首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 421 毫秒
1.
Low cost lime‐based waste materials have recently been used to immobilize metals in contaminated soils. This study was conducted to evaluate the effects of oyster shells and eggshells as lime‐based waste materials on immobilization of cadmium (Cd) and lead (Pb) in contaminated soil, as well as their effects on metal availability to maize plants (Zea mays L.). Oyster shells and eggshells were applied to soils at 1 and 5% w/w, after which they were subject to 420 days of incubation. The toxicity characteristic leaching procedure (TCLP) test was employed to determine the mobility of Cd and Pb in soils. The results showed that the addition of waste materials effectively reduced the metal mobility as indicated by the decrease in the concentration of TCLP‐extractable Cd and Pb, and this was mainly due to significant increases in soil pH (from 6.74 in untreated soil to 7.85–8.13 in treated soil). A sequential extraction indicated that the addition of such alkaline wastes induced a significant decline in the concentration of Cd in the exchangeable fraction (from 23.64% in untreated soil to 1.90–3.81% in treated soil), but it increased the concentration of Cd in the carbonate fraction (from 19.59% in untreated soil to 36.66–46.36% in treated soil). In the case of Pb, the exchangeable fraction was also reduced (from 0.67% in untreated soil to 0.00–0.01% in treated soil), and the fraction of Pb bound to carbonate was slightly increased (from 16.61% in untreated soil to 16.41–18.25% in treated soil). Phytoavailability tests indicated that the metal concentrations in the shoots of maize plant were reduced by 63.39–77.29% for Cd and by 47.34–75.95% for Pb in the amended soils, with no significant differences being observed for the amendment types and the application rates. Overall, these results indicate that oyster shells and eggshells can be used as low cost lime‐based amendments for immobilizing Cd and Pb in contaminated soils.  相似文献   

2.
Mobilization Potential of Hydrophobic Organic Compounds (HOCs) in Contaminated Soils and Waste Materials. Part I: Mobilization Potential of PCBs, PAHs, and Aliphatic Hydrocarbons in the Presence of Solubilizing Substances When using an elution procedure for organic pollutants to estimate the leaching behaviour of contamined soils and waste deposits, the influence of organic matter in solids and eluates adequately has to be considered. In batch tests with a solid/liquid ratio of 1:10, various aqueous solutions were composed, the solubilizing effect of which can be attributed to ubiquitous natural compounds (e. g., phospholipids, humic and carbonic acids). These solutions were evaluated in regard to the mobilization of PAHs, PCBs, and aliphatic hydrocarbons in soil and waste samples. The results were compared with batch tests containing sodium dodecyl sulfate (SDS), the properties and applications of which are selected and optimized in order to simulate the chemical interactions between pollutant and solubilizing substances of natural sources. Under alkaline conditions, the part of eluated pollutants was high because of the release of humic substances indigenous to the sample. Low concentrations of phospholipids and humic acid could decrease the mobility of aliphatic hydrocarbons. The extend of HOC mobilization is affected by specific interdependences between solubilizing substances and reactive matter of the samples. For most samples, 5.0 g/L concentrated SDS solution was able to simulate the most effective natural solutizer potential in regard to the mobilization of PAHs, PCBs, and aliphatic hydrocarbons within the system of batch tests. Whereas elution with pure water caused significant deviations in pollutant composition and too low yields, the use of SDS effected à good conformity. Modified in such a manner, the elution procedure can follow DIN 38414 part 4, when loss of pollutants will be minimized; e. g., centrifugation is needed to separate phases.  相似文献   

3.
Metal mobility at contaminated sites can be assessed by soil water investigations or by leaching tests. Leaching tests are usually carried out in open contact with the atmosphere disregarding possible changes of redox conditions. This can affect the original metal speciation and distribution, particularly when anoxic samples are investigated. In this study, the applicability of common leaching tests (the German S4 test (S4), ammonium nitrate extraction (AmmN), and saturation soil extraction (SSE)) is tested for the assessment of zinc release from sulfide‐bearing flotation residues of a former ore mine. Results are compared to soil solution samples obtained by centrifugation and suction cups. The influence of sample storage on S4 leaching test results is investigated in a long‐term study to assess oxidation kinetics. Within the first 200 days the release of zinc increases with a slope of 0.1 mmol kg–1 d–1 or 6.0 mg kg–1 d–1, respectively. Since oxidation of the sulfide‐bearing samples leads to a significant overestimation of metal release, a feasible modification for the conduction of leaching tests for anoxic material is proposed where oxidation is prevented efficiently. The modified SSE is found to be the only of the tested leaching procedures, which can be recommended for the assessment of current soil water concentrations at anoxic sites if direct investigation of the soil water is impossible due to technical reasons.  相似文献   

