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1.
Abiotic degradation of chlorinated solvents by reactive iron minerals such as iron sulfides, magnetite, green rust, and other Fe(II)‐containing minerals has been observed in both laboratory and field studies. These reactive iron minerals form under iron‐ and sulfate‐reducing conditions which are commonly found in permeable reactive barriers (PRBs), enhanced reductive dechlorination (ERD) treatment locations, landfills, and aquifers that are chemically reducing. The objective of this review is to synthesize current understanding of abiotic degradation of chlorinated solvents by reactive iron minerals, with special focus on how abiotic processes relate to groundwater remediation. Degradation of chlorinated solvents by reactive minerals can proceed through reductive elimination, hydrogenolysis, dehydrohalogenation, and hydrolysis reactions. Degradation products of abiotic reactions depend on degradation pathways and parent compounds. Some degradation products (e.g., acetylene) have the potential to serve as a signature product for demonstrating abiotic reactions. Laboratory and field studies show that various minerals have a range of reactivity toward chlorinated solvents. A general trend of mineral reactivity for degradation of chlorinated solvents can be approximated as follows: disordered FeS > FeS > Fe(0) > FeS2 > sorbed Fe2+ > green rust = magnetite > biotite = vermiculite. Reaction kinetics are also influenced by factors such as pH, natural organic matter (NOM), coexisting metal ions, and sulfide concentration in the system. In practice, abiotic reactions can be engineered to stimulate reactive mineral formation for groundwater remediation. Under appropriate site geochemical conditions, abiotic reactions can occur naturally, and can be incorporated into remedial strategies such as monitored natural attenuation.  相似文献   

2.
This research addresses the challenges of the lack of non‐invasive methods and poor spatiotemporal resolution associated with monitoring biogeochemical activity central to bioremediation of subsurface contaminants. Remediation efforts often include growth of biofilm to contain or degrade chemical contaminants, such as nitrates, hydrocarbons, heavy metals, and some chlorinated solvents. Previous research indicates that nuclear magnetic resonance (NMR) is sensitive to the biogeochemical processes of biofilm accumulation. The current research focuses on developing methods to use low‐cost NMR technology to support in situ monitoring of biofilm growth and geochemical remediation processes in the subsurface. Biofilm was grown in a lab‐scale radial flow bioreactor designed to model the near wellbore subsurface environment. The Vista Clara Javelin NMR logging device, a slim down‐the‐borehole probe, collected NMR measurements over the course of eight days while biofilm was cultivated in the sand‐packed reactor. Measured NMR mean log T2 relaxation times decreased from approximately 710 to 389 ms, indicating that the pore environment and bulk fluid properties were changing due to biofilm growth. Destructive sampling employing drop plate microbial population analysis and scanning electron and stereoscopic microscopy confirmed biofilm formation. Our findings demonstrate that the NMR logging tool can detect small to moderate changes in T2 distribution associated with environmentally relevant quantities of biofilm in quartz sand.  相似文献   

3.
Sites impacted by per- and polyfluoroalkyl substances (PFAS) pose significant challenges to investigation and remediation, including very low cleanup objectives, limited information on natural PFAS degradation processes in the subsurface, and the apparent mobility and persistence of PFAS. Consequently, monitored natural attenuation (MNA) may be considered less applicable to PFAS compared to biodegradable classes of chemicals such as petroleum hydrocarbons and chlorinated solvents that can completely biodegrade to innocuous end products. However, MNA has proven effective for certain non-degrading metals, metalloids, and radionuclides (e.g., chromium, arsenic, and uranium). To assess the applicability of MNA to PFAS, this paper reviews the fate and transport properties of PFAS in conjunction with the various physiochemical factors that control the subsurface movement of chemicals. This analysis demonstrates that two important retention processes: (1) chemical retention in the form of PFAS precursors, and (2) geochemical retention in the form of sorption and matrix diffusion to mitigate the movement and potential impacts of PFAS in groundwater that may form the scientific basis for applying MNA to PFAS contamination. This paper describes the scientific and regulatory basis for using MNA to manage PFAS-impacted groundwater.  相似文献   

