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1.
Ruello ML  Sileno M  Sani D  Fava G 《Chemosphere》2008,70(6):1135-1140
The objective of this study is to provide an insight into the techniques for measuring the lability of heavy metals in solid-phase pool of soils in order to assess the environmental risk arising from pollution. The technique of diffusive gradients in thin films (DGT) and a sequential extraction procedure were used to quantify the labile pools of Cu, Fe, Mn and Ni. These results were compared to metal concentrations in groundwater, measured directly using the in situ piezometers, and to the total concentration of metal in the soils. High concentrations of metal in the directly analysed soil solution compared to DGT measurement were attributed to the presence of colloidal metal. The use of DGT allowed only to calculate leaching parameters of the free ions and labile fractions of the metals. For this reason DGT technique needs preliminary investigation on metal speciation in soil solution before its application as a good tool in the characterization procedure of contaminated sites.  相似文献   

2.
This study investigated the forms of soil P released to solution, accuracy of their determination, and influence of colloids on P sorption/desorption dynamics. A Hagerstown silt loam, amended with dairy and poultry manure or superphosphate at five rates (0, 25, 50, 100, and 200 kg P ha(-1)), was extracted at two soil:solution ratios (1:5 and 1:100) and filtered at three pore sizes (0.8, 0.45, and 0.22 microm). Results showed that relative to the proportion of dissolved organic P (DOP, determined as the difference between total dissolved P [TDP] and P detected by ion chromatography), DRP increased with amendment rate. Relative to Mehlich-3 extractable P, DRP exhibited a power relationship with a much greater potential for soil P release at concentrations in excess of ca. 50 mg Mehlich-3 P kg(-1). Concentrations of DRP, determined by the acid molybdate method, were on average 12.5% greater than P detected by ion chromatography indicating P was solubilised during colorimetric determination. A linear relationship was found between total Al and DRP, which could indicate acid mediated hydrolysis of A1-humic-P substances, although acid mediated desorption of P from colloids cannot be discounted. No difference in solubilised P was found between solutions filtered at 0.22 and 0.45 microm, but was found between 0.8 microm and smaller filter sizes. Organic P extracted from manured soils was more recalcitrant than that extracted from soils amended with superphosphate, the later attributed to its accumulation in more labile pools. The sorption/desorption of P by colloids in solution were greatly affected by the rate of amendment and the soil:solution extraction ratio. More P was sorbed by superphosphate solutions compared to dairy manure amended soil solutions and was attributed to the saturation of colloidal P sorption sites by organic matter. In order to minimise the effects of colloids on P dynamics and the potential for hydrolysis in solution, filtration to at least 0.45 microm is required. However, soils with a lesser aggregate stability may require additional filtration.  相似文献   

3.
Various natural and anthropogenic processes influence heavy metal concentrations within estuaries. In situ, time-integrated DGT measurements made over concurrent tidal phases found significantly higher concentrations of Cu (probability p=0.017), Zn (p=0.003) and Ni (p=0.003) during the flood phase, because the incoming tide passes several point sources. DGT-reactive Cu concentrations significantly decreased with increased tidal-flushing and vice versa within a marina (correlation r=-0.788, p=0.02). DGT measurements also recorded significant increases in Cu (4 out of 4 sites, p<0.001) and Zn (3 out of 4 sites, p< or =0.015) after a 24 mm rainfall event. Finally, DGT-reactive Cu increased significantly (p<0.001) during peak boating times, due to increased numbers of Cu-antifouled boats. This study demonstrates that, with judicious selection of deployment times, DGT measurements enable changes in heavy metal concentrations to be related to various cycles and events within estuaries.  相似文献   

