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1.
The onset of hydrous partial melting in the mantle above the transition zone is dictated by the H2O storage capacity of peridotite, which is defined as the maximum concentration that the solid assemblage can store at P and T without stabilizing a hydrous fluid or melt. H2O storage capacities of minerals in simple systems do not adequately constrain the peridotite water storage capacity because
simpler systems do not account for enhanced hydrous melt stability and reduced H2O activity facilitated by the additional components of multiply saturated peridotite. In this study, we determine peridotite-saturated
olivine and pyroxene water storage capacities at 10–13 GPa and 1,350–1,450°C by employing layered experiments, in which the
bottom ~2/3 of the capsule consists of hydrated KLB-1 oxide analog peridotite and the top ~1/3 of the capsule is a nearly
monomineralic layer of hydrated Mg# 89.6 olivine. This method facilitates the growth of ~200-μm olivine crystals, as well
as accessory low-Ca pyroxenes up to ~50 μm in diameter. The presence of small amounts of hydrous melt ensures that crystalline
phases have maximal H2O contents possible, while in equilibrium with the full peridotite assemblage (melt + ol + pyx + gt). At 12 GPa, olivine and
pyroxene water storage capacities decrease from ~1,000 to 650 ppm, and ~1,400 to 1,100 ppm, respectively, as temperature increases
from 1,350 to 1,450°C. Combining our results with those from a companion study at 5–8 GPa (Ardia et al., in prep.) at 1,450°C,
the olivine water storage capacity increases linearly with increasing pressure and is defined by the relation
C\textH2 \textO\textolivine ( \textppm ) = 57.6( ±16 ) ×P( \textGPa ) - 169( ±18 ). C_{{{\text{H}}_{2} {\text{O}}}}^{\text{olivine}} \left( {\text{ppm}} \right) = 57.6\left( { \pm 16} \right) \times P\left( {\text{GPa}} \right) - 169\left( { \pm 18} \right). Adjustment of this trend for small increases in temperature along the mantle geotherm, combined with experimental determinations
of
D\textH2 \textO\textpyx/olivine D_{{{\text{H}}_{2} {\text{O}}}}^{\text{pyx/olivine}} from this study and estimates of
D\textH2 \textO\textgt/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{gt}}/{\text{olivine}}}} , allows for estimation of peridotite H2O storage capacity, which is 440 ± 200 ppm at 400 km. This suggests that MORB source upper mantle, which contains 50–200 ppm
bulk H2O, is not wet enough to incite a global melt layer above the 410-km discontinuity. However, OIB source mantle and residues
of subducted slabs, which contain 300–1,000 ppm bulk H2O, can exceed the peridotite H2O storage capacity and incite localized hydrous partial melting in the deep upper mantle. Experimentally determined values
of
D\textH2 \textO\textpyx/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{pyx}}/{\text{olivine}}}} at 10–13 GPa have a narrow range of 1.35 ± 0.13, meaning that olivine is probably the most important host of H2O in the deep upper mantle. The increase in hydration of olivine with depth in the upper mantle may have significant influence
on viscosity and other transport properties. 相似文献
2.
Rodney Grapes Sophia Korzhova Ella Sokol Yurii Seryotkin 《Contributions to Mineralogy and Petrology》2011,162(2):253-273
Sekaninaite (XFe > 0.5)-bearing paralava and clinker are the products of ancient combustion metamorphism in the western part of the Kuznetsk
coal basin, Siberia. The combustion metamorphic rocks typically occur as clinker beds and breccias consisting of vitrified
sandstone–siltstone clinker fragments cemented by paralava, resulting from hanging-wall collapse above burning coal seams
and quenching. Sekaninaite–Fe-cordierite (XFe = 95–45) is associated with tridymite, fayalite, magnetite, ± clinoferrosilite and ±mullite in paralava and with tridymite
and mullite in clinker. Unmelted grains of detrital quartz occur in both rocks (<3 vol% in paralavas and up to 30 vol% in
some clinkers). Compositionally variable siliceous, K-rich peraluminous glass is <30% in paralavas and up to 85% in clinkers.
