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1.
In order to fully assess the role of rutile in fractionation of Nb/Ta during partial melting of hydrous metabasalt, we have measured rutile - felsic melt partition coefficients (D values) for Nb and Ta with tonalitic to trondhjemitic compositions at 1.5-3.5 GPa, 900-1350 °C and ∼5.0-20 wt% H2O. DNb, DTa and DNb/DTa range from 17 ± 1 to 246 ± 13, 34 ± 2 to 232 ± 25 and 0.51 ± 0.04 to 1.06 ± 0.13, respectively. For the compositions investigated, melt composition appears to have no observable effect on the partitioning; the effect of pressure is also slight; whereas temperature and H2O have marked effects. DNb, DTa and DNb/DTa increase with decreasing temperature and H2O content, showing a reversal of DNb/DTa from <1.0 to >1.0. Using the data that approached equilibrium and obeyed Henry’s law, expressions describing the dependences of DNb, DTa and DNb/DTa on temperature, pressure and melt H2O content were obtained:
(1)  相似文献   

2.
Partitioning coefficients between olivine and silicate melts   总被引:3,自引:0,他引:3  
J.H. Bdard 《Lithos》2005,83(3-4):394-419
Variation of Nernst partition coefficients (D) between olivine and silicate melts cannot be neglected when modeling partial melting and fractional crystallization. Published natural and experimental olivine/liquidD data were examined for covariation with pressure, temperature, olivine forsterite content, and melt SiO2, H2O, MgO and MgO/MgO + FeOtotal. Values of olivine/liquidD generally increase with decreasing temperature and melt MgO content, and with increasing melt SiO2 content, but generally show poor correlations with other variables. Multi-element olivine/liquidD profiles calculated from regressions of D REE–Sc–Y vs. melt MgO content are compared to results of the Lattice Strain Model to link melt MgO and: D0 (the strain compensated partition coefficient), EM3+ (Young's Modulus), and r0 (the size of the M site). Ln D0 varies linearly with Ln MgO in the melt; EM3+ varies linearly with melt MgO, with a dog-leg at ca. 1.5% MgO; and r0 remains constant at 0.807 Å. These equations are then used to calculate olivine/liquidD for these elements using the Lattice Strain Model. These empirical parameterizations of olivine/liquidD variations yield results comparable to experimental or natural partitioning data, and can easily be integrated into existing trace element modeling algorithms. The olivine/liquidD data suggest that basaltic melts in equilibrium with pure olivine may acquire small negative Ta–Hf–Zr–Ti anomalies, but that negative Nb anomalies are unlikely to develop. Misfits between results of the Lattice Strain Model and most light rare earth and large ion lithophile partitioning data suggest that kinetic effects may limit the lower value of D for extremely incompatible elements in natural situations characterized by high cooling/crystallization rates.  相似文献   

3.
Tang  Yong  Zhang  Hui 《中国地球化学学报》2015,34(2):194-200
Acta Geochimica - The partition coefficients of W, Nb, and Ta between the P-rich peraluminous granitic melt and the coexisting aqueous fluid were determined at 800–850&nbsp;°C and...  相似文献   

4.
Mineral/melt trace element partition coefficients were determined for rutile (TiO2) for a large number of trace elements (Zr, Hf, Nb, Ta, V, Co, Cu, Zn, Sr, REE, Cr, Sb, W, U, Th). Whilst the high field strength elements (Zr, Hf, Nb, Ta) are compatible in rutile, other studied trace elements are incompatible (Sr, Th, REE). In all experiments we found DTa > DNb, DHf > DZr and DU > DTh. Partition coefficients for some polyvalent elements (Sb, W, and Co) were sensitive to oxygen fugacity. Melt composition exerts a strong influence on HFSE partition coefficients. With increasing polymerization of the melt, rutile/melt partition coefficients for the high field strength elements Zr, Hf, Nb and Ta increase about an order of magnitude. However, DNb/DTa and DHf/DZr are not significantly affected by melt composition. Because DU ? DTh, partial melting of rutile-bearing eclogite in subducted lithosphere may cause excesses of 230Th over 238U in some island arc lavas, whereas dehydration of subducted lithosphere may cause excesses of 238U over 230Th. From our partitioning results we infer partition coefficients for protactinium (Pa) which we predict to be much lower than previously anticipated. Contrary to previous studies, our data imply that rutile should not significantly influence observed 231Pa-235U disequilibria in certain volcanic rocks.  相似文献   

