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1.
The mass emissions rate of contaminants from nonaqueous-phase liquids (NAPLs) is a driving factor in remediation efforts, whether those efforts are designed to remove, transform, or stabilize the entrapped NAPL or down-gradient aqueous concentrations. Enhancement of mass flux from NAPL source zones has been previously reported in the presence of microbial reductive dechlorination activity in systems containing NAPL with a low proportion of tetrachloroethene (PCE) or a low residual saturation (e.g., 2%). The results reported here demonstrate reductive dechlorination of PCE at residual saturations of 35%, obtained under two different column flow velocities and NAPL configurations. Mass flux in biotic columns was approximately 45% greater than that in uninoculated columns, due to both the presence of daughter products and higher concentrations of PCE in the effluent from biotic columns. Daughter product concentrations were greater in columns with NAPL emplaced only in the lower quarter compared to those with NAPL throughout, and in columns run at the slower velocity. The elevated PCE concentrations in biotic column effluents suggest the influence of microbially generated surfactants, which was supported by surface tension measurements. These results demonstrate the potential significance of bioactivity within NAPL source zones on NAPL longevity and down-gradient aqueous concentrations.  相似文献   

2.
In situ pumping of micellular solutions of surfactant (S) and cosurfactant (CoS) in water (W) through contaminated soils or aquifers offers potential for enhanced remediation of residual nonaqueous‐phase liquids (NAPLs). Extremely low interfacial tension generated between a W/S/CoS mixture and residual NAPL in soil pores may initially mobilize the NAPL, which is then transported temporarily as a separate phase by immiscible displacement. The NAPL is then solubilized by micro‐emulsification as the W/S/CoS mixture forms a stable W/S/CoS/NAPL micro‐emulsion that undergoes miscible displacement through the pore space. This remediation technique was tested under laboratory conditions by sequentially flushing a saline solution and a W/S/CoS mixture through columns of a sandy soil recently contaminated with residual leaded gasoline (LG). Prior to the flushings, the soil was initially contaminated by applying a W/S/CoS/LG microemulsion. A simple conceptual transport model with kinetic clogging of soil pores adequately described breakthrough curves for gasoline and organolead in the soil columns.  相似文献   

3.
Surfactants can potentially improve the efficiency of pump‐and‐treat technology for remediation of aquifers contaminated by nonaqueous phase liquids (NAPLs). However, the formation of emulsions during the removal process can Increase the viscosity in the system. This can result in pore clogging and reduction of flow, which inhibits the contaminant removal process. Formation of viscous emulsions has been identified in previous research as one of the probable causes for in situ field test failures using surfactant‐enhanced soil‐flushing technology. However, the effects of in situ emulsification and viscosity increases have not been quantified previously. The purpose of this article is to investigate effects of in situ emulsification on the remediation process. Laboratory column studies examined the mobilization of m‐xylene from porous media using a 1% alcohol ethoxylate surfactant solution (Witconol® SN90). Effects of in situ emulsification were determined. Glass columns (1.1 cm i.d. × 30 cm) were packed with 0.2‐mm glass beads to model soil media. Viscosities of emulsion solutions prepared with 1 % SN90 and various concentrations of m‐xylene were measured and compared with effluent collected during column‐flushing experiments. It was determined that as m‐xylene concentration in the emulsion solution Increases, viscosity increases. Viscosity increases caused a decrease in relative permeability within the soil column. As a result, the hydraulic gradient required to maintain a constant flowrate of 1.1 ml/min (using a syringe pump) through the soil column increased. Results show that a relatively small increase in viscosity could have a noticeable effect on the mobilization process. It is suggested that the surfactant/contaminant systems be screened to determine emulsion theology and the potential effects on the remediation process. The use of low‐concentration alcohol cosurfactants to reduce system viscosity was evaluated and was shown to be ineffective.  相似文献   

4.
Column experiments were conducted to compare the use of surfactants as a part of primary pumping to remove free phase NAPL to the use of surfactants to reduce or recover residual LNAPL in secondary treatment. Eight surfactant blends were tested, for a total of 48 column experiments. The column experiments show that the use of surfactants during primary pumping: (1) can potentially increase the amount of free product recovered; (2) can potentially reduce the amount of residual NAPL remaining after primary pumping; and (3) performs better than the use of surfactants to mobilize trapped residual NAPL.  相似文献   