4.
Chlorinated degreasing solvents are multicomponent liquids containing not only the chlorinated hydrocarbons with which their name is associated (e.g., trichloroethylene or |TCE]. perchloroethylene or [PCE], 1,1,1-trichlorocihane [TCA]) but also a number of organic additives included as corrosion inhibitors and antioxidants. The additives, such as 1,4-dioxane, are likely to be of significant public-health importance as ground water contaminants due to their toxicity, solubility, and mobility. Following their use in vapor degreasing systems by industry, chlorinated degreasing solvents will also contain about 25% solubilized oil and grease.
A number of physical-chemical properties become especially important in the light of the multicomponent nature of these solvents. First, the higher aqueous solubility and lower sorption of the additives makes it is reasonable to expect that faster moving plumes of these solvent additives will precede plumes of the chlorinated hydrocarbons. Second, due to high losses of chlorinated hydrocarbons by volatilization from vapor degreasers during years in the middle of the century, it is probable that background concentrations of these hydrocarbons are present in ground water flow systems due to their downwind washout. Finally, the solubilized oil and grease may cause profound changes to the wettability of aquifer materials contacted by the solvents during their subsurface migration. It is argued, therefore, that the wettability of aquifer materials contaminated by chlorinated degreasing solvents needs to be experimentally determined before remediation of DNAPL at each site, rather than being simply assumed as water wet.  相似文献   

5.
Geochemical effects on metals following permanganate oxidation of DNAPLs   总被引:2,自引:0,他引:2  
Crimi ML  Siegrist RL 《Ground water》2003,41(4):458-469
The application of in situ chemical oxidation for dense, nonaqueous phase liquid (DNAPL) remediation requires delivery of substantial levels of oxidant chemicals into the subsurface to degrade target DNAPLs and to satisfy natural oxidant demand. This practice can raise questions regarding changes in subsurface conditions, yet information regarding potential effects, especially at the field scale, has been lacking. This paper describes an evaluation of the effects on metals associated with in situ chemical oxidation using potassium permanganate at Launch Complex 34 (LC34), Cape Canaveral Air Station, Florida. At LC34, high concentrations of permanganate (1 to 2 wt%) were injected into the subsurface as part of a demonstration of DNAPL remediation technologies. In a companion experimental effort at the Colorado School of Mines, field samples were characterized and laboratory batch and mini-column studies were completed to assess effects of permanganate oxidation on metals in the subsurface one year after completion of the field demonstration. Results indicated there was potential for long-term immobilization of a portion of introduced manganese and no treatment-induced loss in subsurface permeability due to deposition of manganese oxides particles, which are a product of the oxidation reactions. Permanganate treatment did cause elevated manganese, chromium, and nickel concentrations in site ground water within the treated region. Some of these metals effects can be attenuated during downgradient flow through uncontaminated and untreated aquifer sediments.  相似文献   

6.
Successful in situ groundwater remediation relies on the adequate distribution of treatment materials within the subsurface. Zero‐valent iron (ZVI) is widely used for the remediation of soils contaminated with chlorinated organic compounds. Because ZVI is a solid, various techniques are used to distribute ZVI in the subsurface; however, a major uncertainty in this process involves determining the distribution of the iron during emplacement. A method of mapping the distribution of ferromagnetic material such as ZVI is by magnetic susceptibility (MS), a novel approach that is highly sensitive, quantitative, objective, and easily applied in field. The method has been tested in the laboratory on synthetic cores containing EHC®, an organic amendment containing 40 to 50% ZVI, using an MS meter with two types of sensors (loop and handheld). Both sensors have high sensitivity (e.g., 1% disseminated EHC is easily detected), whereas the hand‐held sensor has greater spatial resolution (e.g., differences are notable on a scale of 1 cm). Following the laboratory studies, the handheld instrument was used to perform field measurements for multiple pilot studies and a full‐scale application of EHC using various delivery methods (pneumatic fracturing, hydraulic fracturing, and direct injection) to construct a biobarrier at a field remedial site. The MS method has proven invaluable in quantifying amendment distribution and ensuring appropriate application of this remedial technology.  相似文献   