4.
Investigation on the Pollution Potential of Waterworks Sludges Several contaminated sludges from water treatment plants with known or estimated concentrations of trace elements were investigated for their leaching characteristics and long-term stability using standard and advanced test procedures. Potentially hazardous elements in the sludge are zinc, nickel, and arsenic with concentrations of up to 1.2 g/kg dry matter (mass). Preliminary sorption tests with synthetic sludge components like iron hydroxide, manganese oxide, silicate clay minerals, and chitine powder as a model organic component showed that Cu is associated with the organic phase wheras arsenic is predominantly bound to the iron oxide minerals. The recently suggested pHstat test procedure was used to assess the leaching characteristics of metals at typical pH values. This procedure was compared with the DEV-S4 test, the current standard test in Germany, consisting of a simple lixiviation of the solids with water, without pH control. The pHstat test yields results which are much better to interprete than those obtained by the DEV-S4 procedure. The iron and manganese sludges are well buffered against changes in pH and redox potential so that low pH values and/or reducing conditions can hardly occur. Thus, in deposited material a sudden leaching of heavy metals is unlikely and due to the presence of iron and manganese oxides the pentavalent arsenic is protected against conversion into the highly mobile trivalent form at neutral to low pH. Co-deposition with reducing organic matter and alkaline stabilisation material or waste (like fly ash) could influence the binding properties and should be strictly avoided.  相似文献   

5.
Agricultural soils have been analyzed to elucidate whether the trace metal distribution changes in relation to agricultural activities and to predict environmental risk. In addition to the extractability of Cu, Mn, Ni, Pb, and Zn in soils was compared by single extraction (hydrochloric acid (HCl), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), calcium chloride (CaCl2), water (H2O)), and sequential extraction procedures. The modified Community Bureau of Reference (BCR) sequential extraction procedure (three‐step) used to extraction of metals in soil samples. The extraction capacity of the analyzed metals was found by using single extraction procedures in the order: HCl > EDTA > DTPA > CaCl2 > H2O. A single correlation analysis was used to investigate the relationship between extractable metal concentrations in soil solutions and metal accumulation in wheat grains. Simple correlation analyses indicated that the extractable Pb and Ni of soils by HCl, EDTA, and DTPA single extraction procedures were significantly correlated with the metal contents of wheat grains. For CaCl2, H2O, and BCR extraction procedures there was a relatively poor correlation between the extractable Cu, Mn, Ni, Pb, and Zn of soils and metal contents of wheat grains.  相似文献   

6.
李传琼  王鹏  陈波  李燕 《湖泊科学》2018,30(1):139-149
于2015年1月和7月在赣江干流和主要支流37个采样点共采集74个水样,分析赣江水系15种溶解态金属元素(Be、Al、V、Mn、Fe、Co、Ni、Cu、As、Mo、Cd、Sb、Tl、Pb、U)的空间分布特征和污染来源的贡献率.结果表明:多数水样的溶解态金属元素浓度符合水质标准,主要的超标元素是Fe,样品超标率为21.60%,其次为As(8.10%)、Mn(4.05%)、Tl(4.05%)和Al(1.35%).Be、Al、V、Fe、Co、Ni、Cu、U浓度在枯水期显著高于丰水期,其他元素差异不显著.依据溶解态金属元素的空间分布特征,赣江流域可分为3个区域:湘水、章水和赣江赣州市段(C1),桃江、袁水和锦江(C2),其他区域(C3);溶解态金属元素水平大小排序为C1C2C3,其中Be、Al、Cu、Mo、Sb、As浓度在C1最高,V、Mn、Fe、Ni、Cd浓度在C2最高.采矿废水、矿渣和农田土壤降雨淋滤、钢铁冶炼废水是赣江溶解金属元素的主要来源;Be、Al、Cu、Pb、U的污染源超过40%来自采矿废水,Cu、As、Mo、Cd的污染源超过35%来自矿渣和农田土壤降雨淋滤,V、Mn、Co、Ni的污染源超过41%来自钢铁冶炼废水.  相似文献   

