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1.
Diffusion profiles in minerals are increasingly used to determine the duration of geological events. For this purpose, the
distinction between growth and diffusion zoning is critical; it requires the understanding of complex features associated
with multicomponent diffusion. Seed-overgrowth interdiffusion experiments carried out in the range 1,050–1,250°C at 1.3 GPa
have been designed to quantify and better understand Fe–Mg–Ca interdiffusion in garnet. Some of the diffusion profiles measured
by analytical transmission electron microscope show characteristic features of multicomponent diffusion such as uphill diffusion,
chemical solitary waves, zero-flux planes and complex diffusion paths. We implemented three different methods to calculate
the interdiffusion coefficients of the D matrix from the experimental penetration curves and determined that with Ca as the dependent component, the crossed coefficients
of the D matrix are negative. Experiments and numerical simulations indicate that: (1) uphill diffusion in garnet can be observed
indifferently on the three components Fe, Mg and Ca, (2) it takes the form of complementary depletion/repletion waves and
(3) chemical waves occur preferentially on initially flat concentration profiles. Derived D matrices are used to simulate the fate of chemical waves in time, in finite crystals. These examples show that the flow of
atoms in multicomponent systems is not necessarily unidirectional for all components; it can change both in space along the
diffusion profile and in time. Moving zero-flux planes in finite crystals are transitory features that allow flux reversals
of atoms in the diffusion zone. Interdiffusion coefficients of the D matrices are also analyzed in terms of eigenvalues and eigenvectors. This analysis and the experimental results show that
depending on the composition of the diffusion couple, (1) the shape of chemical waves and diffusion paths changes; (2) the
width of the diffusion zone for each component may or may not be identical; and (3) the width of diffusion calculated at a
given D and duration may greatly vary. D matrices were retrieved from thirteen sets of diffusion profiles. Data were cast in Arrhenius relations. Linear regressions
of the data yield activation energies equal to 368, 148, 394, 152 kJ mol−1 at 1 bar and frequency factors Do equal to 2.37 × 10−6, −4.46 × 10−16, −1.31 × 10−5, 9.85 × 10−15 m2 s−1 for [(D)\tilde]FeFeCa \tilde{D}_{FeFe}^{Ca} , [(D)\tilde]FeMgCa \tilde{D}_{FeMg}^{Ca} , [(D)\tilde]MgFeCa \tilde{D}_{MgFe}^{Ca} , [(D)\tilde]MgMgCa \tilde{D}_{MgMg}^{Ca} , respectively. These values can be used to calculate interdiffusion coefficients in Fe–Mg–Ca garnets and determine the duration
of geological events in high temperature metamorphic or magmatic garnets. 相似文献
2.
Diffusion of dissolved SiO2 in H2O at 1 GPa, with implications for mass transport in the crust and upper mantle 总被引:4,自引:0,他引:4
Cation diffusion rates at 690 ± 30 °C have been calculated by inverse modelling of observed manganese (Mn) zonation profiles
in 40 garnets from two kyanite-bearing metapelite samples from the High Himalayan Crystalline Series, Zanskar, northwest India.
Knowledge of the initial growth profile of Mn in garnet is a pre-requisite for this technique. Following previous workers
we model Mn partitioning into growing garnet in terms of a Rayleigh fractionation process, and demonstrate that the Mngarnet:whole rock partition coefficient is 60–100. Three-dimensional zonation profiles were obtained by successively grinding and polishing
∼1 cm slabs of each sample at 0.1–0.2 mm intervals and analysing the garnets at each stage, thus ensuring that core sections
were measured. The diffusion model assumes that garnet has a spherical geometry and behaves as a closed system, and simulates
diffusive modification of the hypothetical Mn Rayleigh growth profile for each garnet. The derived measure of the time-integrated
diffusion history for each garnet is then combined with radiometric and field-relation constraints for the duration of the
Himalayan metamorphic event to calculate cation diffusion rates. The average cation interdiffusion rate calculated for garnets
in the two samples examined is (6 ± 3.2) × 10−23 m2s−1. This interdiffusion rate pertains to a temperature of 690 ± 30 °C, which is 0.97 × T
PEAK, the peak temperature conditions experienced by the samples estimated using standard thermobarometric techniques. Garnet
compositions are Py2–17Alm65–77Gro6–16Sp1–17. These new diffusion data are consistent with, and more precise than, existing high-temperature (>1000 °C) experimentally
determined diffusion data, although some uncertainties remain difficult to constrain. Qualitative comparison between diffusively
modified Mn growth profiles in garnets from the Scottish Dalradian and the Himalayan garnets suggests that the duration of
metamorphism affecting the Dalradian garnets was 10–20 times longer than that endured by the Himalayan garnets.
