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1.
The heat capacity at constant pressure, C
p, of chlorapatite [Ca5(PO4)3Cl – ClAp], and fluorapatite [Ca5(PO4)3F – FAp], as well as of 12 compositions along the chlorapatite–fluorapatite join have been measured using relaxation calorimetry
[heat capacity option of the physical properties measurement system (PPMS)] and differential scanning calorimetry (DSC) in
the temperature range 5–764 K. The chlor-fluorapatites were synthesized at 1,375–1,220°C from Ca3(PO4)2 using the CaF2–CaCl2 flux method. Most of the chlor-fluorapatite compositions could be measured directly as single crystals using the PPMS such
that they were attached to the sample platform of the calorimeter by a crystal face. However, the crystals were too small
for the crystal face to be polished. In such cases, where the sample coupling was not optimal, an empirical procedure was
developed to smoothly connect the PPMS to the DSC heat capacities around ambient T. The heat capacity of the end-members above 298 K can be represented by the polynomials: C
pClAp = 613.21 − 2,313.90T
−0.5 − 1.87964 × 107
T
−2 + 2.79925 × 109
T
−3 and C
pFAp = 681.24 − 4,621.73 × T
−0.5 − 6.38134 × 106
T
−2 + 7.38088 × 108
T
−3 (units, J mol−1 K−1). Their standard third-law entropy, derived from the low-temperature heat capacity measurements, is S° = 400.6 ± 1.6 J mol−1 K−1 for chlorapatite and S° = 383.2 ± 1.5 J mol−1 K−1 for fluorapatite. Positive excess heat capacities of mixing, ΔC
pex, occur in the chlorapatite–fluorapatite solid solution around 80 K (and to a lesser degree at 200 K) and are asymmetrically
distributed over the join reaching a maximum of 1.3 ± 0.3 J mol−1 K−1 for F-rich compositions. They are significant at these conditions exceeding the 2σ-uncertainty of the data. The excess entropy of mixing, ΔS
ex, at 298 K reaches positive values of 3–4 J mol−1 K−1 in the F-rich portion of the binary, is, however, not significantly different from zero across the join within its 2σ-uncertainty. 相似文献
2.
Mauro Gemmi Marco Merlini Alessandro Pavese Nadia Curetti 《Physics and Chemistry of Minerals》2008,35(7):367-379
Phengite samples (2M
1 and 3T politypes) and a synthetic end-member muscovite specimen were studied by in situ high-temperature synchrotron radiation X-ray
diffraction. The measured volume thermal expansion of 2M
1 phengite (<α
V> ≈ 36.6 × 10−6 K−1) was systematically greater than <α
V> of the 3T polytype (≈33.3 × 10−6 K−1). A positive linear correlation between the average thermal expansion on (001) plane and the mean tetrahedral rotation angle
at ambient condition is proposed on the ground of new measurements and literature data. Dehydroxylation processes were observed
in 2M
1, starting at 1,000 K in 3T at 800 and 945 K in synthetic muscovite. Rietveld refinements allowed a determination of structural variations upon heating
of phengite samples and their dehydroxylate phases. The phengite structure expands by regularizing the tetrahedral sheet and
by reducing the bond length differences between the outer and inner coordination shell of the interlayer site. The dehydroxylate
phase derived from 2M
1 is characterized by fivefold polyhedra in the low temperature form as a consequence of two OH groups reacting to form H2O + O (residual). The dehydroxylate exhibits an increase of the cation–cation distances along the M–Or–M bonds with respect
to low-temperature phengite structures. For the 3T phase, we were unable to achieve completion of dehydroxylation. The refined structural model of the dehydroxylate phase shows
two hydroxyl sites, but at a short distance from one another. This result suggests that the dehydroxylation reaction did not
proceed to completion.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
3.