4.
Tolerance and metal uptake are two essential characteristics required for phytoextraction of metals from contaminated soils. We compared tolerance and Cu uptake of Elsholtzia splendens (reported previously to be a Cu hyperaccumulator) with Silene vulgaris (the Imsbach population, a well-known Cu-tolerant excluder species), using 30 soils varying widely in total Cu concentration (19-8645 mg kg(-1)). We further investigated the effectiveness of different soil testing methods for predicting plant metal uptake. The results showed that both Elsholtzia splendens and Silene vulgaris were tolerant to Cu, especially Silene vulgaris. However, Elsholtzia splendens did not hyperaccumulate Cu, but behaved as a typical Cu excluder like Silene vulgaris. The concentrations of Cu in both plants correlated more closely with 1 M NH4NO3 extractable Cu, soil solution Cu, or effective Cu concentration determined using DGT, than with soil total Cu, EDTA extractable Cu or free Cu2+ activity. The relationships between soil solution properties and root Cu concentrations were further investigated using multiple regression. The results showed that increasing soil solution pH increased root Cu concentration when free Cu2+ activity was held constant, suggesting a higher phytoavailability of free Cu2+ at a higher pH. Soil solution DOC appeared to play two contrasting roles on the phytoavailability of Cu: (1) reducing Cu availability by complexing Cu; and (2) increasing Cu availability at the same level of free Cu2+ activity by providing a strong buffer for free Cu2+. The results are consistent with the intensity/capacity concept for phytoavailability of metals in soils.  相似文献   

5.
Soil testing procedures to address metals bioavailability currently use air-dried soil rewetted almost until saturation. Such practices may influence the redox state of soil and the related dynamics of metals. To assess this potential impact, a metal-contaminated soil was air-dried and rewetted to 90% water holding capacity. We monitored over a 21-day incubation period the temporal changes of soil redox potential and solution Cd concentration (either total or free). Other physico-chemical parameters were followed notably pH, ionic strength (I) and the concentrations of NO(3)(-), Mn, Fe and SO(4)(2-) in solution. Soil redox potential showed the progressive establishment of strong reducing conditions in soil, in agreement with the temporal changes of NO(3)(-), Mn, Fe and SO(4)(2-) concentrations. It decreased by 13 pe units over the culture period leading to sulphate-reducing conditions (pe<-3) within only 21days. Solution Cd concentration increased transitorily over the first 100-150h of incubation (2-fold increase) in relation with the parallel increase in the concentration of competing cations for adsorption (Ca, Mg). It steeply decreased over the last 300h of incubation (30-fold decrease) as a result of Cd precipitation as Cd sulphides. This biphasic evolution of Cd dynamics was related to the temporal changes of Cd resupply from the solid phase. Using the technique of DGT we described the kinetics of Cd resupply over time and needed to invoke the existence of two pools of Cd.  相似文献   

6.
7.
Wu S  Wu E  Qiu L  Zhong W  Chen J 《Chemosphere》2011,83(4):429-434
To assess the toxic effects of phenanthrene on earthworms, we exposed Eisenia fetida to artificial soils supplemented with different concentrations (0.5, 2.5, 12.5, mgkg(-1) soil) of phenanthrene. The residual phenanthrene in the soil, the bioaccumulation of phenanthrene in earthworms, and the subsequent effects of phenanthrene on growth, anti-oxidant enzyme activities, and lipid peroxidation (LPO) were determined. The degradation rate of low concentrations of phenanthrene was faster than it was for higher concentrations, and the degradation half-life was 7.3d (0.5 mgkg(-1)). Bioaccumulation of phenanthrene in the earthworms decreased the phenanthrene concentration in soils, and phenanthrene content in the earthworms significantly increased with increasing initial soil concentrations. Phenanthrene had a significant effect on E. fetida growth, and the 14-d LC(50) was calculated as 40.67 mgkg(-1). Statistical analysis of the growth inhibition rate showed that the concentration and duration of exposure had significant effects on growth inhibition (p<0.001). Superoxide dismutase (SOD) activity increased at the beginning (2 and 7d) and decreased in the end (14 and 28 d). Catalase (CAT) activity in all treatments was inhibited from 1 to 14 d of exposure. However, no significant perturbations in malondialdehyde (MDA) content were noted between control and phenanthrene-treated earthworms except after 2d of exposure. These results revealed that bioaccumulation of phenanthrene in E. fetida caused concentration-dependent, sub-lethal toxicity. Growth and superoxide dismutase activity can be regarded as sensitive parameters for evaluating the toxicity of phenanthrene to earthworms.  相似文献   