5.
Solubility curves of water-hydrogen fluid were studied using a high-pressure gas apparatus at a pressure of 200 MPa under variable fluid composition in haplogranite (Ab 39 Or 32 Qtz 29, 950°C), Na-disilicate (Na2Si2O5, 950°C), and albite melts (1200°C). The mole fraction of hydrogen in experiments was controlled directly by Ar-H2 mixtures using a specially designed cell with a Shaw membrane. $ X_{H_2 }^{Ar - H_2 } $ X_{H_2 }^{Ar - H_2 } ranged from 0 to 1. In some experiments with haplogranite and Na-disilicate melts under oxidizing conditions, in order to increase the accuracy of experimental parameters, the fugacities of oxygen and hydrogen were controlled using the double-capsule technique and the solid-phase buffer mixtures Ni-NiO (NNO) and Co-CoO (CCO). The addition of H2 to the H2O-saturated systems ($ X_{H_2 }^{H_2 O - H_2 } $ X_{H_2 }^{H_2 O - H_2 } ≥ 0.012) results in the appearance of a distinct maximum on the solubility curves at $ X_{H_2 }^{H_2 O - H_2 } $ X_{H_2 }^{H_2 O - H_2 } = 0.05–0.07 (H2 mole fractions were calculated for real H2O-H2 mixtures of real gases), and the maximum content of H2O-H2 fluid increases relative to the H2O-saturated melts by 1.51 wt % for haplogranite melt at $ X_{H_2 } $ X_{H_2 } = 0.063, 2.68 wt % for albite melt at $ X_{H_2 } $ X_{H_2 } = 0.066, and 3.54 wt % for Na-disilicate melt at $ X_{H_2 } $ X_{H_2 } = 0.067. A further increase in H2 content in the gas mixture decreases the solubility of H2O-H2 fluid in the melts, and under pure H2 pressure, the contents of fluid components are 0.08 wt % in haplogranite melt and 0.06 wt % in albite melt. The 1H NMR study of aluminosilicate and Na-silicate glasses obtained under the pressure of H2O and H2O-H2 fluids suggests different mechanisms of the dissolution of H2O and H2O-H2 fluids in magmatic melts. In addition to the spectra of dissolved water fluid, the spectra of quenched glasses synthesized under H2O-H2 fluid pressure exhibited a narrow line of molecular hydrogen with a width at half height of 1.8–2.0 kHz at $ X_{H_2 } $ X_{H_2 } ≥ 0.653 for albite and $ X_{H_2 } $ X_{H_2 } ≥ 0.063 for Na-disilicate and two lines at $ X_{H_2 } $ X_{H_2 } ≥ 0.063 for the haplogranite composition.  相似文献   