A series of synthetic Ca-Tschermak–diopside (CaAlAlSiO6–CaMgSi2O6) clinopyroxenes were investigated by powder infrared spectroscopy at room temperature in the wavenumber range 80–2,000 cm−1. Measurable local structural heterogeneities in the crystals are suggested by the line broadening parameter, Δcorr that are
observed for intermediate solid-solution compositions. The broadening is most pronounced in the high wavenumber region of
the IR spectra that contains stretching modes involving the TO4 polyhedra. The effective line widths for three selected wavenumber regions deviate positively from linear behavior. This
is also observed for the enthalpy of mixing of this solid solution. The relationship between “excess Δcorr”, δΔcorr, and heat
of mixing, ΔH
mix, behavior was investigated for this clinopyroxene series and for several other binary silicate solid solutions. The ΔH
mix versus δΔcorr slope values show a linear relationship with respect to the integrated excess volume of the various solid solutions. 相似文献
4.
Genming Luo Junhuang Huang Shucheng Xie Paul B. Wignall Xinyan Tang Xianyu Huang Hongfu Yin 《International Journal of Earth Sciences》2010,99(4):775-784
This paper investigates kerogen carbon isotopes, the difference between carbonate and kerogen carbon isotopes (Δ13Ccarb-kero = δ
13Ccarb − δ
13Ckero) and the difference between carbonate and n-C19 alkane compound-specific carbon isotopes (Δ13Ccarb-n-C19 = δ
13Ccarb − δ
13C
n-C19) during the Permian–Triassic transition at Meishan, South China. The results show that kerogen carbon isotopes underwent
both gradual and sharp shifts in beds 23–25 and 26–29, respectively. The differences between carbonate and organic carbon
isotopes, both the Δ13Ccarb-kero and Δ13Ccarb-n-C19, which are mainly affected by CO2-fixing enzyme and pCO2, oscillated frequently during the Permian–Triassic transition. Both the variations of Δ13Ccarb-n-C19 and Δ13Ccarb-kero coupled with the alternation between cyanobacteria and green sulfur bacteria indicated by biomarkers. The episodic low values
of Δ13Ccarb-n-C19 corresponded to episodic blooms of green sulfur bacteria, while the episodic high values of Δ13Ccarb-n-C19 corresponded to episodic blooms of cyanobacteria. The relationships between the variation of carbon isotopes and biota show
that the microbes which flourished after the extinction of macroorganism affected the carbon isotope fractionation greatly.
Combining the carbon isotope compositions and the pattern of size variation of the conodont Neogondolella, this paper supposes that anoxia of the photic zone at bed 24 was episodic and it would be caused by the degradation of terrigenous
organic matters by sulfate reducing bacteria in the upper water column. Considered together with results from previous research,
the high resolution variation of the biogeochemistry presents the sequence of the important geo-events during the Permian–Triassic
crisis. 相似文献
5.
Tanja Waterwiese Niranjan D. Chatterjee Ivana Dierdorf Jörg Göttlicher Herbert Kroll 《Contributions to Mineralogy and Petrology》1995,121(1):61-73
Internally consistent thermodynamic datasets available at present call for a further improvement of the data for nepheline
(Holland and Powell 1988; Berman 1991). Because nepheline is a common rock-forming mineral, an attempt has been made to improve
on the present state of knowledge of its thermodynamic properties. To achieve that goal, two heterogeneous reactions involving
nepheline, albite, jadeite and a-quartz in the system NaAlSiO4-SiO2 have been reversed bylong duration runs in the range 460 ≤ T(°C) ≤ 960 and 10 ≤ P(kbar) ≤ 22. Given sufficiently long run times, thealbite run products approach internal equilibrium with respect to their Al,Si order-disorder states. Using appropriate thermochemical, thermophysical, and volumetric data,
Landau expansion for albite, and the relevant reaction reversals, a refined thermodynamic dataset (ΔfHi0 and Si0) has been derived for nepheline, jadeite, a-quartz, albite, and monalbite. Our refined data agree very well with theircalorimetric counterparts, but have smaller uncertainties. The refined dataset for ΔfHi0 and Si0, including their uncertainties and correlation, help generate the NaAlSiO4-SiO2 phase diagram including 2a confidence interval for eachP-T curve (Fig. 5).
Editorial responsibility: W. Schreyer 相似文献
6.
