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   

The effect of As, Co, and Ni impurities on pyrite oxidation kinetics: Batch and flow-through reactor experiments with synthetic pyrite     

Stephen Lehner 《Geochimica et cosmochimica acta》2008,72(7):1788-1800

Pyrite samples synthesized with As, Co, or Ni impurities and without added impurities were oxidized in batch and mixed flow-through reactors in the presence of 1 mM ferric iron, at pH 2. Six samples from each dopant population were used to provide a statistically robust comparison; two natural samples from Leadville, CO (major impurities Pb, As, Bi, Ag, Zn) and Elba, Italy (Co, As) were also included. In each experiment, three reaction progress variables were monitored: ferric iron, ferrous iron, and sulfate. The pyrite samples with impurities have average oxidation rates that are faster than the undoped samples, with As- and Co-doped pyrite having the highest rates. As, Co, and Ni were released to solution in accordance with their concentrations in the solid samples. As concentrations in the batch reactor experiments tended to remain constant, in contrast to Co and Ni, which increased over time. Initial rates, calculated from the batch reactor experiments, were faster than the steady-state rates calculated from the mixed flow-through reactor experiments. Apparent rates calculated using sulfate were faster than apparent rates calculated using ferric and ferrous iron, reflecting oxidation of ferrous iron in solution by dissolved oxygen. The results imply that impurities in pyrite do contribute to its reactivity, in agreement with studies using electrochemical methods. Oxidation rate differences among pyrite samples with different impurities are probably too small to warrant explicit consideration in environmental modeling applications, but are important to understanding pyrite oxidation mechanisms and semiconducting properties.  相似文献   

Sequence stratigraphy and inferred relative sea-level change from the onshore British Jurassic     

Stephen P. Hesselbo 《Proceedings of the Geologists' Association. Geologists' Association》2008,119(1):19-34

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The occurrence and geochemistry of arsenic in groundwaters of the Newark basin of Pennsylvania     

Stephen C. Peters  Lori Burkert 《Applied Geochemistry》2008

Elevated As concentrations in groundwater in the eastern United States have been recognized predominantly in the accretionary geologic terranes of northern New England. A retrospective examination of more than 18,000 existing groundwater samples from the Pennsylvania Department of Environmental Protection (PA DEP) Drinking Water and Sampling Information System database indicates that elevated groundwater As concentrations occur throughout the northern half of the Piedmont Province of Pennsylvania. Chemical analyses of 53 samples collected in 2005 from drinking water wells in this area all had detectable As, and 23% of these samples contained elevated (>133 nmol/L or >10 μg/L) concentrations of As. Elevated concentrations of As in the groundwater samples were most common in the Mesozoic sedimentary strata composed of sandstone and red mudstone with interbedded gray shale, and gray to black siltstone and shale. Arsenic was typically not elevated in groundwater of diabase intrusions of the Newark Basin or in crystalline and calcareous aquifers to the north of the Newark Basin. Geochemical parameters such as pH and oxidation–reduction potential can indicate mobility mechanisms of As in some regions. In this area, measured groundwater conditions were predominantly oxidizing (Eh > +50 mV), and more than 85% of samples contained arsenate as the dominant As species. Variations in pH were strongly correlated to the As concentration, with highest As concentrations observed at pH values greater than 6.4. The original source of As is most likely the black and gray shales that contain some arsenian pyrite with groundwater concentrations likely to be controlled by adsorption/desorption reactions with Fe oxides in the red mudstone aquifer materials.  相似文献   

Quantitative sinkhole hazard assessment. A case study from the Ebro Valley evaporite alluvial karst (NE Spain)     

Francisco Gutiérrez  Jesús Guerrero  Pedro Lucha 《Natural Hazards》2008,45(2):211-233

Quantitative sinkhole hazard assessments in karst areas allow calculation of the potential sinkhole risk and the performance of cost-benefit analyses. These estimations are of practical interest for planning, engineering, and insurance purposes. The sinkhole hazard assessments should include two components: the probability of occurrence of sinkholes (sinkholes/km² year) and the severity of the sinkholes, which mainly refers to the subsidence mechanisms (progressive passive bending or catastrophic collapse) and the size of the sinkholes at the time of formation; a critical engineering design parameter. This requires the compilation of an exhaustive database on recent sinkholes, including information on the: (1) location, (2) chronology (precise date or age range), (3) size, and (4) subsidence mechanisms and rate. This work presents a hazard assessment from an alluvial evaporite karst area (0.81 km²) located in the periphery of the city of Zaragoza (Ebro River valley, NE Spain). Five sinkholes and four locations with features attributable to karstic subsidence where identified in an initial investigation phase providing a preliminary probability of occurrence of 0.14 sinkholes/km² year (11.34% in annual probability). A trenching program conducted in a subsequent investigation phase allowed us to rule out the four probable sinkholes, reducing the probability of occurrence to 0.079 sinkholes/km² year (6.4% in annual probability). The information on the severity indicates that collapse sinkholes 10–15 m in diameter may occur in the area. A detailed study of the deposits and deformational structures exposed by trenching in one of the sinkholes allowed us to infer a modern collapse sinkhole approximately 12 m in diameter and with a vertical throw of 8 m. This collapse structure is superimposed on a subsidence sinkhole around 80 m across that records at least 1.7 m of synsedimentary subsidence. Trenching, in combination with dating techniques, is proposed as a useful methodology to elucidate the origin of depressions with uncertain diagnosis and to gather practical information with predictive utility about particular sinkholes in alluvial karst settings: precise location, subsidence mechanisms and magnitude, and timing and rate of the subsidence episodes.  相似文献