgCl₂ and CaCl₂) which are also present in aquifers and carbonate reservoirs.     

Geobarometry of ultramafic xenoliths from Loihi Seamount,Hawaii, on the basis of CO2 inclusions in olivine

Abundant fluid inclusions in olivine of dunite xenoliths (～1–3 cm) in basalt dredged from the young Loihi Seamount, 30 km southeast of Hawaii, are evidence for three coexisting immiscible fluid phases—silicate melt (now glass), sulfide melt (now solid), and dense supercritical CO₂ (now liquid + gas)—during growth and later fracturing of some of these olivine crystals. Some olivine xenocrysts, probably from disaggregation of xenoliths, contain similar inclusions.Most of the inclusions (2–10 μm) are on secondary planes, trapped during healing of fractures after the original crystal growth. Some such planes end abruptly within single crystals and are termed pseudosecondary, because they formed during the growth of the host olivine crystals. The “vapor” bubble in a few large (20–60 μm), isolated, and hence primary, silicate melt inclusions is too large to be the result of simple differential shrinkage. Under correct viewing conditions, these bubbles are seen to consist of CO₂ liquid and gas, with an aggregate ? = ～ 0.5–0.75 g cm^?3, and represent trapped globules of dense supercritical CO₂ (i.e., incipient “vesiculation” at depth). Some spinel crystals enclosed within olivine have attached CO₂ blebs. Spherical sulfide blebs having widely variable volume ratios to CO₂ and silicate glass are found in both primary and pseudosecondary inclusions, demonstrating that an immiscible sulfide melt was also present.Assuming olivine growth at ～ 1200°C and hydrostatic pressure from a liquid lava column, extrapolation of CO₂P-V-T data indicates that the primary inclusions were trapped at ～ 220–470 MPa (2200–4700 bars), or ～ 8–17 km depth in basalt magma of ? = 2.7 g cm^?3. Because the temperature cannot change much during the rise to eruption, the range of CO₂ densities reveals the change in pressure from that during original olivine growth to later deformation and rise to eruption on the sea floor. The presence of numerous decrepitated inclusions indicates that the inclusion sample studied is biased by the loss of higher-density inclusions and suggests that some part of these olivine xenoliths formed at greater depths.     

Eutectic between wollastonite II and calcite contrasted with thermal barrier in MgO-SiO2-CO2 at 30 kilobars,with applications to kimberlite-carbonatite petrogenesis

In the join CaCO₃-CaSiO₃ at 30 kbars, calcite melts at 1615°C, wollastonite II at 1600°C, and a binary eutectic occurs at 1365°C with liquid composition 43 wt.% CaCO₃, 57 wt.% CaSiO₃. The eutectic liquid quenches to a glass with few quench crystals. In the join MgCO₃-MgSiO₃ at 30 kbars, magnesite melts at 1590°C, enstatite at 1837°C, and the fields for the primary crystallization of magnesite and enstatite are separated by a thermal barrier near 1900°C for the melting of forsterite in the presence of CO₂. Only about 10 wt.% MgSiO₃ dissolves in the carbonate liquid. These data, are considered together with incomplete results for joins CaMgSi₂O₆-CaMg(CO₃)₂, CaMgSi₂O₆-MgCO₃, CaMgSi₂O₆-CaCO₃, and other published data in the system CaO-MgO-SiO₂-CO₂. A thermal barrier separates the silicate and carbonate liquids in MgO-SiO₂-CO₂ but, in the quaternary system, silicate liquids with dissolved CO₂ can follow fractionation paths around the forsterite field to the fields for the primary crystallization of carbonates. This suggests that fractional crystallization of CO₂-bearing ultrabasic magma at 100 km depth can produce residual carbonatite magma.     

