An interlaboratory comparison of piston-cylinder pressure calibration using the albite-breakdown reaction

The pressure of the reaction albite=jadeite and quartz was measured at 600° C by workers in six geophysical laboratories for the purpose of comparing pressure calibration procedures for the solid-pressure piston-cylinder apparatus. All groups used the same starting mix of crystalline reactant and products and all obtained hydrothermal reversals of the equilibrium. Solid pressure media used included talc, NaCl, boron nitride, pyrophyllite, pyrex glass and crushable ceramic. Various means of calibration were used, including internal standardization by transitions in indicator substances and the piston-in, piston-out bracketing method.There was agreement among all groups—the average preferred value of 16.3 kilobars at 600° C is enclosed by all of the error brackets assigned by the various investigators. This average preferred value is lower by nearly two kilobars than the often-quoted extrapolation of Birch and LeComte's data (1960). It will be important for both petrology and high-pressure technology to test this result in a very high gas pressure apparatus.     

Stability of almandine in the system FeO-(Fe2O3)-Al2O3-SiO2-(H2O) at elevated pressures

Almandine, although decomposing in the presence of metallic iron into the anhydrous subsolidus assemblage fayalite + ferrocordierite + hercynite solid solution at low pressures, melts incongruently to hercynite_ss + quartz + liquid at 10 kb. At pressures between about 12 and 20 kb the products of incongruent melting are hercynite_ss + liquid only, and at still higher pressures almandine melts congruently. For the intermediate pressures between 2 and 10 kb not investigated a sequence of probable breakdown and melting relations involving the phases ferrocordierite, fayalite, hercynite_ss, quartz, and liquid is derived through Schreinemakers' analyses.The lower temperature stability limit of almandine in the presence of water at low oxygen fugacities and pressures of 15 to 20 kb lies between 550° and 600° C as at low pressures. It is marked, however, by the breakdown to a hydrous assemblage involving chloritoid and the new phase aluminous deerite. Since the anhydrous melting at these pressures occurs between 1300° and 1400° C, the thermal stability range of almandine increases drastically with pressure. Its upper breakdown limit shows in principle a similar behavior as those of other garnet end members.     

Electrical conductivity measurements on olivines and pyroxenes under defined thermodynamic activities as a function of temperature and pressure

Electrical conductivities of Ni₂SiO₄, Fe₂SiO₄, and MgSiO₃ were measured on synthetic powders in the temperature range 340° to 1,100° C and at pressures up to 20 kbars. For ternary compounds such as olivines and pyroxenes the control of two further variables, like the chemical activities of two components are needed, besides temperature and pressure. The activities of the corresponding binary oxides were controlled by equilibrating the samples with their neighbour-phases. Control of the oxygen partial pressure was achieved by buffer techniques. From the slopes of the lg σ vs. 1/T lines the activation energies were calculated for 10 kbar: 0.56 eV and 2.7 eV for Ni₂SiO₄ in equilibrium with SiO₂ and Ni/NiO-buffer for the temperature range 500°–800°C and 800°–1,000°C resp. 0.52 eV for Fe₂SiO₄ in equilibrium with SiO₂ and metallic iron, and 0.38 eV in equilibrium with SiO₂ and magnetite; 1.11 eV for MgSiO₃ in equilibrium with SiO₂, and 1.25 eV in equilibrium with Mg₂SiO₄.     

The effect of biodegradation on steranes and terpanes in crude oils

Steranes and terpanes biodegrade at a slower rate than isoprenoids and survive moderate biodegradation. Heavy biodegradation results in destruction of regular steranes, survival of diasteranes (20R better than 20S) and tricyclic terpanes and transformation of hopanes to Ring A/B demethylated hopanes. These survivors can be used as source fingerprints in biodegraded crudes. The structure of predominant steranes in undegraded to moderately degraded fossil fuels was proven to be 14β, 17β(H) (20R + S) by molecular spectroscopy. These compounds plus the 20S epimers of regular 5α-steranes (20R) were identified as major constituents and their 5β-counterparts as minor components in a cholestane isomerizate (300°C, Pt on C), allowing assessment of relative thermodynamic stabilities. An observed increase of optical activity in heavily degraded crudes from three different basins is interpreted to be the result of bacterial transformation of terpanes and steranes to new optically active species plus enrichment of the latter by n + isoparaffin depletion rather than total bacterial synthesis. Diagnostic ion profiling by GC-MS-C is a convenient tool for surveying the relative abundance of individual diasteranes and regular steranes plus distinguishing epimeric and ring skeletal isomeric series in complex fossil fuel mixtures. A new practical method of determining the absolute quantities of individual steranes by spiking with 5β-cholane and integration of mass chromatograms is described.     