Received: 5 June 1996 / Accepted: 29 January 1997 相似文献
3.
Sascha André Borinski Ulrich Hoppe Sumit Chakraborty Jibamitra Ganguly Santanu Kumar Bhowmik 《Contributions to Mineralogy and Petrology》2012,164(4):571-586
We have carried out a combined theoretical and experimental study of multicomponent diffusion in garnets to address some unresolved issues and to better constrain the diffusion behavior of Fe and Mg in almandine–pyrope-rich garnets. We have (1) improved the convolution correction of concentration profiles measured using electron microprobes, (2) studied the effect of thermodynamic non-ideality on diffusion and (3) explored the use of a mathematical error minimization routine (the Nelder-Mead downhill simplex method) compared to the visual fitting of concentration profiles used in earlier studies. We conclude that incorporation of thermodynamic non-ideality alters the shapes of calculated profiles, resulting in better fits to measured shapes, but retrieved diffusion coefficients do not differ from those retrieved using ideal models by more than a factor of 1.2 for most natural garnet compositions. Diffusion coefficients retrieved using the two kinds of models differ only significantly for some unusual Mg–Mn–Ca-rich garnets. We found that when one of the diffusion coefficients becomes much faster or slower than the rest, or when the diffusion couple has a composition that is dominated by one component (>75 %), then profile shapes become insensitive to one or more tracer diffusion coefficients. Visual fitting and numerical fitting using the Nelder-Mead algorithm give identical results for idealized profile shapes, but for data with strong analytical noise or asymmetric profile shapes, visual fitting returns values closer to the known inputs. Finally, we have carried out four additional diffusion couple experiments (25–35 kbar, 1,260–1,400 °C) in a piston-cylinder apparatus using natural pyrope- and almandine-rich garnets. We have combined our results with a reanalysis of the profiles from Ganguly et al. (1998) using the tools developed in this work to obtain the following Arrhenius parameters in D = D 0 exp{–[Q 1bar + (P–1)ΔV +]/RT} for D Mg* and D Fe*: Mg: Q 1bar = 228.3 ± 20.3 kJ/mol, D 0 = 2.72 (±4.52) × 10−10 m2/s, Fe: Q 1bar = 226.9 ± 18.6 kJ/mol, D 0 = 1.64 (±2.54) × 10−10 m2/s. ΔV + values were assumed to be the same as those obtained by Chakraborty and Ganguly (1992). 相似文献
4.
A. L. Perchuk M. Burchard H.-P. Schertl W. V. Maresch T. V. Gerya H.-J. Bernhardt O. Vidal 《Contributions to Mineralogy and Petrology》2009,157(5):573-592
We demonstrate the possibility of studying several diffusion couples in a single run, i.e. under almost similar P–T–t– conditions, allowing direct comparison of the diffusion rates in different diffusion couples. Thus the duration of experimental
study and the risk of failure of expensive experimental equipment can be decreased considerably. The diffusion experiments
were carried out in piston-cylinder apparatus. Gem-quality garnets of almandine, spessartine and grossular compositions together
with inclusion-rich eclogitic garnets were embedded in a powder of natural pyrope and annealed together under dry conditions
at P = 1.9–3.2 GPa and T = 1,070–1,400°C. Diffusion profiles were measured by electron microprobe and fitted numerically on the basis of multicomponent
diffusion theory. The datasets derived from different diffusion couples yields parameters of the Arrhenius equation for Ca,
Mg and Fe in natural eclogitic garnets and Mg, Mn and Fe in gem-quality garnets. We have also studied the effect of grain-boundary
diffusion in the sintered pyrope matrix on interdiffusion on the basis of 2D modeling. Under conditions analogous to those
of our experimental runs, we show that observed irregularities in some measured diffusion profiles (not applied for the diffusion
modeling) can be directly related to the superposition of local grain-boundary diffusion on dominant volume diffusion. 相似文献
5.