7.
In situ remediation technologies have the potential to alter subsurface properties such as natural organic matter (NOM) content or character, which could affect the organic carbon‐water partitioning behavior of chlorinated organic solvents, including dense nonaqueous phase liquids (DNAPLs). Laboratory experiments were completed to determine the nature and extent of changes in the partitioning behavior of trichloroethene (TCE) caused by in situ chemical oxidation or in situ surfactant flushing. Sandy porous media were obtained from the subsurface at a site in Orlando, Florida. Experiments were run using soil slurries in zero‐headspace reactors (ZHRs) following a factorial design to study the effects of porous media properties (sand vs. loamy sand with different total organic carbon [TOC] contents), TCE concentration (DNAPL presence or absence), and remediation agent type (potassium permanganate vs. activated sodium persulfate, Dowfax 8390 vs. Tween 80). Results revealed that the fraction of organic carbon (foc) of porous media after treatment by oxidants or surfactants was higher or lower relative to that in the untreated media controls. Isotherm experiments were run using the treated and control media to measure the distribution coefficient (Kd) of TCE. Organic carbon‐water partitioning coefficient values (Koc) calculated from the experimental data revealed that Koc values for TCE in the porous media were altered via treatment using oxidants and surfactants. This alteration can affect the validity of estimates of contaminant mass remaining after remediation. Thus, potential changes in partitioning behavior should be considered to help avoid decision errors when judging the effectiveness of an in situ remediation technology.  相似文献   

8.
ZVI‐Clay is an emerging remediation approach that combines zero‐valent iron (ZVI)‐mediated degradation and in situ stabilization of chlorinated solvents. Through use of in situ soil mixing to deliver reagents, reagent‐contaminant contact issues associated with natural subsurface heterogeneity are overcome. This article describes implementation, treatment performance, and reaction kinetics during the first year after application of the ZVI‐Clay remediation approach at Marine Corps Base Camp Lejeune, North Carolina. Primary contaminants included trichloroethylene, 1,1,2,2‐tetrachloroethane, and related natural degradation products. For the field application, 22,900 m3 of soils were treated to an average depth of 7.6 m with 2% ZVI and 3% sodium bentonite (dry weight basis). Performance monitoring included analysis of soil and water samples. After 1 year, total concentrations of chlorinated volatile organic compounds (CVOCs) in soil samples were decreased by site‐wide average and median values of 97% and >99%, respectively. Total CVOC concentrations in groundwater were reduced by average and median values of 81% and >99%, respectively. In several of the soil and groundwater monitoring locations, reductions in total CVOC concentrations of greater than 99.9% were apparent. Further reduction in concentrations of chlorinated solvents is expected with time. Pre‐ and post‐mixing average hydraulic conductivity values were 1.7 × 10?5 and 5.2 × 10?8 m/s, respectively, indicating a reduction of about 2.5 orders of magnitude. By achieving simultaneous contaminant mass depletion and hydraulic conductivity reduction, contaminant flux reductions of several orders of magnitude are predicted.  相似文献   

9.
DyeLIF? is a new version of laser‐induced fluorescence (LIF) for high‐resolution three‐dimensional subsurface mapping of nonaqueous phase liquids (NAPLs) in the subsurface. DyeLIF eliminates the requirement that the NAPL contains native fluorophores (such as those that occur in compounds like polynuclear aromatic hydrocarbons [PAHs]) and can therefore be used to detect chlorinated solvents and other nonfluorescing NAPLs that had previously been undetectable with conventional LIF tools. With DyeLIF, an aqueous solution of water and nontoxic hydrophobic dye is continuously injected ahead of the sapphire detection window while the LIF probe is being advanced in the subsurface. If soil containing NAPL is penetrated, the injected dye solvates into the NAPL within a few milliseconds, creating strong fluorescence that is transmitted via fiber‐optic filaments to aboveground optical sensors. A detailed field evaluation of the novel DyeLIF technology was performed at a contaminated industrial site in Lowell, Massachusetts, USA where chlorinated solvent dense nonaqueous phase liquid (DNAPL) persists below the water table in sandy sediments. Continuously cored boreholes were drilled adjacent to 5 of 30 DyeLIF probes that were advanced at that site. The cores were subsampled in high resolution to generate discrete‐depth soil samples as splits at the same depths where DNAPL was detected in the colocated DyeLIF probes. The cores were analyzed above ground using (1) colorimetric screening using hydrophobic dye tests, (2) laboratory extraction and quantitative chemical analysis, (3) “Benchtop” DyeLIF, and (4) volumetric moisture content. Correlation between DyeLIF and aboveground analyses of the soil cores was excellent: 98% agreement with positive DNAPL detections in samples where DNAPL pore saturations were >0.7% (based on quantitative soil analyses) and the ex situ tests. DyeLIF produced the equivalent of one aboveground colorimetric dye test every 0.2 inch (0.5 cm) of probing. With average daily probing of 395 linear feet (120.4 m), this was the equivalent of 12,039 discrete‐depth colorimetric dye tests/day. Because DyeLIF is an in situ measurement, there are no issues with soil core recovery like there would be for conventional ex situ colorimetric dye tests and 100% characterization of the probed intervals is achieved. Tracking the injection rate and pressure of the dye solution provides simultaneous data regarding relative soil permeability, similar to other direct push (DP) hydraulic profiling tools. Conventional LIF is considered the premier DP tool to identify and map NAPL containing PAHs in the subsurface or confirm its absence. While chlorinated solvent DNAPLs at some field sites contain impurities (e.g., solvated greases or oils) that make them detectable with conventional LIF techniques, at other sites, the DNAPL cannot be detected with conventional LIF. At such sites, the injection of a hydrophobic dye ahead of the sapphire window with the DyeLIF system now makes the LIF technology applicable to the many types of NAPLs that were previously invisible using conventional LIF techniques.  相似文献   