Gene Expression Analysis for Exposure to Estrogenic Substances

Zebrafish (Danio rerio) were exposed with 17β‐estradiol (E2) and nonylphenol (NP) in different concentrations. Gene expression analysis was carried out by two different approaches. First, RT‐PCR experiments were performed for the examination of expression levels of the two marker genes vitellogenin and aromatase. This approach showed a significant increase in the expression of the vitellogenin gene in exposed male fish (500 ng/L 17β‐estradiol and 250 μg/L nonylphenol). This egg yolk protein is usually not synthesized in male vertebrates. A slight decrease of expression of the aromatase gene was observed in exposed female zebrafish. Aromatase is known to catalyze the conversion of androgens to estrogens. Second, DNA microarray experiments were carried out, which allow the simultaneous examination of the expression levels of a great number of marker genes. The microarray experiments resulted in an up‐regulation of vitellogenin up to 850‐fold. In addition, several other genes were identified to be up‐regulated by estrogens, for example the high mobility group box protein ssrp1 (78‐fold) or the chaperonin containing t‐complex polypeptide 1, beta subunit cctb (22‐fold).     

Formation of Al-rich titanite (CaTiSiO4O–CaAlSiO4OH) reaction rims on ilmenite in metamorphic rocks as a function of fH2O and fO2

Reaction rims of titanite on ilmenite are described in samples from four terranes of amphibolite-facies metapelites and amphibolites namely the Tamil Nadu area, southern India; the Val Strona area of the Ivrea-Verbano Zone, northern Italy, the Bamble Sector, southern Norway, and the northwestern Austroalpine Ötztal Complex. The titanite rims, and hence the stability of titanite (CaTiSiO₄O) and Al–OH titanite, i.e. vuaganatite (hypothetical end-member CaAlSiO₄OH), are discussed in the light of fH₂O- and fO₂-buffered equilibria involving clinopyroxene, amphibole, biotite, ilmenite, magnetite, and quartz in the systems CaO–FeO/Fe₂O₃–TiO₂–SiO₂–H₂O–O₂ (CFTSH) and CaO–FeO/Fe₂O₃–Al₂O₃–SiO₂–H₂O–O₂ (CFASH) present in each of the examples. Textural evidence suggests that titanite reaction rims on ilmenite in rocks from Tamil Nadu, Val Strona, and the Bamble Sector originated most likely due to hydration reactions such as clinopyroxene + ilmenite + quartz + H₂O = amphibole + titanite and oxidation reactions such as amphibole + ilmenite + O₂ = titanite + magnetite + quartz + H₂O during amphibolite-facies metamorphism, or, as in the case of the Ötztal Complex, during a subsequent greenschist-facies overprint. Overstepping of these reactions requires fH₂O and fO₂ to be high for titanite formation, which is also in accordance with equilibria involving Al–OH titanite. This study shows that, in addition to P, T, bulk–rock composition and composition of the coexisting fluid, fO₂ and fH₂O also play an important role in the formation of Al-bearing titanite during amphibolite- and greenschist-facies metamorphism.     

Subsolidus Phase Relations in the System MgO-SiO_2-Cr-O and Thermodynamic Properties of Related Cr~(2+)-Containing End-members

Subsolidus phase relations have been determined in the systems SiO2-Cr-O and MgO-SiO2-Cr-O in equilibrium with metallic Cr, at 1100 to 1500℃ and 0 to 2.88 GPa. The results show that there are no ternary phases in the SiO2-Cr-O system at these conditions, i.e., only the assemblage eskolaite-Cr-metal-quartz (or tridymite) is found. In the MgO-containing system, however, extensive substitution of Cr2+ for Mg is observed in (Mg, Cr2+)2SiO4 olivine, (Mg, Cr2+)2Si2O6 pyroxene, and (Mg, Cr2+)Cr2O4 spinel. Cr3+ levels in olivine and pyroxene are below detection limits. The pyroxene is orthohombic at XCrPx2+ < 0.2, monoclinic at higher XCrPx2+ . Thestructure of the spinels becomes tetragonally distorted at XCr2+Sp >0.2. The experimental datahave been fitted to a thermodynamic model, and the authors obtained the mixing parameter (W) of Mg-Cr2+ in olivine, pyroxene and spinel, and the relation between temperatures and free energies of formation for the end-members: Cr2+-olivine (Cr2SiO4), Cr2+-pyroxene (Cr2Si2O6)