Petrogenetic grid for ultrahigh-pressure metamorphism in the model system CaO-MgO-SiO2-CO2-H2O

Abstract Petrogenetic grids for ultrahigh-pressure (UHP) metamorphism were calculated at different X_co2 conditions in the model system CaO-MgO-SiO₂-CO₂-H₂O involving coesite (Co), diopside (Di), dolomite (Do), enstatite (En), forsterite (Fo), magnesite (Ms), quartz (Qz), talc (Tc), tremolite (Tr) using a published internally consistent thermodynamic data set. Two P-T grids at X_co2= 0.01 and 0.5 are described. In the calculated P-T grid at X_co2= 0.01, four out of 10 stable invariant points, Co-En-Ms-Tc, Co-Di-En-Tc-Tr, Co-Di-Ms-Tc-Tr and Di-En-Ms-Tc-Tr lie within the stability field of coesite. If the fluid phase has X_co2= 0.5, no invariant point is stable under UHP conditions. Some magnesite-bearing assemblages are stabilized by the following three reactions: Di + Ms = Do + Fo + CO₂, Ms + Tr = Do + Fo + CO₂+ H₂O and Ms + Tc = Fo+ CO₂+ H₂O at X_co2= 0.01 and by reaction Ms + Tc = Fo + CO₂+ H₂O together with these three at X_co2= 0.5. Ten possible UHP assemblages for mafic and ultramafic compositions at very low X_co2 conditions include the following: Co-Do-Ms, Co-Di-Ms, Co-Di-Tc, Di-Ms-Tc, Di-En-Tc-, Di-En-Ms, Co-Di-En, Di-En-Fo, Di-Fo-Ms, Di-Do-Fo. Among them, talc-bearing assemblages are restricted to X_co2 < 0.02 and their high-P limit is 31.7 kb (749°C) at X_co2= 0.01. Dolomite-magnesite-silica assemblages have large P-T stability fields even if X_co2 is as low as 0.1, and could occur in cold subduction zones with very low geothermal gradients. Reported UHP coesite-dolomite assemblage is restricted only to a calc-silicate rock interlayered with marble where X_co2 is relatively higher; no such assemblage appears for mafic and ultramafic rocks with low X_co2 evidenced by the occurrence of diopside (or omphacite) at the expense of dolomite + coesite. The effect of X_co2 on the stability of coesite-dolomite-magnesite, diopside-enstatite-magnesite, diopside-talc assemblages is examined and the occurrence of coesite-dolomite, magnesite-bearing and talc-bearing assemblages in the Dabie UHP rocks are interpreted by employing the calculated P-T grids.     

Elasticity of single-crystal SmAlO3, GdAlO3 and ScAlO3 perovskites

The adiabatic single-crystal elastic moduli of SmAlO₃, GdAlO₃ and ScAlO₃, all with the orthorhombic perovskite structure, have been measured by Brillouin spectroscopy under ambient conditions. These 3 compounds display various degrees of crystallographic distortion from the ideal cubic perovskite structure. We find that longitudinal moduli in directions parallel to the axes of a pseudocubic subcell are nearly equal and insensitive to distortions of the crystal structure from cubic symmetry, whereas, the moduli C₁₁ and C₂₂, parallel to the orthorhombic axes, display pronounced anisotropy with the exception of ScAlO₃. The shear moduli also correlate with distortion from cubic symmetry, as measured by rotation, or tilt angles, of the AlO₆ octahedra. Our data support the observations of Liebermann et al. that perovskite-structure compounds define consistent elasticity trends relating bulk modulus and molar volume, and sound speed and mean atomic weight. These relationships have been used to estimate bulk and shear moduli for the high-pressure polymorphs of CaSiO₃ and MgSiO₃ with the perovskite structure.     