C. O'Reilly G. R. T. Jenkin M. Feely D. H. M. Alderton A. E. Fallick 《Contributions to Mineralogy and Petrology》1997,129(2-3):120-142
Fluid inclusions in granite quartz and three generations of veins indicate that three fluids have affected the Caledonian
Galway Granite. These fluids were examined by petrography, microthermometry, chlorite thermometry, fluid chemistry and stable
isotope studies. The earliest fluid was a H2O-CO2-NaCl fluid of moderate salinity (4–10 wt% NaCl eq.) that deposited late-magmatic molybdenite mineralised quartz veins (V1) and formed the earliest secondary inclusions in granite quartz. This fluid is more abundant in the west of the batholith,
corresponding to a decrease in emplacement depth. Within veins, and to the east, this fluid was trapped homogeneously, but
in granite quartz in the west it unmixed at 305–390 °C and 0.7–1.8 kbar. Homogeneous quartz δ18O across the batholith (9.5 ± 0.4‰n = 12) suggests V1 precipitation at high temperatures (perhaps 600 °C) and pressures (1–3 kbar) from magmatic fluids. Microthermometric data
for V1 indicate lower temperatures, suggesting inclusion volumes re-equilibrated during cooling. The second fluid was a H2O-NaCl-KCl, low-moderate salinity (0–10 wt% NaCl eq.), moderate temperature (270–340 °C), high δD (−18 ± 2‰), low δ18O (0.5–2.0‰) fluid of meteoric origin. This fluid penetrated the batholith via quartz veins (V2) which infill faults active during post-consolidation uplift of the batholith. It forms the most common inclusion type in
granite quartz throughout the batholith and is responsible for widespread retrograde alteration involving chloritization of
biotite and hornblende, sericitization and saussuritization of plagioclase, and reddening of K-feldspar. The salinity was
generated by fluid-rock interactions within the granite. Within granite quartz this fluid was trapped at 0.5–2.3 kbar, having
become overpressured. This fluid probably infiltrated the Granite in a meteoric-convection system during cooling after intrusion,
but a later age cannot be ruled out. The final fluid to enter the Granite and its host rocks was a H2O-NaCl-CaCl2-KCl fluid with variable salinity (8–28 wt% NaCl eq.), temperature (125–205 °C), δD (−17 to −45‰), δ18O (−3 to + 1.2‰), δ13CCO2 (−19 to 0‰) and δ34Ssulphate (13–23‰) that deposited veins containing quartz, fluorite, calcite, barite, galena, chalcopyrite sphalerite and pyrite (V3). Correlations of salinity, temperature, δD and δ18O are interpreted as the result of mixing of two fluid end-members, one a high-δD (−17 to −8‰), moderate-δ18O (1.2–2.5‰), high-δ13CCO2 (> −4‰), low-δ34Ssulphate (13‰), high-temperature (205–230 °C), moderate-salinity (8–12 wt% NaCl eq.) fluid, the other a low-δD (−61 to −45‰), low-δ18O (−5.4 to −3‰), low-δ13C (<−10‰), high-δ34Ssulphate (20–23‰) low-temperature (80–125 °C), high-salinity (21–28 wt% NaCl eq.) fluid. Geochronological evidence suggests V3 veins are late Triassic; the high-δD end-member is interpreted as a contemporaneous surface fluid, probably mixed meteoric
water and evaporated seawater and/or dissolved evaporites, whereas the low-δD end-member is interpreted as a basinal brine
derived from the adjacent Carboniferous sequence. This study demonstrates that the Galway Granite was a locus for repeated
fluid events for a variety of reasons; from expulsion of magmatic fluids during the final stages of crystallisation, through
a meteoric convection system, probably driven by waning magmatic heat, to much later mineralisation, concentrated in its vicinity
due to thermal, tectonic and compositional properties of granite batholiths which encourage mineralisation long after magmatic
heat has abated.
Received: 3 April 1996 / Accepted: 5 May 1997 相似文献
7.