10.
Use of electrophoresis for transporting nano-iron in porous media   总被引:1,自引:0,他引:1  
Research has been conducted to evaluate if electrophoresis could transport surface stabilized nanoscale zero-valent iron (nZVI) through fine grained sand with the intent of remediating a contaminant in situ. The experimental procedure involved determining the transport rates of polymer modified nZVI and hematite in fine grained sands under an applied electrical gradient under different physical and chemical conditions. Results indicated transport of polymer modified nZVI and hematite can be accomplished by electrophoresis, with rates found to be much higher than diffusion alone and comparable to those predicted by electrokinetic theory. This study indicates there is potential for this method to deliver polymer modified nZVI into contaminated zones within fine grained sands for the purpose of remediation.  相似文献   

11.
The aim of this paper is to show the concise chemico-physical adsorbent performance of water purification systems utilizing geo-(e.g., allophane, clinoptilolite, and smectite) and bio-polymer materials(e.g.,chitosan or cellulose nanocomposite materials) and to propose an optimal ground-water remediation technique. The performance of geo-materials is evaluated based on the individual sorption and immobilization capacities for various priority substances and pollutants(e.g., lead, zinc, cadmium, c...  相似文献   

12.
Monitored Natural Attenuation of Contaminants in the Subsurface: Processes   总被引:2,自引:0,他引:2  
Among the alternatives considered for the remediation of soil and ground water at hazardous wastes sites are the use of natural processes to reduce or remove the contaminants of concern, Under favorable conditions, the use of natural attenuation can result in significant cost savings and compensate for uncertainties encountered in complex subsurface settings. In order to demonstrate that natural processes are effective in reaching established goals it is necessary to determine that transformation processes are taking place at a rate which is protective of human health and the environment, and that these processes will continue for an acceptable period of time.
While chemical transformation, dispersion, dilution, sorption, and volatilization are discussed, aerobic and anaerobic degradation comprise the major processes for the reduction of contaminant mass in the subsurface. In discussing the mechanisms of natural attenuation, chlorinated aliphatics and petroleum hydrocarbons are used as examples because of their significant impact on subsurface contamination and the effect of their physiochemical properties on attenuation processes.  相似文献   

13.
Phytoremediation is an environmental remediation technique that takes advantage of plant physiology and metabolism. The unique property of heavy metal hyperaccumulation by the macrophyte Eleocharis acicularis is of great significance in the phytoremediation of water and sediments contaminated by heavy metals at mine sites. In this study, a field cultivation experiment was performed to examine the applicability of E. acicularis to the remediation of water contaminated by heavy metals. The highest concentrations of heavy metals in the shoots of E. acicularis were 20 200 mg Cu/kg, 14 200 mg Zn/kg, 1740 mg As/kg, 894 mg Pb/kg, and 239 mg Cd/kg. The concentrations of Cu, Zn, As, Cd, and Pb in the shoots correlate with their concentrations in the soil in a log‐linear fashion. The bioconcentration factor for these elements decreases log‐linearly with increasing concentration in the soil. The results indicate the ability of E. acicularis to hyperaccumulate Cu, Zn, As, and Cd under natural conditions, making it a good candidate species for the phytoremediation of water contaminated by heavy metals.  相似文献   