8.
The combined effect of time and temperature on elemental release and speciation from a metal contaminated soil (Master Old Site, MOS) was investigated. The soil was equilibrated at 10, 28, 45, 70 and 90 degrees C for 2 days, 2 weeks, and 2 months in the laboratory. Dissolved organic carbon (DOC), total soluble elements (by ICP), and labile metals (by DPASV) were determined in the filtered (0.22 microm) supernatants. For the samples equilibrated at 90 degrees C, DOC fractions were size fractionated by filtration and centrifugation; a subsample was only centrifuged while another was also filtered through a 0.45 microm filter. Analyses of the supernatants (ICP, DPASV, DOC) were performed on all size fraction subsamples. Dissolved organic carbon (DOC) increased both with temperature and incubation time; however, metal behavior was not as uniform. In general, total soluble metal release (ICP) paralleled the behavior of DOC, increasing with both time and temperature, and confirming the importance of soil organic matter (SOM) in metal retention. Voltammetric analysis (dpasv) of Cu and Zn showed that very little of these metals remains labile in solution due, presumably, to complexation with dissolved organic matter. Labile concentrations of Cd, on the other hand, constituted a significant portion (50%) of total soluble Cd. Copper and Al increased in solution with time (up to 2 months) and temperature up to 70 degrees C; however, at 90 degrees C the soluble concentration declined sharply. The same behavior was observed after equilibration for longer periods of time (550 days) at lower temperatures (23 and 70 degrees C). While concentrations of labile Cu and total soluble Cu and Al increased in the unfiltered samples, the trend remained the same. DPASV analysis showing shifts in labile Cu complexes with temperature and time, together with the results from the unfiltered samples, lead to the hypothesis that Cu was complexing with large polymers that could form at the elevated temperature, and thus be removed from the analyzed solution. It is possible that Cu and Al released by SOM oxidation has re-sorbed or complexed to more recalcitrant organic matter or to mineral phases. Variations in the relative molecular size fractions present within the DOC pool produced by increased time and temperature may influence the element-DOC complexes present in solution and their behavior in soil environments.  相似文献   

9.
Given the difficulties caused by low-permeable soils in bioremediation, a new electrokinetic technology is proposed, based on laboratory results with phenanthrene, to afford bioremediation of polycyclic aromatic hydrocarbons (PAH) in clay soils. Microbial activity in a clay soil historically polluted with creosote was promoted using a specially designed electrokinetic cell with a permanent anode-to-cathode flow and controlled pH. The rates of phenanthrene losses during treatment were tenfold higher in soil treated with an electric field than in the control cells without current or microbial activity. Results from experiments with Tenax-assisted desorption and mineralization of 14C-labeled phenanthrene indicated that phenanthrene biodegradation was limited by mass-transfer of the chemical. We suggest that the enhancement effect of the applied electric field on phenanthrene biodegradation resulted from mobilization of the PAH and nutrients dissolved in the soil fluids.  相似文献   

10.
Vertical profiles of metals were measured by the in situ application of DGT (diffusive gradients in thin films). Well-defined laboratory systems ensured the good reproducibility and precision DGT accumulated metals on a chelex resin after diffusional transport through a layer of hydrogel. Three kinds of DGT probes (with three thicknesses of diffusive gel: 0.40 mm, 0.80 mm and 1.92 mm) measured interfacial concentration and induced flux from solid to solution phase which had intricate variations with depth. The DGT induced flux and interfacial concentration of four metals belonged to “partially sustained” state, indicating a labile equilibrium of metals between solid phase and porewater. The concentration profiles showed the good correlation between Mn and Co and peak concentrations of Mn and Fe between −2.00 cm and −5.25 cm with depth.  相似文献   

11.
Objective of this study was to evaluate the effects of hydroxypropyl-beta-cyclodextrin (HPCD) on the removal of phenanthrene from solid phase. Batch tests for the phenanthrene distribution between aqueous and solid phase were conducted in the presence of HPCD. Column tests and numerical simulations were conducted to evaluate the roles of HPCD cavities and interaction rates between water, HPCD, and solid phase in the enhanced removal of phenanthrene. Experimental results showed that HPCD was effective in removing sorbed phenanthrene from subsurface environment, primarily due to its negligible sorption to the solid phase and the partitioning of phenanthrene into HPCD cavities. From the numerical simulations, it was found that rate-limited partitioning of phenanthrene into HPCD cavities was most influential factor in the enhanced elution of phenanthrene. Sorption and desorption rate of phenanthrene between aqueous and solid phase was very fast or near equilibrium state. Interaction rates of contaminant between water, HPCD, and solid phase could be affected by other factors such as soil types and organic matter contents. Results from this study implied that HPCD flushing could be effectively applied for the removal of hydrophobic organic pollutants existing in the soils as sorbed or NAPL state.  相似文献   