Capillary pressure for the sand–CO2–water system under various pressure conditions. Application to CO2 sequestration

Accurate modeling of storage of carbon dioxide (CO₂) in heterogeneous aquifers requires experiments of the capillary pressure as function of temperature and pressure. We present a method with which static drainage and imbibition capillary pressures can be measured continuously as a function of saturation at various temperature (T) and pressure (P) conditions. The measurements are carried out at (T, P) conditions of practical interest. Static conditions can be assumed as small injection rates are applied. The capillary pressure curves are obtained for the unconsolidated sand–distilled water–CO₂ system. The experimental results show a decrease of drainage and imbibition capillary pressure for increasing CO₂ pressures and pronounced dissolution rate effects for gaseous CO₂. Significant capillary pressure fluctuations and negative values during imbibition are observed at near critical conditions. The measurement procedure is validated by a numerical model that simulates the experiments.     

Disproportionation of Ni2SiO4 to stishovite plus bunsenite at high pressures and temperatures

Samples of Ni₂SiO₄ in both olivine and spinel phases have been compressed to pressures above 140 kbar in a diamond-anvil cell and heated to temperatures of 1400–1800°C using a continuous YAG laser. After quenching and releasing pressure, X-ray diffraction examination indicates that the samples disproportionate to a mixture of stishovite (SiO₂) and bunsenite (NiO) at pressures between 140 and 190 kbar. The exact disproportionation pressure is not certain due to transient increases in pressure during the local and rapid heating. However, thermodynamic calculations suggest that the transition pressure is about 192 ± 4 kbar at 1545°C and that the equation of the spinel-mixed oxides phase boundary isP(kbar) = 121 + (0.046 ± 0.020) T (°C).     

Pyroxene-garnet solid-solution equilibria in the systems Mg4Si4O12Mg3Al2Si3O12 and Fe4Si4O12Fe3Al2Si3O12 at high pressures and temperatures

Pyroxene-garnet solid-solution equilibria have been studied in the pressure range 41–200 kbar and over the temperature range 850–1,450°C for the system Mg₄Si₄O₁₂Mg₃Al₂Si₃O₁₂, and in the pressure range 30–105 kbar and over the temperature range 1,000–1,300°C for the system Fe₄Si₄O₁₂Fe₃Al₂Si₃O₁₂. At 1,000°C, the solid solubility of enstatite (MgSiO₃) in pyrope (Mg₃Al₂Si₃O₁₂) increases gradually to 140 kbar and then increases suddenly in the pressure range 140–175 kbar, resulting in the formation of a homogeneous garnet with composition Mg₃(Al_0.8Mg_0.6Si_0.6)Si₃O₁₂. In the MgSiO₃-rich field, the three-phase assemblage of β- or γ-Mg₂SiO₄, stishovite and a garnet solid solution is stable at pressures above 175 kbar at 1,000°C. The system Fe₄Si₄O₁₂Fe₃Al₂Si₃O₁₂ shows a similar trend of high-pressure transformations: the maximum solubility of ferrosilite (FeSiO₃) in almandine (Fe₃Al₂Si₃O₁₂) forming a homogeneous garnet solid solution is 40 mol% at 93 kbar and 1,000°C.If a pyrolite mantle is assumed, from the present results, the following transformation scheme is suggested for the pyroxene-garnet assemblage in the mantle. Pyroxenes begin to react with the already present pyrope-rich garnet at depths around 150 km. Although the pyroxene-garnet transformation is spread over more than 400 km in depth, the most effective transition to a complex garnet solid solution takes place at depths between 450 and 540 km. The complex garnet solid solution is expected to be stable at depths between 540 and 590 km. At greater depths, it will decompose to a mixture of modified spinel or spinel, stishovite and garnet solid solutions with smaller amounts of a pyroxene component in solution.     

