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1.
Amending soils with compost may lead to accumulation of metals and their fractions at various concentrations in the soil profile. The objectives of this study were to determine 1) the accumulation of Cu, Fe, Mn, and Zn with depth and 2) the distribution of water soluble, exchangeable, carbonate, Fe-Mn oxides, organic and residual forms of each metal in soils amended with MSW compost, co-compost, biosolids compost and inorganic fertilizer (as control). Total concentrations of Cu, Fe, Mn and Zn were concentrated in the 0-22 cm soil layer and scant in the rock layer. These metals were in the decreasing order of Fe > Mn > Zn > or = Cu. Copper, Fe, and Zn were predominantly in the residual form followed by fractions associated with Fe-Mn oxides, carbonate, organic, exchangeable and water soluble in all treatments except MSW compost amended soil where the organic fraction was higher than the carbonate fraction. In fertilizer, co-compost and biosolids compost treated soils Mn concentrated mainly in the Fe-Mn oxides form followed by residual, carbonate, and organic forms whereas, in MSW compost treated soil the same pattern occurred except that Mn organic fraction was higher than that in the carbonate form. The MSW compost has a greater potential to be used as a soil amendment to supply plants with Cu, Mn and Zn than other treatments in calcareous soils of south Florida.  相似文献   

2.
Use of sequential extraction to assess metal partitioning in soils   总被引:12,自引:0,他引:12  
The state of heavy metal pollution and the mobility of Cd, Cu, Ni, Cr, Pb and Zn were studied in three texturally different agricultural soil profiles near a Cu-Ni smelter in Harjavalta, Finland. The pseudo-total concentrations were determined by an aqua regia procedure. Metals were also determined after division into four fractions by sequential extraction with (1) acetic acid (exchangeable and specifically adsorbed metals), (2) a reducing agent (bound to Fe/Mn hydroxides), (3) an oxidizing agent (bound to soil organic matter) and (4) aqua regia (bound to mineral structures). Fallout from the smelter has increased the concentrations of Cd, Cu and Ni in the topsoil, where 75-90% of Cd, 49-72% of Cu and 22-52% of Ni occurred in the first two fractions. Slight Pb and Zn pollution was evident as well. High proportions of mobile Cd, Cu and Ni also deeper in the sandy soil, closest to the smelter, indicated some downward movement of metals. The hydroxide-bound fraction of Pb dominated in almost all soils and horizons, while Ni, Cr and Zn mostly occurred in mineral structures. Aqua regia extraction is usefully supplemented with sequential extraction, particularly in less polluted soils and in soils that exhibit substantial textural differences within the profiles.  相似文献   

3.
Sequential extraction procedures are widely used to estimate the quantity of trace metals bound to different solid fractions in contaminated soils. However, reliability of speciation of trace metals by these procedures remains largely unexamined. In the present study, the selectivity of each extraction step was tested by observing the effect of reversing the extraction order in the procedure. Two different sequential extraction methods and their reversed modes were used for metal fractionation in sewage sludge-amended soils. Significantly increased amounts of extractable metals (Cd, Cu, Pb and Zn) were evident in the sludge-amended soils compared to control soil by all extraction schemes; however, the amounts of metals extracted by each step were strongly dependent on the order of extraction, the type of reagents and the nature of the individual metals. Caution is advised in deducing the forms of soil metals from sequential extraction results from metal-contaminated soils.  相似文献   

4.
Leaching of heavy metals from contaminated soils using EDTA   总被引:40,自引:0,他引:40  
Ethylenediaminetetraacetic acid (EDTA) extraction of Zn, Cd, Cu and Pb from four contaminated soils was studied using batch and column leaching experiments. In the batch experiment, the heavy metals extracted were virtually all as 1:1 metal-EDTA complexes. The ratios of Zn, Cd, Cu and Pb of the extracted were similar to those in the soils, suggesting that EDTA extracted the four heavy metals with similar efficiency. In contrast, different elution patterns were obtained for Zn, Cd, Cu and Pb in the column leaching experiment using 0.01 M EDTA. Cu was either the most mobile or among the most mobile of the four heavy metals, and its peak concentration corresponded with the arrival of full strength EDTA in the leachate. The mobility of Zn and Cd was usually slightly lower than that of Cu. Pb was the least mobile, and its elution increased after the peaks of Cu and Zn. Sequential fractionations of leached and un-leached soils showed that heavy metals in various operationally defined fractions contributed to the removal by EDTA. Considerable mobilisation of Fe occurred in two of the four soils during EDTA leaching. Decreases in the Fe and Mn oxide fraction of heavy metals after EDTA leaching occurred in both soils, as well as in a third soil that showed little Fe mobilisation. The results suggest that the lability of metals in soil, the kinetics of metal desorption/dissolution and the mode of EDTA addition were the main factors controlling the behaviour of metal leaching with EDTA.  相似文献   

