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1.
Adsorption of orthophosphate anions in aqueous solution by cationized milled solid wood residues was characterized as a function of sorbate-to-sorbent ratio (approximately equal to 0.001-2.58 mmol of P/g substrate), pH (3-9), ionic strength, I (no I control; 0.001 and 0.01 M NaCl), reaction time (4 min to 24 h), and in the presence of other competing anions (0.08-50 mM SO4(2-); 0.08-250 mM NO3-). Sorption isotherms revealed the presence of two kinds of adsorption sites corresponding to high and low binding affinities for orthophosphate anions. Consequently, a two-site Langmuir equation was needed to adequately describe the data over a range of solution conditions. In addition to higher sorption capacity, cationized bark possessed a higher binding energy for orthophosphate anions compared to cationized wood. The sorption capacity and binding energy for bark were 0.47 mmol of P g(-1) and 295.7 L mmol(-1), respectively, and for wood, the corresponding values were 0.27 mmol g(-1) and 61.4 L mmol(-1). Both the sorption capacity and binding energy decreased with increasing I, due to competition from Cl- ions for the available anion-exchange sites. The surface charge characteristics of cationized bark (pHzpc = 7.9) acted in concert with orthophosphate speciation to create a pH-dependent sorption behavior. Orthophosphate uptake was quite rapid and attained equilibrium levels after 3 h. Both SO4(2-) and NO3- influenced percent removal but required high relative competing anion to H2PO4- molar ratios, i.e., 2.5-3 for SO4(2-) and 25 for NO3-, to cause appreciable reduction. These results support our hypothesis that adsorption of orthophosphate anions on cationized bark involves ion exchange and other specific Lewis acid-base interactions.  相似文献   

2.
Observation of surface precipitation of arsenate on ferrihydrite   总被引:3,自引:0,他引:3  
X-ray diffraction and Raman spectroscopy were used in this study to characterize arsenate phases in the arsenate-ferrihydrite sorption system. Evidence has been obtained for surface precipitation of ferric arsenate on synthetic ferrihydrite at acidic pH (3-5) underthe following experimental conditions: sorption density of As/Fe approximately 0.125-0.49 and arsenic equilibrium concentration of <0.02-440 mg/L. Surface precipitation occurred under apparently undersaturated (in the bulk solution phase) conditions, and probably involved initial uptake of arsenate by surface complexation followed by transition to ferric arsenate formation on the surface as indicated by XRD analysis. At basic pH (i.e., pH 8), however, no ferric arsenate was observed in arsenate-ferrihydrite samples at a sorption density of As/Fe approximately 0.125-0.30 and an arsenic equilibrium concentration of 2.0-1100 mg/ L. At pH 8, arsenate is sorbed on ferrihydrite predominantly via surface adsorption, and the XRD patterns resemble basically that of ferrihydrite.  相似文献   

3.
Heavy metal pollution in the aqueous environment is a problem of global concern. Biosorption has been considered as a promising technology for the removal of low levels of toxic metals from industrial effluents and natural waters. A modified fungal biomass of Penicillium chrysogenum with positive surface charges was prepared by grafting polyethylenimine (PEI) onto the biomass surface in a two-step reaction. The presence of PEI on the biomass surface was verified by FTIR and X-ray photoelectron spectroscopy (XPS) analyses. Due to the high density of amine groups in the long chains of PEI molecules on the surface, the modified biomass was found to possess positive zeta potential at pH below 10.4 as well as high sorption capacity for anionic Cr(VI). Using the Langmuir adsorption isotherm, the maximum sorption capacity for Cr(VI) at a pH range of 4.3-5.5 was 5.37 mmol/g of biomass dry weight, the highest sorption capacity for Cr(VI) compared to other sorbents reported in the literature. Scanning electronic microscopy (SEM) provided evidence of chromium aggregates formed on the biomass surface. XPS results verified the presence of Cr(III) on the biomass surface in the pH range 2.5-10.5, suggesting that some Cr(VI) anions were reduced to Cr(III) during the sorption. The sorption kinetics indicated that redox reaction occurred on the biomass surface, and whether the converted Cr(III) ions were released to solution or adsorbed on the biomass depended on the solution pH. Sorption mechanisms including electrostatic interaction, chelation, and precipitation were found to be involved in the complex sorption of chromium on the PEI-modified biomass.  相似文献   