7.
Comparison of Selected Elution Procedures for the Valuation of the Mobility of Metals from Sediment and Sewage Sludge Several methods of extraction are generally used to evaluate environmental or ecological toxicity and deposition of waste material. In this paper, the application of the German standard methods DIN 38414-S7, DIN 38414-S4, pHstat method, “Schweizer method” (elution test, Switzerland), and some variants of the pHstat method on two very different samples are described. A rudimental sediment and a municipal sewage sludge are chosen as sample materials. The metal contents of extract solutions are determined by ICP-OES. The results of the DIN-S4 extractions depend definitely on the mechanic way of movement, i.e. the amount of heavy metals which are mobilized out of the samples differs considerably. In fact, DIN-S7 in combination with DIN-S4 is not sufficient to estimate the mobility of heavy metals. Solid samples should only be evaluated by applying a combination of several methods of extraction. The usefulness of the pHstat method for an evaluation is discussed.  相似文献   

8.
Metallic contaminants associated with sediments showed various behaviours depending on physicochemical conditions. A contaminated sediment core from a harbour in the Bay of Seine was sampled to derive information about metal solubilization from anoxic sediment. In these anaerobic surroundings, physicochemical processes depended on the organic matter cycle, on vertical variation of redox conditions and on precipitation conditions of iron and manganese. In the studied core, anoxic conditions were developed at -15 cm depth. A three-step sequential extraction procedure, modified from the BCR method (now the SM&T), was applied to the anoxic sediment in order to evaluate the potential mobility of fixed metals. Zinc was the most labile metal, recovered in the first extraction stages, and was associated with the non-residual fraction of sediment. Lead was the least labile metal, with up to 70% associated with the residual fraction of the sediment. Copper was associated with organic matter, and its mobility was controlled by the concentration and degradation of the organic fraction. Discharge of organic-rich dredged sediments at sea results in degradation of contained organic matter and may affect the environmental impact of these metals significantly. These results therefore help to improve the waste management of such contaminated sediments.  相似文献   

9.
A study was conducted to evaluate monitored natural attenuation (MNA) as a remedy for arsenic in groundwater at a former phosphate mining and manufacturing facility. The mineralogy, speciation, and lability of arsenic in phosphatic wastes present in soils were characterized using sequential extraction procedures, leaching experiments, batch adsorption tests, and microchemical speciation analysis. A PHREEQC-based reactive transport model was also parameterized using these laboratory results, and it was used to evaluate the importance of identified attenuation mechanisms on arsenic concentrations along a vertical flow path from a shallow, alluvial aquifer to the underlying Floridan aquifer. Arsenic was found to occur in several chemical forms in phosphatic wastes, including unstable sulfide minerals, adsorbed surface complexes, and relatively insoluble phosphate and oxide minerals. Most arsenic was associated with stable minerals. The reactive transport model predicted that historical leaching of solid-phase waste materials in soils would not have generated enough arsenic to explain the concentrations observed in downgradient groundwater; instead, the source of arsenic to groundwater was likely acidic and saline process water that infiltrated though unlined ponds and ditches during historical manufacturing operations. A key factor affecting the long-term effectiveness of natural attenuation of arsenic in groundwater is the occurrence and stability of iron oxyhydroxides in aquifer sediments. According to laboratory and reactive transport model results, sufficient levels were found to be present at the site to effectively limit arsenic migration at concentrations exceeding drinking water standards in the future in the Floridan aquifer. This study presents the geochemical evaluations that are needed to satisfy EPA guidelines on determining whether or not MNA is an acceptable remedy for a site. It specifically details the characterization and modeling that were used to demonstrate effectiveness at a site where MNA was ultimately selected as the remedy for arsenic in groundwater.  相似文献   