14.
Soil gas was sampled using active sampling techniques and passive collectors at three sites in Tennessee to evaluate the effectiveness of these techniques for locating chlorinated solvent sources and flowpaths in karst aquifers. Actively collected soil gas samples were analyzed in the field with a portable gas chromatograph, and the passive soil gas collectors were analyzed in the lab with gas chromatography/mass spectrometry. Results of the sampling indicate that the effectiveness of both techniques is highly dependent on the distribution of the contaminants in the subsurface, the geomorphic and hydrogeologic characteristics of the site, and, in one case, on seasonal conditions. Both active and passive techniques identified areas of elevated subsurface chlorinated solvent concentrations at a landfill site where contamination remains concentrated in the regolith. Neither technique detected chlorinated solvents known to be moving in the bedrock at a manufacturing site characterized by thick regolith and an absence of surficial karst features. Passive soil gas sampling had varied success detecting flowpaths for chloroform in the bedrock at a train derailment site characterized by shallow regolith and abundant surficial karst features. At the train derailment site, delineation of the contaminant flowpath through passive soil gas sampling was stronger and more detailed under winter conditions than summer.  相似文献   

15.
This investigation had the purpose of evaluating the reliability of a sequential extraction procedure according to Zeien and Brümmer (1989) which is performed routinely to analyse the distribution of heavy metals to different soil phases. Reliability was tested by two hypotheses. According to the first hypothesis an error propagation increased during a morefold extraction of heavy metals from a single soil sample to such an extend that it does not allow a statistical comparison of different analyses. This assumption was confirmed in an interlaboratory study of five participants applying the sequential extraction scheme on two different soils. The heavy metal amounts extracted by the different partners were of the same magnitude, but from the results no statistical correspondence at the 95% confidence level could be observed. The second hypothesis stated that also weak extraction agents were able to release metals from the more immobile soil fractions, especially if the amount of easily soluble metals was comparatively small. To answer this question the sequential extraction was modified by carrying out selected weak extraction steps several times. As expected the intensified extraction conditions caused a decrease of the element content within the more resistant phases. However, the additional release in the first four extraction steps of Pb, Mn, Fe, and Zn was only in the range of 5 to 10%. Furthermore, it was observed that a single EDTA extraction (step four within the sequential extraction scheme) was capable to extract the same amount of metals as the first four extraction steps of the original scheme at a variation of about 15%. From these results it was concluded that the EDTA step alone already represents a reliable pool of mobilisable metals. Thus it can be maintained that such a simple single EDTA extraction can be used to assess the environmental risk from heavy metal contaminated soils or to predict the potential heavy metal release of soil remediation processes.  相似文献   

16.
In situ thermal desorption (ISTD) was used for the treatment of eight separate source zones containing chlorinated solvents in a tight loess (silt/clay) above the water table. The source areas were as much as 365 m (1200 feet) apart. A target volume of 38,200 m3 (49,950 cubic yards) of subsurface material to a depth of 9.1 m (30 feet) was treated in a period of 177 days. Energy was delivered through 367 thermal conduction heater borings, and vapors were extracted from 68 vertical vacuum wells. A vapor extraction and capture system, including a surface cover and vertical vacuum wells next to heater borings, provided for effective pneumatic control and capture of the chlorinated volatile organic compound (CVOC) vapors. A central treatment system, based on condensation and granular activated carbon filtration, was used to treat the vapors. Approximately 5675 kg (12,500 pounds) of contaminants was recovered in the extracted vapors. Forty-seven soil samples were used to document remedial performance. Based on these, the concentrations of the target contaminants were reduced to below the target remedial goals in all eight areas, typically with concentrations below 0.01 mg/kg in locations that had had CVOC concentrations higher than 1000 mg/kg. Turn-key costs for the thermal remediation were $3.9 million, and the unit treatment cost, including all utilities, was $103 per cubic meter treated ($79 per cubic yard).  相似文献   