4.
The systematics and mechanisms of Zn uptake by hydroxyapatite (HAP) in preequilibrated suspensions open to PCO2 were characterized using a combination of batch sorption experiments, X-ray diffraction (XRD), and extended X-ray absorption fine structure spectroscopy (EXAFS) over a wide range of pH and Zn concentrations. Sorption isotherms of Zn(II) on HAP at pH 5.0 and 7.3 show an initial steep slope at low Zn(II) concentrations, followed by a plateau up to [Zn] < approximately 750 microM, suggesting Langmuir-type behavior. At [Zn] > 750 microM, a sharp rise in the pH 5.0 isotherm suggests precipitation, whereas slight continued uptake in the pH 7.3 isotherm is suggestive of an additional uptake mechanism. The sorption isotherm at pH 9.0 shows a steep uptake step at [Zn] < or = 0.8 microM, followed by an increasing linear trend up to [Zn] = 5 microM, without any indication of a maximum, suggesting that precipitation is an important uptake process at this pH. Zn K edge EXAFS results show a first oxygen shell at 1.96-1.98 +/- 0.02 A in sorption samples with [Zn]tot < or = 250 microM at pH 5.0, 7.3, and 9.0, consistent with tetrahedral coordination. EXAFS results reveal additional P and Ca neighbors that support formation of an inner-sphere Zn surface complex where the Zn is coordinated to surface P04 tetrahedra in a corner-sharing bidentate fashion, bridging a Ca atom. In contrast, EXAFS and XRD data indicate that precipitation of Zn3(PO4)2-4H2O (hopeite) dominates the mode of Zn uptake at [Zn]tot > or = 3 mM at pH 5.0. Principal component analysis and linear combination fits of EXAFS data reveal a mixture of inner-sphere Zn surface complexation and precipitation of Zn5(OH)6(CO3)2 (hydrozincite) in sorption samples for [Zn]tot = 5 mM at pH 7.3 and for [Zn]tot = 1 mM at pH 9.0.  相似文献   

5.
Solution chemistry (pH, ionic strength (I), and sorbate-to-sorbent ratio) effects on ciprofloxacin sorption to hydrous oxides of Al (HAO) and Fe (HFO) were investigated using macroscopic and spectroscopic analyses. Sorption to both HAO and HFO showed a strong pH-dependent behavior, following the fraction of zwitterionic species over the entire pH range studied. Increase in I from 0.01 to 0.5 M had an insignificant effect on the extent of ciprofloxacin sorption, and isotherms were well-described by the Langmuir model. HFO possessed a higher sorption capacity (0.066 mmol kg(-1)) than HAO (0.041 mmol kg(-1)). Ligand-promoted dissolution of hydrous oxides, more pronounced for HAO, was observed in the presence of ciprofloxacin, but at a fairly high initial concentration (0.5 mM). Attenuated total reflectance Fourier transform infrared spectroscopy analysis indicated that different types of ciprofloxacin surface complexes are formed with HAO and HFO; while a monodentate mononuclear complex (with -COO-) appears likely between ciprofloxacin and HAO, keto O and one O from COO- seem to be involved in the formation of a six-membered ring with Fe on the HFO surface. The study results are expected to increase our understanding of the environmental reactivity of fluoroquinolones, an important class of antimicrobial compounds.  相似文献   

6.
As a contribution to the determination of the sorption-behaviour of barks, the sorption isotherms for 20°C of inner and outer bark of spruce, pine, horse-chestnut, poplar and birch were taken up. Whereas the outer bark of poplar and birch, probably due to a high content of suberin, was less hygroscopic than the inner bark, the sorption isotherms of the outer bark of spruce, pine and horse-chestnut up to approximately 90% relative humidity lay above the comparative curves of the inner bark. The sorption isotherms of the inner bark of spruce, pine and poplar rose extremely above 90% relative humidity and at 100% reached moisture contents of 101–105%. These extremely high moisture contents might be caused by the existence of water soluble sugars in these inner barks.  相似文献   

