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1.
In anoxic environments, microbial fermentation is the first metabolic process in the path of organic matter degradation. Since little is known about carbon isotope fractionation during microbial fermentation, we studied mixed-acid fermentation of different saccharides (glucose, cellobiose, and cellulose) in Clostridium papyrosolvens. The bacterium was grown anaerobically in batch under different growth conditions, both in pure culture and in co-culture with Methanobacterium bryantii utilizing H2/CO2 or Methanospirillum hungatei utilizing both H2/CO2 and formate. Fermentation products were acetate, lactate, ethanol, formate, H2, and CO2 (and CH4 in methanogenic co-culture), with acetate becoming dominant at low H2 partial pressures. After complete conversion of the saccharides, acetate was 13C-enriched (αsacc/ac = 0.991-0.997), whereas lactate (αsacc/lac = 1.001-1.006), ethanol (αsacc/etoh = 1.007-1.013), and formate (αsacc/form = 1.007-1.011) were 13C-depleted. The total inorganic carbon produced was only slightly enriched in 13C, but was more enriched, when formate was produced in large amounts, as 12CO2 was preferentially converted with H2 to formate. During biomass formation, 12C was slightly preferred (αsacc/biom ≈ 1.002). The observations in batch culture were confirmed in glucose-limited chemostat culture at growth rates of 0.02-0.15 h−1 at both low and high hydrogen partial pressures. Our experiments showed that the carbon flow at metabolic branch points in the fermentation path governed carbon isotope fractionation to the accumulated products. During production of pyruvate, C isotopes were not fractionated when using cellulose, but were fractionated to different extents depending on growth conditions when using cellobiose or glucose. At the first catabolic branch point (pyruvate), the produced lactate was depleted in 13C, whereas the alternative product acetyl-CoA was 13C enriched. At the second branch point (acetyl-CoA), the ethanol formed was 15.6-18.6‰ depleted in 13C compared to the alternative product acetate. At low hydrogen partial pressures, as normally observed under environmental conditions, fermentation of saccharides should mainly result in the production of acetate that is only slightly enriched in 13C (<3‰).  相似文献   

2.
The nine elastic constants of andalusite and sillimanite have been determined, using the technique of Brillouin scattering. They are, in megabars, for andalusite: c 11=2.334, c 22=2.890, c 33=3.801, c 44=0.995, c 55=0.878, c 66=1.123, c 23=0.977, c 13=1.162, c 12=0.814; for sillimanite: c 11=2.873, c 22=2.319, c 33=3.884, c 44=1.224, c 55=0.807, c 66=0.893, c 23=1.586, c 13=0.834, c 12=0.947. Both structures are characterized by chains of edge-linked coordination octahedra extending parallel to the crystallographic c direction, cross-linked by polyhedra of lower coordination. In each structure the stiffness measured parallel to c is greater than that measured normal to c. The shear moduli can be directly correlated with the relative rigidity of the cross-linking structures.  相似文献   

3.
《Applied Geochemistry》1999,14(1):17-25
The nucleation induction period of CaCO3 in NaCl brines in the absence and presence of scale inhibitors was experimentally measured at temperatures from 25 to 90°C. A semi-empirical mathematical inhibitor model is presented for the CaCO3 scale control in industrial processes based upon nucleation theory and experimental observations. Results show that the minimum inhibitor dosage (Cinh) may be obtained from: Cinh=f(s)/binh log [tinh/t0], where tinh is the inhibition time, e.g., 20 min, t0 is the nucleation induction period in the absence of inhibitors, binh is the inhibitor efficiency, and f(s) is the safety factor, e.g., 2. Important factors for the kinetics of both nucleation and inhibition have been incorporated in this model including the calcite saturation index (SI), temperature (T), and the molar ratio of Ca to HCO3 alkalinity (R). In this paper, model parameters are presented for commonly used inhibitors, including 1-hydroxyethylidene-1,1-diphosphonic-acid (HEDP) and nitrilotri(methylene phosphonic) acid (NTMP). Results show that HEDP and NTMP are the best inhibitors for calcite scaling in the systems examined.  相似文献   