5.
A growing number of incidents of nonaqueous phase liquid (NAPL) spills in the recent past have warranted development of innovative and cost‐effective remediation technologies. Of particular concern is the entrapment of LNAPL (NAPL lighter than water) in the form of ganglia or blobs near the water table by virtue of strong capillary forces. The residual ganglia are the leftover component after pumping of free product and typically occupy 20 to 60% of the pore space. Mobilization of these ganglia would require unrealistically high hydraulic gradients and is often beyond the scope of pump‐and‐treat processes. This paper deals with the feasibility of in situ implementation of localized vibrations for controlled mobilization and collection of LNAPL ganglia. Specifically, the paper covers three components. First, the principles involved in soil‐water‐NAPL interactions under the influence of vibrations are discussed. The effects of vibrations on a soil‐NAPL‐water medium are postulated in terms of pore structure and relative density changes, changes in the permeability of the medium as a result of the changes in pore structure, and development of cyclic pore pressures. Second, results from bench‐scale experiments are presented that involved vibrating contaminated soils under the simultaneous influence of hydraulic gradients. A bench‐scale model consisting of a vibrator integrated with an injection and pumping system was found to be successful in these experiments. The results from the tests showed that up to 85% removal of ganglia can be achieved using this process. Third, the principles involved in the vibratory mobilization were applied to in situ conditions to develop a methodology to estimate the zone of influence of the process. The analogy between this process and an existing geotechnical process known as vibroflotation is exploited to demonstrate the methodology.  相似文献   

6.
Many hydrocarbon‐contaminated soils contain nonaqueous phase liquid (NAPL) following releases from facilities such as underground storage tanks and pipelines. The recovery of free product by pumping from extraction wells or trenches is often an essential prerequisite step prior to further remedial actions. Vacuum‐enhanced NAPL recovery (sometimes referred to as dual‐phase extraction or bioslurping) has attracted recent attention because it offers a means to increase NAPL recovery rates compared with conventional methods, and to accomplish dewatering, while also facilitating vapor‐based unsaturated zone cleanup. A conceptual model is presented that recognizes the effects that vacuum‐enhanced recovery has on soil water and NAPL, with a focus on liquid residing at negative gage pressures and therefore lacking sufficient potential energy to flow into a conventional recovery well or trench. The imposition during vacuum‐enhanced recovery of subatmospheric pressures within the subsurface can reduce the required potential energy (i.e., the entry suction), allowing liquid to be extracted that hitherto had not been able to flow into the well; moreover, it induces both pneumatic and hydraulic gradients toward the vacuum source that increase the rate of water and NAPL recovery. This conceptual model was tested during a 3‐week‐long pilot study at a South Carolina industrial site at which diesel fuel had been discovered in a saprolite formation. During Phase 1 of the pilot study, conventional recovery (liquid only) was carried out from a well screened at the water table, while during Phase 2 dual‐phase extraction was performed at the same well. The application of 27 kPa vacuum resulted in an increase in NAPL recovery from negligible (Phase 1) to approximately 6.6 l/d (Phase 2), with a concurrent increase in water recovery from approximately 190 to 760 l/ d. Neutron moisture probe observations revealed that vadose‐zone liquids underwent redistribution toward the extraction well in response to the onset of Phase 2, also in accordance with the conceptual model. An understanding of soil physical relationships is crucial to the successful application of these and other in situ soil remediation technologies.  相似文献   

7.
Two decades after the manufacture and use of polychlorinated biphenyls (PCBs) were banned, PCB contamination remains widespread in the environment. Technologies available for PCB remediation are limited and often impractical for soils with dispersed PCB contamination. In this study, two remediation processes have been integrated for use on PCB-contaminated soils. This remediation strategy links in situ surfactant washing of PCBs from soil with aerobic biodegradation of the resulting surfactant-PCB solution by two field application vectors (F A Vs), Pseudomonas putida IFL5::TnPCB and Ralstonia eutropha B30F4::TnPCB, which utilize surfac-tants as growth substrates and cometabolize PCBs. A bench-scale demonstration of this process was performed using PCB-contaminated soils from an electric power substation site. In a 2-day recycling wash using a 1% (wt/vol) surfactant solution, greater than 70% of the PCBs were removed from the soil. In the biodegradation phase, greater than 90% of the surfactant and 35% of the PCBs were biodegraded in 12 days. The residual PCBs were partitioned onto a solid carrier resulting in greater than 90% removal of PCBs from the bioreactor effluent and a 50-fold reduction in the amount of PCB-contaminated material.  相似文献   