12.
Diffusive gradients in thin films (DGT) is a dynamic, in situ measuring technique that can be used to supply diverse information on concentrations and behaviour of solutes. When deployed in soils and sediments, quantitative interpretation of DGT measurements requires the use of a numerical model. An improved version of the DGT induced fluxes in soils and sediments model (DIFS), working in two dimensions (2D DIFS), was used to investigate the accuracy with which DGT measurements can be used to estimate the distribution coefficient for labile metal (KD) and the response time of the soil to depletion (TC). The 2D DIFS model was used to obtain values of KD and TC for Cd, Zn and Ni in three different soils, which were compared to values determined previously using 1D DIFS for these cases. While the 1D model was shown to provide reasonable estimates of KD, the 2D model refined the estimates of the kinetic parameters. Desorption rate constants were shown to be similar for all three metals and lower than previously thought. Calculation of an error function as KD and TC are systematically varied showed the spread of KD and TC values that fit the experimental data equally well. These automatically generated error maps reflected the quality of the data and provided an appraisal of the accuracy of parameter estimation. They showed that in some cases parameter accuracy could be improved by fitting the model to a sub-set of data.  相似文献   

13.
Gao Y  Zhu L 《Chemosphere》2004,55(9):1169-1178
Uptake, accumulation and translocation of phenanthrene and pyrene by 12 plant species grown in various treated soils were comparatively investigated. Plant uptake and accumulation of phenanthrene and pyrene were correlated with their soil concentrations and plant compositions. Root or shoot accumulation of phenanthrene and pyrene in contaminated soils was elevated with the increase of their soil concentrations. Significantly positive correlations were shown between root concentrations or root concentration factors (RCFs) of phenanthrene and pyrene and root lipid contents. The RCFs of phenanthrene and pyrene for plants grown in contaminated soils with initial phenanthrene concentration of 133 mgkg(-1) and pyrene of 172 mgkg(-1) were 0.05-0.67 and 0.23-4.44, whereas the shoot concentration factors of these compounds were 0.006-0.12 and 0.004-0.12, respectively. For the same soil-plant treatment, shoot concentrations and concentration factors of phenanthrene and pyrene were generally much lower than root. Translocations of phenanthrene and pyrene from shoots to roots were undetectable. However, transport of these compounds from roots to shoots usually was the major pathway of shoot accumulation. Plant off-take of phenanthrene and pyrene only accounted for less than 0.01% of dissipation enhancement for phenanthrene and 0.24% for pyrene in planted versus unplanted control soils, whereas plant-promoted biodegradation was the predominant contribution of remediation enhancement of soil phenanthrene and pyrene in the presence of vegetation.  相似文献   

14.
Objective of this study was to evaluate the effects of hydroxypropyl‐β‐cyclodextrin (HPCD) on the removal of phenanthrene from solid phase. Batch tests for the phenanthrene distribution between aqueous and solid phase were conducted in the presence of HPCD. Column tests and numerical simulations were conducted to evaluate the roles of HPCD cavities and interaction rates between water, HPCD, and solid phase in the enhanced removal of phenanthrene. Experimental results showed that HPCD was effective in removing sorbed phenanthrene from subsurface environment, primarily due to its negligible sorption to the solid phase and the partitioning of phenanthrene into HPCD cavities. From the numerical simulations, it was found that rate‐limited partitioning of phenanthrene into HPCD cavities was most influential factor in the enhanced elution of phenanthrene. Sorption and desorption rate of phenanthrene between aqueous and solid phase was very fast or near equilibrium state. Interaction rates of contaminant between water, HPCD, and solid phase could be affected by other factors such as soil types and organic matter contents. Results from this study implied that HPCD flushing could be effectively applied for the removal of hydrophobic organic pollutants existing in the soils as sorbed or NAPL state.  相似文献   

15.
Cattani I  Fragoulis G  Boccelli R  Capri E 《Chemosphere》2006,64(11):1972-1979
In this study, potentially bioavailable copper was estimated in two soils (a fungicide polluted and a natural soil) using a passive sampling technique, DGT. As plants can alter copper mobility and bioavailability in the soil, the rhizosphere properties of Zea mays L. were investigated using rhizoboxes.