4.
The thirteen single-crystal elastic moduli for diopside as determined by the acoustic technique based on Brillouin scattering are: c11=2.23, c22=1.71, c33=2.35, c44=0.74, c55=0.67, c66=0.66, c12=0.77, c13=0.81, c15=0.17, c23=0.57, c25=0.07, c35=0.43, c46=0.073. The Reuss bound of the adiabatic bulk and shear moduli calculated from these data are K s=1.08 Mbar and G=0.651 Mbar. The room-pressure isothermal bulk modulus, K T , and the pressure derivative of the bulk modulus, K′ T have also been determined on a four-circle diffractometer, from a single crystal mounted in a gasketed opposed-anvil diamond cell, giving values of K T =1.13 Mbar and K′ T =4.8. The principal axes of the strain ellipsoid, calculated from the elastic moduli and observed in the static compression data, are identical, and the linear compressibilities are in reasonable agreement. The single-crystal elastic moduli can be correlated with the structural features of diopside.  相似文献   

5.
A natural Ca-rich pigeonite (En47Fs43Wo10), free of augite exsolution products, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2 1 /c (a=9.719(7) Å, b=8.947(9) Å, c=5.251(3) Å, β=108.49(5), V=433.0(6) Å3), was annealed up to 1000 °C to induce a phase transition from P2 1 /c to C2/c symmetry. Complete single-crystal X-ray diffraction data collections were carried out in situ at 650, 750, 850 and 950 °C after the crystal had reached equilibrium for the Fe–Mg intracrystalline exchange reaction at each temperature. The variation, with increasing temperature, of lattice parameters, of intensity of hkl reflections with h + k=2n + 1 (which vanish at high temperature) and of some geometrical parameters from structure refinement, showed that the displacive phase transition P2 1 /c?C2/c was continuous in character. This contrasts with the first-order character for the HT phase transition in pigeonite containing significantly less calcium.  相似文献   

6.
The uncertainty in the spatial distributions of consolidation settlement (s c) and time (t p) for Songdo New City is evaluated by using a probabilistic procedure. Ordinary kriging and three theoretical semivariogram models are used to estimate the spatial distributions of geo-layers which affect s c and t p in this study. The spatial map of mean (μ) and standard deviation (σ) for s c and t p are determined by using a first-order second moment method based on the evaluated statistics and probability density functions (PDFs) of soil properties. It is shown that the coefficients of variation (COVs) of the compression ratio [C c/(1 + e 0)] and the coefficient of consolidation (c v) are the most influential factors on the uncertainties of s c and t p, respectively. The μ and σ of the s c and t p, as well as the probability that s c exceeds 100 cm [P(s c > 100 cm)] and the probability that t p exceeds 36 months [P(t p > 36 months)] in Sect. 1, are observed to be larger than those of other sections because the thickness of the consolidating layer in Sect. 1 is the largest in the entire study area. The area requiring additional fill after the consolidation appears to increase as the COV of C c/(1 + e 0) increases and as the probabilistic design criterion (α) decreases. It is also shown that the area requiring the prefabricated vertical drains installation increases as the COV of c v increases and as the α decreases. The design procedure presented in this paper could be used in the decision making process for the design of geotechnical structures at coastal reclamation area.  相似文献   

7.
Effluent sludge from an anaerobic digester was used as a source of nitrogen, phosphate, sulfur, and other nutrients in the culture medium of ethanol production by the yeast Saccharomyces cerevisiae. Several pretreatments (mechanical, chemical, thermal, and thermo-chemical) were performed on the anaerobic digested sludge (ADS) to make the nutrients accessible to the yeast cells. Preliminary experiments revealed that S. cerevisiae is not able to assimilate the carbon content of the ADS. However, when glucose was added to the medium, ethanol production was observed. The yield of ethanol using untreated ADS was only 10 % of the theoretical yield, but alkaline pretreatment improved it up to 43 %. By separating the hydrolysate of alkaline-treated ADS from the suspended solids, the ethanol yield from the supernatant was further improved up to 65 % of theoretical yield. Alkaline-treated ADS exhibited competitive performance with the mixture of yeast extract and mineral salts in ethanol fermentation.  相似文献   

