Influence of temperature,composition, silica activity and oxygen fugacity on the H<Subscript>2</Subscript>O storage capacity of olivine at 8 GPa     

Anthony C. Withers  Marc M. Hirschmann 《Contributions to Mineralogy and Petrology》2008,156(5):595-605

Olivine crystals were grown in the presence of a hydrous silicate fluid during multi-anvil experiments at 8 GPa and 1,000–1,600°C. Experiments were conducted both in a simple system (FeO–MgO–SiO₂–H₂O) and in a more complex system containing additional elements (CaO–Na₂O–Al₂O₃–Cr₂O₃–TiO₂–FeO–MgO–SiO₂–H₂O). Silica activity was buffered by the presence of either pyroxene (high a _SiO2) or ferropericlase (low a _SiO2), and was buffered by the presence of Ni + NiO or Fe + FeO, or constrained by the presence of Fe₂O₃. Raman spectroscopy was used to identify pyroxene polymorphs in the run products. Clinoenstatite was present in the 1,000°C experiment, and enstatite in experiments at 1,400–1,520°C. The H₂O content of olivine was measured using secondary ion mass spectroscopy, and infrared spectroscopy was used to investigate the nature of hydrous defects. The H₂O storage capacity of olivine decreases with increasing temperature at 8 GPa. In contrast to previous experimental results at ≤2 GPa, no significant effect of varying oxygen fugacity is evident, but H₂O storage capacity is enhanced under conditions of low silica activity. No significant growth of low wavenumber (<3,400 cm⁻¹) peaks, generally associated with high at low pressure, was observed in the FTIR spectra of olivine from the high experiments. Our experiments show that previous high pressure H₂O storage capacity measurements for olivine synthesized under more oxidizing conditions than the Earth’s mantle are not likely to be compromised by the of the experiments. However, the considerable effect of temperature on H₂O storage capacity in olivine must be taken into account to avoid overestimation of the bulk upper mantle H₂O storage capacity.  相似文献   

Evolution of subcontinental lithospheric mantle beneath eastern China: Re–Os isotopic evidence from mantle xenoliths in Paleozoic kimberlites and Mesozoic basalts     

Hong-Fu Zhang  Steven L. Goldstein  Xin-Hua Zhou  Min Sun  Jian-Ping Zheng  Yue Cai 《Contributions to Mineralogy and Petrology》2008,155(3):271-293

The ages of subcontinental lithospheric mantle beneath the North China and South China cratons are less well-constrained than the overlying crust. We report Re–Os isotope systematics of mantle xenoliths entrained in Paleozoic kimberlites and Mesozoic basalts from eastern China. Peridotite xenoliths from the Fuxian and Mengyin Paleozoic diamondiferous kimberlites in the North China Craton give Archean Re depletion ages of 2.6–3.2 Ga and melt depletion ages of 2.9–3.4 Ga. No obvious differences in Re and Os abundances, Os isotopic ratios and model ages are observed between spinel-facies and garnet-facies peridotites from both kimberlite localities. The Re–Os isotopic data, together with the PGE concentrations, demonstrate that beneath the Archean continental crust of the eastern North China Craton, Archean lithospheric mantle of spinel- to diamond-facies existed without apparent compositional stratification during the Paleozoic. The Mesozoic and Cenozoic basalt-borne peridotite and pyroxenite xenoliths, on the other hand, show geochemical features indicating metasomatic enrichment, along with a large range of the Re–Os isotopic model ages from Proterozoic to Phanerozoic. These features indicate that lithospheric transformation or refertilization through melt-peridotite interaction could be the primary mechanism for compositional changes during the Phanerozoic, rather than delamination or thermal-mechanical erosion, despite the potential of these latter processes to play an important role for the loss of garnet-facies mantle. A fresh garnet lherzolite xenolith from the Yangtze Block has a Re depletion age of ∼1.04 Ga, much younger than overlying Archean crustal rocks but the same Re depletion ages as spinel lherzolite xenoliths from adjacent Mesozoic basalts, indicating Neoproterozoic resetting of the Re–Os system in the South China Craton.  相似文献   

THERIA_G: a software program to numerically model prograde garnet growth   总被引：6，自引：4，他引：2  