Joint cross-well and single-well seismic studies of CO2 injection in an oil reservoir

A series of time‐lapse seismic cross‐well and single‐well experiments were conducted in a diatomite reservoir to monitor the injection of CO₂ into a hydrofracture zone, based on P‐ and S‐wave data. A high‐frequency piezo‐electric P‐wave source and an orbital‐vibrator S‐wave source were used to generate waves that were recorded by hydrophones as well as 3‐component geophones. During the first phase the set of seismic experiments was conducted after the injection of water into the hydrofractured zone. The set of seismic experiments was repeated after a time period of seven months during which CO₂ was injected into the hydrofractured zone. The questions to be answered ranged from the detectability of the geological structure in the diatomic reservoir to the detectability of CO₂ within the hydrofracture. Furthermore, it was intended to determine which experiment (cross‐well or single‐well) is best suited to resolve these features. During the pre‐injection experiment, the P‐wave velocities exhibited relatively low values between 1700 and 1900 m/s, which decreased to 1600–1800 m/s during the post‐injection phase (?5%). The analysis of the pre‐injection S‐wave data revealed slow S‐wave velocities between 600 and 800 m/s, while the post‐injection data revealed velocities between 500 and 700 m/s (?6%). These velocity estimates produced high Poisson's ratios between 0.36 and 0.46 for this highly porous (～50%) material. Differencing post‐ and pre‐injection data revealed an increase in Poisson's ratio of up to 5%. Both velocity and Poisson's ratio estimates indicate the dissolution of CO₂ in the liquid phase of the reservoir accompanied by an increase in pore pressure. The single‐well data supported the findings of the cross‐well experiments. P‐ and S‐wave velocities as well as Poisson's ratios were comparable to the estimates of the cross‐well data. The cross‐well experiment did not detect the presence of the hydrofracture but appeared to be sensitive to overall changes in the reservoir and possibly the presence of a fault. In contrast, the single‐well reflection data revealed an arrival that could indicate the presence of the hydrofracture between the source and receiver wells, while it did not detect the presence of the fault, possibly due to out‐of‐plane reflections.     

High-temperature elasticity of the fluorite-structure compounds CaF2, SrF2 and BaF2

The elastic moduli of single-crystal CaF₂, SrF₂ and BaF₂ have been determined by the ultrasonic pulse superposition technique as a function of temperature from T = 298 to T = 650°K. These new data are consistent with other data obtained by ultrasonic pulse techniques in the region of room temperature and are superior to previous high-temperature data from resonance experiments. The elastic moduli (c) are represented by quadratic functions in T over the experimental temperature range with the curvature in the same sense for all the moduli. Evaluation of the temperature derivatives of the elastic moduli at constant volume indicates that the dominant temperature effect is extrinsic for (?K_S/?T)_P and intrinsic for (?μ/?T)_P, where K_S and μ are the isotropic bulk and shear moduli, respectively. For the series CaF₂SrF₂BaF₂, |(?c/?T)_p| decreases with increasing molar volume for all moduli; however there are no theoretical or empirical grounds on which to derive a simple relationship between (?c/?T)_P and crystallographic parameters.     

Vitamin B12 and Reduced Titanium for Remediation of Residual Chlorinated Solvents: Field Experiment

A first pilot-scale field experiment using vitamin B₁₂ and reduced titanium was conducted in an in situ vertical circulation column at CFB Borden. The objective of the experiment was to test the applicability of the technology for restoring aquifer source zones contaminated by chlorinated solvents—tetrachloroethene (PCE) and 1,1,1-trichloroethane (1,1,1-TCA)—in a mixture of dense nonaqueous phase liquids (DNAPLs). Vitamin B₁₂ promotes the reductive dechlorination of chlorinated organics. A highly reducing and slightly alkaline environment must be maintained (Eh < - 480 mV and 7 < pH < 9) to maximize the rate of degradation. In this field test, PCE and 1,1,1-TCA degraded to a limited extent under experimental conditions, with 1,1,1-TCA degrading more readily. Indigenous bacteria were found to metabolize citrate, which caused titanium to precipitate, limiting degradation. The addition of glucose at the end of a second field season effectively limited citrate degradation and helped recover the optimal redox potential by keeping reduced titanium in solution. A laboratory column was used to confirm field results. The column also produced a significant biomass, which provided an additional source of organic carbon onto which the solvents sorbed.     