7.
This paper intends to evaluate the uptake of cadmium ions from aqueous solution by 21 hydroxyapatite samples which have been synthesized in different conditions. It has been determined thatthe variation on the hydroxyapatite sorption capacity is neither related to sample solubility nor to hydroxyapatite Ca/P molar ratio. Cd2+ sorption is controlled by sample BET surface area, which shows a direct dependence on the hydroxyapatite crystallite dimensions. The hydroxyapatite pore distribution presented modes at 1000 and 60,000 A, corresponding to intracrystallite voids and voids between the agglomerate of these crystallites, respectively. Pores belonging to the former mode immobilize the major part of Cd2+. The influence of sample thermal treatment on Cd2+ sorption efficiency has been studied using hydroxyapatite samples calcined at temperatures ranging from 500 to 1140 degrees C. Similarly to nonthermally treat samples, the Cd2+ sorption on calcined hydroxyapatite could be described by Langmuir isotherms. The results showed that the maximum sorption capacity decreased from 0.631 mmol g(-1) for the noncalcined sample to 0.150 mmol g(-1) for the one calcined at 900 degrees C. This drop in the sorption capacity could also be explained by a reduction in its specific surface area, which is induced bythe increase of the crystal size.  相似文献   

8.
The sorption of uranyl onto hydrous ferric oxide (HFO) or hematite was measured by discontinuously titrating the suspensions with uranyl at pH 5.9, 6.8, and 7.8 under Pco2 = 10(-35)atm (sorption isotherms). Batch reactors were used with equilibration times up to 48 days. Sorption of 1 microM uranyl onto HFO was also measured versus pH (sorption edge). A diffuse double layer surface complexation model was calibrated by invoking three sorption species that were consistent with spectroscopic evidence for predominance of bidentate complexes at neutral pH and uranyl-carbonato complexes: > SOH:UO2OH(+1), (> SO)2: UO2CO3(-2), and (> SO)2:(UO2)3(OH)5(-1). The model was consistent with previously published isotherm and edge data. The model successfully predicted sorption data onto hematite, only adjusting for different measured specific surface area. Success in application of the model to hematite indicates that the hydrated surface of hematite has similar sorptive reactivity as HFO.  相似文献   

9.
Sequestration of Ni(II) on diatomite as a function of time, pH, and temperature was investigated by batch, XPS, and EXAFS techniques. The ionic strength-dependent sorption at pH < 7.0 was consistent with outer-sphere surface complexation, while the ionic strength-independent sorption at pH = 7.0-8.6 was indicative of inner-sphere surface complexation. EXAFS results indicated that the adsorbed Ni(II) consisted of ~6 O at R(Ni-O) ≈ 2.05 ?. EXAFS analysis from the second shell suggested that three phenomena occurred at the diatomite/water interface: (1) outer-sphere and/or inner-sphere complexation; (2) dissolution of Si which is the rate limiting step during Ni uptake; and (3) extensive growth of surface (co)precipitates. Under acidic conditions, outer-sphere complexation is the main mechanism controlling Ni uptake, which is in good agreement with the macroscopic results. At contact time of 1 h or 1 day or pH = 7.0-8.0, surface coprecipitates occur concurrently with inner-sphere complexes on diatomite surface, whereas at contact time of 1 month or pH = 10.0, surface (co)precipitates dominate Ni uptake. Furthermore, surface loading increases with temperature increasing, and surface coprecipitates become the dominant mechanism at elevated temperature. The results are important to understand Ni interaction with minerals at the solid-water interface, which is helpful to evaluate the mobility of Ni(II) in the natural environment.  相似文献   

10.
Phosphate sorption on Fe- and Al-oxide minerals helps regulate the solubility and mobility of P in the environment. The objective of this study was to characterize phosphate adsorption and precipitation in single and binary systems of Fe- and Al-oxide minerals. Varying concentrations of phosphate were reacted for 42 h in aqueous suspensions containing goethite, ferrihydrite, boehmite, or noncrystalline (non-xl) Al-hydroxide, and in 1:1 (by mass) mixed-mineral suspensions of goethite/boehmite and ferrihydrite/ non-xl Al-hydroxide at pH 6 and 22 degrees C. X-ray absorption near edge structure (XANES) spectroscopy was used to detect precipitated phosphate and distinguish PO4 associated with Fe(III) versus Al(III) in mixed-mineral systems. Changes in the full width at half-maximum height (fwhm) in the white-line peak in P K-XANES spectra provided evidence for precipitation in Al-oxide single-mineral systems, but not in goethite or ferrihydrite systems. Similarly, adsorption isotherms and XANES data showed evidence for precipitation in goethite/boehmite mixtures, suggesting that mineral interactive effects on PO4 sorption were minimal. However, sorption in ferrihydrite/non-xl Al-hydroxide systems and a lack of XANES evidence for precipitation indicated that mineral interactions inhibited precipitation in these binary mixtures.  相似文献   