6.
The behaviour of niobium and tantalum in magmatic processes has been investigated by conducting MnNb2O6 and MnTa2O6 solubility experiments in nominally dry to water-saturated peralkaline (aluminium saturation index, A.S.I. 0.64) to peraluminous (A.S.I. 1.22) granitic melts at 800 to 1035 °C and 800 to 5000 bars. The attainment of equilibrium is demonstrated by the concurrence of the solubility products from dissolution, crystallization, Mn-doped and Nb- or Ta-doped experiments at the same pressure and temperature. The solubility products of MnNb2O6 (Ksp Nb) and MnTa2O6 (Ksp Ta) at 800 °C and 2 kbar both increase dramatically with alkali contents in water-saturated peralkaline melts. They range from 1.2 × 10−4 and 2.6 × 10−4 mol2/kg2, respectively, in subaluminous melt (A.S.I. 1.02) to 202 × 10−4 and 255 × 10−4 mol2/kg2, respectively, in peralkaline melt (A.S.I. 0.64). This increase from the subaluminous composition can be explained by five non-bridging oxygens being required for each excess atom of Nb5+ or Ta5+ that is dissolved into the melt. The Ksp Nb and Ksp Ta also increase weakly with Al content in peraluminous melts, ranging up to 1.7 × 10−4 and 4.6 × 10−4 mol2/kg2, respectively, in the A.S.I. 1.22 composition. Columbite-tantalite solubilities in subaluminous and peraluminous melts (A.S.I. 1.02 and 1.22) are strongly temperature dependent, increasing by a factor of 10 to 20 from 800 to 1035 °C. By contrast columbite-tantalite solubility in the peralkaline composition (A.S.I. 0.64) is only weakly temperature dependent, increasing by a factor of less than 3 over the same temperature range. Similarly, Ksp Nb and Ksp Ta increase by more than two orders of magnitude with the first 3 wt% H2O added to the A.S.I. 1.02 and 1.22 compositions, whereas there is no detectable change in solubility for the A.S.I. 0.64 composition over the same range of water contents. Solubilities are only slightly dependent on pressure over the range 800 to 5000 bars. The data for water-saturated sub- and peraluminous granites have been extrapolated to 600 °C, conditions at which pegmatites and highly evolved granites may crystallize. Using a melt concentration of 0.05 wt% MnO, 70 to 100 ppm Nb or 500 to 1400 ppm Ta are required for manganocolumbite and manganotantalite saturation, respectively. The solubility data are also used to model the fractionation of Nb and Ta between rutile and silicate melts. Predicted rutile/melt partition coefficients increase by about two orders of magnitude from peralkaline to peraluminous granitic compositions. It is demonstrated that the γNb2O5/γTa2O5 activity coefficient ratio in the melt phase depends on melt composition. This ratio is estimated to decrease by a factor of 4 to 5 from andesitic to peraluminous granitic melt compositions. Accordingly, all the relevant accessory phases in subaluminous to peraluminous granites are predicted to incorporate Nb preferentially over Ta. This explains the enrichment of Ta over Nb observed in highly fractionated granitic rocks, and in the continental crust in general. Received: 9 August 1996 / Accepted: 26 February 1997  相似文献   

7.
The crystal liquid partitioning of Zr and Nb has been measured experimentally between diopsidic clinopyroxene and melts in the system Di-Ab-An. Nb was found to be excluded from diopside (D(Nb) is always less than 0.02). D(Zr) is quite variable, ranging from 0.05 to 0.45. D(Zr) is positively correlated with the Al content of both the melt and the pyroxene and is negatively correlated with temperature. Both D(Zr) and D(Nb) were found to be independent of oxygen fugacity. This implies that neither Zr or Nb suffer valence changes over a range of oxygen fugacities spanning both lunar and terrestrial conditions.  相似文献   

8.
铌与钽的某些地球化学问题   总被引:16,自引:1,他引:16  
针对地球圈层之间Nb、Ta质量不平衡的难题,较系统收集分析了我国基性岩墙(脉)群、太古宙基性火山岩、碱性岩、大火成岩省火山岩,俯冲带中富Nb玄武岩、高压变质岩、花岗岩类的Nb、Ta含量、比值、相关同位素组成以及Nb、Ta实验地球化学资料.这些资料表明,Nb、Ta在这些岩类中的分布呈现非常不均匀变化,除花岗岩外,上述岩石的Nb/Ta比值均高于或近于球粒陨石值17.5.花岗岩中的幔源斜长花岗岩及与裂谷、热点环境有关的碱性花岗岩Nb/Ta比值近于地球平均值,而普通S型及I型花岗岩,特别是高演化花岗岩,Nb/Ta比值均明显低于球粒陨石(<10),甚至呈现Nb/Ta≤1.这些资料表明,在不均匀的地幔中可能存在呈布丁状分布的Nb/Ta比值高于球粒陨石的储源.金红石的稳定性及Nb、Ta分配系数实验资料不支持地球深部存在高Nb/Ta比值的含金红石榴辉岩.  相似文献   