CO2 measurements on 1-cm3 ice samples with an IR laserspectrometer (IRLS) combined with a new dry extraction device

A new dry gas extraction and analysis method for small (1 cm³) ice samples is presented. The extraction device, cooled to ?20°C, contains two movable steel needle matrices for crushing the ice. During the crushing process the gas escaping from the ice sample is continuously analyzed for CO₂ with an infrared laserspectrometer. This method enables a fast measurement (few minutes) of the CO₂ concentration in the air bubbles with high spatial resolution in the ice core and a minimum potential contamination. An important CO₂ contamination source due to an interaction of water vapour with surfaces is shortly discussed.The reproducibility of extraction and analysis is ±2%. We analyzed CO₂ concentrations in the trapped air from different ice cores originating from the Greenland ice sheet and from Antarctica.     

Pyroxenes in the system Mg2Si2O6-CaMgSi2O6 at high pressure

The enstatite-diopside solvus in the system Mg₂Si₂O₆-CaMgSi₂O₆ has been experimentally determined within the pressure range 5–40 kbars and the temperature range 900–1500°C. Experiments involving reversal of the phase boundaries by unmixing from glass starting material and by reaction of pure clinoenstatite and diopside showed difficulty in achieving equilibration due to persistence of metastable, subcalcic clinopyroxene and to the sluggishness of reaction rate. The experimental data showed that the temperature dependence of the diopside limb is less than previously accepted. At 1500°C and 30 kbars subcalcic diopside found by Davis and Boyd (1966) is shown to be metastable with respect to enstatite and more calcic diopside of composition En_42.3Di_57.7. The solvus widens with increasing pressure between 5 and 40 kbars at 1200°C, but at 900°C the pressure effect on the solvus is very small. The stability relationships of the four pyroxenes, protoenstatite, enstatite, iron-free pigeonite and diopside are summarized, based on data from the literature and the present study.     

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.     

Atmospheric14C changes resulting from fossil fuel CO2 release and cosmic ray flux variability

A high-precision tree-ring record of the atmospheric¹⁴C levels between 1820 and 1954 is presented. Good agreement is obtained between measured and model calculated 19th and 20th century atmospheric Δ¹⁴C levels when both fossil fuel CO₂ release and predicted natural variations in¹⁴C production are taken into account. The best fit is obtained by using a ?-diffusion model with an oceanic eddy diffusion coefficient of 3 cm²/s, a CO₂ atmosphere-ocean gas exchange rate of 21 moles m^?2 yr^?1 and biospheric residence time of 60 years.For trees in the state of Washington the measured 1949–1951 atmospheric Δ¹⁴C level was20.0±1.2%. below the 1855–1864 level. Model calculations indicate that in 1950 industrial CO₂ emissions are responsible for at least 85% of the Δ¹⁴C decline, whereas natural variability accounts for the remaining 15%.     

Stability field of knorringite Mg3Cr2Si3O12 at high pressure and its implication to the occurrence of Cr-rich pyrope in the upper mantle

The stability field of knorringite (Mg₃Cr₂Si₃O₁₂) is studied experimentally. Knorringite is stable at pressures above 10.5 GPa at 1200°C and 11.8 GPa at 1400°C. Below these pressures, knorringite decomposes to enstatite + eskolaite. A phase diagram of the pyrope-knorringite system is described based on the available experimental data. The solubility of the knorringite molecule in pyrope is essentially dependent only on pressure, and the Cr/Cr+Al value of garnet is considered to be an indicator of the minimum pressure of equilibration. Consideration of the genesis of Cr-rich pyrope and other peridotitic inclusions in diamonds indicates that the fractionation process should have taken place, at least at depths to ca. 240 km, to give rise to the Cr-rich complement of Cr-poor upper mantle materials such as undepleted lherzolite. The knorringite-rich peridotitic suite in diamond will be identified with this complement, which may be the material constituting the deep upper mantle.     