11.
Biogeochemical iron cycling often generates systems where aqueous Fe(II) and solid Fe(III) oxides coexist. Reactions between these species result in iron oxide surface and phase transformations, iron isotope fractionation, and redox transformations of many contaminant species. Fe(II)-induced recrystallization of goethite and hematite has recently been shown to cause the repartitioning of Ni(II) at the mineral-water interface, with adsorbed Ni incorporating into the iron oxide structure and preincorporated Ni released back into aqueous solution. However, the effect of Fe(II) on the fate and speciation of redox inactive species incompatible with iron oxide structures is unclear. Arsenate sorption to hematite and goethite in the presence of aqueous Fe(II) was studied to determine whether Fe(II) causes substantial changes in the sorption mechanisms of such incompatible species. Sorption isotherms reveal that Fe(II) minimally alters macroscopic arsenate sorption behavior except at circumneutral pH in the presence of elevated concentrations (10?3 M) of Fe(II) and at high arsenate loadings, where a clear signature of precipitation is observed. Powder X-ray diffraction demonstrates that the ferrous arsenate mineral symplesite precipitates under such conditions. Extended X-ray absorption fine structure spectroscopy shows that outside this precipitation regime arsenate surface complexation mechanisms are unaffected by Fe(II). In addition, arsenate was found to suppress Fe(II) sorption through competitive adsorption processes before the onset of symplesite precipitation. This study demonstrates that the sorption of species incompatible with iron oxide structure is not substantially affected by Fe(II) but that such species may potentially interfere with Fe(II)-iron oxide reactions via competitive adsorption.  相似文献   

12.
Little information is available concerning cosorbing oxyanion and metal contaminants in the environment, yet in most metal-contaminated areas, cocontamination by arsenate [AsO4, As(V)] is common. This study investigated the cosorption of As(V) and Zn on goethite at pH 4 and 7 as a function of final solution concentration. Complimentary extended X-ray absorption fine structure (EXAFS) spectroscopic data were collected at the As and Zn K-edges in order to glean information about the coordination environment of As and Zn at the goethite-water interface. Macroscopic sorption studies revealed that As(V) and Zn sorption on goethite increased in cosorption experiments beyond that suggested by single sorption isotherms. At pH 4 and 7, As(V) surface saturation was 3.2 and 2.2 micromol m(-2), respectively, and Zn surface saturation was absent at pH 4 and approximately 1.0 micromol m(-2) at pH 7. Arsenate sorption on goethite increased in the presence of Zn by 29% and by more than 500% at pH 4 and 7, respectively. In the presence of As(V), Zn sorption on goethite increased by 800 and 1300% at pH 4 and 7, respectively. More As(V) than Zn sorbed on goethite below surface saturation at pH 7. Above surface saturation, the Zn:As surface density ratio (SDR) remained constant at 0.91 +/- 0.03. At pH 4, the Zn:As SDR was less than 1 throughout the concentration range. Below As(V) surface saturation on goethite, As(V) formed bidentate binuclear bridging complexes on Fe and/or Zn octahedra, while Zn mainly formed edge-sharing complexes with Fe at the goethite surface. Above surface saturation, Zn was increasingly complexed by AsO4, gradually forming an adamite-like [Zn2(AsO4)OH] surface precipitate on goethite. Precipitated contaminants are more stable due to the limited dissolution kinetics of their solid phase. This study may therefore prove useful in remediation strategies of sites knowingly contaminated with oxyanions and metals.  相似文献   

13.
Lemon peel constitutes a potential source of dietary fiber to formulate new and healthier products, as well as a source of essential oils. The relationship between moisture content and water activity provides useful information for lemon peel processing, especially for drying and storage. Water sorption isotherms of lemon peel were obtained using a standardized conductivity hygrometer at four different temperatures (20, 30, 40 and 50 °C) and wide ranges of moisture content (5.381-0.002 kg water/kg dry solid) and water activity (0.984-0.106). One theoretical (GAB) and four empirical equations (Oswin, Henderson, Halsey and Ratti) were used for modelling sorption isotherms. After evaluating the models according to several criteria, the GAB model appeared as the best option. Isosteric heats of sorption were assessed from experimental sorption isotherm data using different methods.  相似文献   