Faruk Aydin Richard M. Thompson Orhan Karsli Hinako Uchida Jason B. Burt Robert T. Downs 《Contributions to Mineralogy and Petrology》2009,158(1):131-147
Chemical and structural data are reported for C2/c pyroxene phenocrysts collected from three potassic series (Group A: basanite-tephrite, Group B: tephrite-phonolitic tephrite,
Group C: alkaline basalt-trachybasalt) of the Neogene alkaline volcanics (NAVs) in northeastern Turkey, in order to investigate
the evolution of the magmatic plumbing system and the location of magma chamber(s) with crystallization conditions. The rock
series hosting the clinopyroxene phenocrysts show generally porphyritic texture and have a variable phenocryst-rich nature
(20–58%), with phenocryst assemblages characterized by cpx ± ol ± plag ± foid ± amp ± bio. The clinopyroxene phenocrysts can
be chemically classified as Ti- and Fe3+-rich Al-diopsides for Groups A and B (AB-cpxs) and Ti- and Fe3+-poor Al-diopsides for Group C (C-cpxs). They have poorly variable composition, clustering in the diopside field. Structurally,
the diopside groups have nearly similar a (ranging from 9.73 to 9.75 ?), V
cell (437.2–440.9 ?3), and 〈beta〉 angle values (106.01°–106.23°), but some differences in polyhedral parameters and geometries of the AB-cpxs and C-cpxs have
been observed. For example, the AB-cpxs are characterized by larger c (5.27–5.30 vs. 5.25–5.28 ?), V
T (2.27–2.30 vs. 2.23–2.28 ?3), and V
M2 (25.53–25.72 vs. 25.41–25.59 ?3) values and smaller b (8.87–8.88 vs. 8.88–8.91 ?) and V
M1 (11.49–11.63 vs. 11.64–11.83 ?3) values with respect to the C-cpxs. In addition, the AB-cpxs show higher values of V
M2/V
M1 (2.20–2.23) due to large V
M2 and small V
M1 compared to the V
M2/V
M1 ratios of the C-cpxs (<2.19). Such differences in the crystal structure of the AB-cpxs and C-cpxs from the NAVs are partly
related to different crystallization pressures, but mostly related to variation in melt composition and, possibly, the influence
of other crystallizing mineral phases. In particular, R(M2-O1) and R(M1-O2) (i.e. bond lengths) differences in the clinopyroxenes
of different groups support the presence of evolved host rocks with different alkaline character (i.e. silica-undersaturated
Groups A–B and silica-saturated Group C). Based on the cpx-geothermobarometry, the crystallization pressures for the C-cpxs
are lower than 4.5 kbars, but the AB-cpxs have relatively high-pressure values (5.6–10.6 kbars), suggesting that the AB-cpxs
crystallized in higher pressure environments. The relatively higher crystallization temperatures of the AB-cpxs also indicate
higher cooling rates. The P–T estimates suggest that the source regions of the clinopyroxene phenocrysts from the NAVs were crustal magma chambers in a
closed plumbing system at a moderate- to low-pressure regime. 相似文献
8.
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
9.
The oxidation of dihydroxyaromatics to benzoquinones by FeIII (hydr)oxides is important in respiratory electron shuttling by microorganisms and has been extensively studied. Prior publications
have noted that the Gibbs Free Energy (ΔG) for the forward reaction is sensitive to dihydroxyaromatic structure, pH, and concentrations of reactants and products.
Here, we address the back reaction, benzoquinone reduction by FeII. Rates markedly increase with increasing pH, in accord with increases in ΔG. Ring substituents that raise the potential of the p-benzoquinone/hydroquinone half reaction raise reaction rates: –OCH3 < –CH3 < –C6H5 < –H < –Cl. p-Naphthoquinone, with a reduction potential lower than the five substituted p-benzoquinones just listed, yields the lowest reaction rates. The complexity of the reaction is reflected in lag periods and
less-pronounced S-shaped time course curves. Benzoquinone reduction by FeII may be an important link in networks of electron transport taking place in suboxic and anoxic environments. 相似文献
10.