9.
The effect of fluorine on the solubilities of Mn-columbite (MnNb2O6), Mn-tantalite (MnTa2O6), zircon (ZrSiO4) and hafnon (HfSiO4) were determined in highly fluxed, water-saturated haplogranitic melts at 800 to 1000 °C and 2 kbar. The melt composition corresponds to the intersection of the granite minimum with the albite–orthoclase tieline (Ab72Or28) in the quartz–albite–orthoclase system (Q–Ab–Or), which is representative of a highly fluxed melt, from which high field strength element minerals may crystallize. The melt contains 1.7 wt.% P2O5, 1.05 wt.% Li2O and 1.83 wt.% B2O3. The main purpose of this study is to examine the effect of F on columbite, tantalite, zircon and hafnon solubility for a melt with this composition. Up to 6 wt.% fluorine was added as AgF in order to keep the aluminum saturation index (ASI, molar Al/[Na + K]) of the melt constant. In an additional experiment F was added as AlF3 to make a glass peraluminous. The nominal ASI of the melts are close to 1 for the minimum composition and approximately 1.32 in peraluminous glasses, but if Li is considered as an alkali, the molar ratio Al/[Na + K + Li] of the melts are alkaline (0.87) and subaluminous (1.09), respectively.The molar solubility products [MnO] 1 [Nb2O5] and [MnO] 1 [Ta2O5] are nearly independent of the F content of the melt, at approximately 18.19 ± 1.2 and 43.65 ± 2.5 × 10 4 (mol2/kg2), respectively for the minimum composition. By contrast, there is a positive dependence of zircon and hafnon solubilities on the fluorine content in the minimum composition, which increases from 2.03 ± 0.03 × 10 4 (mol/kg) ZrO2 and 4.04 ± 0.2 × 10 4 (mol/kg) HfO2 for melts with 0 wt.% F to 3.81 ± 0.3 × 10 4 (mol/kg) ZrO2 and 6.18 ± 0.04 × 10 4 (mol/kg) HfO2 for melts with 8 wt.% F. Comparison of the data from this work and previous studies indicates that ASI of the melt seems to have a stronger effect than the contents of fluxing elements in the melt and the overall conclusion is that fluorine is less important (relative to melt compositions) than previously thought for the control on the behavior of high field strength elements in highly evolved granitic melts. Moreover, this study confirms that although Nb, Ta, Zr and Hf are all high field strength elements, Nb–Ta and Zr–Hf are complexed differently in the melt.  相似文献   

10.
11.
Partition coefficients for olivine-melt and orthopyroxene-melt systems   总被引:3,自引:0,他引:3  
Thermodynamic analysis shows that olivinemelt and orthopyroxene-melt partition coefficients for many elements should be approximately linear functions of DMg. These simple relationships can be combined with the constraint of mineral stoichiometry to allow the direct calculation of partition coefficients for these elements if the major element chemistry of the melt phase is known. A large dataset of published and unpublished experimental mineral-melt pairs for compositions in the range komatiite to andesite has allowed the determination of the empirical constants required for this calculation. The precision of these parameterisations is demonstrated by comparing the values calculated with those observed. Comparison of phenocryst-matrix partition coefficients with those measured from experimental mineral-melt pairs demonstrates that experimentally determined partition coefficients are equivalent to those in magmatic processes. There are therefore no significant kinetic factors precluding magmatic partitioning being reproduced on an experimental timescale. The model provides a set of simple tests for equilibrium and enables the chemical evolution of a magma fractionating olivine or orthopyroxene to be modelled. An empirical equation for distinguishing orthopyroxene from other low-Ca pyroxenes in chemical analyses of experimental runs is also presented.  相似文献   

12.
Many models for plagioclase-melt equilibria have been proposed over the past 30 years, but the focus is increasingly on the effects of water content and pressure. However, many geological and petrological applications concern low pressure and low water systems, such as the differentiation of large terrestrial basaltic magma chambers, and lunar and asteroidal magmatism. There is, therefore, a justified need to quantify the influence of anhydrous liquid composition on the composition of equilibrium plagioclase at 1-atm. With this in mind, a database of over 500 experimentally determined plagioclase-liquid pairs has been created. The selected low pressure, anhydrous, experiments include both natural and synthetic liquids, whose compositions range from basalt to rhyolite. Four equations are proposed, derived from this data. The first is based on a thermodynamically inspired formalism, explicitly integrating the effect of temperature. This equation uses free energies and activities of crystalline anorthite available from the literature. For the activity of anorthite in the liquid phase, it is found that current models of the activity of individual oxides are insufficient to account for the experimental results. We have therefore derived an empirical expression for the variation of anorthite activity in the liquid as a function of melt composition, based upon inversion of the experimental data. Using this expression allows the calculation of plagioclase composition with a relative error less than 10%. However, in light of the fact that temperature is not necessarily known for many petrological applications, an alternative set of T-independent equations is also proposed. For this entirely empirical approach, the database has been divided into three compositional groups, treated independently for regression purposes: mafic–ultramafic, alkali-rich mafic–ultramafic, and intermediate-felsic. This separation into distinct subgroups was found to be necessary to maintain errors below acceptable limits, but results across group boundaries were found to be comparable. Overall, 50% of plagioclase compositions are predicted to within 2% of the experimentally derived value, and 90% to within 5%, representing a significant improvement over existing models.  相似文献   