Compared to the total concentration, the soluble and the potentially bioavailable copper concentration in the bulk soils were generally low (less than 0.20% and 0.06% respectively), with a sixfold increase in the rhizosphere of the polluted soil. Our results suggest that maize cultivation in a polluted vineyard soil could increase the potentially available fraction of copper. DGTs showed a good sensitivity to soil properties and to root-induced changes in the rhizosphere, but the potentially bioavailable copper could not be related to the copper concentration in the above ground parts of maize. The results suggest that DGT may be used to predict some effects of the cultivation of polluted soils, for example, metal mobility and increased availability, but they cannot mimic the uptake of a tolerant plant.

For both soils, dissolved organic carbon (DOC) concentrations were threefold higher in the rhizosphere than in the bulk soil, whilst bioaccumulation in leaves and roots was not significant. DOC production, usually effective in ion mobilization and assimilation, may help also in the reduction of Cu uptake at toxic concentrations. The sequestration of available Cu in soil and soil solution by DOC seems to contribute to maize tolerance.  相似文献   


16.
Larner BL  Seen AJ  Snape I 《Chemosphere》2006,65(5):811-820
This work has been the first application of DGT samplers for measuring metals in water and sediment porewater in the Antarctic environment, and whilst DGT water sampling was restricted to quantification of Cd, Fe and Ni, preconcentration using Empore chelating disks provided results for an additional nine elements (Sn, Pb, Al, Cr, Mn, Co, Cu, Zn, As). Although higher concentrations were measured for some metals (Cd, Ni, Pb) using the Empore technique, most likely due to particulate-bound or colloidal species becoming entrapped in the Empore chelating disks, heavy metal concentrations in the impacted Brown Bay were found to be comparable with the non-impacted O'Brien Bay. Sediment porewater sampling using DGT also indicated little difference between Brown Bay and O'Brien Bay for many metals (Cd, Al, Cr, Co, Ni, Cu), however, greater amounts of Pb, Mn, Fe and As were accumulated in DGT probes deployed in Brown Bay compared with O'Brien Bay, and a higher accumulation of Sn was observed in Brown Bay inner than any of the other three sites sampled. Comparison of DGT derived porewater concentrations with actual porewater concentrations showed limited resupply of Cd, Pb, Al, Cr, Mn, Co, Ni, Cu, Zn and As from the solid phase to porewater, with these metals appearing to be strongly bound to the sediment, however, resupply of Fe and Sn was apparent. Based upon our observations here, we suggest that Sn, and to a lesser extent Pb, are critical contaminants.  相似文献   

17.
Seven metals (Cd, Co, Cr, Cu, Fe, Ni and Pb) were monitored at the Seine-Aval wastewater treatment plant during 6 sampling campaigns in April 2004. Particulate and dissolved metals have been measured in 24 h composite samples at each treatment stage (primary settling, secondary activated sludge and tertiary flocculation by FeCl3). In addition, the diffusive gradient in thin film technique (DGT) was used to determine the dissolved inert and labile metal fraction. Although all treatment stages were able to decrease particulate metals concentrations in wastewater, most dissolved metals concentrations were mainly affected during primary settling. This unexpected result was attributed to tertiary sludge filtrate recirculation. Metals added via the FeCl3 reagent at the tertiary treatment were shown to lower the overall Cr removal from wastewater and to enrich Ni in effluents. The plant operating conditions (recirculation and reagent addition) appear therefore as important as treatment processes for the metals removal. Total metal fluxes were highly decreased by the whole treatment plant for Cd, Cr, Cu and Pb and to a lesser extend for Co and Ni. However, the labile metal fluxes were poorly decreased for Cu (18%), not significantly decreased for Ni and increased for Fe. The labile fraction of Cd, Co and Cr was not detectable at any stage of the plant. Discharged labile fluxes, at least for Ni, were potentially significant compared to the labile metal fluxes in the river measured downstream the plant. Treated urban wastewater discharges should be carefully considered as a possible source of bioavailable trace metals.  相似文献   