The paralavas resulted from extensive fusion of sandstone–siltstone (clinker), and sideritic/Fe-hydroxide material contained
within them, with the proportion of clastic sediments ≫ ferruginous component. Calculated dry liquidus temperatures of the
paralavas are 1,120–1,050°C and 920–1,050°C for clinkers, with calculated viscosities at liquidus temperatures of 101.6–7.0 and 107.0–9.8 Pa s, respectively. Dry liquidus temperatures of glass compositions range between 920 and 1,120°C (paralava) and 920–960°C
(clinker), and viscosities at these temperatures are 109.7–5.5 and 108.8–9.7 Pa s, respectively. Compared with worldwide occurrences of cordierite–sekaninaite in pyrometamorphic rocks, sekaninaite occurs
in rocks with XFe (mol% FeO/(FeO + MgO)) > 0.8; sekaninaite and Fe-cordierite occur in rocks with XFe 0.6–0.8, and cordierite (XFe < 0.5) is restricted to rocks with XFe < 0.6. The crystal-chemical formula of an anhydrous sekaninaite based on the refined structure is
| \textK0.02 |(\textFe1.542 + \textMg0.40 \textMn0.06 )\Upsigma 2.00M [(\textAl1.98 \textFe0.022 + \textSi1.00 )\Upsigma 3.00T1 (\textSi3.94 \textAl2.04 \textFe0.022 + )\Upsigma 6.00T2 \textO18 ]. \left| {{\text{K}}_{0.02} } \right|({\text{Fe}}_{1.54}^{2 + } {\text{Mg}}_{0.40} {\text{Mn}}_{0.06} )_{\Upsigma 2.00}^{M} [({\text{Al}}_{1.98} {\text{Fe}}_{0.02}^{2 + } {\text{Si}}_{1.00} )_{\Upsigma 3.00}^{T1} ({\text{Si}}_{3.94} {\text{Al}}_{2.04} {\text{Fe}}_{0.02}^{2 + } )_{\Upsigma 6.00}^{T2} {\text{O}}_{18} ]. 相似文献
3.
Monticellite is a common magmatic mineral in the groundmass of kimberlites. A new oxygen barometer for kimberlite magmas is
calibrated based on the Fe content of monticellite, CaMgSiO4, in equilibrium with kimberlite liquids in experiments at 100 kPa from 1,230 to 1,350°C and at logfO2 from NNO-4.1 to NNO+5.3 (where NNO is the nickel–nickel oxide buffer). The XFeMtc/XFeliq was found to decrease with increasing fO2, consistent with only Fe2+ entering the monticellite structure. Although the XFe-in-monticellite varies with temperature and composition, these dependencies are small compared to that with fO2. The experimental data were fitted by weighted least square regression to the following relationship:
\Updelta \textNNO = \frac{ log[ 0.858( ±0.021)\fracX\textFe\textLiq X\textFe\textMtc ] - 0.139( ±0.022) }0.193( ±0.004) \Updelta {\text{NNO}} = \frac{{\left\{ {\log \left[ {0.858( \pm 0.021)\frac{{X_{\text{Fe}}^{\text{Liq}} }}{{X_{\text{Fe}}^{\text{Mtc}} }}} \right] - 0.139( \pm 0.022)} \right\}}}{0.193( \pm 0.004)} where ΔNNO is the fO2 relative to that of the Nickel-bunsenite (NNO) buffer and XFeliq/XFeMtc is the ratio of mole fraction of Fe in liquid and Fe-in-monticellite (uncertainties at 2σ). The application of this oxygen
barometer to natural kimberlites from both the literature and our own investigations, assuming the bulk rock FeO is that of
their liquid FeO, revealed a range in fO2 from NNO-3.5 to NNO+1.7. A range of Mg/(Mg + Fe2+) (Mg#) for kimberlite melts of 0.46–0.88 was derived from the application of the experimentally determined monticellite-liquid
Kd Fe2+–Mg to natural monticellites. The range in Mg# is broader and less ultramafic than previous estimates of kimberlites, suggesting
an evolution under a wide range of petrologic conditions. 相似文献
4.