Pasquale Crea Concetta De Stefano Frank J. Millero Silvio Sammartano Virender K. Sharma 《Aquatic Geochemistry》2010,16(3):447-466
Oxidized glutathione (GSSG), which has four carboxylic and two amino groups, interacts with metal ions and may affect the
bioavailability and geochemistry of metals in natural waters. In the present paper, six stepwise protonation constants
K\textHi K^{\text{H}}_{i} for GSSG were measured as a function of salinity, S = 5–35‰ at t = 25°C (and in NaCl/MgCl2 mixtures at different ionic strengths), in order to provide thermodynamic data for their acid base properties, which are
useful for studying the interaction with metals in these media. The protonation enthalpies (ΔH
i
/kJ mol−1) were also determined at t = 25°C. The results were interpreted using the SIT model and Pitzer equations. The seawater model with the interaction parameters
accounts for the differences between the values in NaCl and seawater. The results suggest that it is important to consider
all of the ionic interactions in natural waters in examining the proton dissociation of GSSG. 相似文献
11.
The accepted standard state entropy of titanite (sphene) has been questioned in several recent studies, which suggested a
revision from the literature value 129.3 ± 0.8 J/mol K to values in the range of 110–120 J/mol K. The heat capacity of titanite
was therefore re-measured with a PPMS in the range 5 to 300 K and the standard entropy of titanite was calculated as 127.2
± 0.2 J/mol K, much closer to the original data than the suggested revisions. Volume parameters for a modified Murgnahan equation
of state: V
P,T
= V
298° × [1 + a°(T − 298) − 20a°(T − 298)] × [1 – 4P/(K
298 × (1 – 1.5 × 10−4 [T − 298]) + 4P)]1/4 were fit to recent unit cell determinations at elevated pressures and temperatures, yielding the constants V
298° = 5.568 J/bar, a° = 3.1 × 10−5 K−1, and K = 1,100 kbar. The standard Gibbs free energy of formation of titanite, −2456.2 kJ/mol (∆H°f = −2598.4 kJ/mol) was calculated from the new entropy and volume data combined with data from experimental reversals on the
reaction, titanite + kyanite = anorthite + rutile. This value is 4–11 kJ/mol less negative than that obtained from experimental
determinations of the enthalpy of formation, and it is slightly more negative than values given in internally consistent databases.
The displacement of most calculated phase equilibria involving titanite is not large except for reactions with small ∆S. Re-calculated baric estimates for several metamorphic suites yield pressure differences on the order of 2 kbar in eclogites
and 10 kbar for ultra-high pressure titanite-bearing assemblages. 相似文献
12.
The standard thermodynamic properties at 25°C, 1 bar (ΔG
fo, ΔH
fo, S
o, C
Po, V
o, ω) and the coefficients of the revised Helgeson–Kirkham–Flowers equations of state were evaluated for several aqueous complexes
formed by dissolved metals and either arsenate or arsenite ions. The guidelines of Shock and Helgeson (Geochim Cosmochim Acta
52:2009–2036, 1988) and Sverjensky et al. (Geochim Cosmochim Acta 61:1359–1412, 1997) were followed and corroborated with alternative approaches, whenever possible. The SUPCRT92 computer code was used to generate
the log K of the destruction reactions of these metal–arsenate and metal–arsenite aqueous complexes at pressures and temperatures required
by the EQ3/6 software package, version 7.2b. Apart from the AlAsO4o and FeAsO4o complexes, our log K at 25°C, 1 bar are in fair agreement with those of Whiting (MS Thesis, Colorado School of Mines, Golden, CO, 1992). Moreover, the equilibrium constants evaluated in this study are in good to fair agreement with those determined experimentally
for the Ca–dihydroarsenate and Ca–hydroarsenate complexes at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) and for Fe(III)–hydroarsenate complex at 25°C (Raposo et al., J Sol Chem 35:79–94, 2006), whereas the disagreement with the log K measured for the Ca–arsenate complex at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) might be due to uncertainties in this measured value. The implications of aqueous complexing between dissolved metals and
arsenate/arsenite ions were investigated for seawater, high-temperature geothermal liquids and acid mine drainage and aqueous
solutions deriving from mixing of acid mine waters and surface waters.
Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
13.