Sylvie Demouchy Stephen J. Mackwell David L. Kohlstedt 《Contributions to Mineralogy and Petrology》2007,154(3):279-289
Interdiffusion of Fe and Mg in (Mg,Fe)O has been investigated experimentally under hydrous conditions. Single crystals of
MgO in contact with (Mg0.73Fe0.27)O were annealed hydrothermally at 300 MPa between 1,000 and 1,250°C and using a Ni–NiO buffer. After electron microprobe
analyses, the dependence of the interdiffusivity on Fe concentration was determined using a Boltzmann–Matano analysis. For
a water fugacity of ∼300 MPa, the Fe–Mg interdiffusion coefficient in Fe
x
Mg1−x
O with 0.01 ≤ x ≤ 0.25 can be described by with and C = −80 ± 10 kJ mol−1. For x = 0.1 and at 1,000°C, Fe–Mg interdiffusion is a factor of ∼4 faster under hydrous than under anhydrous conditions. This enhanced
rate of interdiffusion is attributed to an increased concentration of metal vacancies resulting from the incorporation of
hydrogen. Such water-induced enhancement of kinetics may have important implications for the rheological properties of the
lower mantle.
相似文献
Sylvie DemouchyEmail: |
6.
Ca-(Fe,Mg) interdiffusion experiments between natural single crystals of grossular (Ca2.74Mg0.15 Fe0.23Al1.76Cr0.04Si3.05O12) and almandine (Ca0.21Mg0.40 Fe2.23Mn0.13Al2.00Cr0.08Si2.99O12 or Ca0.43Mg0.36Fe2.11 Al1.95Si3.04O12), were undertaken at 900–1100 °C and 30 kbar, and pressures of 15.0–32.5 kbar at 1000 °C. Samples were buffered by Fe/FeO
in most cases. Diffusion profiles were determined by electron microprobe. Across the experimental couples the interdiffusion
coefficients (D˜) were almost independent of composition. The diffusion rates in an unbuffered sample were significantly faster than in buffered
samples. The temperature dependence of the D˜ (Ca-Fe,Mg) interdiffusion coefficients may be described by
at 30 kbar and 900–1100 °C. This activation energy is marginally higher than previous experimental studies involving Ca-free
garnets; the interdiffusion coefficients are higher than previous studies for Fe-Mg and Fe-Mn exchange in garnet. The pressure
dependence of D˜ (Ca-Fe,Mg) at 1000 °C yielded an activation volume of 11.2 cm3 mol−1, which is higher than previous results from studies involving garnet and olivine. Comparison with simulation studies suggests
a vacancy mechanism for divalent ion migration in garnet, with extrinsic processes being dominant up to very high temperatures.
Received: 15 December 1996 / Accepted: 3 November 1998 相似文献
7.
Xiaoyu Zhang Jibamitra Ganguly Motoo Ito 《Contributions to Mineralogy and Petrology》2010,159(2):175-186
We have experimentally determined the tracer diffusion coefficients (D*) of 44Ca and 26Mg in a natural diopside (~Di96) as function of crystallographic direction and temperature in the range of 950–1,150 °C at 1 bar and f(O2) corresponding to those of the WI buffer. The experimental data parallel to the a*, b, and c crystallographic directions show significant diffusion anisotropy in the a–c and b–c planes, with the fastest diffusion being parallel to the c axis. With the exception of logD*(26Mg) parallel to the a* axis, the experimental data conform to the empirical diffusion “compensation relation”, converging to logD ~ −19.3 m2/s and T ~ 1,155 °C. Our data do not show any change of diffusion mechanism within the temperature range of the experiments. Assuming
that D* varies roughly linearly as a function of angle with respect to the c axis in the a–c plane, at least within a limited domain of ~20° from the c-axis, our data do not suggest any significant difference between D*(//c) and D*(⊥(001)), the latter being the diffusion data required to model compositional zoning in the (001) augite exsolution lamellae
in natural clinopyroxenes. Since the thermodynamic mixing property of Ca and Mg is highly nonideal, calculation of chemical
diffusion coefficient of Ca and Mg must take into account the effect of thermodynamic factor (TF) on diffusion coefficient.
We calculate the dependence of the TF and the chemical interdiffusion coefficient, D(Ca–Mg), on composition in the diopside–clinoenstatite mixture, using the available data on mixing property in this binary
system. Our D*(Ca) values parallel to the c axis are about 1–1.5 log units larger than those Dimanov et al. (1996). Incorporating the effect of TF, the D(Ca–Mg) values calculated from our data at 1,100–1,200 °C is ~0.6–0.7 log unit greater than the experimental quasibinary D((Ca–Mg + Fe)) data of Fujino et al. (1990) at 1 bar, and ~0.6 log unit smaller than that of Brady and McCallister (1983) at 25 kb, 1,150 °C, if our data are normalized to 25 kb using activation volume (~4 and ~6 cm3/mol for Mg and Ca diffusion, respectively) calculated from theoretical considerations. 相似文献
8.
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: |
9.
