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1.
The diffusion of Ni and Co was measured at atmospheric pressure in synthetic monocrystalline forsterite (Mg2SiO4) from 1,200 to 1,500 °C at the oxygen fugacity of air, along [100], with the activities of SiO2 and MgO defined by either forsterite + periclase (fo + per buffer) or forsterite + protoenstatite (fo + en buffer). Diffusion profiles were measured by three methods: laser-ablation inductively-coupled-plasma mass-spectrometry, nano-scale secondary ion mass spectrometry and electron microprobe, with good agreement between the methods. For both Ni and Co, the diffusion rates in protoenstatite-buffered experiments are an order of magnitude faster than in the periclase-buffered experiments at a given temperature. The diffusion coefficients D M (M = Ni or Co) for the combined data set can be fitted to the equation:
$$\log \,D_{\text{M}} \,\left( {{\text{in}}\,{\text{m}}^{2} \,{\text{s}}^{ - 1} } \right) = - 6.77( \pm 0.33) + \Delta E_{\text{a}} (M)/RT + 2/3\log a_{{SiO_{2} }}$$
with Ea(Ni) = ? 284.3 kJ mol?1 and Ea(Co) = ? 275.9 kJ mol?1, with an uncertainty of ±10.2 kJ mol?1. This equation fits the data (24 experiments) to ±0.1 in log D M. The dependence of diffusion on \(a_{{{\text{SiO}}_{2} }}\) is in agreement with a point-defect model in which Mg-site vacancies are charge-balanced by Si interstitials. Comparative experiments with San Carlos olivine of composition Mg1.8Fe0.2SiO4 at 1,300 °C give a slightly small dependence on \(a_{{{\text{SiO}}_{2} }}\), with D \(\propto\) (\(a_{{{\text{SiO}}_{2} }}^{0.5}\)), presumably because the Mg-site vacancies increase with incorporation of Fe3+ in the Fe-bearing olivines. However, the dependence on fO2 is small, with D \(\propto\) (fO2)0.12±0.12. These results show the necessity of constraining the chemical potentials of all the stoichiometric components of a phase when designing diffusion experiments. Similarly, the chemical potentials of the major-element components must be taken into account when applying experimental data to natural minerals to constrain the rates of geological processes. For example, the diffusion of divalent elements in olivine from low SiO2 magmas, such as kimberlites or carbonatites, will be an order of magnitude slower than in olivine from high SiO2 magmas, such as tholeiitic basalts, at equal temperatures and fO2.
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2.
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3.
Isotope fractionation during the evaporation of silicate melt and condensation of vapor has been widely used to explain various isotope signals observed in lunar soils, cosmic spherules, calcium–aluminum-rich inclusions, and bulk compositions of planetary materials. During evaporation and condensation, the equilibrium isotope fractionation factor (α) between high-temperature silicate melt and vapor is a fundamental parameter that can constrain the melt’s isotopic compositions. However, equilibrium α is difficult to calibrate experimentally. Here we used Mg as an example and calculated equilibrium Mg isotope fractionation in MgSiO3 and Mg2SiO4 melt–vapor systems based on first-principles molecular dynamics and the high-temperature approximation of the Bigeleisen–Mayer equation. We found that, at 2500 K, δ25Mg values in the MgSiO3 and Mg2SiO4 melts were 0.141?±?0.004 and 0.143?±?0.003‰ more positive than in their respective vapors. The corresponding δ26Mg values were 0.270?±?0.008 and 0.274?±?0.006‰ more positive than in vapors, respectively. The general \(\alpha - T\) equations describing the equilibrium Mg α in MgSiO3 and Mg2SiO4 melt–vapor systems were: \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.264 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\) and \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.340 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\), respectively, where m is the mass of light isotope 24Mg and m′ is the mass of the heavier isotope, 25Mg or 26Mg. These results offer a necessary parameter for mechanistic understanding of Mg isotope fractionation during evaporation and condensation that commonly occurs during the early stages of planetary formation and evolution.  相似文献   

4.