10.
Heavy metal polluted sites are bearing an acute hazardous risk for the groundwater, but also a potential one. While the acute risk can be assessed directly via seepage water measurements, determination of the potential risk is much more complex. It results from the sum of all reactions that are capable to mobilize heavy metals under worst case environ-mental conditions. Using a fourfold sequential extraction (SE4) such a worst case was simulated for four soils highly contaminated with Pb, Zn, and Cu. The resulting potential mobilizable amounts ϕpm have been compared with those derived from 6 single extractions. By means of variance analyses, it is shown that ϕpm of lead can be represented by a single extraction with NH2OH. In contrary, ϕpm of zinc can be represented using the pHstat test or an extraction with aqua regia, while ϕpm of copper can be represented only by aqua regia extraction. The water-soluble amounts deriving from the DEV-S4 test do not correlate with the potential mobilizable amounts of any metal. Therefore, an assessment of contaminated sites should include an aqua regia extraction additionally to the seepage water analysis.  相似文献   

11.
Dredged sediments are being chemically treated with phosphoric acid on an industrial scale.The effectiveness of the treatment was evaluated by performing the chemical reaction in a tubular reactor, followed by convective drying and maturation of the treated sediment at ambient temperature and finally thermal destruction of the organic matter by calcinations(500℃-900℃).The influence of acid concentration and calcination temperature on the specific surface area of the sediment was investigated. The stabilization of the heavy metals was evaluated by leaching tests and sequential extraction procedures.The phosphoric acid treatment is effective in reducing heavy metal mobility,a prerequisite for recycling the sediments in various construction materials.  相似文献   

12.
Sequential extraction procedures are widely used to characterize the different operational fractions with different potential toxicity of metals in environmental solid samples. The present work describes the application of different analytical approaches for sequential extraction of aluminum to evaluate its mobility, availability, and persistent chemical forms in sediment samples of different fresh water ecosystems (lake, canal, and river). The conventional BCR three‐stage sequential extraction procedure (C‐BCR) was modified at each stage, by applying ultrasonic device (U‐BCR), in order to shorten the required shaking time of 16 h for each three steps (excluding the hydrogen peroxide digestion in step 3, which was not performed with ultrasonic bath), could be completed in 40, 50, and 45 min, respectively. The aluminum in all extracts were determination by atomic absorption spectrometry using nitrous oxide – acetylene flame. The accuracy of results obtained from C‐BCR and proposed U‐BCR was verified with literature reported values of certified sediment sample (BCR 701). The overall recoveries of aluminum obtained by proposed U‐BCR were found in the range of 96.7–113% of those values obtained with C‐BCR for all fractions. Use of ultrasonic device, provided a large saving in extraction time relative to conventional shaking. It was observed that major part of Al in real sediment samples (80–83% of total Al) were bound to residual fraction. The acid soluble fraction of aluminum extracted by 0.11 mol/L CH3COOH has good correlation with aluminum content in corresponding water samples of each ecosystem.  相似文献   

13.
太湖地区丘陵旱地土壤磷的吸持解吸特征   总被引:16,自引:1,他引:15  
高超  张桃林 《湖泊科学》2001,13(3):255-260
旱地土壤中流失的磷是地表水体中磷的重要来源,本文通过模拟实验对比太湖地区丘陵旱地土壤和水稻土对磷的吸持解吸特征,结果表明虽然旱地土壤对磷的固定能力略高于水稻土,但由于旱地土壤的有效磷水平普遍高于水稻土,因而前者磷的吸持饱和度(DPS)要大大高于后者,这就决定了旱地土壤中的磷被淋溶或以溶解态随径流流失的风险和数量也同于水稻土,磷吸持饱和度是土壤磷素水平和土壤固磷能力的综合指标,更能反映土壤固相中的磷进入液相的难易程序,可以作为评价水-土界面磷迁移能力 重要指标。  相似文献   

14.
The toxicity of intact sediments and sediment extracts, from both an uncontaminated site and a site contaminated by pulp-mill effluents, was tested in a five months study. The deposit-feeding amphipod Monoporeia affinis was exposed in soft-bottom flow-through water microcosms. To examine potential toxicity a set of reproduction endpoints was used including fecundity and different embryo aberrations such as malformed eggs. Among extracts, the aliphatic/monoaromatic and diaromatic fractions along with the total extract were shown to cause the highest toxicity measured as malformed eggs, while the polyaromatic fraction caused toxicity at background levels. A comparison between sediment extracts and pulp mill contaminated intact sediment, however, showed no toxicity of the intact sediment. Thus, the extraction procedure seems to increase bioavailability and subsequently toxicity as compared to the intact sediments in situ. In toxicity testing using fractionated extracts of sediments in a toxicity identification evaluation (TIE) procedures, caution should therefore be taken when assessing bioavailable contaminants in contaminated areas. This should be taken in account both in determining remediation priorities as well as in ecological risk assessments.  相似文献   

