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401.
Jürgen Konzett Daniel J. Frost Alexander Proyer Peter Ulmer 《Contributions to Mineralogy and Petrology》2008,155(2):215-228
Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO2–TiO2–Al2O3–Fe2O3–FeO–MnO–MgO–CaO–Na2O–K2O–P2O5 and SiO2–TiO2–Al2O3–MgO–CaO–Na2O to investigate the Ca-Eskola (CaEs Ca0.5□0.5AlSi2O6) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO2 ± TiO2 ± kyanite as a function of P, T, and bulk composition. The results show that CaEsss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative
anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEsss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison,
no significant increase in CaEsss with increasing P could be observed. If the formation of oriented SiO2-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these
textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites
cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEsss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes
are not necessarily restricted to ultrahigh pressure metamorphic conditions.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
402.
Li-Sr-Nd isotope signatures of the plume and cratonic lithospheric mantle beneath the margin of the rifted Tanzanian craton (Labait) 总被引:3,自引:2,他引:1
Sonja Aulbach Roberta L. Rudnick William F. McDonough 《Contributions to Mineralogy and Petrology》2008,155(1):79-92
Lithium concentrations and isotopic compositions of olivine and 87Sr/86Sr and 143Nd/144Nd of coexisting clinopyroxene from peridotite xenoliths from the Quaternary Labait volcano, Tanzania, document the influence
of rift-related metasomatism on the ancient cratonic mantle. Olivines show negative correlations between Fo content and both
δ7Li and Li concentrations. Olivines in iron-rich peridotites (Fo85–87) have high Li concentrations (3.2–4.8 ppm) and heavy δ7Li (+5.2 to +6.6). In contrast, olivines in ancient, refractory peridotites have lower Li concentrations (∼2 ppm) and relatively
light δ7Li (+2.6 to +3.5). This reflects mixing between ancient, refractory cratonic lithosphere and asthenosphere-derived rift magmas.
A uniquely fertile, deformed, high-temperature garnet lherzolite, interpreted to be from the base of the lithosphere, has
a 87Sr/86Sr of 0.7029 and 143Nd/144Nd of 0.51286, similar to HIMU oceanic basalts. It provides the best estimate of the Sr–Nd isotope composition of the upwelling
mantle (i.e., plume, sensu lato) underlying this portion of the East African Rift, and is slightly less radiogenic compared
to previous estimates of the plume that were based on rift basalts. Although elevated δ7Li are not exclusive to HIMU source regions, the data collectively indicate that the plume beneath Labait has HIMU characteristics
in Sr, Nd and Li isotope composition.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
403.
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.
相似文献
F. GaidiesEmail: |
404.
G. Caro V.C. Bennett B. Bourdon T.M. Harrison A. von Quadt S.J. Mojzsis J.W. Harris 《Chemical Geology》2008,247(1-2):253-265
146Sm–142Nd and 147Sm–143Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe 207Pb/206Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?142Nd = ? 6 ± 12 ppm, ?143Nd = ? 32.5, and 147Sm/144Nd = 0.1150. These results do not confirm previous claims for a 30 ppm 142Nd excess in South African cratonic mantle. The lack of a 142Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?142Nd = 8 ± 10 ppm, ?143Nd = 45 ± 1, and 147Sm/144Nd = 0.5891. Back-calculation of this present-day ?143Nd yields an unrealistic estimate for the initial ?143Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the 147Sm–143Nd system. Examination of 146,147Sm–142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of 146Sm–142Nd systematics in Jack Hills zircons. 相似文献
405.
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
406.
Imad A.M. Ahmed Neil M.J. Crout Scott D. Young 《Geochimica et cosmochimica acta》2008,72(6):1498-1512
Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing 109Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric PCO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd2+ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R2 = 0.992). It differentiates between two ‘pools’ of sorbed Cd2+ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd2+ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R2 = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of ∼175 d, for release to a ‘zero-sink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption. 相似文献
407.
Atomistic simulations have been carried out to investigate the mechanisms of noble gas incorporation in minerals using both the traditional two-region approach and the “supercell” method. The traditional two-region approach has been used to calculate defect energies for Ne, Ar, Kr and Xe incorporation in MgO, CaO, diopside and forsterite in the static limit and at one atmosphere pressure. The possibilities of noble gas incorporation via both substitution and interstitial mechanisms are studied. The favored mechanism varies from mineral to mineral and from noble gas to noble gas. In all minerals studied, the variation of the solution energies of noble gas substitution with atomic radius appears approximately parabolic, analogous to those for 1+, 2+, 3+ and 4+ trace element incorporation on crystal lattice sites. Noble gas solution energies thus also fall on a curve, similar to those previously observed for cations with different charges, but with much lower curvature.The “supercell” method has been used to investigate the pressure dependence of noble gas incorporation in the same systems. Results indicate a large variation of the solubility of the larger noble gases, Kr and Xe with pressure. In addition, explicit simulation of incorporation at the (0 0 1) surface of MgO shows that the solubility of the heavier noble gases may be considerably enhanced by the presence of interfaces. 相似文献
408.