Diffusion couple experiments with wet half (up to 4.6 wt%) and dry half were carried out at 789–1,516 K and 0.47–1.42 GPa to investigate water diffusion in a peralkaline rhyolitic melt with major oxide concentrations matching Mount Changbai rhyolite. Combining data from this work and a related study, total water diffusivity in peralkaline rhyolitic melt can be expressed as:
$ D_{{{\text{H}}_{ 2} {\text{O}}_{\text{t}} }} = D_{{{\text{H}}_{ 2} {\text{O}}_{\text{m}} }} \left( {1 - \frac{0.5 - X}{{\sqrt {[4\exp (3110/T - 1.876) - 1](X - X^{2} ) + 0.25} }}} \right), $
$ {\text{with}}\;D_{{{\text{H}}_{ 2} {\text{O}}_{\text{m}} }} = \exp \left[ { - 1 2. 7 8 9- \frac{13939}{T} - 1229.6\frac{P}{T} + ( - 27.867 + \frac{60559}{T})X} \right], $
where D is in m2 s?1, T is the temperature in K, P is the pressure in GPa, and X is the mole fraction of water and calculated as X = (C/18.015)/(C/18.015 + (100 ? C)/33.14), where C is water content in wt%. We recommend this equation in modeling bubble growth and volcanic eruption dynamics in peralkaline rhyolitic eruptions, such as the ~1,000-ad eruption of Mount Changbai in North East China. Water diffusivities in peralkaline and metaluminous rhyolitic melts are comparable within a factor of 2, in contrast with the 1.0–2.6 orders of magnitude difference in viscosities. The decoupling of diffusivity of neutral molecular species from melt viscosity, i.e., the deviation from the inversely proportional relationship predicted by the Stokes–Einstein equation, might be attributed to the small size of H2O molecules. With distinct viscosities but similar diffusivity, bubble growth controlled by diffusion in peralkaline and metaluminous rhyolitic melts follows similar parabolic curves. However, at low confining pressure or low water content, viscosity plays a larger role and bubble growth rate in peralkaline rhyolitic melt is much faster than that in metaluminous rhyolite.
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5.
The crystallization of plagioclase-bearing assemblages in mantle rocks is witness of mantle exhumation at shallow depth. Previous experimental works on peridotites have found systematic compositional variations in coexisting minerals at decreasing pressure within the plagioclase stability field. In this experimental study we present new constraints on the stability of plagioclase as a function of different Na2O/CaO bulk ratios, and we present a new geobarometer for mantle rocks. Experiments have been performed in a single-stage piston cylinder at 5–10 kbar, 1050–1150?°C at nominally anhydrous conditions using seeded gels of peridotite compositions (Na2O/CaO?=?0.08–0.13; X Cr = Cr/(Cr?+?Al)?=?0.07–0.10) as starting materials. As expected, the increase of the bulk Na2O/CaO ratio extends the plagioclase stability to higher pressure; in the studied high-Na fertile lherzolite (HNa-FLZ), the plagioclase-spinel transition occurs at 1100?°C between 9 and 10 kbar; in a fertile lherzolite (FLZ) with Na2O/CaO?=?0.08, it occurs between 8 and 9 kbar at 1100?°C. This study provides, together with previous experimental results, a consistent database, covering a wide range of P–T conditions (3–9 kbar, 1000–1150?°C) and variable bulk compositions to be used to define and calibrate a geobarometer for plagioclase-bearing mantle rocks. The pressure sensitive equilibrium:
$$\mathop {{\text{M}}{{\text{g}}_{\text{2}}}{\text{Si}}{{\text{O}}_{\text{4}}}^{{\text{Ol}}}}\limits_{{\text{Forsterite}}} +\mathop {{\text{CaA}}{{\text{l}}_{\text{2}}}{\text{S}}{{\text{i}}_{\text{2}}}{{\text{O}}_{\text{8}}}^{{\text{Pl}}}}\limits_{{\text{Anorthite}}~} =\mathop {{\text{CaA}}{{\text{l}}_{\text{2}}}{\text{Si}}{{\text{O}}_{\text{6}}}^{{\text{Cpx}}}}\limits_{{\text{Ca-Tschermak}}} +{\text{ }}\mathop {{\text{M}}{{\text{g}}_{\text{2}}}{\text{S}}{{\text{i}}_{\text{2}}}{{\text{O}}_{\text{6}}}^{{\text{Opx}}}}\limits_{{\text{Enstatite}}} ,$$
has been empirically calibrated by least squares regression analysis of experimental data combined with Monte Carlo simulation. The result of the fit gives the following equation:
$$P=7.2( \pm 2.9)+0.0078( \pm 0.0021)T{\text{ }}+0.0022( \pm 0.0001)T{\text{ }}\ln K,$$
$${R^2}=0.93,$$
where P is expressed in kbar and T in kelvin. K is the equilibrium constant K?=?a CaTs × a en/a an × a fo, where a CaTs, a en, a an and a fo are the activities of Ca-Tschermak in clinopyroxene, enstatite in orthopyroxene, anorthite in plagioclase and forsterite in olivine. The proposed geobarometer for plagioclase peridotites, coupled to detailed microstructural and mineral chemistry investigations, represents a valuable tool to track the exhumation of the lithospheric mantle at extensional environments.