15.
Using a Simple Soil Column Method to Evaluate Soil Phosphorus Leaching Risk   总被引:3,自引:0,他引:3  
The impacts of soil P leaching on water eutrophication have widely been concerned. However, there is no dependable method to quantitatively estimate the P leaching risk of soils. In this study, a simple soil column method was developed using two calcareous Fluvisols, silt loam and loam. The soil column was 20 cm in length and 5 cm in diameter, and distilled water was continuously supplied from the top. The volume and dissolved reactive P (DRP) concentrations of leachate were measured. Results showed that DRP concentrations in leachate increased slowly for the low soil Olsen‐P levels but rapidly for the high Olsen‐P levels. According to these two‐phase changes in the DRP versus soil Olsen‐P contents, the thresholds of P leaching risk were estimated to be 41.1 and 62.3 mg P kg?1 (Olsen‐P) for silt loam and loam, respectively. The P leaching intensity of soils increased by 3‐ to 540‐fold if the soil Olsen‐P contents accumulated from 6.6 to 155.5 mg P kg?1. The outcomes derived from this study regarding the determination of P leaching threshold and intensity by the soil column method also need a further verification on more soils with a wide range of physical and chemical properties.  相似文献   

16.
Pesticides used to maintain golf course turf can threaten ground water. This concern is particularly important in most of New York's Long Island, where generally sandy soils overlie a sole source aquifer. This study uses two methods to evaluate the potential for pesticides that are commonly used on Long Island's golf courses to leach to ground water.
Adapting the Pesticide Root Zone Model (PRZM). Release 1. for dense turf and applying site-specific soil data, certain pesticides, including metalaxyl and trichlorfon, are identified as potential problem leachers. PRZM simulations also identify the Long Island soils, including the sandy Plymouth and Carver soils, which arc most vulnerable to leaching.
When adequate input data for PRZM is unavailable, the ground water ubiquity score (GUS) method may be useful. GUS teachability classifications of pesticides commonly applied on Long Island golf courses, and of pesticides actually detected in ground water samples taken on Long Island, agree with PRZM predictions and the field data. The GUS method is applied to the evaluation of the leaching potential of pesticide degradation products (DCPA, maneb, and mancozeb metabolites), and the degradation products are shown to be a greater threat to ground water than their parent compounds.
These methods are potentially useful in designing ground water monitoring programs and for guiding the pesticide use and selection decisions of golf course managers.  相似文献   

17.
Simulating nonequilibrium transport of atrazine through saturated soil   总被引:5,自引:0,他引:5  
Mao M  Ren L 《Ground water》2004,42(4):500-508
Atrazine, an herbicide widely used for selective control of grassy weeds in the fields where maize is grown, is a potential ground water contaminant in China and, consequently, there is interest in predicting its mobility in agricultural soils. In this study, we determined the nonequilibrium transport characteristics of atrazine in Shahe soil (Beijing sandy loam) using the advection-dispersion equation, and using a sensitivity analysis, we evaluated the contribution of the uncertainty in a given input parameter to the overall uncertainty in model results. The asymmetrical shape and tailing of the atrazine breakthrough curve (BTC) showed that atrazine was subject to nonequilibrium transport. The observed atrazine BTC was best fitted by the chemical nonequilibrium model with a nonlinear least-squares optimization approach. Results from the sensitivity analysis indicated that the retardation factor was the most sensitive parameter. Considering the reliability of the estimated parameters, the best fit to the atrazine BTC was obtained by fixing the retardation factor based on the linear distribution coefficient, and by calculating the dispersion coefficient from the bromide BTC and the average pore water velocity from the measured data; nonequilibrium parameters were the only unknown parameters that were optimized. Model verification procedures were based on best-fit parameters optimized from one soil column experiment and applied to simulate the transport of atrazine in the duplicate experiment. The results showed there was good agreement between measured and simulated concentrations for atrazine leaching in the soil column.  相似文献   