13.
Partition coefficients between olivine and melt at upper mantle conditions, 3 to 14 GPa, have been determined for 27 trace elements (Li, Be, B, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Sr, Y, Zr, Cs, Ba, La and Ce) using secondary-ion mass-spectrometry (SIMS) and electron-probe microanalysis (EPMA). The general pattern of olivine/melt partitioning on Onuma diagrams resembles those reported previously for natural systems. This agreement strongly supports the argument that partitioning is under structural control of olivine even at high pressure. The partition coefficients for mono- and tri-valent cations show significant pressure dependence, both becoming larger with pressure, and are strongly correlated with coupled substitution into cation sites in the olivine structure. The dominant type of trace element substitution for mono- and tri-valent cations into olivine changes gradually from (Si, Mg)↔(Al, Cr) at low pressure to (Si, Mg)↔(Al, Al) and (Mg, Mg)↔(Na, Al) at high pressure. The change in substitution type results in an increase in partition coefficients of Al and Na with pressure. An inverse correlation between the partition coefficients for divalent cations and pressure has been observed, especially for Ni, Co and Fe. The order of decreasing rate of partition coefficient with pressure correlates to strength of crystal field effect of the cation. The pressure dependence of olivine/melt partitioning can be attributed to the compression of cation polyhedra induced by pressure and the compensation of electrostatic valence by cation substitution. Received: March 6, 1997 / Revised, accepted: March 12, 1998  相似文献   

14.
A new and empirical viscosity equation for anhydrous and hydrous natural silicate melts has been developed using the following formulation:
  相似文献   

15.
Partition coefficients of Hf,Zr, and REE between zircon,apatite, and liquid   总被引:25,自引:2,他引:25  
Concentration ratios of Hf, Zr, and REE between zircon, apatite, and liquid were determined for three igneous compositions: two andesites and a diorite. The concentration ratios of these elements between zircon and corresponding liquid can approximate the partition coefficient. Although the concentration ratios between apatite and andesite groundmass can be considered as partition coefficients, those for the apatite in the diorite may deviate from the partition coefficients. The HREE partition coefficients between zircon and liquid are very large (100 for Er to 500 for Lu), and the Hf partition coefficient is even larger. The REE partition coefficients between apatite and liquid are convex upward, and large (D=10–100), whereas the Hf and Zr partition coefficients are less than 1. The large differences between partition coefficients of Lu and Hf for zircon-liquid and for apatite-liquid are confirmed. These partition coefficients are useful for petrogenetic models involving zircon and apatite.  相似文献   

16.
Partition coefficients of uranium between phenocrysts and their host groundmass have been determined by fission-track mapping. The minerals analyzed include plagioclase, K-feldspar, biotite, olivine, clinopyroxene and orthopyroxene. The data for all these minerals show that U is strongly partitioned into the liquid and only a small fraction of the total whole-rock U content is present in the major rock-forming minerals. In volcanic rocks, the bulk of U is usually contained in glass although in acid volcanic rocks a significant portion may also be present in the U-rich accessory minerals.  相似文献   