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6.
The solubility of chromium in chlorite as a function of pressure, temperature, and bulk composition was investigated in the system Cr2O3–MgO–Al2O3–SiO2–H2O, and its effect on phase relations evaluated. Three different compositions with X Cr = Cr/(Cr + Al) = 0.075, 0.25, and 0.5 respectively, were investigated at 1.5–6.5 GPa, 650–900 °C. Cr-chlorite only occurs in the bulk composition with X Cr = 0.075; otherwise, spinel and garnet are the major aluminous phases. In the experiments, Cr-chlorite coexists with enstatite up to 3.5 GPa, 800–850 °C, and with forsterite, pyrope, and spinel at higher pressure. At P > 5 GPa other hydrates occur: a Cr-bearing phase-HAPY (Mg2.2Al1.5Cr0.1Si1.1O6(OH)2) is stable in assemblage with pyrope, forsterite, and spinel; Mg-sursassite coexists at 6.0 GPa, 650 °C with forsterite and spinel and a new Cr-bearing phase, named 11.5 Å phase (Mg:Al:Si = 6.3:1.2:2.4) after the first diffraction peak observed in high-resolution X-ray diffraction pattern. Cr affects the stability of chlorite by shifting its breakdown reactions toward higher temperature, but Cr solubility at high pressure is reduced compared with the solubility observed in low-pressure occurrences in hydrothermal environments. Chromium partitions generally according to \(X_{\text{Cr}}^{\text{spinel}}\) ? \(X_{\text{Cr}}^{\text{opx}}\) > \(X_{\text{Cr}}^{\text{chlorite}}\) ≥ \(X_{\text{Cr}}^{\text{HAPY}}\) > \(X_{\text{Cr}}^{\text{garnet}}\). At 5 GPa, 750 °C (bulk with X Cr = 0.075) equilibrium values are \(X_{\text{Cr}}^{\text{spinel}}\) = 0.27, \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.08, \(X_{\text{Cr}}^{\text{garnet}}\) = 0.05; at 5.4 GPa, 720 °C \(X_{\text{Cr}}^{\text{spinel}}\) = 0.33, \(X_{\text{Cr}}^{\text{HAPY}}\) = 0.06, and \(X_{\text{Cr}}^{\text{garnet}}\) = 0.04; and at 3.5 GPa, 850 °C \(X_{\text{Cr}}^{\text{opx}}\) = 0.12 and \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.07. Results on Cr–Al partitioning between spinel and garnet suggest that at low temperature the spinel- to garnet-peridotite transition has a negative slope of 0.5 GPa/100 °C. The formation of phase-HAPY, in assemblage with garnet and spinel, at pressures above chlorite breakdown, provides a viable mechanism to promote H2O transport in metasomatized ultramafic mélanges of subduction channels.  相似文献   

7.
We have collected high resolution neutron powder diffraction patterns from Na2SO4·10D2O over the temperature range 4.2–300 K following rapid quenching in liquid nitrogen, and over a series of slow warming and cooling cycles. The crystal is monoclinic, space-group P21/c (Z = 4) with a = 11.44214(4) Å, b = 10.34276(4) Å, c = 12.75486(6) Å, β = 107.847(1)°, and V = 1436.794(8) Å3 at 4.2 K (slowly cooled), and a = 11.51472(6) Å, b = 10.36495(6) Å, c = 12.84651(7) Å, β = 107.7543(1)°, V = 1460.20(1) Å3 at 300 K. Structures were refined to R P (Rietveld powder residual, \( R_{P} = {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } \mathord{\left/ {\vphantom {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } {\sum {I_{\text{obs}} } }}} \right. \kern-\nulldelimiterspace} {\sum {I_{\text{obs}} } }} \)) better than 2.5% at 4.2 K (quenched and slow cooled), 150 and 300 K. The sulfate disorder observed previously by Levy and Lisensky (Acta Cryst B34:3502–3510, 1978) was not present in our specimen, but we did observe changes with temperature in deuteron occupancies of the orientationally disordered water molecules coordinated to Na. The temperature dependence of the unit-cell volume from 4.2 to 300 K is well represented by a simple polynomial of the form V = ? 4.143(1) × 10?7 T 3 + 0.00047(2) T2 ? 0.027(2) T + 1437.0(1) Å3 (R 2 = 99.98%). The coefficient of volume thermal expansion, α V , is positive above 40 K, and displays a similar magnitude and temperature dependence to α V in deuterated epsomite and meridianiite. The relationship between the magnitude and orientation of the principal axes of the thermal expansion tensor and the main structural elements are discussed; freezing in of deuteron disorder in the quenched specimen affects the thermal expansion, manifested most obviously as a change in the behaviour of the unit-cell parameter β.  相似文献   

8.