F. Gaidies  C. de Capitani  R. Abart 《Contributions to Mineralogy and Petrology》2008,155(5):657-671

We present the software program THERIA_G, which allows for numerical simulation of garnet growth in a given volume of rock along any pressure–temperature–time (P–T–t) path. THERIA_G assumes thermodynamic equilibrium between the garnet rim and the rock matrix during growth and accounts for component fractionation associated with garnet formation as well as for intracrystalline diffusion within garnet. In addition, THERIA_G keeps track of changes in the equilibrium phase relations, which occur during garnet growth along the specified P–T–t trajectory. This is accomplished by the combination of two major modules: a Gibbs free energy minimization routine is used to calculate equilibrium phase relations including the volume and composition of successive garnet growth increments as P and T and the effective bulk rock composition change. With the second module intragranular multi-component diffusion is modelled for spherical garnet geometry. THERIA_G allows to simulate the formation of an entire garnet population, the nucleation and growth history of which is specified via the garnet crystal size frequency distribution. Garnet growth simulations with THERIA_G produce compositional profiles for the garnet porphyroblasts of each size class of a population and full information on equilibrium phase assemblages for any point along the specified P–T–t trajectory. The results of garnet growth simulation can be used to infer the P–T–t path of metamorphism from the chemical zoning of garnet porphyroblasts. With a hypothetical example of garnet growth in a pelitic rock we demonstrate that it is essential for the interpretation of the chemical zoning of garnet to account for the combined effects of the thermodynamic conditions of garnet growth, the nucleation history and intracrystalline diffusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

F. GaidiesEmail:

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An experimental study of the grain-scale processes of peridotite melting: implications for major and trace element distribution during equilibrium and disequilibrium melting   总被引：1，自引：0，他引：1  

Mauro Lo Cascio  Yan Liang  Nobumichi Shimizu  Paul C. Hess 《Contributions to Mineralogy and Petrology》2008,156(1):87-102

The grain-scale processes of peridotite melting were examined at 1,340°C and 1.5 GPa using reaction couples formed by juxtaposing pre-synthesized clinopyroxenite against pre-synthesized orthopyroxenite or harzburgite in graphite and platinum-lined molybdenum capsules. Reaction between the clinopyroxene and orthopyroxene-rich aggregates produces a melt-enriched, orthopyroxene-free, olivine + clinopyroxene reactive boundary layer. Major and trace element abundance in clinopyroxene vary systematically across the reactive boundary layer with compositional trends similar to the published clinopyroxene core-to-rim compositional variations in the bulk lherzolite partial melting studies conducted at similar P–T conditions. The growth of the reactive boundary layer takes place at the expense of the orthopyroxenite or harzburgite and is consistent with grain-scale processes that involve dissolution, precipitation, reprecipitation, and diffusive exchange between the interstitial melt and surrounding crystals. An important consequence of dissolution–reprecipitation during crystal-melt interaction is the dramatic decrease in diffusive reequilibration time between coexisting minerals and melt. This effect is especially important for high charged, slow diffusing cations during peridotite melting and melt-rock reaction. Apparent clinopyroxene-melt partition coefficients for REE, Sr, Y, Ti, and Zr, measured from reprecipitated clinopyroxene and coexisting melt in the reactive boundary layer, approach their equilibrium values reported in the literature. Disequilibrium melting models based on volume diffusion in solid limited mechanism are likely to significantly underestimate the rates at which major and trace elements in residual minerals reequilibrate with their surrounding melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

Preservation of Fe isotope heterogeneities during diagenesis and metamorphism of banded iron formation     

C. D. Frost  F. von Blanckenburg  R. Schoenberg  B. R. Frost  S. M. Swapp 《Contributions to Mineralogy and Petrology》2008,155(1):135-135

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Controls on porphyroblast size along a regional metamorphic field gradient     