Sogdianite, a double-ring silicate of composition
( \textZr0. 7 6 \textTi0. 3 84 + \textFe0. 7 33 + \textAl0.13 )\Upsigma = 2 ( \square 1. 1 5 \textNa0. 8 5 )\Upsigma = 2 \textK[\textLi 3 \textSi 1 2 \textO 30 ] ( {\text{Zr}}_{0. 7 6} {\text{Ti}}_{0. 3 8}^{4 + } {\text{Fe}}_{0. 7 3}^{3 + } {\text{Al}}_{0.13} )_{\Upsigma = 2} \left( {\square_{ 1. 1 5} {\text{Na}}_{0. 8 5} } \right)_{\Upsigma = 2} {\text{K}}[{\text{Li}}_{ 3} {\text{Si}}_{ 1 2} {\text{O}}_{ 30} ] from Dara-i-Pioz, Tadjikistan, was studied by the combined application of 57Fe M?ssbauer spectroscopy and electronic structure calculations. The M?ssbauer spectrum confirms published microprobe and
X-ray single-crystal diffraction results that indicate that Fe3+ is located at the octahedral A-site and that no Fe2+ is present. Both the measured and calculated quadrupole splitting, ΔE
Q, for Fe3+ are virtually 0 mm s−1. Such a value is unusually small for a silicate and it is the same as the ΔE
Q value for Fe3+ in structurally related sugilite. This result is traced back to the nearly regular octahedral coordination geometry corresponding
to a very symmetric electric field gradient around Fe3+. A crystal chemical interpretation for the regular octahedral geometry and the resulting low ΔE
Q value for Fe3+ in the M?ssbauer spectrum of sogdianite is that structural strain is largely “taken up” by weak Li–O bonds permitting highly
distorted LiO4 tetrahedra. Weak Li–O bonding allows the edge-shared more strongly bonded Fe3+O6 octahedra to remain regular in geometry. This may be a typical property for all double-ring silicates with tetrahedrally
coordinated Li. 相似文献
5.
M. N. Taran H. Ohashi K. Langer A. A. Vishnevskyy 《Physics and Chemistry of Minerals》2011,38(5):345-356
Comparison of polarized optical absorption spectra of natural Ca-rich diopsides and synthetic NaCrSi2O6 and LiCrSi2O6 clinopyroxenes, evidences as vivid similarities, as noticeable differences. The similarities reflect the fact that in all
cases Cr3+ enters the small octahedral M1-site of the clinopyroxene structure. The differences are due to some iron content in the natural
samples causing broad intense near infrared bands of electronic spin-allowed dd transitions of Fe2+(M1, M2) and intervalence Fe2+/Fe3+ charge-transfer transition, and by different symmetry and different local crystal fields strength of Cr3+ in the crystal structures. The positions of the spin-allowed bands of Cr3+, especially of the low energy one caused by the electronic 4
A
2g → 2
T
1g transition, are found to be in accordance with mean M1–O distances. The local relaxation parameter ε calculated for limCr
3+ → 0 from the spectra and interatomic
á Cr - O
ñ \left\langle {Cr - O} \right\rangle and
á Mg - O
ñ \left\langle {Mg - O} \right\rangle distances yields a very high value, 0.96, indicating that in the clinopyroxene structure the local lattice relaxation around
the “guest” ion, Cr3+, deviates greatly from the “diffraction” value, ε = 0, than in any other known Cr3+-bearing systems studied so far. Under pressure the spin-allowed bands of Cr3+ shift to higher energies and decrease in intensity quite in accordance with the crystal field theoretical expectations, while
the spin-forbidden absorption lines remain practically unshifted, but also undergo a strong weakening. There is no evident
dependence of the Racah parameter B of Cr3+ reflecting the covalence of the oxygen-chromium bond under pressure: within the uncertainty of determination it may be regarded