8.
9.
Time-variant reliability analysis for a typical unsaturated soil slope is performed. Eight rainfall conditions are considered, and three slope models are set up for studying the influence of shear strength parameters, hydraulic conductivity parameters, rainfall intensity and duration on the reliability of the soil slope. Sensitivity analysis shows that when the saturated hydraulic conductivity (k s) is very small, the variation of hydraulic conductivity has little effect on the reliability index (β). For saving the computation effort, only the shear strength parameters are needed in performing the reliability analysis in this condition. With the increase of k s, the importance of hydraulic conductivity becomes large. The reliability index of the soil slope is changing with time (t), and the shape of β–t curves for different slope model is quite different for they depend on the value of k s. When k s is very small, β keeps decreasing for all the 18 simulation days. With the increase of k s, β decreases to its minimum value at about the cessation day of rainfall events, and it then increases gradually due to the redistribution of suction in the soil slope.  相似文献   

10.
Heyrovskýite has a composition range from 6(Pb0.83Bi0.10(Ag, Cu)0.07) S . Bi2S3 to 6(Pb0.92Bi0.05(Ag, Cu)0.03) S . Bi2S3. It is orthorhombic. Crystal forms {100}, {010}, {120}, {140}, {250}, and {321} (?) were observed; {010} and {140} are dominant. Elongated c, flattened (010). a:b:c morph=0.432:1:0.128. Cell parameters a=13.705±0.013 Å, b=31.194±0.033, c=4.121±0.003, a:b:c X-ray=0.439:1:0.132. The diffraction symbol is Bb, compatible with Bbmm, Bb21 m, Bbm2. Morphology corresponds to point groups mmm or mm2, reducing the possible space groups to Bbmm and Bbm2. Density at 20 °C is 7.17 g/cm3, calculated, 7.18; Z=4. Micro-indentation hardness (VHN) (50 g load) is 166 to 234 kp/mm2. Strongly anisotropic; reflectance strongly variable, roughly the same as of galena. Etch tests: HNO3 (1:1) and HCl (1:1) positive, FeCl3 20%, HgCl2 5%, KCN 20%, and KOH 40% all negative. Powder data are identical with those for phase II of Otto and Strunz (1968). Heyrovskýite is associated with galena and cosalite at H?rky, Czechoslovakia.  相似文献   

11.
The isotopic composition of carbon and oxygen in a calcite precipitating CO2-H2O-CaCO3 solution is preserved in the calcite precipitated. For the interpretation of isotopic proxies from stalagmites knowledge of the evolution of δ13C and δ18O in the solution during precipitation is required. A system of differential equations is presented from which this evolution can be derived. Both, irreversible loss of carbon and oxygen from the solution with precipitation time τ and exchange of oxygen in the carbonates with the oxygen in the water with exchange time T are considered. For carbon, where no exchange is active, a modified equation of Rayleigh-distillation is found, which takes into account that precipitation stops at ceq, the saturation concentration of DIC with respect to calcite, and that ceq as well as the precipitation time τ is slightly different for the heavy and the light isotope. This, however, requires introducing a new parameter γ = (Aeq/Beq)/(A0/B0), which has to be determined experimentally. (Aeq/Beq) is the isotopic ratio for the heavy (A) and the light isotope (B) at both chemical and isotopic equilibrium and (A0/B0) is the initial isotopic ratio of the solution. In the case of oxygen, where exchange is present, the isotopic shifts are reduced with increasing values of the precipitation time τ. For τ ? T the solution stays in isotopic equilibrium with the oxygen in the water during the entire time in which precipitation is active. The isotopic ratios in a calcite precipitating solution R(t)/R0 = (1 + δ(t)/1000) for carbon are plotted versus those of oxygen. R0 is the isotopic ratio at time t = 0, when precipitation starts and δ(t) the isotopic shift in the solution after time t. These show positive correlations for the first 50% of calcite, which can precipitate. Their slopes increase with increasing values of τ and they closely resemble Hendy-tests performed along growth layers of stalagmites. Our results show that stalagmites, which grow by high supply of water with drip times less than 50 s, exhibit positive correlations between δ13C and δ18O along a growth layer. But in spite of this the isotopic composition of oxygen in the solution at the apex is in isotopic equilibrium with the oxygen in the water, and therefore also that of calcite deposited at the apex.  相似文献   