14.
The sorption of Pu(VI) onto manganite (MnOOH) and hausmannite (Mn3O4) was studied as a function of time, solution pH, and initial plutonium concentration. Kinetic experiments indicate that the surface complexation of plutonium occurs over the first 24 h of contact with the mineral surface. The sorption increases with pH beginning at pH 3 until it reaches a maximum value of 100% at pH 8 (0.0011-0.84 micromol of Pu/m2 of manganite and 0.98-1.2 micromol of Pu/m2 of hausmannite) and then decreases over the pH range from 8 to 10. The ratio of solid to solution was 10 mg/mL for manganite experiments and 4 mg/mL for hausmannite samples. Carbonate was not excluded from the experiments. The amount of plutonium removed from the solution by the minerals is determined by a combination of factors including the plutonium solution species, the surface charge of the mineral, and the mineral surface area. X-ray absorption fine structure taken at the Pu L(III) edge were compared to plutonium standard spectra and showed that Pu(VI) was reduced to Pu(IV) after contact with the minerals. Plutonium sorption to the mineral surface is consistent with an inner-sphere configuration, and no evidence of PuO2 precipitation is observed. The reduction and complexation of Pu(VI) by manganese minerals has direct implications on possible migration of Pu(VI) species in the environment.  相似文献   

15.
We examined the adsorption of the allelopathic aromatic acids (AA), cinnamic and coumaric, to different charcoals (biochars) as part of a study on bioavailability of natural signaling chemicals in soil. Sorption isotherms in pH 7 buffer, where the AAs are >99% dissociated, are highly nonlinear, give distribution ratios as high as 10(4.8) L/kg, and are insensitive to Ca(2+) or Mg(2+). In unbuffered media, sorption becomes progressively suppressed with loading and is accompanied by release of OH(-) with a stoichiometry approaching 1 at low concentrations, declining to about 0.4-0.5 as the pH rises. Sorption of cinnamate on graphite as a model for charcoal was roughly comparable on a surface area basis, but released negligible OH(-). A novel scheme is proposed that explains the pH dependence of adsorption and OH(-) stoichiometry and the graphite results. In a key step, AA(-) undergoes proton exchange with water. To overcome the unfavorable proton exchange free energy, we suggest AA engages in a type of hydrogen bond recognized to be of unusual strength with a surface carboxylate or phenolate group having a comparable pK(a). This bond is depicted as [RCO(2)···H···O-surf](-). The same is possible for AA(-), but results in increased surface charge. The proton exchange pathway appears open to other weak acid adsorbates, including humic substances, on carbonaceous materials.  相似文献   

16.
Arsenic derived from natural sources occurs in groundwater in many countries, affecting the health of millions of people. The combined effects of As(V) reduction and diagenesis of iron oxide minerals on arsenic mobility are investigated in this study by comparing As(V) and As(III) sorption onto amorphous iron oxide (HFO), goethite, and magnetite at varying solution compositions. Experimental data are modeled with a diffuse double layer surface complexation model, and the extracted model parameters are used to examine the consistency of our results with those previously reported. Sorption of As(V) onto HFO and goethite is more favorable than that of As(III) below pH 5-6, whereas, above pH 7-8, As(II) has a higher affinity for the solids. The pH at which As(V) and As(III) are equally sorbed depends on the solid-to-solution ratio and type and specific surface area of the minerals and is shifted to lower pH values in the presence of phosphate, which competes for sorption sites. The sorption data indicate that, under most of the chemical conditions investigated in this study, reduction of As(V) in the presence of HFO or goethite would have only minor effects on or even decrease its mobility in the environment at near-neutral pH conditions. As(V) and As(III) sorption isotherms indicate similar surface site densities on the three oxides. Intrinsic surface complexation constants for As(V) are higher for goethite than HFO, whereas As(III) binding is similar for both of these oxides and also for magnetite. However, decrease in specific surface area and hence sorption site density that accompanies transformation of amorphous iron oxides to more crystalline phases could increase arsenic mobility.  相似文献   