8.
Preliminary evaluations of the feasibility of thermal remediation techniques such as hot water flooding and steam flushing can be conducted with a knowledge of the influence of temperature on organic fluid properties such as interfacial tension, density, viscosity, solubility, vapor pressure, and Henry's constant. Relationships quantifying the effect of these fluid properties on organic removal and empirical equations for predicting the thermal variation of fluid properties are reviewed. Methods for measuring these properties are reviewed and applied to the characterization of perchloroethylene and a transformer oil. The importance of various removal mechanisms associated with thermal remediation is evaluated for these two fluids. Perchloroethylene solubilities increased by approximately 60% as temperature increased from 30°C to 90°C, suggesting that increased solubilization at higher temperatures would not be a significant removal mechanism. Viscosity and density reductions for both NAPLs were small, indicating that hydraulic displacement of NAPL would not be greatly enhanced with hot water or steam flushing. Interfacial tension decreases were not great enough to cause concem about downward remobilization of pools and residual zones of NAPLs. Capillary numbers for hot water flooding decreased for both NAPL, suggesting that hot water flooding would not enhance hydraulic removal of entrapped NAPL.  相似文献   

9.
The clean-up of soils co-contaminated with heavy metals and organic compounds is a contemporary issue of remediation efforts. Column flushing was conducted to investigate the performance of nonionic surfactant and/or organic acid solutions, 4000 mg/L Tween 80 (TW80), and/or 0.04 mol/L citric acid (CA), to enhance the simultaneous removal of phenanthrene and copper (II) from the co-contaminated sandy soil. The flushing effects were compared when TW80, CA, TW80 after CA (CA/TW80), CA after TW80 (TW80/CA), and a mixture of TW80 and CA (TW80-CA) were used as flushing agents. The maximum concentrations of phenanthrene in effluent solutions occurred at 3.3, 4.7, 5.3, and 15.3 h during TW80, TW80/CA, TW80-CA, and CA/TW80 flushing and those of copper (II) at 2.7, 3.3, 3.3, and 14.0 h during CA, CA/TW80, TW80-CA, and TW80/CA flushing, respectively. Phenanthrene was mainly desorbed through partitioning into TW80 micelles in aqueous phase while copper (II) was effectively removed through complexation with CA. The removal efficiencies were up to 81.5%, 5.9%, 99.9%, 91.6%, and 99.8% for phenanthrene, and 0.1%, 76.7%, 85.7%, 78.1%, and 84.4% for copper (II) by TW80, CA, TW80/CA, TW80-CA, and CA/TW80. However, it took a long time to use TW80/CA and CA/TW80 to clean phenanthrene and copper (II) efficiently. The overall removal efficiencies of contaminants in the soil column increased with flushing time in the Sigmoidal Model. The results indicated that a combination of TW80 and CA has potential for in situ clean-up of heavy metals and polycyclic aromatic hydrocarbons (PAHs) from co-contaminated soils.  相似文献   

10.
A model is formulated to describe dissolution of naphthalene from an insoluble nonaqueous phase liquid (NAPL) and its subsequent biodegradation in the aqueous phase in completely mixed batch reactors. The physicochemical processes of equilibrium partitioning and mass transfer of naphthalene between the NAPL and aqueous phases were incorporated into the model. Biodegradation kinetics were described by Monod's microbial growth kinetic model, modified to account for the inhibitory effects of 1,2-naphthoquinone formed during naphthalene degradation under certain conditions. System parameters and biokinetic coefficients pertinent to the NAPL-water systems were determined either by direct measurement or from nonlinear regression of the naphthalene mineralization profiles obtained from batch reactor tests with two-component NAPLs comprised of naphthalene and heptamethylnonane. The NAPLs contained substantial mass of naphthalene, and naphthalene biodegradation kinetics were evaluated over the time required for near complete depletion of naphthalene from the NAPL. Model predictions of naphthalene mineralization time profiles compared favorably to the general trends observed in the data obtained from laboratory experiments with the two-component NAPL, as well as with two coal tars obtained from the subsurface at contaminated sites and composed of many different PAHs (polycyclic aromatic hydrocarbon compounds). The effects of varying the NAPL mass and the naphthalene mole fractions in the NAPL are discussed. It was observed that the time to achieve a given percent removal of naphthalene does not change significantly with the initial mass of naphthalene in a fixed volume of the NAPL. Significant changes in the mineralization profiles are observed when the volume (and mass) of NAPL in the system is changed.  相似文献   