D. W. Fan M. N. Ma W. G. Zhou S. Y. Wei Z. Q. Chen H. S. Xie 《Physics and Chemistry of Minerals》2011,38(2):95-99
The high-pressure X-ray diffraction study of a natural arsenopyrite was investigated up to 28.2 GPa using in situ angle-dispersive
X-ray diffraction and a diamond anvil cell at National Synchrotron Light Source, Brookhaven National Laboratory. The 16:3:1
methanol–ethanol–water mixture was used as a pressure-transmitting medium. Pressures were measured using the ruby-fluorescence
method. No phase change has been observed up to 28.2 GPa. The isothermal equation of state (EOS) was determined. The values
of K
0, and K′
0 refined with a third-order Birch–Murnaghan EOS are K
0 = 123(9) GPa, and K′
0 = 5.2(8). Furthermore, we confirm that the linear compressibilities (β) along a, b and c directions of arsenopyrite is elastically isotropic (β
a
= 6.82 × 10−4, β
b
= 6.17 × 10−4 and β
c
= 6.57 × 10−4 GPa−1). 相似文献
14.
Single-crystal and powder electron paramagnetic resonance (EPR) spectroscopic studies of natural amethyst quartz, before and
after isochronal annealing between 573 and 1,173 K, have been made from 90 to 294 K. Single-crystal EPR spectra confirm the
presence of two substitutional Fe3+ centers. Powder EPR spectra are characterized by two broad resonance signals at g = ~10.8 and 4.0 and a sharp signal at g = 2.002. The sharp signal is readily attributed to the well-established oxygen vacancy electron center E
1′. However, the two broad signals do not correspond to any known Fe3+ centers in the quartz lattice, but are most likely attributable to Fe3+ clusters on surfaces. The absolute numbers of spins of the Fe3+ species at g = ~10.8 have been calculated from powder EPR spectra measured at temperatures from 90 to 294 K. These results have been used
to extract thermodynamic potentials, including Gibbs energy of activation ΔG, activation energy E
a, entropy of activation ΔS and enthalpy of activation ΔH for the Fe3+ species in amethyst. In addition, magnetic susceptibilities (χ) have been calculated from EPR data at different temperatures. A linear relationship between magnetic susceptibility and
temperature is consistent with the Curie–Weiss law. Knowledge about the stability and properties of Fe3+ species on the surfaces of quartz is important to better understanding of the reactivity, bioavailability and heath effects
of iron in silica particles. 相似文献
15.
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
16.
Petrogenesis of early cretaceous carbonatite and ultramafic lamprophyres in a diatreme in the Batain Nappes,Eastern Oman continental margin 总被引:1,自引:0,他引:1
S. Nasir S. Al-Khirbash H. Rollinson A. Al-Harthy A. Al-Sayigh A. Al-Lazki T. Theye H.-J. Massonne E. Belousova 《Contributions to Mineralogy and Petrology》2011,161(1):47-74
Allochthonous carbonatite and ultramafic lamprophyre occur in a diatreme at the beach of the Asseelah village, northeastern
Oman. The diatreme consists of heterogeneous deposits dominated by ‘diatreme facies’ pyroclastic rocks. These include aillikite
and carbonatite, which intrude late Jurassic to early Cretaceous cherts and shales of the Wahra Formation within the Batain
nappes. Both rock types are dominated by carbonate, altered olivine, Ti–Al–phlogopite and Cr–Al–spinel and contain varying
amounts of apatite and rutile. The carbonatite occur as fine-grained heterolithic breccias with abundant rounded carbonatite
xenoliths, glimmerite and crustal xenoliths. The aillikite consists of pelletal lapilli tuff with abundant fine-grained carbonatite
autoliths and crustal xenoliths, which resemble those in the carbonatite breccia. The aillikite and carbonatite are characterized