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.     

230Th/234U and 14C dating of a lowstand coral reef beneath the insular shelf off Irabu Island, Ryukyus, southwestern Japan

Abstract   High-resolution seismic reflection profiles delineated the distribution of mound-shaped reflections, which were interpreted as reefs, beneath the insular shelf western off Irabu Island, Ryukyus, southwestern Japan. A sediment core through one of the mounded structures was recovered from the sea floor at a depth of −118.2 m by offshore drilling and was dated by radiometric methods. The lithology and coral fauna of the core indicate that the mounded structure was composed of coral–algal boundstone suggesting a small-scaled coral reef. High-precision α-spectrometric ²³⁰Th/²³⁴U dating coupled with calibrated accelerator mass spectrometric ¹⁴C ages of corals obtained reliable ages of this reef ranging from 22.18 ± 0.63 to 30.47 ± 0.98 ka. This proves that such a submerged reef was formed during the lowstand stage of marine oxygen isotope stages 3–2. The existence of low-Mg calcite in the aragonitic coral skeleton of 22.18 ± 0.63 ka provides evidence that the reef had once been exposed by lowering of the relative sealevel to at least −126 m during the last glacial maximum in the study area. There is no room for doubt that a coral reef grew during the last glacial period on the shelf off Irabu Island of Ryukyus in the subtropical region of western Pacific.     

High-pressure disproportionation of Co2SiO4 spinel and implications for Mg2SiO4 spinel

Co₂SiO₄ spinel has been found to disproportionate into its isochemically mixed oxides with rocksalt and rutile structures at pressures between 170 and 190 kbar and temperatures between 1400 and 1800°C in a diamond-anvil press. The exact disproportionation pressure is not certain due to transient increases in pressure during the local and rapid heating by a continuous YAG laser. The slope of the phase boundary between the spinel phase and the mixed oxides is calculated to be?33 ± 20bar/deg. This negative slope is consistent with the observed anomalously large entropy of CoO (relative to its isostructural oxides) in entropy vs.(MV)^?1/2 systematics, whereM is the formula weight andV the molar volume. The sign of the slope for a phase boundary in the disproportionation of spinel depends on the values of entropy of the rocksalt oxides as well as the inverse character exhibited in the spinel phases. The normal entropy of MgO suggests that the phase boundary for the disproportionation of Mg₂SiO₄ spinel has positive slope.     

High-pressure phases of Co2GeO4, Ni2GeO4, Mn2GeO4 and MnGeO3: implications for the germanate-silicate modeling scheme and the Earth's mantle

In a diamond-anvil press coupled with YAG laser heating, the spinels of Co₂GeO₄ and Ni₂GeO₄ have been found to disproportionate into their isochemical oxide mixtures at about 250 kbar and 1400–1800°C in the same manner as their silicate analogues. At about the same P-T conditions MnGeO₃ transforms to the orthorhombic perovskite structure (space group Pbnm); the lattice parameters at room temperature and 1 bar are a₀ = 5.084 ± 0.002, b₀ = 5.214 ± 0.002, and c₀ = 7.323 ± 0.003Å with Z = 4 for the perovskite phase. The zero-pressure volume change associated with the ilmenite-perovskite phase transition in MnGeO₃ is ?6.6%. Mn₂GeO₄ disproportionates into a mixture of the perovskite phase of MnGeO₃ plus the rocksalt phase of MnO at P = 250kbar and T = 1400–1800°C. The concept of utilizing germanates as high-pressure models for silicates is valid in general. The results of this study support the previous conclusion that the lower mantle comprises predominantly the orthorhombic perovskite phase of ferromagnesian silicate.