as practically constant. The values of CrO6 octahedral modulus,
k\textpoly\textloc k_{\text{poly}}^{\text{loc}} , derived from high-pressure spectra of natural chromium diopside and synthetic NaCrSi2O6 kosmochlor are very close, ~203 and ~196 GPa, respectively, being, however, nearly twice higher than that of MgO6 octahedron in diopside, 105(4) GPa, obtained by Thompson and Downs (2008). Such a strong stiffening of the structural octahedron, i.e. twice higher value of
k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} comparing with that of
k\textMg2 + \textloc k_{{{\text{Mg}}^{2 + } }}^{\text{loc}} , may be caused by simultaneous substitution of Ca2+ by larger Na+ in the neighboring M2 sites at so-called jadeite-coupled substitution Mg2+ + Ca2+ → Cr3+ + Na+. It is also remarkable that the values of CrO6 octahedral modulus of NaCrSi2O6 kosmochlor obtained here are nearly twice larger than that of 90(16) GPa, evaluated by high-pressure X-ray structural refinement
by Origlieri et al. (2003). Taking into account that the overall compressibility of the clinopyroxene structure should mainly be due to the compressibility
of M1- and M2-sites, our
k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} -value, ~196 GPa, looks much more consistent with the bulk modulus value, 134(1) GPa. 相似文献
6.
Water and Iron effect on the P-T-x coordinates of the 410-km discontinuity in the Earth upper mantle
Fiorenza Deon Monika Koch-Müller Dieter Rhede Richard Wirth 《Contributions to Mineralogy and Petrology》2011,161(4):653-666
We performed multi-anvil experiments in the system MgO-SiO2 ± H2O at 13.0–13.7 GPa and 1,025–1,300°C and in the system MgO-FeO-SiO2 ± H2O, under reducing conditions, at 11.0–12.7 GPa and 1,200°C, to depict the effect of H2O on the P-T-x coordinates of the 410-km discontinuity, i.e. the olivine–wadsleyite phase boundary. The charges were investigated
with Electron Microprobe (EMP), Raman Spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), Secondary Ion Mass Spectrometry
(SIMS) and Electron Energy Loss Spectroscopy (EELS). We observe in the MgO-SiO2-H2O system at 1,200°C a 0.6 GPa shift of the phase boundary to lower pressure compared to dry conditions, due to the stronger
water fractionation into wadsleyite (wad) rather than in olivine (ol). In the MgO-FeO-SiO2-H2O system, we reproduced the triple point, i.e. observed coexisting hydrous ol, wad and ringwoodite (ring). SIMS H quantifications
provided partitioning coefficients for water:
D\textwad/ol\textwater D_{\text{wad/ol}}^{\text{water}} ~ 3.7(5) and
D\textring/ol\textwater D_{\text{ring/ol}}^{\text{water}} ~ 1.5(2) and
D\textwad/ring\textwater D_{\text{wad/ring}}^{\text{water}} ~ 2.5(5). For a bulk composition of x
Fe = 0.1, our data indicate only a slight difference in the width of the loop of the two phase field ol–wad under hydrous conditions
compared to dry conditions, i.e. no broadening with respect to composition but a shift to lower pressures. For bulk compositions
of x
Fe > 0.2, i.e. in regions where wad–ring and ol–ring coexist, we observe, however, an unexpected broadening of the loops with
a shift to higher iron contents. In total, the stability field of hydrous wad expands in both directions, to lower and higher
pressures. Fe3+ concentrations as determined by EELS are very low and are expected to play no role in the broadening of the loops. 相似文献
7.