The crystal chemistry of a ferroaxinite from Colebrook Hill, Rosebery district, Tasmania, Australia, was investigated by electron microprobe analysis in wavelength-dispersive mode, inductively coupled plasma–atomic emission spectroscopy (ICP–AES), 57Fe Mössbauer spectroscopy and single-crystal neutron diffraction at 293 K. The chemical formula obtained on the basis of the ICP–AES data is the following: \( ^{X1,X2} {\text{Ca}}_{4.03} \,^{Y} \left( {{\text{Mn}}_{0.42} {\text{Mg}}_{0.23} {\text{Fe}}^{2 + }_{1.39} } \right)_{\varSigma 2.04} \,^{Z1,Z2} \left( {{\text{Fe}}^{3 + }_{0.15} {\text{Al}}_{3.55} {\text{Ti}}_{0.12} } \right)_{\varSigma 3.82} \,^{T1,T2,T3,T4} \left( {{\text{Ti}}_{0.03} {\text{Si}}_{7.97} } \right)_{\varSigma 8} \,^{T5} {\text{B}}_{1.96} {\text{O}}_{30} \left( {\text{OH}} \right)_{2.18} \). The 57Fe Mössbauer spectrum shows unambiguously the occurrence of Fe2+ and Fe3+ in octahedral coordination only, with Fe2+/Fe3+ = 9:1. The neutron structure refinement provides a structure model in general agreement with the previous experimental findings: the tetrahedral T1, T2, T3 and T4 sites are fully occupied by Si, whereas the T5 site is fully occupied by B, with no evidence of Si at the T5, or Al or Fe3+ at the T1–T5 sites. The structural and chemical data of this study suggest that the amount of B in ferroaxinite is that expected from the ideal stoichiometry: 2 a.p.f.u. (for 32 O). The atomic distribution among the X1, X2, Y, Z1 and Z2 sites obtained by neutron structure refinement is in good agreement with that based on the ICP–AES data. For the first time, an unambiguous localization of the H site is obtained, which forms a hydroxyl group with the oxygen atom at the O16 site as donor. The H-bonding scheme in axinite structure is now fully described: the O16–H distance (corrected for riding motion effect) is 0.991(1) Å and an asymmetric bifurcated bonding configuration occurs, with O5 and O13 as acceptors [i.e. with O16···O5 = 3.096(1) Å, H···O5 = 2.450(1) Å and O16–H···O5 = 123.9(1)°; O16···O13 = 2.777(1) Å, H···O13 = 1.914(1) Å and O16–H···O13 = 146.9(1)°].  相似文献   

9.
The liquidus water content of a haplogranite melt at high pressure (P) and temperature (T) is important, because it is a key parameter for constraining the volume of granite that could be produced by melting of the deep crust. Previous estimates based on melting experiments at low P (≤0.5 GPa) show substantial scatter when extrapolated to deep crustal P and T (700–1000 °C, 0.6–1.5 GPa). To improve the high-P constraints on H2O concentration at the granite liquidus, we performed experiments in a piston–cylinder apparatus at 1.0 GPa using a range of haplogranite compositions in the albite (Ab: NaAlSi3O8)—orthoclase (Or: KAlSi3O8)—quartz (Qz: SiO2)—H2O system. We used equal weight fractions of the feldspar components and varied the Qz between 20 and 30 wt%. In each experiment, synthetic granitic composition glass + H2O was homogenized well above the liquidus T, and T was lowered by increments until quartz and alkali feldspar crystalized from the liquid. To establish reversed equilibrium, we crystallized the homogenized melt at the lower T and then raised T until we found that the crystalline phases were completely resorbed into the liquid. The reversed liquidus minimum temperatures at 3.0, 4.1, 5.8, 8.0, and 12.0 wt% H2O are 935–985, 875–900, 775–800, 725–775, and 650–675 °C, respectively. Quenched charges were analyzed by petrographic microscope, scanning electron microscope (SEM), X-ray diffraction (XRD), and electron microprobe analysis (EMPA). The equation for the reversed haplogranite liquidus minimum curve for Ab36.25Or36.25Qz27.5 (wt% basis) at 1.0 GPa is \(T = - 0.0995 w_{{{\text{H}}_{ 2} {\text{O}}}}^{ 3} + 5.0242w_{{{\text{H}}_{ 2} {\text{O}}}}^{ 2} - 88.183 w_{{{\text{H}}_{ 2} {\text{O}}}} + 1171.0\) for \(0 \le w_{{{\text{H}}_{ 2} {\text{O}}}} \le 17\) wt% and \(T\) is in °C. We present a revised \(P - T\) diagram of liquidus minimum H2O isopleths which integrates data from previous determinations of vapor-saturated melting and the lower pressure vapor-undersaturated melting studies conducted by other workers on the haplogranite system. For lower H2O (<5.8 wt%) and higher temperature, our results plot on the high end of the extrapolated water contents at liquidus minima when compared to the previous estimates. As a consequence, amounts of metaluminous granites that can be produced from lower crustal biotite–amphibole gneisses by dehydration melting are more restricted than previously thought.  相似文献   

10.