Effects of elevated CO2 on the reproduction of two calanoid copepods

Some planktonic groups suffer negative effects from ocean acidification (OA), although copepods might be less sensitive. We investigated the effect of predicted CO₂ levels (range 480–750 ppm), on egg production and hatching success of two copepod species, Centropages typicus and Temora longicornis. In these short-term incubations there was no significant effect of high CO₂ on these parameters. Additionally a very high CO₂ treatment, (CO₂ = 9830 ppm), representative of carbon capture and storage scenarios, resulted in a reduction of egg production rate and hatching success of C. typicus, but not T. longicornis. In conclusion, reproduction of C. typicus was more sensitive to acute elevated seawater CO₂ than that of T. longicornis, but neither species was affected by exposure to CO₂ levels predicted for the year 2100. The duration and seasonal timing of exposures to high pCO₂, however, might have a significant effect on the reproduction success of calanoid copepods.     

A method for shipboard measurement of CO2 partial pressure in seawater

A dynamic method suitable for shipboard measurement of the partial pressure of CO₂ exerted by a seawater sample has been developed. The system consists of a paddle-wheel-type gas-water equilibrator and an infrared gas analyzer. Since the system is open to the atmosphere at the in-take and the exhaust ends, it can be operated stably on shipboard conditions. A precision of ±2% has been obtained for shipboard measurement of pCO₂.     

Oxygen diffusion rates in quartz exchanged with CO2

Oxygen self diffusion rates were determined in quartz samples exchanged with¹⁸O-enriched CO₂ between 745 and 900°C and various pressures, and the diffusion profiles were measured using an ion microprobe. The activation energy (Q) and preexponential factor (D₀) at P(CO₂) = P(tot) = 100 bar, for diffusion parallel to the c-axis are 159 ( ± 13) kJ/g atom and 2.10 (+0.75/ −0.55) × 10⁻⁸ cm²/s. This rate is approximately 100 times slower than that obtained from hydrothermal experiments and 100 times faster than a previous 1-bar quartz-O₂ exchange experiment. The oxygen diffusion rate measured at 0.6 bar, 888°C, and at 900°C in vacuum is in agreement with the previous 1-bar exchange experiments with¹⁸O₂. The effect of higher CO₂ pressures is small. At 900°C, the diffusion rate exchanged with CO₂ is = 2.35 × 10⁻¹⁵ cm²/s at 100 bar, 2.24 × 10⁻¹⁵ cm²/s at 3.45 kbar and 8.13 × 10⁻¹⁵ cm²/s at 7.2 kbar.There is probably a diffusing species, other than oxygen, that enhances the oxygen diffusion rate in these quartz-CO₂ systems, relative to that occurring at very low pressures or in a vacuum. The effect of this diffusing species, however, is not as strong as that associated with H₂O. Preserved oxygen isotope fractionations between coexisting minerals in a slowly cooled, high-grade metamorphic terrane will vary depending upon whether a water-rich phase was present or not. Closure temperatures will be approximately 100°C higher in rocks where no water-rich phase was present during cooling. The measured fractionations between coexisting minerals in metamorphic rocks may potentially be used as a sensor of water presence during retrogression.     

Interfacial tension measurements and wettability evaluation for geological CO2 storage

Interfacial interactions, namely interfacial tension, wettability, capillarity and interfacial mass transfer are known to govern fluid distribution and behavior in porous media. Therefore the interfacial interactions between CO₂, brine and oil and/or gas reservoirs have a significant influence on the effectiveness of any CO₂ storage operations. However, data and knowledge of interfacial properties in storage conditions are scarce. This issue becomes particularly true in the case of deep saline aquifers where limited, economically driven, data collection and archiving are available. In this paper, we present a complete set of brine–CO₂ interfacial tension data at pressure, temperature and salinity conditions, representative of a CO₂ storage operation. A semi-empirical correlation is proposed to calculate the interfacial tension from the experimental data. Wettability is studied at pore scale, using glass micromodels in order to track fluids distribution as a function of the thermodynamic properties and wettability conditions for water–CO₂ systems. With this approach, we show that, in strongly hydrophilic porous media, the CO₂ does not wet the solid surface whereas; if the porous media has less hydrophilic properties the CO₂ significantly wets the surface.