17.
The objective of this study was to provide fundamental knowledge of arsenate sorption on lithium/aluminum layered double hydroxide intercalated by chloride (Li/Al LDH-Cl) and further to reveal the contribution of exposed positive charge surface of Li/Al LDH-CI created by intercalating LiCl into Al(OH)3 layers to arsenate sorption. Therefore, sorption isotherms, envelopes and extended X-ray absorption fine structure (EXAFS) technique were employed to examine the reaction of arsenate on Li/Al LDH-Cl and on gibbsite. Based on an isotherm study, the sorption maximum of Li/Al LDH-Cl for arsenate was approximately six times higher than that of gibbsite. Sorption envelopes of arsenate on Li/Al LDH-Cl displayed a pH-sensitive behavior from pH 4.0 to 7.0, but it was insensitive to pH above pH 7.0, approaching to the pHpzc of Li/Al LDH-Cl (7.22). This transformation with shifted pHs illustrated that there were two types of reaction sites within Li/Al LDH-Cl that participate in arsenate sorption; one is pH-sensitive and the other is not. From EXAFS analysis, arsenate sorbed on Li/Al LDH, reacted not only with Al in the edges of Al-(OH)3 layers, but also with Li located in the vacant octahedral sites within Al(OH)3 layers; however, the decreasing intensity of As(V)-Al shells with increasing pH represented there were fewer As(V)-Al complex existed at higher pH, i.e., the complex between arsenate and Al is pH-sensitive. The superior sorption capability of Li/Al LDH-Cl to that of gibbsite could be attributed to the intercalated Li cations which served as the permanent sorption sites and made the surface of Al(OH)3 have high affinity to arsenate.  相似文献   

18.
Tributyltin (TBT) sorption to four natural sediment samples in artificial seawater was examined under a range of modified pH and salinity conditions. Three of the sediment samples were relatively pristine with regard to TBT contamination, but the fourth was a TBT-contaminated sediment from a commercial marina. Sorption of TBT was described well by linear sorption isotherms, with distribution coefficients ranging from 6.1 to 5210 L/kg depending on the pH and salinity. The sediment organic C content and particle size distribution were important determinants of sorption behavior. The presence of resident TBT in the contaminated marina sediment caused a substantial reduction in further TBT sorption. Desorption of TBT from the marina sediment was described by relatively large observed distribution coefficients ranging from 5100 to 9400 L/kg, suggesting that aging effects may reduce sorption reversibility. Increased artificial seawater salinity generally reduced TBT sorption at pH 4 and 6, but enhanced TBT sorption at pH 8. Regardless of salinity, maximum sorption of TBT was observed at pH 6, which is attributed to an optimal balance between the abundance of cationic TBT+ species and deprotonated surface ligands. Consideration of aqueous TBT speciation along with octanol-water partitioning behavior suggests that hydrophobic partitioning of TBTCl(0) to nonpolar organic matter was important for pH < 6, while partitioning of TBTOH(0) was important at higher pH.  相似文献   

19.
Tannins, which are rich in ortho-hydroxyl groups, have a high affinity for UO2(2+). In this paper, Myrica rubra tannin was immobilized on collagen fiber by an aldehydic cross-linking reaction to prepare a novel adsorbent for uranium (UO2(2+)) recovery from wastewater. The adsorption equilibrium, the adsorption kinetics, and the effects of temperature and pH on the adsorption equilibrium were investigated in detail. It was found that the Myrica rubra tannin immobilized on collagen fiber exhibits an excellent adsorption capacity for UO2(2+). The adsorption capacity at 293 K and pH 5.0 was as high as 1.19 mmol UO2(2+)/g (283.3 mgU/g) when the initial concentration of UO2(2+) in solution was 7.5 mmol/L. The adsorption isotherms could be described by the Freundlich equation, and the increase of temperature promoted the adsorption to UO2(2+) . The adsorption kinetics data were fitted very well by the pseudosecond-order rate model, and the equilibrium adsorption capacity calculated by the pseudo-second-order rate model was almost the same as that determined by the actual measurement with the error < or = 4%. The pH has a significant effect on the adsorption process. According to our experiments, the suitable pH scope should be 5-8.  相似文献   

20.
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