Hydroxyl defects in garnets from mantle xenoliths in kimberlites of the Siberian platform 总被引:12,自引:0,他引:12
A suite of more than 200 garnet single crystals, extracted from 150 xenoliths, covering the whole range of types of garnet
parageneses in mantle xenoliths so far known from kimberlites of the Siberian platform and collected from nearly all the kimberlite
pipes known in that tectonic unit, as well as some garnets found as inclusions in diamonds and olivine megacrysts from such
kimberlites, were studied by means of electron microprobe analysis and single-crystal IR absorption spectroscopy in the v
OH vibrational range in search of the occurrence, energy and intensity of the v
OH bands of hydroxyl defects in such garnets and its potential use in an elucidation of the nature of the fluid phase in the
mantle beneath the Siberian platform. The v
OH single-crystal spectra show either one or a combination of two or more of the following major v
OH bands, I 3645–3662 cm−1, II 3561–3583 cm−1, III 3515–3527 cm−1, and minor bands, Ia 3623–3631 cm−1, IIa 3593–3607 cm−1. The type of combination of such bands in the spectrum of a specific garnet depends on the type of the rock series of the
host xenolith, Mg, Mg-Ca, Ca, Mg-Fe, or alkremite, on the xenolith type as well as on the chemical composition of the respective
garnet. Nearly all garnets contain band systems I and II. Band system III occurs in Ti-rich garnets, with wt% TiO2 > ca. 0.4, from xenoliths of the Mg-Ca and Mg-Fe series, only. The v
OH spectra do not correspond to those of OH− defects in synthetic pyropes or natural ultra-high pressure garnets from diamondiferous metamorphics. There were no indications
of v
OH from inclusions of other minerals within the selected 60 × 60 μm measuring areas in the garnets. The v
OH spectra of pyrope-knorringite- and pyrope-knorringite-uvarovite-rich garnets included in diamonds do not show band systems
I to III. Instead, they exhibit one weak, broad band (Δv
OH 200–460 cm−1) near 3570 cm−1, a result that was also obtained on pyrope-knorringite-rich garnets extracted from two olivine megacrysts. The quantitative
evaluation, on the basis of relevant existing calibrational data (Bell et al. 1995), of the sum of integral intensities of
all v
OH bonds of the garnets studied yielded a wide range of “water” concentrations within the set of the different garnets, between
values below the detection limit of our single-crystal IR method, near 2 × 10−4 wt%, up to 163 × 10−4 wt%. The “water” contents vary in a complex manner in garnets from different xenolith types, obviously depending on a large
number of constraints, inherent in the crystal chemistry as well as the formation conditions of the garnets during the crystallization
of their mantle host rocks. Secondary alteration effects during uplift of the kimberlite, play, if any, only a minor role.
Despite the very complex pattern of the “water” contents of the garnets, preventing an evaluation of a straightforward correlation
between “water” contents of the garnets and the composition of the mantle's fluid phase during garnet formation, at least
two general conclusions could be drawn: (1) the wide variation of “water” contents in garnets is not indicative of regional
or local differences in the composition of the mantle's fluid phase; (2) garnets formed in the high-pressure/high-temperature
diamond-pyrope facies invariably contain significantly lower amounts of “water” than garnets formed under the conditions of
the graphite-pyrope facies. This latter result (2) may point to significantly lower f
H2O and f
O2 in the former as compared to the latter facies.
Received: 25 November 1997 / Accepted: 9 March 1998 相似文献
10.
A history of decompression and metasomatism is preserved in a suite of highly chromian, garnet-rich peridotitic xenoliths from the diamondiferous Newlands and Bobbejaan kimberlites, South Africa. A high proportion of the garnets and chromites in these rocks plot in the diamond-facies fields on Cr2O3–CaO and Cr2O3–MgO wt% plots, and Cr-rich compositions are found in both the harzburgitic and lherzolitic fields. Petrographic evidence suggests that the earliest known mineralogies were those of olivine-bearing, garnet-rich rocks. These were modified by a decompression event that caused recrystallization of garnets and led to orientated spinel and pyroxene inclusions in garnet. Chemical zonation within garnet is divided into (1) external re-equilibration between garnet and matrix; (2) internal re-equilibration between garnet and its inclusions; and (3) metasomatically induced zoning between garnet core and a metasomatic rim. The compositional trajectories associated with zonations (1) and (2) in Ca–Cr plots may be closely modelled by means of sliding, garnet–spinel transition reactions whose slopes vary with bulk Ca composition; at intermediate Ca compositions, the trajectories closely match the slope of the lherzolite line or harzburgite/lherzolite boundary. The decreasing Cr/(Cr + Al) of the garnet in these zonations is in agreement with the evidence for decompression given by the petrographic recrystallization features, and overall decompression of probably 10–20 kb is indicated. We speculate on the age of these events, and consider the possibility of their association with major orogenic events documented by South African crustal rocks at 2.9–2.7 Ga, and events evidenced by peridotite-xenolith Re–Os model ages at 2.8–2.7 Ga. 相似文献
11.