The specific heat capacity (C p) of six variably hydrated (~3.5 wt% H2O) iron-bearing Etna trachybasaltic glasses and liquids has been measured using differential scanning calorimetry from room temperature across the glass transition region. These data are compared to heat capacity measurements on thirteen melt compositions in the iron-free anorthite (An)–diopside (Di) system over a similar range of H2O contents. These data extend considerably the published C p measurements for hydrous melts and glasses. The results for the Etna trachybasalts show nonlinear variations in, both, the heat capacity of the glass at the onset of the glass transition (i.e., C p g ) and the fully relaxed liquid (i.e., C p l ) with increasing H2O content. Similarly, the “configurational heat capacity” (i.e., C p c  = C p l  ? C p g ) varies nonlinearly with H2O content. The An–Di hydrous compositions investigated show similar trends, with C p values varying as a function of melt composition and H2O content. The results show that values in hydrous C p g , C p l and C p c in the depolymerized glasses and liquids are substantially different from those observed for more polymerized hydrous albitic, leucogranitic, trachytic and phonolitic multicomponent compositions previously investigated. Polymerized melts have lower C p l and C p c and higher C p g with respect to more depolymerized compositions. The covariation between C p values and the degree of polymerization in glasses and melts is well described in terms of SMhydrous and NBO/T hydrous. Values of C p c increase sharply with increasing depolymerization up to SMhydrous ~ 30–35 mol% (NBO/T hydrous ~ 0.5) and then stabilize to an almost constant value. The partial molar heat capacity of H2O for both glasses (\( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{g}} \)) and liquids (\( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \)) appears to be independent of composition and, assuming ideal mixing, we obtain a value for \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \) of 79 J mol?1 K?1. However, we note that a range of values for \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \) (i.e., ~78–87 J mol?1 K?1) proposed by previous workers will reproduce the extended data to within experimental uncertainty. Our analysis suggests that more data are required in order to ascribe a compositional dependence (i.e., nonideal mixing) to \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \).  相似文献   

11.
The effect of alkalis on the solubility of H2O and CO2 in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H2O/(H2O + CO2) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H2O solubility (melt equilibrated with pure H2O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO2 content in melts equilibrated with CO2-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO2 contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO2 solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO2 solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO2 solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.  相似文献   

12.
We discuss the experimental results of silicon and oxygen self-diffusion coefficients in forsterite and iron-bearing olivine from the perspective of defect chemistry. Silicon diffusion is dominated by VO ··-associated VSi″″, whereas oxygen diffusion is dominated by hopping of VO ·· under anhydrous conditions, and by (OH)O · under hydrous conditions. By considering the charge neutrality condition of [(OH)O ·] = 2[VMe″] in hydrous forsterite and iron-bearing olivine, we get D Si ∝ (\(C_{{{\text{H}}_{2} {\text{O}}}}\))1/3 and D O ∝ (\(C_{{{\text{H}}_{2} {\text{O}}}}\))0, which explains the experimental results of water effects on oxygen and silicon self-diffusion rates (Fei et al. in Nature 498:213–215, 2013; J Geophys Res 119:7598–7606, 2014). The \(C_{{{\text{H}}_{2} {\text{O}}}}\) dependence of creep rate in the Earth’s mantle should be close to that given by Si and O self-diffusion coefficients obtained under water unsaturated conditions.  相似文献   

13.