by low SiO2 (11–24 wt%), MgO (9.5–12.4 wt%) and K2O (<0.3 wt%), but high CaO (18–22 wt%), Al2O3 (4.75–7.04 wt%), Fe2O3tot (8.7–13.8 wt%) and loss-on-ignition (24–30 wt%). Higher CaO, Fe2O3total, Al2O3, MnO, TiO2, P2O5 and lower SiO2 and MgO content distinguish carbonatite from the aillikite. The associated carbonatite xenoliths and autoliths have intermediate
composition between the aillikite and carbonatite. Mg number is variable and ranges between 58 and 66 in the carbonatite,
66 and 72 in the aillikite and between 48 to 64 in the carbonatite autoliths and xenoliths. The Asseelah aillikite, carbonatite,
carbonatite xenoliths and autoliths overlap in most of their mineral parageneses, mineral composition and major and trace
element chemistry and have variable but overlapping Sr, Nd and Pb isotopic composition, implying that these rocks are related
to a common type of parental magma with variable isotopic characteristics. The Asseelah aillikite, carbonatite and carbonatites
xenoliths are LREE-enriched and significantly depleted in HREE. They exhibit similar smooth, subparallel REE pattern and steep
slopes with (La/Sm)
n
of 6–10 and relative depletion in heavy rare earth elements (Lu = 3–10 chondrite). Initial 87Sr/86Sr ratios vary from 0.70409 to 0.70787, whereas initial 143Nd/144Nd ratios vary between 0.512603 and 0.512716 (εNd
i
between 2.8 and 3.6). 206Pb/204Pb
i
ratios vary between 18.4 and 18.76, 207Pb/204Pb
i
ratios vary between 15.34 and 15.63, whereas 208Pb/204Pb
i
varies between 38.42 and 39.05. Zircons grains extracted from the carbonatite have a mean age of 137 ± 1 Ma (95% confidence,
MSWD = 0.49). This age correlates with large-scale tectonic events recorded in the early Indian Ocean at 140–160 Ma. Geochemical
and isotopic signatures displayed by the Asseelah rocks can be accounted for by vein-plus-wall-rock model of Foley (1992) wherein veins are represented by phlogopite, carbonate and apatite and depleted peridotite constitutes the wall-rock. The
carbonatite and aillikite magmatism is probably a distal effect of the breaking up of Gondwana, during and/or after the rift-to-drift
transition that led to the opening of the Indian Ocean. 相似文献
17.
A pristine magnetite (Fe3O4) specimen was studied by means of Neutron Powder Diffraction in the 273–1,073 K temperature range, in order to characterize
its structural and magnetic behavior at high temperatures. An accurate analysis of the collected data allowed the understanding
of the behavior of the main structural and magnetic features of magnetite as a function of temperature. The magnetic moments
of both tetrahedral and octahedral sites were extracted by means of magnetic diffraction up to the Curie temperature (between
773 and 873 K). A change in the thermal expansion coefficient around the Curie temperature together with an increase in the
oxygen coordinate value above 700 K can be observed, both features being the result of a change in the thermal expansion of
the tetrahedral site. This anomaly is not related to the magnetic transition but can be explained with an intervened cation
reordering, as magnetite gradually transforms from a disordered configuration into a partially ordered one. Based on a simple
model which takes into account the cation-oxygen bond length, the degree of order as a function of temperature and consequently
the enthalpy and entropy of the reordering process were determined. The refined values are ΔH0 = −23.2(1.7) kJ mol−1 and ΔS0 = −16(2) J K−1 mol−1. These results are in perfect agreement with values reported in literature (Mack et al. in Solid State Ion 135(1–4):625–630,
2000; Wu and Mason in J Am Ceramic Soc 64(9):520–522, 1981). 相似文献
18.