12.
Influence of hydrogeochemical processes on temporal changes in groundwater quality in a part of Nalgonda district, Andhra Pradesh, India 总被引:4,自引:3,他引:1
Geochemical processes that take place in the aquifer have played a major role in spatial and temporal variations of groundwater
quality. This study was carried out with an objective of identifying the hydrogeochemical processes that controls the groundwater
quality in a weathered hard rock aquifer in a part of Nalgonda district, Andhra Pradesh, India. Groundwater samples were collected
from 45 wells once every 2 months from March 2008 to September 2009. Chemical parameters of groundwater such as groundwater
level, EC and pH were measured insitu. The major ion concentrations such as Ca2+, Mg2+, Na+, K+, Cl−, and SO4
2− were analyzed using ion chromatograph. CO3
− and HCO3
− concentration was determined by acid–base titration. The abundance of major cation concentration in groundwater is as Na+ > Ca2+ > Mg2+ > K+ while that of anions is HCO3
− > SO4
2− > Cl− > CO3
−. Ca–HCO3, Na–Cl, Ca–Na–HCO3 and Ca–Mg–Cl are the dominant groundwater types in this area. Relation between temporal variation in groundwater level and
saturation index of minerals reveals the evaporation process. The ion-exchange process controls the concentration of ions
such as calcium, magnesium and sodium. The ionic ratio of Ca/Mg explains the contribution of calcite and dolomite to groundwater.
In general, the geochemical processes and temporal variation of groundwater in this area are influenced by evaporation processes,
ion exchange and dissolution of minerals. 相似文献
13.
Alexej N. Platonov Klaus Langer Stanislav S. Matsyuk 《Physics and Chemistry of Minerals》2008,35(6):331-337
In the course of a thorough study of the influences of the second coordination sphere on the crystal field parameters of the
3d
N
-ions and the character of 3d
N
–O bonds in oxygen based minerals, 19 natural Cr3+-bearing (Mg,Ca)-garnets from upper mantle rocks were analysed and studied by electronic absorption spectroscopy, EAS. The
garnets had compositions with populations of the [8]
X-sites by 0.881 ± 0.053 (Ca + Mg) and changing Ca-fractions in the range 0.020 ≤ w
Ca[8] ≤ 0.745, while the [6]
Y-site fraction was constant with x
Cr3+
[6] = 0.335 ± 0.023. The garnets had colours from deeply violet-red for low Ca-contents (up to x
Ca = 0.28), grey with 0.28 ≤ x
Ca ≤ 0.4 and green with 0.4 ≤ x
Ca. The crystal field parameter of octahedral Cr3+ 10Dq decreases strongly on increasing Ca-fraction from 17,850 cm−1 at x
Ca[8] = 0.020 to 16,580 cm−1 at x
Ca[8] = 0.745. The data could be fit with two model which do statistically not differ: (1) two linear functions with a discontinuity
close to x
Ca[8] ≈ 0.3,
(2) one continuous second order function,
The behaviour of the crystal field parameter 10Dq and band widths on changing Ca-contents favour the first model, which is
interpreted tentatively by different influences of Ca in the structure above and below x
Ca[8] ≈ 0.3. The covalency of the Cr–O bond as reflected in the behaviour of the nephelauxetic ratio
decreases on increasing Ca-contents. 相似文献
14.
Quantifying the tectono-metamorphic evolution of pelitic rocks from a wide range of tectonic settings: mineral compositions in equilibrium 总被引:1,自引:0,他引:1
Commonly used thermometer and barometer calibrations are sensitive to mineral assemblage and, thus, bulk-rock composition.
Calculated mineral stabilities for an average pelitic rock over a pressure–temperature (PT) range appropriate for normal, thickened, heated and shallowly subducted continental crust (400–900°C at 0.1–3.0 GPa) reveal
more than one hundred possible assemblages. Individual phase compositions are dependent on the assemblage in which they belong
and combining isopleth sets to represent and reveals several PT-ranges where commonly used mineral thermobarometers are less effective. For example, the garnet-biotite thermometer becomes
increasingly P dependent in the absence of muscovite in high T melt-bearing assemblages, and biotite and plagioclase are not stable at pressures appropriate for lower thickened continental
crust. Compositional thermobarometers involving equilibration between alternative phases (namely garnet, phengite and omphacite)
are presented. Although the equilibrium compositions of phases at any P and T may change significantly as a function of bulk-rock composition, compositional-ratio thermobarometers are typically insensitive
to this, unless a pseudo-univariant reaction is crossed and the buffering assemblage is altered. Quantification of the limits
of efficacy of various thermobarometers allows the mineralogy of metapelites to be used to precisely determine segments of
PT paths and infer their likely tectonic controls.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.