Titanium- and water-rich metamorphic olivine (Fo 86–88) is reported from partially dehydrated serpentinites from the Voltri complex, Ligurian Alps. The rocks are composed of mostly antigorite and olivine in addition to magnetite, chlorite, clinopyroxene and Ti-clinohumite. In situ secondary ion mass spectrometry (SIMS) data show that metamorphic olivine has very high and strongly correlated H2O (up to 0.7 wt%) and TiO2 contents (up to 0.85 wt%). Ti-rich olivine shows colourless to yellow pleochroism. Olivine associated with Ti-clinohumite contains low Ti, suggesting that Ti-rich olivine is not the breakdown product of Ti-clinohumite. Fourier transform infrared spectroscopy (FTIR) absorption spectra show peaks of serpentine, Ti-clinohumite and OH-related Si vacancies. Combining FTIR and SIMS data, we suggest the presence of clustered planar defects or nanoscale exsolutions of Ti-clinohumite in olivine. These defects or exsolutions contain more H2O (x ~ 0.1 in the formula 4Mg2SiO4·(1?x)Mg(OH,F)2·xTiO2) than Ti-clinohumite in the sample matrix (x = 0.34–0.46). In addition to TiO2 and H2O, secondary olivine contains significant Li (2–60 ppm), B (10–20 ppm), F (10–130 ppm) and Zr (0.9–2.1 ppm). It is enriched in 11B (δ11B = +17 to +23 ‰). Our data indicate that secondary olivine may play a significant role in transporting water, high-field strength and fluid-mobile elements into the deeper mantle as well as introduce significant B isotope anomalies. Release of hydrogen from H2O-rich olivine subducted into the deep mantle may result in strongly reduced mantle domains.  相似文献   

14.
Using a diamond-anvil cell and synchrotron X-ray diffraction, the compressional behavior of a synthetic qandilite Mg2.00(1)Ti1.00(1)O4 has been investigated up to about 14.9 GPa at 300 K. The pressure–volume data fitted to the third-order Birch–Murnaghan equation of state yield an isothermal bulk modulus (K T0) of 175(5) GPa, with its first derivative \(K_{T0}^{{\prime }}\) attaining 3.5(7). If \(K_{T0}^{{\prime }}\) is fixed as 4, the K T0 value is 172(1) GPa. This value is substantially larger than the value of the adiabatic bulk modulus (K S0) previously determined by an ultrasonic pulse echo method (152(7) GPa; Liebermann et al. in Geophys J Int 50:553–586, 1977), but in general agreement with the K T0 empirically estimated on the basis of crystal chemical systematics (169 GPa; Hazen and Yang in Am Miner 84:1956–1960, 1999). Compared to the K T0 values of the ulvöspinel (Fe2TiO4; ~148(4) GPa with \(K_{T0}^{{\prime }} = 4\)) and the ringwoodite solid solutions along the Mg2SiO4–Fe2SiO4 join, our finding suggests that the substitution of Mg2+ for Fe2+ on the T sites of the 4–2 spinels can have more significant effect on the K T0 than that on the M sites.  相似文献   

15.
The hydroxyl (O(4)) site composition of biotite can in principle be used to retrieve information about fluid composition during fluid–rock interaction; however, due to low F and Cl content, as well as difficulties involved with analyzing the H2O content using in situ techniques, measuring these species in biotite has remained an elusive goal. Here we present high-precision secondary ion mass spectrometry (SIMS) OH–F–Cl measurements from biotite within metapelites from the Western Adamello Tonalite (WAT) contact aureole, Northern Italy. Fluorine, chlorine and hydrogen are analyzed on the SIMS sequentially by peak-hopping at the same biotite spot; H2O, F and Cl content were measured with a precision (1σ) οφ 0.06 ωτ%, 50 ανδ 5 ππµ, ρεσπεχτι?ελψ. The compositions of isolated biotite crystals in andalusite are compared with that of biotite in the matrix, documenting that halogens and H2O behave refractory in biotite during the time scale of contact metamorphism. The H2O and halogen contents of biotite are mostly locked in during the prograde to peak formation of biotite, and are not reset during further heating or cooling, unless significant biotite recrystallization occurs. It also appears that both Ti content and XMg of the biotite from the Western Adamello contact aureole were not significantly reset during cooling. The concentration of F and Cl does not vary systematically with metamorphic grade, which indicates that these species reflect initial compositions. No significant Rayleigh fractionation behavior was observed for these elements. H2O variations in the biotite from samples throughout the Western Adamello contact aureole suggest that Al-oxy substitution partially controls the variations in OH content through charge balance of the type R2+,VI + OH? = Al3+,VI + O2? + H2, while the Ti-oxy substitution does not seem to influence the O(4) site occupation. The main titanium substitution appears to be the Ti-vacancy (\({\text{2}}{{\text{R}}^{{\text{2}}+}}~=~{\text{T}}{{\text{i}}^{{\text{4}}+}}~+\,{\square ^{{\text{VI}}}}\)) exchange. Variations in H2O and halogen concentrations in biotite define sub mm-scale areas of localized equilibration, even for biotite recrystallized during dehydration reactions that produced large amounts of fluid (chlorite or muscovite breakdown). Similar systematics were observed for Ti4+ and Al3+. These findings further support the increasing number of observations that kinetics control much of the mineralogical reactions occurring in contact aureoles, and hence care is advised in using equilibrium thermodynamics in this environment.  相似文献   

16.