18.
Toxicity of soil spiked with water soluble and insoluble contaminants was assessed with bacteria. Three bioassays were used with common soil bacteria. Water soluble fractions from the soils were estimated in microtiterplates via dehydrogenase activity of B. cereus and growth of P. putida. A new method was developed using B. cereus to include effects of soil particles with bound contaminants. As contaminants p-nitrophenol and 2-naphthol were tested in these systems. Results indicated that the concentration of the contaminants in the soil solution is determined by soil properties. Toxicity of water soluble fractions was not only a result of the toxicant's concentration but further modified by soluble components of the soils. It is not possible to assess soil pollution from toxicity of the water soluble fraction in general, because unknown factors of the soluble soil fraction can influence toxicity greatly. The newly developed contact bioassay with B. cereus showed clearly higher toxicity of 2-naphthol estimated in soil suspension than did the comparable test system with the same bacteria using water soluble fractions only. The results stress the importance of including soil particles into bioassay procedures. It was shown that also water insoluble, bound contaminants can act as toxicants. For an estimation of toxicity under conditions more relevant for the environment, the suggested test system can provide useful information to bioavailability of bound contaminants.  相似文献   

19.
Lime softening produces an estimated 10,000 metric tons of dry drinking water treatment wastes (DWTW) per year, costing an estimated one billion dollars annually for disposal worldwide. Lime softening wastes have been investigated for reuse as internal curing agents or supplementary cementitious materials in concrete as well as a high-capacity sorbent for heavy metal removal. Lead, cadmium, and zinc are common heavy metals in groundwater contaminated by mine tailings. Cement-based filter media (CBFM) are a novel material-class for heavy metal remediation in groundwater. This study investigated the incorporation of DWTW as a recycled, low-cost additive to CBFM for the removal of lead, cadmium, and zinc. Jar testing at three different metal concentrations and breakthrough column testing using synthetic groundwater were performed to measure removal capacity and reaction kinetics. Jar testing results show as DWTW content increases at low concentrations, removal approaches 100% but at high metal concentrations removal decreases due to saturation or exhaustion of the removal mechanisms. Removal occurs through the formation of metal carbonate precipitates, surface sorption, and ion exchange with calcium according to the preferential series Pb+2 > Zn+2 > Cd2+. Removal kinetics were also measured through column testing and exceeded estimated calculations derived from batch jar testing isotherms due to the large formation of oolitic metal carbonates. Lead, cadmium, and zinc was concentrated in the column precipitates from 0.29, 0.23, and 20.0 μg/g in the influent solution to approximately 200, 130, 14,000 μg/g in the reacted DWTW-CBFM. The control and DWTW-CBFM columns had statically similar removal for zinc and lead. In the DWTW-CBFM, cadmium had decreased removal of approximately 25% due to proportionately decreased hydroxide content from cement replacement with 25% DWTW. This study shows the potential for DWTW as an enhancement to CBFM, thereby valorizing an otherwise waste material. Furthermore, the concentrative abilities of CBFM through precipitate and oolitic mineral formation could provide a minable waste product and close the waste-product cycle for DWTW.  相似文献   

20.
The dynamic leaching behaviour of environmentally relevant heavy metals makes it difficult to fix a suitable elution time of leaching tests. With ten different solid materials which were characterized by wavelength-dispersive X-ray fluorescence analysis and by the determination of aqua regia soluble amounts of heavy metals we performed 24 h and long-term leaching tests using the pHstat procedure at pH 4 to be able to compare the resulting acid neutralization capacities (ANC) and heavy metal mobilization. This comparison demonstrates firstly the limitations in predicting the extent of heavy metal release after a longer (geological) time period only from the leached amounts after 24 hours and the ratio of the ANC values measured in the 24 h test and in a long-term experiment, respectively. Secondly, the effect of elution time on the leachability is not uniform but element specific and matrix dependent. Hence, the pHstat leaching test performed in the usual manner does not seem to be suitable particularly for assessing long-term mobilization of heavy metals under acidic conditions. Additional experiments under variation of shaking frequency and time clearly demonstrate the dominant influence of the first parameter on the resulting ANC and support the necessity of further studies to optimize the pHstat leaching procedure before the test can be recommended in regulations for environmental protection.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号