相似文献
Mark J. CaddickEmail: |
15.
Tracer diffusion coefficients of Mg in natural aluminosilicate garnets of composition Alm38Pyr50Gr10Sp2 and Alm73Pyr21Gr5Sp1 have been measured at 1 bar, 750-850° C and at 8.5 GPa, 1300° C by chemically depositing a salt layer enriched in 26Mg on the specially prepared surface of a garnet single crystal. Diffusion anneals at 1 atmosphere (101325 Pa) were carried
out at a controlled f
O
2 of ∼10−17.5 bars maintained by a flowing gas mix of CO-CO2. Annealing conditions were carefully chosen to avoid decomposition of garnet by redox reactions. High pressure anneals were
carried out in a multianvil apparatus. Induced diffusion profiles (0.1–0.6 μm) were measured by an ion-microprobe with SIMS
attachment. Diffusion coefficients at 1 atmosphere are in excellent agreement with extrapolation of data from high P-T experiments (Loomis et al. 1985; Chakraborty and Ganguly 1992) and also with the low temperature (750–900° C) dataset of
Cygan and Lasaga (1985) if the diffusion coefficients are assumed to be proportional to f
O
2
1/6. Such an f
O
2 dependence, however, makes this dataset inconsistent with the recent dataset of Schwandt et al. (1995) on garnets of composition
(Alm15Pyr72Gr13Sp0) unless a strong compositional dependence of Mg tracer diffusivity for Mg-rich garnets is invoked. The present experimental
results show that such a compositional dependence is weak to non-existent for garnets with >38 mole percent almandine component.
It is emphasized that the temperature dependence of diffusion coefficients at constant oxygen fugacities (activation energy
≈54 kcal/mol) are different from that along an oxygen fugacity buffer (activation energy ≈64.5 kcal/mol), as already pointed
out by Chakraborty and Ganguly (1991). This distinction is of importance for modelling natural processes. The measurements
at low temperatures either eliminate the need for, or greatly reduce the uncertainty of, extrapolation of laboratory data
for modelling metamorphic processes. The high pressure results combined with those from Chakraborty and Ganguly (1992) and
Loomis et al. (1985) indicate that pressure dependence of Mg tracer diffusivity in garnets is much stronger than that in forsterite
(Chakraborty et al. 1994). This difference in pressure dependence of diffusivity may be caused by the difference in compressibility
of the coordination polyhedra of Mg between olivines and garnets. Activation volumes of Mg tracer diffusion as high as 8 cm3/mol may be estimated using the present data in combination with earlier results. These data suggest that at a temperature
of 1300° C, Mg tracer diffusion rates in garnets will decrease by an order of magnitude for every 100 km depth. The pressure
effect will be stronger at lower temperatures. For calculations involving diffusion coefficients of garnets at high pressures
(e.g. mantle xenoliths, eclogites) the pressure dependence of diffusivity must be taken into account.
Received: 21 December 1994 / Accepted: 22 September 1995 相似文献
16.
Hugues Raimbourg Bruno Goffé Laurent Jolivet 《Contributions to Mineralogy and Petrology》2007,153(1):1-28
Caledonian eclogite-facies metamorphism partially reworking Grenvillian granulite-facies anorthosite allows us to study the processes of garnet reequilibration at high pressure and to reconstruct the evolution of the unit near metamorphic peak conditions. Our results indicate that eclogite-facies metamorphism happened in two successive phases: first, inherited granulitic garnet was fractured and reequilibrated from their boundaries (crystal or fracture rims); then eclogite-facies minerals were crystallised in the fractures as overgrowths on inherited garnets. The reequilibration of inherited garnets is achieved through Fe2+Mg−1 exchange, whereas eclogite-facies garnets crystallised during the subsequent phase are notably richer in Ca than un- and re-equilibrated granulitic garnet. Pseudosection construction shows that this lack in Ca reequilibration cannot be related to variations in thermodynamic conditions (a
H2O, reacting system composition) between the two phases. From the compilation of the available data, the reequilibration of granulitic garnet seems to be controlled by the inefficient intra- and inter-granular transport properties of Ca compared to Fe2+ and Mg. While these kinetic factors confine garnet reequilibration to Fe2+Mg−1 exchange, the extent of reequilibration along this exchange vector is controlled by partitioning with adjacent omphacite. On the contrary to the diffusional reequilibration of granulitic garnet that lasted for several My according to our modelling of the diffusional relaxation, the strong compositional gradients between eclogite-facies and reequilibrated garnets, which are almost unaffected by diffusional reequilibration, provide evidence that rapid exhumation followed the crystallisation of eclogite-facies minerals. We propose that the movement reversal itself, from burial to exhumation, and associated deformation and fluid flow, triggered this crystallisation event. The resulting evolution near metamorphic peak conditions is therefore strongly asymmetrical: on the one hand, the prograde diffusional relaxation profiles indicate slow movement during the last stages of burial, whereas the unaffected retrograde overgrowth indicates fast exhumation rates. 相似文献
17.