David M. Hirsch 《Contributions to Mineralogy and Petrology》2008,155(4):401-415

Garnet-bearing schists from the Waterville Formation of south-central Maine provide an opportunity to examine the factors governing porphyroblast size over a range of metamorphic grade. Three-dimensional sizes and locations for all garnet porphyroblasts were determined for three samples along the metamorphic field gradient spanning lowest garnet through sillimanite grade, using high-resolution X-ray computed tomography. Comparison of crystal size distributions to previous data sets obtained by stereological methods for the same samples reveals significant differences in mode, mean, and shape of the distributions. Quantitative textural analysis shows that the garnets in each rock crystallized in a diffusion-controlled nucleation and growth regime. In contrast to the typical observation of a correlation between porphyroblast size and position along a metamorphic field gradient, porphyroblast size of the lowest-grade specimen is intermediate between the high- and middle-grade specimens’ sizes. Mean porphyroblast size does not correlate with peak temperatures from garnet-biotite Fe-Mg exchange thermometry, nor is post-crystallization annealing (Ostwald Ripening) required to produce the observed textures, as was previously proposed for these rocks. Robust pseudosection calculations fail to reproduce the observed garnet core compositions for two specimens, suggesting that these calc-pelites experienced metasomatism. For each of these two specimens, Monte Carlo calculations suggest potential pre-metasomatism bulk compositions that replicate garnet core compositions. Pseudosection analyses allow the estimation of the critical temperatures for garnet growth: ∼481, ∼477, and ∼485°C for the lowest-garnet-zone, middle-garnet-zone, and sillimanite-zone specimens, respectively. Porphyroblast size appears to be determined in this case by a combination of the heating rate during garnet crystallization, the critical temperature for the garnet-forming reaction and the kinetics of nucleation. Numerical simulations of thermally accelerated, diffusion-controlled nucleation, and growth for the three samples closely match measured crystal size distributions. These observations and simulations suggest that previous hypotheses linking the garnet size primarily to the temperature at the onset of porphyroblast nucleation can only partially explain the observed textures. Also important in determining porphyroblast size are the heating rate and the distribution of favorable nucleation sites.  相似文献   

Evidence for crustal degassing of CF₄ and SF₆ in Mojave Desert groundwaters     

Daniel A. Deeds  Martin K. Vollmer  Justin T. Kulongoski  Benjamin R. Miller 《Geochimica et cosmochimica acta》2008,72(4):999-1013

Dissolved tetrafluoromethane (CF₄) and sulfur hexafluoride (SF₆) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF₄ and SF₆ are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF₄ from the lithosphere. A gradual basin-wide enhancement in dissolved CF₄ and SF₆ concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF₄ and SF₆ concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF₄, but not of SF₆, is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF₄ and SF₆ into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF₄ and SF₆.  相似文献   

Calcium isotope (δCa) fractionation along hydrothermal pathways, Logatchev field (Mid-Atlantic Ridge, 14°45′N)     

Marghaleray Amini  Anton Eisenhauer  Florian Böhm  Wolfgang Bach  Martin Rosner  Barbara Bock  Folkmar Hauff 《Geochimica et cosmochimica acta》2008,72(16):4107-4122

We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45′N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]_SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]_HydEnd) and thereby adopts a δ^44/40Ca_HydEnd of −0.95 ± 0.07‰ relative to seawater (SW) and a ⁸⁷Sr/⁸⁶Sr isotope ratio of 0.7034(4). We demonstrate that δ^44/40Ca_HydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a δ^44/40Ca of −1.17 ± 0.04‰ (SW) for the host-rocks in the reaction zone and −1.45 ± 0.05‰ (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed δ^44/40Ca for Bulk Earth of −0.92 ± 0.18‰ (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about Δ^44/40Ca = −0.5‰ relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average δ^44/40Ca of −1.54 ± 0.08‰ (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.  相似文献   

The composition and crystallinity of the near-surface regions of weathered alkali feldspars     

Martin R. Lee  Mark E. Hodson  Maureen MacKenzie  Caroline L. Smith 《Geochimica et cosmochimica acta》2008,72(20):4962-4975

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.  相似文献   

The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2   总被引：2，自引：1，他引：1  

Josep M. Soler  Marco Boi  Jos Luis Mogolln  Jordi Cama  Carlos Ayora  Peter S. Nico  Nobumichi Tamura  Martin Kunz 《Applied Geochemistry》2008,23(12):3579-3588

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.  相似文献