Olivier Rouxel Edward Sholkovitz Katrina J. Edwards 《Geochimica et cosmochimica acta》2008,72(14):3413-3430
Dissolved Fe concentrations in subterranean estuaries, like their river-seawater counterparts, are strongly controlled by non-conservative behavior during mixing of groundwater and seawater in coastal aquifers. Previous studies at a subterranean estuary of Waquoit Bay on Cape Cod, USA demonstrate extensive precipitation of groundwater-borne dissolved ferrous iron and subsequent accumulation of iron oxides onto subsurface sands. Waquoit Bay is thus an excellent natural laboratory to assess the mechanisms of Fe-isotope fractionation in redox-stratified environments and determine potential Fe-isotope signatures of groundwater sources to coastal seawater. Here, we report Fe isotope compositions of iron-coated sands and porewaters beneath the intertidal zone of Waquoit Bay. The distribution of pore water Fe shows two distinct sources of Fe: one residing in the upward rising plume of Fe-rich groundwater and the second in the salt-wedge zone of pore water. The groundwater source has high Fe(II) concentration consistent with anoxic conditions and yield δ56Fe values between 0.3 and −1.3‰. In contrast, sediment porewaters occurring in the mixing zone of the subterranean estuary have very low δ56Fe values down to −5‰. These low δ56Fe values reflect Fe-redox cycling and result from the preferential retention of heavy Fe-isotopes onto newly formed Fe-oxyhydroxides. Analysis of Fe-oxides precipitated onto subsurface sands in two cores from the subterranean estuary revealed strong δ56Fe and Fe concentration gradients over less than 2m, yielding an overall range of δ56Fe values between −2 and 1.5‰. The relationship between Fe concentration and δ56Fe of Fe-rich sands can be modeled by the progressive precipitation of Fe-oxides along fluid flow through the subterranean estuary. These results demonstrate that large-scale Fe isotope fractionation (up to 5‰) can occur in subterranean estuaries, which could lead to coastal seawater characterized by very low δ56Fe values relative to river values. 相似文献
409.
Nancy L. Chabot Andrew J. Campbell David S. Draper Munir Humayun Elizabeth Cottrell 《Geochimica et cosmochimica acta》2008,72(16):4146-4158
Earth’s core may contain C, and it has been suggested that C in the core could stabilize the formation of a solid inner core composed of Fe3C. We experimentally examined the Fe-C system at a pressure of 5 GPa and determined the Fe-C phase diagram at this pressure. In addition, we measured solid metal/liquid metal partition coefficients for 17 trace elements and examined the partitioning behavior between Fe3C and liquid metal for 14 trace elements. Solid metal/liquid metal partition coefficients are similar to those found in one atmosphere studies, indicating that the effect of pressure to 5 GPa is negligible. All measured Fe3C/liquid metal partition coefficients investigated are less than one, such that all trace elements prefer the C-rich liquid to Fe3C. Fe3C/liquid metal partition coefficients tend to decrease with decreasing atomic radii within a given period. Of particular interest, our 5 GPa Fe-C phase diagram does not show any evidence that the Fe-Fe3C eutectic composition shifts to lower C contents with increasing pressure, which is central to the previous reasoning that the inner core may be composed of Fe3C. 相似文献
410.
Thermodynamic model for arsenic speciation in sulfidic waters: A novel use of ab initio computations
Recent discoveries demonstrate that the chemistry of arsenic in sulfidic waters is much more complex that previously believed. One implication is that all earlier thermodynamic data on stabilities of As thioanions require revision. Previously used experimental approaches for determining As thioanion stabilities may be inadequate to deal with the full range of complexity. Here we use computational as well as empirical information to construct a provisional model for equilibrium As thioanion distributions in sulfidic waters. Whereas previous authors have argued for either As(III) or As(V) thioanions, the new model predicts that both are important and can occur simultaneously under commonly encountered pH and ΣS−II conditions. At the order of magnitude level, the model reasonably predicts the solubility of As2S3 in sulfidic solutions, provides tentative peak assignments for published Raman spectroscopic data and plausibly accounts for how sulfide modifies the bacterial toxicity of As. The model yields a thermodynamic justification for how sulfide, which is usually regarded as a reducing agent, can counter-intuitively drive oxidation of As(III) to As(V), as has been observed both in the laboratory and in the field. Despite its uncertain accuracy, the model serves as a useful source of new, testable hypotheses about As geochemistry and highlights crucial experimental data needs. 相似文献