Summary Garnet occurs as a significant mineral constituent of felsic garnet-biotite granite in the southern edge of the Třebíč pluton.
Two textural groups of garnet were recognized on the basis of their shape and relationship to biotite. Group I garnets are
1.5–2.5 mm, euhedral grains which have no reaction relationship with biotite. They are zoned having high XMn at the rims and are considered as magmatic. Group II garnets form grain aggregates up to 2.5 cm in size, with anhedral shape
of individual grains. The individual garnet II grains are usually rimmed by biotite and have no compositional zoning. The
core of group I garnets and group II garnets contains 67–80 mol% of almandine, 5–19 mol% of pyrope, 7–17 mol% of spessartine
and 2–4 mol% of grossular. Biotite occurs in two generations; both are magnesian siderophyllites with Fe/(Fe + Mg) = 0.50–0.69.
The matrix biotite in granites (biotite I) has high Ti content (0.09–0.31 apfu) and Fe/(Fe + Mg) ratio between 0.50 and 0.59.
Biotite II forms reaction rims around garnet, is poor in Ti (0.00–0.06 apfu) and has a Fe/(Fe + Mg) ratio between 0.61 and
0.69. The textural relationship between biotite and garnet indicates that garnet reacted with granitic melt to form Ti-poor
biotite and a new granitic melt, depleted in Ti and Mg and enriched in Fe and Al. In contrast to the host durbachites (hornblende-biotite
melagranites), which originated by mixing of crustal melts and upper mantle melts, the origin of garnet-bearing granites is
related to partial melting of the aluminium-rich metamorphic series of the Moldanubian Zone. 相似文献
18.
Breakdown of hydrous ringwoodite to pyroxene and spinelloid at high P and T and oxidizing conditions
To get deeper insight into the phase relations in the end-member system Fe2SiO4 and in the system (Fe, Mg)2SiO4 experiments were performed in a multi-anvil apparatus at 7 and 13 GPa and 1,000–1,200°C as a function of oxygen fugacity.
The oxygen fugacity was varied using the solid oxygen buffer systems Fe/FeO, quartz–fayalite–magnetite, MtW and Ni/NiO. The
run products were characterized by electron microprobe, Raman- and FTIR-spectroscopy, X-ray powder diffraction and transmission
electron microscopy. At fO2 corresponding to Ni/NiO Fe-ringwoodite transforms to ferrosilite and spinelloid according to the reaction: 9 Fe2SiO4 + O2 = 6 FeSiO3 + 5 Fe2.40Si0.60O4. Refinement of site occupancies in combination with stoichiometric Fe3+ calculations show that 32% of the total Fe is incorporated as Fe3+ according to From the Rietveld refinement we identified spl as spinelloid III (isostructural with wadsleyite) and/or spinelloid V. As
we used water in excess in the experiments the run products were also analyzed for structural water incorporation. Adding
Mg to the system increases the stability field of ringwoodite to higher oxygen fugacity and the spinel structure seems to
accept higher Fe3+ but also water concentrations that may be linked. At oxygen fugacity corresponding to MtW conditions similar phase relations
in respect to the breakdown reaction in the Fe-end-member system were observed but with a strong fractionation of Fe into
spl and Mg into coexisting cpx. Thus, through this strong fractionation it is possible to stabilize very Fe-rich wadsleyite
with considerable Fe3+ concentrations even at an intermediate Fe–Mg bulk composition: assuming constant K
D independent on composition and a bulk composition of x
Fe = 0.44 this fractionation would stabilize spl with x
Fe = 0.72. Thus, spl could be a potential Fe3+ bearing phase at P–T conditions of the transition zone but because of the oxidizing conditions and the Fe-rich bulk composition
needed one would expect it more in subduction zone environments than in the transition zone in senso stricto.