18.
The response of ten soils of the lithic Rhodoxeralf type to the supply of lead at concentrations of 500, 1000, 2000, 3000, 4000, 5000 and 6000 mg kg-1 was examined in batch sorption-desorption tests. Lead availability in the soils was found to depend on its partitioning between the soil solution and the solid phase as reflected in adsorption isotherms. The isotherms, of the H type, were consistent with a high affinity of the sorbent for the metal, with which it forms stable inner-sphere complexes on the soil surface. Sorption-desorption tests revealed that some properties of the soils such as their pH (mean=8) and high contents in clays (particularly in kaolinite) and crystalline iron oxides significantly influence Pb sorption, the effect being especially marked at high added metal concentrations. Added lead is largely retained by crystalline iron oxides and the soil clay fraction; the pH of the soil favours the release of variably-charged sites from both. The extent of Pb desorption was small, particularly at the lowest added levels (500 and 1000 mg kg-1). Desorption increased with increasing added Pb concentration and exceeded 50% at 5000 and 6000 mg kg-1; this suggests that Pb is present not only as inner-sphere complexes, but also as outer-sphere complexes and, partly, as precipitates. The desorption isotherms consist of three segments that exhibit significant differences depending on the added Pb concentration, namely: 500-1000, 2000-4000 and 5000-6000 mg kg-1.  相似文献   

19.
Sorption of phenanthrene by soils contaminated with heavy metals   总被引:4,自引:0,他引:4  
Gao Y  Xiong W  Ling W  Xu J 《Chemosphere》2006,65(8):1355-1361
The fate of polycyclic aromatic hydrocarbons (PAHs) in soils with co-contaminants of heavy metals has yet to be elucidated. This study examined sorption of phenanthrene as a representative of PAHs by three soils contaminated with Pb, Zn or Cu. Phenanthrene sorption was clearly higher after the addition of heavy metals. The distribution coefficient (K(d)) and the organic carbon-normalized distribution coefficient (K(oc)) for phenanthrene sorption by soils spiked with Pb, Zn or Cu (0-1000 mg kg(-1)) were approximately 24% larger than those by unspiked ones, and the higher contents of heavy metals added into soils resulted in the larger K(d) and K(oc) values. The enhanced sorption of phenanthrene in the case of heavy metal-contaminated soils could be ascribed to the decreased dissolved organic matter (DOM) in solution and increased soil organic matter (SOM) as a consequence of DOM sorption onto soil solids. Concentrations of DOM in equilibrium solution for phenanthrene sorption were lower in the case of the heavy metal-spiked than unspiked soils. However, the decreased DOM in solution contributed little to the enhanced sorption of phenanthrene in the presence of metals. On the other hand, the sorbed DOM on soil solids after the addition of heavy metals in soils was found to be much more reactive and have far stronger capacity of phenanthrene uptake than the inherent SOM. The distribution coefficients of phenanthrene between water and the sorbed DOM on soil solids (K(ph/soc)) were about 2-3 magnitude larger than K(d) between water and inherent SOM, which may be the dominant mechanism of the enhanced sorption of phenanthrene by soils with the addition of heavy metals.  相似文献   

20.
Influence of salinity on bioremediation of oil in soil   总被引:11,自引:0,他引:11  
Spills from oil production and processing result in soils being contaminated with oil and salt. The effect of NaCl on degradation of oil in a sandy-clay loam and a clay loam soil was determined. Soils were treated with 50 g kg(-1) non-detergent motor oil (30 SAE). Salt treatments included NaCl amendments to adjust the soil solution electrical conductivities to 40, 120, and 200 dS m(-1). Soils were amended with nutrients and incubated at 25 degrees C. Oil degradation was estimated from the quantities of CO(2) evolved and from gravimetric determinations of remaining oil. Salt concentrations of 200 dS m(-1) in oil amended soils resulted in a decrease in oil mineralized by 44% for a clay loam and 20% for a sandy-clay loam soil. A salt concentration of 40 dS m(-1) reduced oil mineralization by about 10% in both soils. Oil mineralized in the oil amended clay-loam soil was 2-3 times greater than for comparable treatments of the sandy-clay loam soil. Amending the sandy-clay loam soil with 5% by weight of the clay-loam soil enhanced oil mineralization by 40%. Removal of salts from oil and salt contaminated soils before undertaking bioremediation may reduce the time required for bioremediation.  相似文献   

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