12.
The kinetics of smectite illitization in shale samples from eight wells have been modeled using the equation −dS/dt = kK0.25S5 [Cuadros, J., Linares J., 1996. Experimental kinetic study of the smectite-to-illite transformation. Geochim. Cosmochim. Acta60, 439-453], where S is the proportion of smectite layers in illite-smectite (I-S), t is time, k is the rate constant and K is the concentration of potassium. The I-S compositions and the physical parameters were obtained from the literature. Potassium concentration is the only unknown parameter and it was chosen to fit the experimental data. I propose that this variable is termed “effective K concentration,” as it is affected not by the actual K concentration alone but also by those of other cations that compete with K for the smectite interlayer sites, especially Ca, by ion mobility in the sediments and possibly by other variables. The kinetic equation allows an accurate fit to the experimental data in all the wells, reproducing both the illitization onset and the patterns of the plots of % smectite vs. depth. The relative changes of the values of “effective K concentration” compare well with K/Ca equivalent ratios in the whole rock. Three of the modeled wells, located in near proximity, produced similar “effective K concentration” patterns. These results support the validity of the equation used in the models. They also suggest that this equation can be used to assess K concentrations in sediments and K mobility within basins.  相似文献   

13.
Indole is a highly recalcitrant aromatic heterocyclic organic compound consisting of a five-membered nitrogen-containing pyrrole ring fused to a six-membered benzene ring. This study presents the results of the electro-chemical mineralization of indole in an aqueous solution using platinum-coated titanium (Pt/Ti) electrode. A central composite design was used to investigate the effect of four parameters namely initial pH (pHo), current density (j), conductivity (k) and treatment time (t) at 5 levels. Multiple responses namely chemical oxygen demand (COD) removal (Y 1) and specific energy consumption (Y 2) were simultaneously maximized and minimized, respectively, by optimizing the parameters affecting the mineralization of indole by using the desirability function approach. At the operating conditions of pH 8.6, j = 161 A/m2, k = 6.7 mS/cm and t = 150 min, 83.8% COD removal with specific energy consumption of 36.3 kWh/kg of COD removed was observed. Ultra performance liquid chromatography, UV–visible spectroscopy, Fourier transform infrared spectroscopy and cyclic voltammetry of the indole solution were performed at the optimum condition of the treatment so as to report a plausible mechanism of indole degradation. Field emission scanning electron microscopy analysis of electrodes before and after treatment was performed for determining the changes on anode surface during the treatment. Thermal analysis of the solid residue (scum) obtained was also performed for exploring its disposal prospects. Present study shows that electro-chemical oxidation can be used for mineralization of nitrogenous heterocyclic compounds such as indole.  相似文献   

14.
A pyroxene with composition LiNiSi2O6 was synthesized at T = 1,473 K and P = 2.0 GPa; the cell parameters at T = 298 K are a = 9.4169(6) Å, b = 8.4465(7) Å, c = 5.2464(3) Å, β = 110.534(6)°, V = 390.78(3) Å3. TEM examination of the LiNiSi2O6 pyroxene showed the presence of h + k odd reflections indicative of a primitive lattice, and of antiphase domains obtained by dark field imaging of the h + k odd reflections. A HT in situ investigation was performed by examining TEM selected area diffraction patterns collected at high temperature and synchrotron radiation powder diffraction. In HTTEM the LiNiSi2O6 was examined together with LiCrSi2O6 pyroxene. In LiCrSi2O6 the h + k odd critical reflections disappear at about 340 K; they are sharp up to the transition temperature and do not change their shape until they disappear. In LiNiSi2O6 the h + k odd reflections are present up to sample deterioration at 650 K. A high temperature synchrotron radiation powder diffraction investigation was performed on LiNiSi2O6 between 298 and 773 K. The analysis of critical reflections and of changes in cell parameters shows that the space group is P-centred up to the highest temperature. The comparative analysis of the thermal and spontaneous strain contributions in P21/c and C2/c pyroxenes indicates that the high temperature strain in P-LiNiSi2O6 is very similar to that due to thermal strain only in C2/c spodumene and that a spontaneous strain contribution related to pre-transition features is not apparent in LiNiSi2O6. A different high-temperature behaviour in LiNiSi2O6 with respect to other pyroxenes is suggested, possibly in relation with the presence of Jahn–Teller distortion of the M1 polyhedron centred by low-spin Ni3+.  相似文献   