17.
The effects of F, B2O3 and P2O5 on the H2O solubility in a haplogranite liquid (36 wt. % SiO2, 39 wt. % NaAlSi3O8, 25 wt. % KAlSi3O8) have been determined at 0.5, 1, 2, and 3 kb and 800, 850, and 900°C. The H2O solubility increases with increasing F and B content of the melt. The H2O solubility increase in more important at high pressure (2 and 3 kb) than at low pressure (0.5 kb). At 2 kb and 800°C, the H2O solubility increases from 5.94 to 8.22 wt. % H2O with increasing F content in the melt from 0 to 4.55 wt. %, corresponding to a linear H2O solubility increase of 0.53 mol H2O/mol F. With addition of 4.35 wt. % B2O3, the H2O solubility increases up to 6.86 wt. % H2O at 2 kb and 800°C, corresponding to a linear increase of 1.05 mol H2O/mol B2O3. The results allow to define the individual effects of fluorine and boron on H2O solubility in haplogranitic melts with compositions close to that of H2O-saturated thermal minima (at 0.5–3 kb). Although P has a dramatic effect on the phase relations in the haplogranite system, its effect on the H2O solubility was found to be negligible in natural melt compositions. The concominant increase in H2O solubility and F can not be interpreted on the basis of the available spectroscopic data (existence of hydrated aluminofluoride complexes or not). In contrast, hydrated borates or more probably boroxol complexes have been demonstrated in B-bearing hydrous melts.  相似文献   

18.
Doklady Earth Sciences - Experimental data on the Nb, Ta, Ti, Ce, and La concentrations in felsic magmatic melts of various alkalinity and alumina content upon dissolving ilmenorutile,...  相似文献   

19.
The partitioning behavior of cerium, europium, gadolinium and ytterbium between an aqueous “vapor” phase and water saturated silicate melt have been experimentally examined using a new experimental approach employing radioactive tracers and a double-capsule technique. Equilibrium was established by reversing the partition coefficient1 and by betatrack autoradiography. Aqueous solution compositions were varied by adding different amounts of chloride and in some cases fluoride or carbon dioxide. The H2O contents of the Spruce Pine pegmatite melts were varied by conducting experiments at 4.0 kb, 800°C and at 1.25 kb, 800°C. A jadeite-nepheline composition (75 wt% Jadeite) also was employed at 4.0 kb, 800°C.The chloride experiments (Spruce Pine 4 kb, 800°C) show a linear relationship between the cube of the chloride molality and the partition coefficients of the trivalent rare earths. Europium, under the experimental fO2 conditions (quartz-fayalite-magnetite buffer), varied linearly as the fifth power of the chloride molality. At the chloride molalities examined (<1.1 mC1), all the rare earths partitioned preferentially into the melt phase (KPRE <1). Relative to pure water, the presence of chloride and fluoride fon increased the partitioning of the individual rare earths into the vapor phase, while carbon dioxide did not. Europium anomalies were recorded 1n all experiments, particularly those involving the Spruce P1ne melt at 4.0 kb and 800°C which displayed a large positive europium anomaly at all chloride molalities. Furthermore, a relative fractionation of the trivalent rare earths was also observed in these experiments, such that KPCe>KPGd>KPYb. The smaller ytterbium ion was consistently concentrated in the melt phase relative to the other rare earths in all experiments on the Spruce Pine composition. Experiments on the jadeite-nepheline composition showed no relative fractionation and a positive europium anomaly. The 1.25 kb experiment on the Spruce Pine composition showed a negative europium anomaly in plots of KpRE vs. REE.The overall rare earth partitioning at a constant chloride molality (mCl = .914) was such that KPSP(1.25 kb) > KPSP(4.0 kb) > KPJd-Ne(4.0 kb), where SP = Spruce Pine, Jd-Ne = jadeitenepheli Using the model of Burnnam (1975), It is suggested that the trivalent rare earth partitioning is related to the cube of the melt octahedral site concentration; a property which 1n hydrous melts 1s dependent on melt composition and hydroxyl molality. Excellent agreement was found for the Spruce Pine melt, whereas the jadeite-nepheline melt gave apparent hydroxyl molalities which were too high for the measured partition coefficient. Additional octahedral sites are proposed for this unusual composition perhaps due to some aluminum in 6-fold coordination. The apparent compositional variation of europium partitioning at a constant oxygen fugacity is believed to be related to both the octahedral melt site concentration for trlvalent europium and an 8-coordinated site concentration for divalent europium. Any parameter which affects the numbers of these sites (PH2O, melt composition) will affect the rare earth partitioning. The observed dependency of the partition coefficient on the structural state of the melt could be as significant as its dependency on crystalline structural constraints. Furthermore, since PH2O can drastically effect the melt structural state, its effects could be reflected in melt/crystal partition coefficients.  相似文献   

20.
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