We report new experimental data on the composition of magmatic amphiboles synthesised from a variety of granite (sensu lato) bulk compositions at near-solidus temperatures and pressures of 0.8–10 kbar. The total aluminium content (Altot) of the synthetic calcic amphiboles varies systematically with pressure (P), although the relationship is nonlinear at low pressures (<2.5 kbar). At higher pressures, the relationship resembles that of other experimental studies, which suggests of a general relationship between Altot and P that is relatively insensitive to bulk composition. We have developed a new Al-in-hornblende geobarometer that is applicable to granitic rocks with the low-variance mineral assemblage: amphibole + plagioclase (An15–80) + biotite + quartz + alkali feldspar + ilmenite/titanite + magnetite + apatite. Amphibole analyses should be taken from the rims of grains, in contact with plagioclase and in apparent textural equilibrium with the rest of the mineral assemblage at temperatures close to the haplogranite solidus (725 ± 75 °C), as determined from amphibole–plagioclase thermometry. Mean amphibole rim compositions that meet these criteria can then be used to calculate P (in kbar) from Altot (in atoms per formula unit, apfu) according to the expression:
$${\textit{P }}\left( {\text{kbar}} \right) = 0.5 + 0.331\left( 8 \right) \times {\text{Al}}^{\text{tot}} + 0.995\left( 4 \right) \times \left( {{\text{Al}}^{\text{tot}} } \right)^{2}$$
This expression recovers equilibration pressures of our calibrant dataset, comprising both new and published experimental and natural data, to within ±16 % relative uncertainty. An uncertainty of 10 % relative for a typical Altot value of 1.5 apfu translates to an uncertainty in pressure estimate of 0.5 kbar, or 15 % relative. Thus the accuracy of the barometer expression is comparable to the precision with which near-solidus amphibole rim composition can be characterised.
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17.
In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO2 and ZrO2; Al/(Na + K) molar ~1.2] at a pressure of 10 kbar and temperatures of ~1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO2 contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4–7.0 wt%. TiO2 contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO2 concentrations (0.2–1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO2 in rutile $ \left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) $ in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of ~1,400 to 675 °C) yields the following temperature-dependent expression: $ {\text{ln}}\left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) + {\text{ln}}\left( {a_{{{\text{SiO}}_{2} }} } \right) = 2.638(149) - 9969(190)/T({\text{K}}) $ , where silica activity $ a_{{{\text{SiO}}_{2} }} $ in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and $ \mathop X\nolimits_{{{\text{ZrO}}_{2} }}^{\text{rt}} $ . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of ~100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ for each experiment, zircon Ti concentrations (ppm) can be related to temperature over the range of ~1,400 to 1,200 °C by the expression: $ \ln \left( {\text{Ti ppm}} \right)^{\text{zrc}} + \ln \left( {a_{{{\text{SiO}}_{2} }} } \right) - \ln \left( {a_{{{\text{TiO}}_{2} }} } \right) = 13.84\left( {71} \right) - 12590\left( {1124} \right)/T\left( {\text{K}} \right) $ . After accounting for differences in $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ , Ti contents of zircon from experiments run with bulk compositions based on the natural granite overlap with the concentrations measured on zircon from experiments using the synthetic bulk compositions. Coupled with data from the literature, this suggests that at T ≥ 1,100 °C, natural levels of minor and trace elements in “granitic” melts do not appear to influence the solubility of Ti in zircon. Whether this is true at magmatic temperatures of crustal hydrous silica-rich liquids (e.g., 800–700 °C) remains to be demonstrated. Finally, measured $ D_{\text{Ti}}^{{{\text{zrc}}/{\text{melt}}}} $ values (calculated on a weight basis) from the experiments presented here are 0.007–0.01, relatively independent of temperature, and broadly consistent with values determined from natural zircon and silica-rich glass pairs.  相似文献   

18.