11.
A laboratory-scale physical model was constructed for visual observation of the basic 2-D flow characteristics of a gasoline spill through an unconfined aquifer and the subsequent treatment with a surfactant. The model consists of a parallel-plate glass tank (1?m×1?m×5?cm) packed with Ottawa sand. Gasoline was released from a point source in the vadose zone. As the specific gravity of gasoline is less than one (LNAPL), it pooled above the water saturated pores of the tension saturated region of water. Beyond the lens of gasoline, the height of the capillary fringe was reduced due to capillary pollution. The gasoline lens was then treated with an aqueous phase surfactant solution of 2% dodecyl benzene sulfonate (anionic) and 2% polyethoxylate nonyl phenol (nonionic). This surfactant solution reduced the interfacial tension between the gasoline and the aqueous phase by an order of magnitude. The surfactant solution was released from the same point source in the vadose zone as the gasoline. As a result, the location and geometry of the gasoline lens and the polluted capillary fringe were significantly altered. These changes were investigated using vertical equilibrium models, the capillary number, the buoyancy number and the total trapping number to evaluate the approach of pretreatment as a potential remediation strategy.  相似文献   

12.
The remediation of dense non-aqueous phase liquids has always been a concern of both public and scientific interest groups. In this research work a modified physical concept of (bio)remediation of a volatile chlorinated hydrocarbon (VCHC) contamination was elaborated under laboratory conditions and modeled with HYDRUS-2D. In field dechlorination is influenced by both physicochemical and hydraulic properties of the substrate, e.g. texture, pore size distribution, pore liquid characteristics, e.g. viscosity, pH, surface tension, and dependent on the degree of saturation of the vadose zone. Undisturbed soil cores (100 cm³) were sampled from a Spolic Technosol. Considering hydraulic properties and functions, unsaturated percolation was performed with vertically and horizontally structured samples. VCHC concentrations were calculated prior, during, and after each percolation cycle. According to laboratory findings, microemulsion showed the most efficient results with regard to flow behavior in the unsaturated porous media and its accessibility for bacteria as nutrient. The efficiency of VCHC remediation could be increased by the application of a modified pump-and-treat system: the injection of bacteria Dehalococcoides ethanogenes with microemulsion, and extraction at a constant matric potential level of ?6 kPa. Achieved data was used for HYDRUS-2D simulations, modeling in situ conditions, demonstrating the practical relevance (field scale) of performed unsaturated percolation (core scale), and in order to exclude capillary barrier effects.  相似文献   

13.
The kinetics of microbial degradation of naphthalene from a two-component non-aqueous-phase liquid (NAPL) coated onto uniformly sized nonporous particles were evaluated in a completely mixed batch reactor (CMBR) system and in flow-through column systems to examine the differences in the biodegradation kinetic coefficients, micro(max), the maximum specific growth rate coefficient, and K(s), the half saturation constant in the two systems. The values of these coefficients were estimated by nonlinear least-squares regression of the naphthalene mineralization profiles obtained from both CMBR and column biodegradation experiments. The results show that the range of values for micro(max) and K(s) obtained from column systems are very similar to the range of values obtained from CMBR systems. This suggests that coefficients estimated from CMBR or column systems are equally applicable for modeling studies. The presence of microorganisms and the development of biofilms at the NAPL-water interface reduced the mass transfer rates of naphthalene from the NAPL by 60% in CMBR and by 70% in column systems. If such changes in mass transfer coefficients are not accounted for, significantly erroneous values of biokinetic coefficients may be obtained.  相似文献   