The chemistry of garnet can provide clues to the formation of skarn deposits. The chemical analyses of garnets from the Astamal Fe-LREE distal skarn deposit were completed using an electron probe micro-analyzer. The three types of garnet were identified in the Astamal skarn are: (I) euhedral coarse-grained isotropic garnets (10–30 mm across), which are strongly altered to epidote, calcite and quartz in their rim and core, with intense pervasive retrograde alteration and little variation in the overall composition (Adr94.3–84.4 Grs8.5–2.7 Alm1.9–0.2) (garnet I); (II) anhedral to subhedral brecciated isotropic garnets (5–10 mm across) with minor alteration, a narrow compositional range along the growth lines (Adr82–65.4 Grs21.9–11.7 Alm11.1–2.4) and relatively high Cu (up to 1997 ppm) and Ni (up to 1283 ppm) (garnet II); and (III) subhedral coarser grained garnets (> 30 mm across) with moderate alteration, weak diffusion and irregular zoning of discrete grossular-almandine-rich domains (Adr84.2–48.8 Grs32.4–7.6 Alm19.9–3.5) (garnet III). In the third type, the almandine content increases with increasing grossular/andradite ratio and increasing substitutions of Al for Fe3 +.Almost all three garnet types have been replaced by fine-grained, dark-brown allanite that is typically disseminated and has the same relief as andradite. The Cu content increases while Ni content decreases slightly towards the rim of garnet II and garnet III. Copper in garnet II is positively correlated with increasing almandine content and decreasing andradite content, indicating that the almandine structure, containing relatively more Fe2 +, is more suitable than andradite and grossular to host divalent cations such as Cu2 +. Nickel in garnet II is positively correlated with increasing andradite content, total Fe, and decreasing almandine content. This is because Ni2 + substitutes for Fe3 + in the Y (octahedral) position. There are unusual discrete grossular-almandine rich domains within andraditic garnet III, indicating the low diffusivity of Ca compared to Fe at high temperatures. 相似文献
8.
Relative humidity (
P\textH 2 \textO P_{{{\text{H}}_{ 2} {\text{O}}}} , partial pressure of water)-dependent dehydration and accompanying phase transitions in NAT-topology zeolites (natrolite,
scolecite, and mesolite) were studied under controlled temperature and known
P\textH 2 \textO P_{{{\text{H}}_{ 2} {\text{O}}}} conditions by in situ diffuse-reflectance infrared Fourier transform spectroscopy and parallel X-ray powder diffraction.
Dehydration was characterized by the disappearance of internal H2O vibrational modes. The loss of H2O molecules caused a sequence of structural transitions in which the host framework transformation path was coupled primarily
via the thermal motion of guest Na+/Ca2+ cations and H2O molecules. The observation of different interactions of H2O molecules and Na+/Ca2+ cations with host aluminosilicate frameworks under high- and low-
P\textH 2 \textO P_{{{\text{H}}_{ 2} {\text{O}}}} conditions indicated the development of different local strain fields, arising from cation–H2O interactions in NAT-type channels. These strain fields influence the Si–O/Al–O bond strength and tilting angles within and
between tetrahedra as the dehydration temperature is approached. The newly observed infrared bands (at 2,139 cm−1 in natrolite, 2,276 cm−1 in scolecite, and 2,176 and 2,259 cm−1 in mesolite) result from strong cation–H2O–Al–Si framework interactions in NAT-type channels, and these bands can be used to evaluate the energetic evolution of Na+/Ca2+ cations before and after phase transitions, especially for scolecite and mesolite. The 2,176 and 2,259 cm−1 absorption bands in mesolite also appear to be related to Na+/Ca2+ order–disorder that occur when mesolite loses its Ow4 H2O molecules. 相似文献
9.
Mineral-specific IR absorption coefficients were calculated for natural and synthetic olivine, SiO2 polymorphs, and GeO2 with specific isolated OH point defects using quantitative data from independent techniques such as proton–proton scattering,
confocal Raman spectroscopy, and secondary ion mass spectrometry. Moreover, we present a routine to detect OH traces in anisotropic
minerals using Raman spectroscopy combined with the “Comparator Technique”. In case of olivine and the SiO2 system, it turns out that the magnitude of ε for one structure is independent of the type of OH point defect and therewith
the peak position (quartz ε = 89,000 ± 15,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}), but it varies as a function of structure (coesite ε = 214,000 ± 14,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}; stishovite ε = 485,000 ± 109,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}). Evaluation of data from this study confirms that not using mineral-specific IR calibrations for the OH quantification in
nominally anhydrous minerals leads to inaccurate estimations of OH concentrations, which constitute the basis for modeling
the Earth’s deep water cycle. 相似文献
10.