Jaidong Ko Nancy E. Brown Alexandra Navrotsky Charles T. Prewitt Tibor Gasparik 《Physics and Chemistry of Minerals》1989,16(8):727-733
The phase boundary between MnTiO3 I (ilmenite structure) and MnTiO3 II (lithium niobate structure) has been determined by analysis of quench products from reversal experiments in a cubic anvil
apparatus at 1073–1673 K and 43–75 kbar using mixtures of MnTiO3 I and II as starting materials. Tight brackets of the boundary give P(kbar)=121.2−0.045 T(K). Thermodynamic analysis of this boundary gives ΔHo=5300±1000 J·mol−1, ΔSo = 1.98 ±1J·K−1· mol−1. The enthalpy of transformation obtained directly by transposed-temperature-drop calorimetry is 8359 ±2575 J·mol−1. Possible topologies of the phase relations among the ilmenite, lithium niobate, and perovskite polymorphs are constrained
using the above data and the observed (reversible with hysteresis) transformation of II to III at 298 K and 20–30 kbar (Ross
et al. 1989). The observed II–III transition is likely to lie on a metastable extension of the II–III boundary into the ilmenite
field. However the reversed I–II boundary, with its negative dP/ dT does represent stable equilibrium between ilmenite and lithium niobate, as opposed to the lithium niobate being a quench
product of perovskite. We suggest a topology in which the perovskite occurs stably at low T and high P with a triple point (I, II, III) at or below 1073 K near 70 kbar. The I–II boundary would have a negative P-T slope while the II–III and I–III boundaries would be positive, implying that entropy decreases in the order lithium niobate,
ilmenite, perovskite. The inferred positive slope of the ilmenite-perovskite transition in MnTiO3 is different from the negative slopes in silicates and germanates. These thermochemical parameters are discussed in terms
of crystal structure and lattice vibrations. 相似文献
19.
Estelle Auzanneau M. W. Schmidt D. Vielzeuf J. A. D Connolly 《Contributions to Mineralogy and Petrology》2010,159(1):1-24
Phengite chemistry has been investigated in experiments on a natural SiO2–TiO2-saturated greywacke and a natural SiO2–TiO2–Al2SiO5-saturated pelite, at 1.5–8.0 GPa and 800–1,050°C. High Ti-contents (0.3–3.7 wt %), Ti-enrichment with temperature, and a
strong inverse correlation of Ti-content with pressure are the important features of both experimental series. The changes
in composition with pressure result from the Tschermak substitution (Si + R2+ = AlIV + AlVI) coupled with the substitution: AlVI + Si = Ti + AlIV. The latter exchange is best described using the end-member Ti-phengite (KMgTi[Si3Al]O10(OH)2, TiP). In the rutile-quartz/coesite saturated experiments, the aluminoceladonite component increases with pressure while
the muscovite, paragonite and Ti-phengite components decrease. A thermodynamic model combining data obtained in this and previous
experimental studies are derived to use the equilibrium MgCel + Rt = TiP + Cs/Qz as a thermobarometer in felsic and basic
rocks. Phengite, rutile and quartz/coesite are common phases in HT-(U)HP metamorphic rocks, and are often preserved from regression
by entrapment in zircon or garnet, thus providing an opportunity to determine the T–P conditions of crystallization of these rocks. Two applications on natural examples (Sulu belt and Kokchetav massif) are presented
and discussed. This study demonstrates that Ti is a significant constituent of phengites that could have significant effects
on phase relationships and melting rates with decreasing P or increasing T in the continental crust. 相似文献
20.
Sicheng Wang Xi Liu Yingwei Fei Qiang He Hejing Wang 《Physics and Chemistry of Minerals》2012,39(3):189-198
Using a conventional high-T furnace, the solid solutions between magnesiochromite and manganochromite, (Mg1−x
Mn
x
)Cr2O4 with x = 0.00, 0.19, 0.44, 0.61, 0.77 and 1.00, were synthesized at 1,473 K for 48 h in open air. The ambient powder X-ray diffraction
data suggest that the V–x relationship of the spinels does not show significant deviation from the Vegard’s law. In situ high-T powder X-ray diffraction measurements were taken up to 1,273 K at ambient pressure. For the investigated temperature range,
the unit-cell parameters of the spinels increase smoothly with temperature increment, indicating no sign of cation redistribution
between the tetrahedral and octahedral sites. The V–T data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (aT = a0 + a1 T + a2 T - 2 \alpha_{T} = a_{0} + a_{1} T + a_{2} T^{ - 2} ), which yielded insignificant a
2 values. The effect of the composition on a
0 is adequately described by the equation a
0 = [17.7(8) − 2.4(1) × x] 10−6 K−1, whereas that on a
1 by the equation a
1 = [8.6(9) + 2.1(11) × x] 10−9 K−2. 相似文献