14.
A rotating disk apparatus was used to investigate the biodegradation of PAHs from non-aqueous phase liquids to solutions of Brij 35. The mass transfer of PAHs in absence of surfactant solution was not large enough to replenish the degraded PAHs. The addition of surfactant resulted in an overall enhancement of biodegradation rates compared to that observed in pure aqueous solution. This is because surfactant partition significant amount of PAHs into the bulk phase, where uptake occurs but the supply of PAHs to the aqueous phase through micellar solubilization at latter period limited biodegradation rates. It was demonstrated the relationship between biodegradation rate and surfactant dose and the mechanisms controlling the mass transfer of PAH from NAPLs. The satisfactory comparison of the experimental data with the predictions of a model, which parameters were determined from independent solubilization and dissolution experiments and based on the main assumption that the solutes must be present in the true aqueous phase to be degraded, allows us to conclude the absence of direct uptake of PAHs by bacteria.  相似文献   

15.
The bioavailability of naphthalene present as a component of a complex nonaqueous phase liquid(NAPL) comprised by nine aromatic compounds was investigated. Specifically, the effects of naphthalene mass transfer from the NAPL to the aqueous phase on rates of its microbial degradation were examined. The investigations were conducted using a pure culture, ATCC 17484, and a mixed culture of naphthalene-degrading bacteria, the former having been implicated previously in the direct uptake of sorbed naphthalene. The studies were conducted in mass-transfer-limited, segregated-phase reactors(SPRs) in which both the NAPL and aqueous phases were internally well-mixed. A 30-day active biodegradation period was preceded and followed by a 5-7-day period devoid of bioactivity, during which time the rates and extents of mass transfer of components from the NAPL to the aqueous phase were quantified. The NAPL-phase naphthalene mass depletion profiles during biodegradation were compared to those predicted by assuming maximum mass depletion under mass-transfer-limited conditions using both pre- and post-biodegradation dissolution rate and equilibrium parameters. The observed mass depletion rates were high during the initial stages of biodegradation but decreased significantly in later stages. Throughout biodegradation, even in the initial rapid stage, mass depletion rates never exceeded maximum predicted rates based on pre-biodegradation mass transfer parameters. Reduced depletion rates in the later stages appear to relate to mass transfer hindrance caused by formation of biofilms at the NAPL-water interface.  相似文献   

16.
The bioavailability of naphthalene present as a component of a complex nonaqueous phase liquid (NAPL) comprised by nine aromatic compounds was investigated. Specifically, the effects of naphthalene mass transfer from the NAPL to the aqueous phase on rates of its microbial degradation were examined. The investigations were conducted using a pure culture, ATCC 17484, and a mixed culture of naphthalene-degrading bacteria, the former having been implicated previously in the direct uptake of sorbed naphthalene. The studies were conducted in mass-transfer-limited, segregated-phase reactors (SPRs) in which both the NAPL and aqueous phases were internally well-mixed. A 30-day active biodegradation period was preceded and followed by a 5-7-day period devoid of bioactivity, during which time the rates and extents of mass transfer of components from the NAPL to the aqueous phase were quantified. The NAPL-phase naphthalene mass depletion profiles during biodegradation were compared to those predicted by assuming maximum mass depletion under mass-transfer-limited conditions using both pre- and post-biodegradation dissolution rate and equilibrium parameters. The observed mass depletion rates were high during the initial stages of biodegradation but decreased significantly in later stages. Throughout biodegradation, even in the initial rapid stage, mass depletion rates never exceeded maximum predicted rates based on pre-biodegradation mass transfer parameters. Reduced depletion rates in the later stages appear to relate to mass transfer hindrance caused by formation of biofilms at the NAPL-water interface.  相似文献   

17.
Soil flushing using aqueous solutions is employed to solubilise contaminants. As water solubility is the controlling mechanism of dissolution, additives (surfactants, cosolvents, etc.) are used to enhance efficiencies and reduce the treatment time compared to the use of water alone. The use of surfactant alone gives efficiencies of about 80–85 % in laboratory experiments, but the amounts of product to be injected are very important, which does not seem to be economically sustainable. Studies indicate that when soil flushing is applied in the field, efficiency is very variable; it can vary from almost 0 % to almost 100 %. This illustrates the importance of knowledge of the field (soil heterogeneities, type of contamination, etc.). Using only one product (surfactant, cosolvent, cyclodextrin) often gives moderate efficiencies and needs very large amounts of products, with a product:pollutant ratio higher than 100:1. On the other hand, the use of more complex methods involving micro emulsions or several products with polymer injection lead to high efficiencies at first and a product:pollutant ratio that can be lower than 5. The importance of the initial saturation of the non-aqueous phase liquid is highlighted: the higher the initial saturation, the higher the efficiency. For initial saturations lower than 1 %, soil flushing may not be a very efficient technique. This paper provides an overview of recent studies in the area of soil and groundwater remediation, from laboratory columns scale to pilot and real sites. The research has focused on chlorinated solvents as they are extremely difficult to treat.  相似文献   