The present work aims in discussing a principle that distinguishes between elastic parameters sets, $ \{ \Upphi \} \equiv \{ K_{0} , \, K^{\prime}, \, V_{0} ,\ldots\} The present work aims in discussing a principle that distinguishes between elastic parameters sets,
{ \Upphi } o { K0 , K￠, V0 ,?} \{ \Upphi \} \equiv \{ K_{0} , \, K^{\prime}, \, V_{0} ,\ldots\} , on the basis of an energetic criterion: once a reference set,
{ \UpphiR } \{ \Upphi_{R} \} , is given, another one can be fixed,
{ \Upphi min } \left\{ {\Upphi_{ \min } } \right\} , so that they are as close as possible to each other, but yield non-equivalent deformation energy curves
\Updelta G({ \Upphi } )\textdeform \Updelta G(\{ \Upphi \} )_{\text{deform}} , i.e. they give
\Updelta G({ \UpphiR } )\textdeform \Updelta G(\{ \Upphi_{R} \} )_{\text{deform}} and
\Updelta G({ \Upphi min } )\textdeform \Updelta G(\{ \Upphi_{ \min } \} )_{\text{deform}} such that
| \Updelta G({ \Upphi min } )\textdeform - \Updelta G({ \UpphiR } )\textdeform | 3 1×s[\Updelta G\textdeform ]. \left| {\Updelta G(\{ \Upphi_{ \min } \} )_{\text{deform}} - \Updelta G(\{ \Upphi_{R} \} )_{\text{deform}} } \right| \ge 1\times \sigma [\Updelta G_{\text{deform}} ]. ΔG
deform, calculated using the equation of state (EoS), and its uncertainty σ[ΔG
deform], obtained by a propagation of the errors affecting
{ \Upphi } \{ \Upphi \} are crucial to fix which mineral assemblage forms at P–T conditions and allow one to assess the reliability of such a prediction. We explore some properties related to the principle
introduced, using the average values of the elastic parameters found in literature and related uncertainties for di-octahedral
mica, olivine, garnet and clinopyroxene. Two elementary applications are briefly discussed: the effect of refining V
0 in fitting EoSs to P–V experimental data, in the case of garnet and omphacite, and the phengite 3T–2M
1 relative stability, controlled by pressure. 相似文献
11.
Complex Growth Textures in a Polymetamorphic Metabasite from the Kraubath Massif (Eastern Alps) 总被引：1，自引：0，他引：1
Zoned garnet and amphibole occur in metabasites of the KraubathMassif, Eastern Alps, that contain relic magmatic clinopyroxene.The amphibole composition gradually changes from core (XMg =0·83) to rim (XMg = 0·6–0·7). A numberof compositional varieties of garnet occur in the metabasite.An older porphyroblastic garnet (Py23–27, Alm41–43,Grs29–33) has two different compositional domains, onerelatively rich in Mg (Py27–30) and the other rich inCa (Grs35–38) with a low Mg (Py20–25) content. Theyoungest variety, which forms rims on, or microveins in, theporphyroblastic garnet, has high Ca and low Mg (Grs40–57,Py2–7, Alm46–51). The amphibole cores and garnetporphyroblasts are interpreted to represent minerals formedduring Variscan regional metamorphism under amphibolite-faciesconditions. Alpine metamorphism is represented by the most recentCa-rich and Mg-poor variety of garnet that coexists with theamphibole rims, epidote and chlorite. Fracturing in the porphyroblasticgarnet probably originated during retrogression of the Variscanamphibolite-facies assemblages. Textural relations suggest thatthe garnet in the microveins formed by dehydration of hydrousphases during an Alpine metamorphic overprint that reached P–Tconditions of 550–583°C at 1·0 GPa. KEY WORDS: microveins; garnet; metabasites; Kraubath Massif; Eastern Alps 相似文献
12.