15.
Ground-based (Big Bear Solar Observatory) and extra-atmospheric (SOHO/MDI) measurements of the photospheric line-of-sight magnetic field of one active and two quiet regions are used to calculate power spectra of the field, taking into account the characteristic function for the diffraction limit of the telescope resolution. At high frequencies, the physically meaningful linear interval in the spectrum extends to a wave number of k=4.6 Mm?1 (spatial scale l=1.4 Mm) for the quiet regions and k=3.35 Mm?1 (l=1.9 Mm) for the active region. A high-frequency spectral break at k≥3 Mm?1 is associated with the characteristic telescope function; the position of the break and the spectral slope beyond the break do not reflect the turbulent state of the field. As the field recording improves, the break shifts toward higher frequencies. The spectral indices in the physically meaningful linear interval are substantially different for the active and quiet regions: in the active region (NOAA 8375), the spectrum behaves as E(k)≈k ?1.7 (very close to the Kolmogorov index, ?5/3) in the interval 0.78≤k≤3.35 Mm?1, while in the quiet regions E(k)≈k ?1.3 for 0.77≤k≤4.57 Mm?1. This difference can be explained by the additional effect of a small-scale turbulent dynamo in the unperturbed photosphere. In this case, this mechanism can generate at least 6% of the magnetic energy of the photospheric line-of-sight field in quiet regions.  相似文献   

16.
A unifying theory of kinetic rate laws, based on order parameter theory, is presented. The time evolution of the average order parameter is described by $$\langle Q\rangle \propto \smallint P(x)e^{^{^{^{^{^{^{ - xt} } } } } } } dx = L(P)$$ where t is the time, x is the effective inverse susceptibility, and L indicates the Laplace transformation. The probability function P(x) can be determined from experimental data by inverse Laplace transformation. Five models are presented:
  1. Polynomial distributions of P(x) lead to Taylor expansions of 〈Q〉 as $$\langle Q\rangle = \frac{{\rho _1 }}{t} + \frac{{\rho _2 }}{{t^2 }} + ...$$
  2. Gaussian distributions (e.g. due to defects) lead to a rate law $$\langle Q\rangle = e^{ - x_0 t} e^{^{^{^{^{\frac{1}{2}\Gamma t^2 } } } } } erfc\left( {\sqrt {\frac{\Gamma }{2}} t} \right)$$ where x 0 is the most probable inverse time constant, Γ is the Gaussian line width and erfc is the complement error integral.
  3. Maxwell distributions of P are equivalent to the rate law 〈Q〉∝e?kt .
  4. Pseudo spin glasses possess a logarithmic rate law 〈Q〉∝lnt.
  5. Power laws with P(x)=x a lead to a rate law: ln〈Q〉=-(α + 1) ln t.
The power spectra of Q are shown for Gaussian distributions and pseudo spin glasses. The mechanism of kinetic gradient coupling between two order parameters is evaluated.  相似文献   

17.
Ureolysis-driven calcite precipitation has potential to seal porosity and fracture networks in rocks thus preventing groundwater flow and contaminant transport. In this study urea hydrolysis and calcite precipitation rates for the model bacterium Sporosarcina pasteurii were compared with those of indigenous groundwater communities under conditions required to precipitate large volumes of calcite (up to 50 g L−1). We conducted microcosm experiments in oxic artificial and anoxic natural groundwaters (collected from the Permo-Triassic sandstone aquifer at Birmingham, UK) that were inoculated with aerobically grown S. pasteurii. The rate constants for urea hydrolysis, kurea, ranged between 0.06 and 3.29 d−1 and were only affected by inoculum density. Higher Ca2+ concentration (50-500 mM Ca2+) as well as differences in fO2 did not inhibit the ureolytic activity of S. pasteurii and did not significantly impact kurea. These results demonstrate that S. pasteurii has potential to improve calcite precipitation in both oxic and anoxic groundwaters, especially if indigenous communities lack ureolytic activity. Urea hydrolysis by indigenous groundwater communities was investigated in anoxic, natural groundwaters amended with urea and CaCl2. A notable increase in ureolysis rates was measured only when these communities were stimulated with dilute nutrients (with best results from blackstrap molasses). Furthermore, there was a considerable lag time (12-20 days) before ureolysis and calcite precipitation began. Calculated ureolysis rate constants, kurea, ranged between 0.03 and 0.05 d−1 and were similar to kurea values produced by S. pasteurii at low inoculum densities. Overall, this comparative study revealed that the growth of ureolytic microorganisms present within groundwaters can easily be stimulated to enhance rates of urea hydrolysis in the subsurface, and thus can be used to induce calcite precipitation in these environments. The time required for urea hydrolysis to begin is almost instantaneous if an inoculum of S. pasteurii is included, while it may take several weeks for ureolytic groundwater communities to grow and become ureolytically active.  相似文献   