18.
A series of batch reactor experiments was carried out to examine the effect of a nonaqueous phase liquid (NAPL) on the biodegradation of a hydrophobic solute. A mathematical program model that describes physical processes of solute solubilization and partitioning between the NAPL and aqueous phases as well as microbial degradation and oxygen utilization was used to analyze the test data. The model calculates the cumulative changes in concentration of substrate, cell mass, carbon dioxide, and dissolved oxygen as a function of time. The equations incorporate the effects of solute solubilization, partitioning, biodegradation, as well as oxygen availability. Hexadecane was used as the model NAPL and was not biodegraded in the timeframe of the experiments performed. The model solute was the polyaromatic hydrocarbon, phenanthrene. In agreement with several previous studies, experimental measurements showed that hexadecane increased rates of mineralization of 15 mg phenanthrene when present at low mass but decreased rates at high mass. Model results suggest that partitioning of the phenanthrene into the hexadecane phase limits bioavailability at high NAPL mass. Further the model suggests that mineralization rates were higher with the low NAPL mass because aqueous phenanthrene concentrations were higher in those treatments from ca. 20 to 40 h than in other treatments. Finally, experiments showed that the presence of hexadecane, at all masses tested, resulted in a lower cell yield, effectively increasing the amount of CO2 produced during the experiment. Model results suggest that this is due to changes in phenanthrene metabolism that are induced by the presence of the hexadecane phase. Model studies aimed at increasing rates of biodegradation by modifying operating conditions are described along with practical approaches to implementing these modifications.  相似文献   

19.
ABSTRACT

In situ deposited non-aqueous phase liquid (IDN) sediments have unique characteristics that inherently mitigate the movement of separate phase liquids. IDN sediments are composed of oil-particle aggregates (OPAs). OPAs consist of an oil bead or globule with attached solid particles, such as clay platelets, silt and sand granules, and/or organic materials. IDN sediments develop at locations where a continual or near continual discharge of non-aqueous phase liquids (NAPLs) have occurred over a period of time. IDN sediments consist of an open network of small pores where fluids are retained. Although the pore structure is very open, the pore openings are relatively small, which appears to inhibit fluid movement. In particular, capillary pressure analyses indicate that NAPL was not generally released until pressures of at least 15 pounds per square inch (psi) were induced. In addition, centrifuge testing at 1,000 G shows that NAPL immobility is observed in samples at NAPL saturations as high a 12%. These data suggest that NAPL is retained within the smallest pores and is encapsulated within a network of larger pores filled with water. Although the sediment contains NAPL, this original OPA structure appears to inhibit the oil beads from coalescing, preventing NAPL flow.  相似文献   

20.
ABSTRACT

Sediments composed of oil-particle aggregates (OPAs) have unique physical characteristics. These in situ deposited sediments develop at locations where a continual or nearly continual discharge of non-aqueous phase liquids (NAPLs) have occurred, or are occurring through time. The NAPL discharged into the surface water body interacts with suspended particles in the water column. The particles adhere to the suspended NAPL, which generally is in the form of a bead, and produce a discrete aggregate. As the aggregate grows in response to additional particle adherence, the density of the unit increases and deposition occurs. The resulting sediment consists of a collection of discrete OPAs that form a network with small pores, where oil is tightly bound and/or contained. Porosity, water content, and dry bulk density measurements indicate the sediment formed by OPA deposition is physically unique. Although the sediment consists of a very open pore structure, the pore openings are relatively small, typically being less than 5 microns in diameter. These small pores inhibit fluid movement. Results of physical property testing suggest the OPA structure is retained upon deposition. Although the sediment contains NAPL, this original OPA structure inhibits the oil beads from coalescing, which would enable NAPL flow.  相似文献   

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