Matteo Alvaro Fernando Cámara M. Chiara Domeneghetti Fabrizio Nestola Vittorio Tazzoli 《Contributions to Mineralogy and Petrology》2011,162(3):599-613
A natural Ca-poor pigeonite (Wo6En76Fs18) from the ureilite meteorite sample PCA82506-3, free of exsolved augite, was studied by in situ high-temperature single-crystal
X-ray diffraction. The sample, monoclinic P21/c, was annealed up to 1,093°C to induce a phase transition from P21/c to C2/c symmetry. The variation with increasing temperature of the lattice parameters and of the intensity of the b-type reflections (h + k = 2n + 1, present only in the P21/c phase) showed a displacive phase transition P21/c to C2/c at a transition temperature T
Tr = 944°C, first order in character. The Fe–Mg exchange kinetics was studied by ex situ single-crystal X-ray diffraction in
a range of temperatures between the closure temperature of the Fe–Mg exchange reaction and the transition temperature. Isothermal
disordering annealing experiments, using the IW buffer, were performed on three crystals at 790, 840 and 865°C. Linear regression
of ln k
D versus 1/T yielded the following equation:
ln k\textD = - 3717( ±416)/T(K) + 1.290( ±0.378); (R2 = 0.988) \ln \,k_{\text{D}} = - 3717( \pm 416)/T(K) + 1.290( \pm 0.378);\quad (R^{2} = 0.988) . The closure temperature (T
c) calculated using this equation was ∼740(±30)°C. Analysis of the kinetic data carried out taking into account the e.s.d.'s
of the atomic fractions used to define the Fe–Mg degree of order, performed according to Mueller’s model, allowed us to retrieve
the disordering rate constants C
0
K
dis+ for all three temperatures yielding the following Arrhenius relation:
ln( C0 K\textdis + ) = ln K0 - Q/(RT) = 20.99( ±3.74) - 26406( ±4165)/T(K); (R2 = 0.988) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = \ln \,K_{0} - Q/(RT) = 20.99( \pm 3.74) - 26406( \pm 4165)/T(K);\quad (R^{2} = 0.988) . An activation energy of 52.5(±4) kcal/mol for the Fe–Mg exchange process was obtained. The above relation was used to calculate
the following Arrhenius relation modified as a function of X
Fe (in the range of X
Fe = 0.20–0.50):
ln( C0 K\textdis + ) = (21.185 - 1.47X\textFe ) - \frac(27267 - 4170X\textFe )T(K) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = (21.185 - 1.47X_{\text{Fe}} ) - {\frac{{(27267 - 4170X_{\text{Fe}} )}}{T(K)}} . The cooling time constant, η = 6 × 10−1 K−1 year−1 calculated on the PCA82506-3 sample, provided a cooling rate of the order of 1°C/min consistent with the extremely fast late
cooling history of the ureilite parent body after impact excavation. 相似文献
13.
Li diffusion in zircon 总被引：2，自引：2，他引：0
Diffusion of Li under anhydrous conditions at 1 atm and under fluid-present elevated pressure (1.0–1.2 GPa) conditions has
been measured in natural zircon. The source of diffusant for 1-atm experiments was ground natural spodumene, which was sealed
under vacuum in silica glass capsules with polished slabs of zircon. An experiment using a Dy-bearing source was also conducted
to evaluate possible rate-limiting effects on Li diffusion of slow-diffusing REE+3 that might provide charge balance. Diffusion experiments performed in the presence of H2O–CO2 fluid were run in a piston–cylinder apparatus, using a source consisting of a powdered mixture of spodumene, quartz and zircon
with oxalic acid added to produce H2O–CO2 fluid. Nuclear reaction analysis (NRA) with the resonant nuclear reaction 7Li(p,γ)8Be was used to measure diffusion profiles for the experiments. The following Arrhenius parameters were obtained for Li diffusion
normal to the c-axis over the temperature range 703–1.151°C at 1 atm for experiments run with the spodumene source:
|
D\textLi = 7.17 ×10 - 7 exp( - 275 ±11 \textkJmol - 1 /\textRT)\textm2 \texts - 1. D_{\text{Li}} = 7.17 \times 10^{ - 7} { \exp }( - 275 \pm 11\,{\text{kJmol}}^{ - 1} /{\text{RT}}){\text{m}}^{2} {\text{s}}^{ - 1}. 相似文献
14.