18.
Annealing experiments on agate were performed to investigate grain growth kinetics and the effect of crystallographic anisotropy on normal grain growth of quartz. The experiments were conducted using a piston-cylinder apparatus at 700–800°C and 0.5 GPa for 0–66 h. The grain growth rate was expressed by D n −D 0 n  = kt with k = k 0 exp(−H*/RT) where D 0 is the initial grain size at t = 0, with n = 4.4 ± 0.3, and H* = 191.3 ± 11.0 kJ/mol is the activation enthalpy and logk 0  = 19.8 ± 1.4. While the grain aspect ratios are nearly constant at ~0.7 (short/long) during grain growth, the longest axis in individual grains tends to be oriented parallel to their c-axis, indicating that a primary crystal-preferred orientation of c-axis of the agate could result in the development of a weak shape-preferred orientation during grain growth.  相似文献   

19.
To estimate the behavior of ethanol-blended dissolved BTEX hydrocarbons in groundwater, a quantitative tracing study instead of qualitative analysis was carried out by using a large sand tank, into which 2-L solution including bromide, ethanol and dissolved BTEX was injected under a controlled hydraulic condition. Mean residence time (MRT), pore volume swept by solute (V p), retardation coefficient (R) and biodegradation rate constant (k) of injected solutes were estimated. Compared with bromide that was used as a conservative tracer, ethanol and BTEX had shorter MRT and smaller V p with the sequence of EtOH < T < E < m/p-X < o-X < B < Br. Biodegradation was confirmed as evidenced by the consumptions of dissolved oxygen (DO), nitrate and sulfate, and the production of acetate. The sequence of k as EtOH > T > E > m/p-X > o-X > B was just opposite to the sequences of MRT and V p. The relationship among above sequences implies that MRT and V p can be used as indicators to assess in situ biodegradability of a solute. Biodegradation of a reactive solute can make its MRT shortened and V p shrunk. In addition, the sorption of ethanol could be neglected (R = 1.0), whereas BTEX compounds were adsorbed (R = 1.04–1.15). It should be noted that biodegradation of a solute can affect the estimation of its retardation coefficient. To our knowledge, this paper provides an available route to quantitatively estimate biodegradability of a solute in groundwater.  相似文献   

20.
A concentrated load with step-function time behaviour is placed normal to the planar, pervious boundary of a porous elastic half space (PEHS) with compressible constituents. A planar fault exists in the PEHS in such a way that the poroelastic behaviour of the medium is unhindered. We derive an approximate but integral-free expression for CFSCPP, i.e., changes in fault stability due to changes in pore pressure, at a point not too far off the line along which the load acts. But, in the interest of simplicity, the main discussion is focussed on a consideration of CFSCPP at a point P located on the fault at depth z directly beneath the load. It is convenient to introduce dimensionless time t D directly proportional to real time t. The constant of proportionality is 4c/z 2, where c is hydraulic diffusivity. The derived approximate expression gives results with an accuracy of greater than 99% for limited values of t D after the load is imposed. We learn from the derived expression that, for a given z, fault stability undergoes an initial sudden decrease commensurate with the undrained pore pressure induced in the PEHS. This is followed by a more gradual decrease in fault stability with increasing t D until a minimum is reached. The real time t to minimum fault stability increases with z. The magnitude of CFSCPP decreases with z as z ?2 for a given t D in the permissible range. The derived expression and the inferences based on it should be useful during earth science investigations of the possible hazards due to reactivation of a pre-existing shallow fault when a civil engineering project involving imposition of a heavy load on the earth’s surface is to be executed nearby. They should be useful also for investigations if a shallow earthquake occurs near such a project soon after its execution.  相似文献   

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