相似文献
M. Koch-MüllerEmail: |
19.
Jibamitra Ganguly Weiji Cheng Sumit Chakraborty 《Contributions to Mineralogy and Petrology》1998,131(2-3):171-180
Diffusion couples made from homogeneous gem quality natural pyrope and almandine garnets were annealed within graphite capsules
under anhydrous conditions at 22–40 kbar, 1057–1400 °C in a piston-cylinder apparatus. The concentration profiles that developed
in each couple were modeled to retrieve the self diffusion coefficients [D(I)] of the divalent cations Fe, Mg, Mn and Ca.
Because of their usually low concentrations and lack of sufficient compositional change across the interface of the diffusion
couples, only a few reliable data can be obtained for D(Ca) and D(Mn) from these experiments. However, nine sets of D(Fe)
and D(Mg) data were retrieved in the above P-T range, and cast in the form of Arrhenian relation, D=D
0exp{−[Q(1 bar)+PΔV
+]/RT}. The values of the activation energy (Q) and activation volume (ΔV
+) depend on whether f
O2 is constrained by graphite in the system C-O or held constant. For the first case, we have for Fe:Q(1 bar)=65,532±10,111 cal/mol, D
0=3.50 (±2.30)×10−5 cm2/s, ΔV
+=5.6(±2.9) cm3/mol, and for Mg:Q(1 bar)=60,760±8,257 cal/mol, D
0=4.66 (±2.48)×10−5 cm2/s, ΔV
+=5.3(±3.0) cm3/mol. Here the ΔV
+ values have been taken from Chakraborty and Ganguly (1992). For the condition of constant f
O2, the Q values are ∼9 kcal lower and ΔV
+ values are ∼4.9 cm3/mol larger than the above values. Lower temperature extrapolation of the Arrhenian relation for D(Mg) is in good agreement
with the Mg tracer diffusion data (D
*
Mg) of Chakraborty and Rubie (1996) and Cygan and Lasaga (1985) at 1 bar, 750–900 °C, when all data are normalized to the same
pressure and to f
O2 defined by graphite in the system C-O. The D
*
Mg data of Schwandt et al. (1995), on the other hand, are lower by more than an order of magnitude than the low temperature
extrapolation of the present data, when all data are normalized to the same pressure and to f
O2 defined by the graphite buffer. Comparison of the D(Fe), D(Mg) and D(Mn) data in the pyrope-almandine diffusion couple with
those in the spessartine-almandine diffusion couple of Chakraborty and Ganguly (1992) shows that the self diffusion of Fe
and Mn are significantly enhanced with the increase in Mn/Mg ratio; the enhancement effect on D(Mg) is, however, relatively
small. Proper application of the self diffusion data to calculate interdiffusion coefficient or D matrix elements for the purpose of modeling of diffusion processes in natural garnets must take into account these compositional
effects on D(I) along with the effects of thermodynamic nonideality, f
O2, and pressure.
Received: 8 May 1997 / Accepted: 2 October 1997 相似文献
20.
Summary Elevated P contents of up to 0.086 apfu (1.21 wt.% P2O5) were found in garnet from leucocratic granitic rocks (orthogneisses, granites, barren to highly evolved pegmatites) in the
Moldanubicum and Silesicum, Czech Republic, and in complex granitic pegmatites from southern California, USA, and Australia.
Minor concentrations (0.15–0.55 wt.% P2O5) appear ubiquitous in garnet from leucocratic granitic rocks of different origins and degrees of fractionation. Concentrations
of P are not related to Mn/(Mn + Fe) that vary from 0.12–0.86 and to textural types of garnet (i.e., isolated anhedral to
euhedral grains and nodules, graphic and random garnet–quartz aggregates, subsolidus veins of fine-grained garnet). Garnet
compositions exhibit negative correlations for P/Si and P/R2+ where R2+ = Fe + Mn + Mg + Ca, while Al is constant at ∼2.05 apfu. Concentrations of Na are largely below 0.02 apfu but positively correlate with P. The main substitution may involve A-site vacancy and/or the presence of some light element(s) in the crystal structure. The substitution □P2 R2+ −1Si−2 and/or alluaudite-type Na□P3 R2+ −1Si−3 seem the most likely P-incorporating mechanisms. The partitioning of P among garnet and associated minerals in granitic systems
remains unclear; however, it directly affects the distribution of Y and REEs. 相似文献