D. Howell I. G. Wood D. P. Dobson A. P. Jones L. Nasdala J. W. Harris 《Contributions to Mineralogy and Petrology》2010,160(5):705-717
The pressure and temperature conditions of formation of natural diamond can be estimated by measuring the residual stress
that an inclusion remains under within a diamond. Raman spectroscopy has been the most commonly used technique for determining
this stress by utilising pressure-sensitive peak shifts in the Raman spectrum of both the inclusion and the diamond host.
Here, we present a new approach to measure the residual stress using quantitative analysis of the birefringence induced in
the diamond. As the analysis of stress-induced birefringence is very different from that of normal birefringence, an analytical
model is developed that relates the spherical inclusion size, R
i, host diamond thickness, L, and measured value of birefringence at the edge of the inclusion,
\Updelta n(R\texti )\textav \Updelta n(R_{\text{i}} )_{\text{av}} , to the peak value of birefringence that has been encountered; to first order
\Updelta n\textpk = (3/4)(L/R\texti ) \Updelta n(R\texti )\textav \Updelta n_{\text{pk}} = (3/4)(L/R_{\text{i}} ) \, \Updelta n(R_{\text{i}} )_{\text{av}} . From this birefringence, the remnant pressure (P
i) can be calculated using the photoelastic relationship
\Updelta n\textpk = - (3/4)n3 q\textiso P\texti \Updelta n_{\text{pk}} = - (3/4)n^{3} q_{\text{iso}} P_{\text{i}} , where q
iso is a piezo-optical coefficient, which can be assumed to be independent of crystallographic orientation, and n is the refractive index of the diamond. This model has been used in combination with quantitative birefringence analysis
with a MetriPol system and compared to the results from both Raman point and 2D mapping analysis for a garnet inclusion in
a diamond from the Udachnaya mine (Russia) and coesite inclusions in a diamond from the Finsch mine (South Africa). The birefringence
model and analysis gave a remnant pressure of 0.53 ± 0.01 GPa for the garnet inclusion, from which a source pressure was calculated
as 5.7 GPa at 1,175°C (temperature obtained from IR analysis of the diamond host). The Raman techniques could not be applied
quantitatively to this sample to support the birefringence model; they were, however, applied to the largest coesite inclusion
in the Finsch sample. The remnant pressure values obtained were 2.5 ± 0.1 GPa (birefringence), 2.5 ± 0.3 GPa (2D Raman map),
and 2.5–2.6 GPa (Raman point analysis from all four inclusions). However, although the remnant pressures from the three methods
were self-consistent, they led to anomalously low source pressure of 2.9 GPa at 1,150°C (temperature obtained from IR analysis)
raising serious concerns about the use of the coesite-in-diamond geobarometer. 相似文献
15.
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.
16.
David L. Naftz Frank J. Millero Blair F. Jones W. Reed Green 《Aquatic Geochemistry》2011,17(6):809-820
Great Salt Lake (GSL) is one of the largest and most saline lakes in the world. In order to accurately model limnological
processes in GSL, hydrodynamic calculations require the precise estimation of water density (ρ) under a variety of environmental conditions. An equation of state was developed with water samples collected from GSL to
estimate density as a function of salinity and water temperature. The ρ of water samples from the south arm of GSL was measured as a function of temperature ranging from 278 to 323 degrees Kelvin
(oK) and conductivity salinities ranging from 23 to 182 g L−1 using an Anton Paar density meter. These results have been used to develop the following equation of state for GSL (σ = ± 0.32 kg m−3):
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