The rate of non-oxidative galena dissolution in seawater compositions over the pH range of 2–4.5 was determined from batch reactor experiments. The derivative at zero time of a polynomial fit of the Pb concentration versus time data for the first 30 min was used to determine the rate. A plot of RGn (rate of galena dissolution) versus pH for data from six experiments is linear (R2?=?0.96), with a slope of 0.5. The rate equation describing the rate of galena dissolution as a function of hydrogen ion activity is
$$R_{\text{Gn}} = - \,10^{ - 10.72} \left( {a_{{{\text{H}}^{ + } }} } \right)^{0.50}$$
Varying the concentration of dissolved oxygen produced no significant effect on the measured rates. The activation energy, based on four experiments carried out over the temperature range of 7–30 °C, is 61.1 kJ/mol.
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19.
The crystal structure and chemical composition of a crystal of (Mg14?x Cr x )(Si5?x Cr x )O24 (x ≈ 0.30) anhydrous Phase B (Anh-B) synthesized in the model system MgCr2O4–Mg2SiO4 at 12 GPa and 1600 °C have been investigated. The compound was found to be orthorhombic, space group Pmcb, with lattice parameters a = 5.900(1), b = 14.218(2), c = 10.029(2) Å, V = 841.3(2) Å3 and Z = 2. The structure was refined to R 1 = 0.065 using 1492 independent reflections. Chromium was found to substitute for both Mg at the M3 site (with a mean bond distance of 2.145 Å) and Si at the octahedral Si1 site (mean bond distance: 1.856 Å), according to the reaction Mg2+ + Si4+ = 2Cr3+. Such substitutions cause a reduction in the volume of the M3 site and an increase in the volume of the Si-dominant octahedron with respect to the values typically observed for pure Anh-B and Fe2+-bearing Anh-B. Taking into account that Cr3+ is not expected to be Jahn–Teller active, it appears that both the Cr3+–for–Mg and Cr3+–for–Si substitutions in the Anh-B structure decrease the distortion of the octahedra. Electron microprobe analysis gave the Mg13.66(8)Si4.70(6)Cr0.62(4)O24 stoichiometry for the studied phase. The successful synthesis of this phase provides new information for the possible mineral assemblages occurring in the Earth’s deep upper mantle and shed new light on the so-called X discontinuity that has been observed at 275–345 km depth in several subcontinental and subduction zone environments.  相似文献   

20.
Theoretical and practical considerations are combined to place limits on the iron content of an FePt alloy that is in equilibrium with silicate melt, olivine and a gas phase of known \(f_{{\text{O}}_{\text{2}} }\) . Equilibrium constants are calculated for the reactions: (1) $$2{\text{Fe}}^{\text{o}} + {\text{SiO}}_{\text{2}} + {\text{O}}_{\text{2}} \rightleftharpoons {\text{Fe}}_{\text{2}} {\text{SiO}}_{\text{4}}$$ (2) $${\text{Fe}}^{\text{o}} + \frac{1}{2}{\text{O}}_{\text{2}} \rightleftharpoons {\text{FeO}}$$ . These equilibria may be used to choose an appropriate iron activity for the FePt alloy of an experiment. The temperature dependence of the equilibrium constants is calculated from experimental data. The Gibbs free energy of reaction (1) obtained using thermochemical data is in close agreement with ΔGrxn calculated from the experimental data. Reaction (1) has the advantage that it is independent of the Fe2+/Fe3+ ratio of the melt, but is limited to applications where olivine is a crystallizing phase and requires a formulation for \(a_{{\text{SiO}}_{\text{2}} }^{{\text{liq}}}\) . Reaction (2) uses an empirical approximation for the FeO/Fe2O3 ratio of the liquid, and is independent of olivine saturation. However, it requires a formulation for a FeO liq . Either equilibrium constant may be used to calculate the appropriate FePt alloy in equilibrium with a silicate melt. If experiments are conducted at an \(f_{{\text{O}}_{\text{2}} }\) parallel that of a buffer assemblage, a small range of FePt alloys may be used over a large temperature interval. For example, an alloy containing from 6 % to 9 % Fe by weight is in equilibrium with olivine-saturated tholeiites and komatiites at the quartzfayalite-magnetite buffer over the temperature interval 1,400° C to 1,100° C. Lunar basalt liquids in equilibrium with olivine at 1/2 log unit below the iron-wüstite buffer require an FePt alloy that contains 30–50 wt. % iron over a similar temperature interval.  相似文献   

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