17.
Chlorinated solvents are one of the most commonly detected groundwater contaminants in industrial areas. Identification of polluters and allocation of contaminant sources are important concerns in the evaluation of complex subsurface contamination with multiple sources. In recent years, compound‐specific isotope analyses (CSIA) have been employed to discriminate among different contaminant sources and to better understand the fate of contaminants in field‐site studies. In this study, the usefulness of dual isotopes (carbon and chlorine) was shown in assessments of groundwater contamination at an industrial complex in Wonju, Korea, where groundwater contamination with chlorinated solvents such as trichloroethene (TCE) and carbon tetrachloride (CT) was observed. In November 2009, the detected TCE concentrations at the study site ranged between nondetected and 10,066 µg/L, and the CT concentrations ranged between nondetected and 985 µg/L. In the upgradient area, TCE and CT metabolites were detected, whereas only TCE metabolites were detected in the downgradient area. The study revealed the presence of separate small but concentrated TCE pockets in the downgradient area, suggesting the possibility of multiple contaminant sources that created multiple comingling plumes. Furthermore, the variation of the isotopic (δ13C and δ37Cl) TCE values between the upgradient and downgradient areas lends support to the idea of multiple contamination sources even in the presence of detectable biodegradation. This case study found it useful to apply a spatial distribution of contaminants coupled with their dual isotopic values for evaluation of the contaminated sites and identification of the presence of multiple sources in the study area.  相似文献   

18.
In situ bioreclamation is a proven technology that cost-effectively treats organic contamination in subsurface environments. As a remediation strategy, it reduces both the contamination dissolved in ground water, as well as residual soil-bound contamination.
To maximize biodegradation, the technology is applied after conducting laboratory studies. Application of the technology involves infiltrating necessary nutrients to the contaminated subsurface.
Results of a specific case study indicate excellent performance with rapid cleanup of petroleum hydrocarbon contamination from soils and ground water.
Costs associated with in situ bioreclamation technology showed a savings of approximately 50 percent over simple pump-and-treat technology. Time frame for cleanup was shown to be approximately 30 percent of the projected time frame of simple pump-and-treat technology.  相似文献   

19.
湖泊沉积物的重金属污染防治一直是环境领域的热点问题.本研究采用氨基生物炭作为覆盖材料,利用梯度扩散薄膜技术(DGT),研究了上覆水不同pH及水流扰动条件下Cu(Ⅱ)、Pb(Ⅱ)在沉积物水界面间的原位释放特征,以及氨基生物炭对湖泊沉积物重金属污染的原位修复效果.研究结果表明,在0 r/min或100 r/min水动力条件下,可移动态重金属离子有不断由沉积物向其他介质扩散的趋势,1.81 kg/m 2的氨基生物炭覆盖强度可降低Cu(Ⅱ)、Pb(Ⅱ)释放通量达89%以上,有效减小了水环境中重金属的潜在生态风险.在pH=5的酸性及pH=9的碱性水环境中原位修复效果较差,水体中大量的H+或络合物均会削弱氨基生物炭对重金属离子的吸附,当上覆水在pH=7的中性条件时原位修复效果最佳.100 r/min水流扰动下的上覆水Cu(Ⅱ)、Pb(Ⅱ)含量在释放平衡时较0 r/min条件下高出0.036~0.096μg/mL,说明高强度的水流扰动易造成覆盖材料的扬起和浮动,导致覆盖材料与重金属发生解吸.  相似文献   

20.
Contamination from the use of chlorinated solvents, often classified as dense nonaqueous phase liquids (DNAPLs) when in an undissolved state, represents an environmental challenge with global implications. Mass-transfer limitations due to rate-limited dissolution can lead to long-term aquifer persistence for even small volumetric fractions. The identification of DNAPL source zones located beneath the water table is critical to ultimately achieve site remediation and aquifer restoration. This paper provides a comparison of the advantages and disadvantages of many of the methods being used for detecting and delineating DNAPL contaminant source zones. The objective is to determine which options are best to pursue based on site characteristics, method performance, and method costs. DNAPL characterization methods are grouped into approaches, which include site preparation, characterization, and data-processing activities necessary to design an effective remediation system. We compare the different approaches based on the level of chemical and hydrogeologic resolution, and the need for additional data requirements. Our findings can be used to assist with selection of appropriate site remediation management options.  相似文献   

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