5.
The distribution and chemical fractionation of heavy metals retained in mangrove soils receiving wastewater were examined by soil column leaching experiments. The columns, filled with mangrove soils collected from two swamps in Hong Kong and the People's Republic of China, were irrigated three times a week for 150 days with synthetic wastewater containing 4 mg l(-1) Cu, 20 mg l(-1) Zn, 20 mg l(-1) Mn and 0.4 mg l(-1) Cd. Soil columns leached with artificial seawater (without any heavy metals) were used as the control. At the end of the leaching experiments, soil samples from each column were divided into five layers according to its depth viz. 0-1, 1-3, 3-5, 5-10 and > 10 cm, and analyzed for total and extractable heavy metal content. The fractionation of heavy metals in the surface soil samples (0-1 cm) was investigated by the sequential extraction technique. In both types of mangrove soils, the surface layer (0-1 cm) of the columns receiving wastewater had significantly higher concentrations of total Cu, Cd, Mn and Zn than the control. Concentrations declined significantly with soil depth. The proportion of exchangeable heavy metals in soils receiving wastewater was significantly higher than that found in the control, about 30% of the total heavy metals accumulated in the soil masses of the treated columns were extracted by ammonium acetate at pH 4. The sequential extraction results show that in native mangrove soils (the soils without any treatment), the major portion of Cu, Zn, Mn and Cd was associated with the residual and precipitated fractions with very low concentrations in more labile phases. However, in mangrove soils receiving wastewater, a significantly higher percentage of Mn, Zn and Cd was found in the water-soluble and exchangeable fractions. Copper appeared to be more strongly adsorbed in mangrove soils than the other heavy metals. In general, heavy metal accumulation in the surface mangrove soils collected in Hong Kong was higher than those in the PRC, although the metals in the latter soil type were more strongly bound. These findings suggest that whether the heavy metal retained in managrove soils becomes a secondary source or a permanent sink would depend on the kinds of heavy metals and also the types of mangrove soils.  相似文献   

6.
The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the “labile”, “acid-soluble”, “organic”, “crystalline oxide”, “pyritic” and “residual” fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The “acid-soluble”, “organic” and “pyritic” fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite.  相似文献   

7.
The availability of Cd, Cr, Cu, Ni, Mn, Pb and Zn present in the finest size particles of urban soils is studied by comparing the concentrations in the clay fraction with those extracted from the whole soil by either single-extraction or sequential extraction method. Many metals are preferentially present in the finest particles as compared to coarser fractions. This is true for most metals studied, except Mn and, perhaps, Cd. Those metals present in the clay fraction are often in easily bio-accessible forms, especially Cu, Pb and Zn. The results suggest that bio-accessible forms of these three metals are distributed among the three sequential fractions, and even the fraction considered as ‘residual’ is also bio-accessible to a significant extent. The statistical analysis shows some distinctions among metals that are compared to the ‘urban’, ‘natural’, or intermediate behaviour of the various metals as proposed earlier in the literature.  相似文献   

8.
Available information on soil contamination by trace elements in the Sudbury Cu/Ni mining and smelting region consists largely of total elemental concentration data. Little is known about the mode of occurrence and behaviour of Cu and Ni (the main metallic contaminants) in the soils of the region. In this study, sequential extraction and Scanning Electron Microscopy and Energy Dispersive X-ray Analysis (SEM/EDX) observations were complementarily used to define Cu and Ni forms in the Sudbury soils, so as to assess metal mobility. Most Cu (on average 75%) was associated with 'non-residual' soil forms, whereas Ni was mainly (on average 60%) associated with inorganic 'residual' forms of a sulphide and oxide nature. Therefore, Cu occurs in the soils in more mobile forms than Ni. Consequently, Cu should be removed from these soils at a faster rate than Ni. This is an unusual finding, because generally Ni is known to be more mobile in soils than Cu. SEM/EDX analysis confirmed the greater Cu mobility by showing that the metal was strongly associated with organic matter and was homogeneously distributed on the clay fraction surfaces. Nickel occurred alone or was associated with Fe oxides in various size fractions. Both elements were found as sulphides but Ni was often included in the silicate matrices of spherical particles in associations with Fe. SEM/EDX observations have shown that Cu and Ni are associated with soil forms which would not have been predicted by the sequential extraction alone, such as carbonaceous material, silicate spheres and carbonate particles, supporting complementary use of the two techniques.  相似文献   

9.
A new extraction procedure with cationic exchange resins is proposed for the assessment of heavy metal lability in polluted soils. This method classifies soluble metal compounds in three levels according to their lability: very labile, moderately labile and non-labile. The concept of lability is based on the use of resins with different ability to interact with metals. The proposed procedure was applied to five samples of polluted soils. In the five soils, soluble Cd was found to be very labile, soluble Ni and Pb were mostly non-labile, Mn and Zn lability depended on the soil, while Cu had a fraction of moderately labile forms in four of the five soils. The resin extraction procedure was compared with the DTPA and CaCl2 extractions.  相似文献   

10.
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   

11.
The concentrations and chemical partitioning of heavy metals in the sediment cores of the Pearl River Estuary were studied. Based on Pearson correlation coefficients and principal component analysis results, Al was selected as the concentration normalizer for Pb, while Fe was used as the normalizing element for Co, Cu, Ni and Zn. In each profile, sections with metal concentrations exceeding the upper 95% prediction interval of the linear regression model were regarded as metal enrichment layers. The heavy metal accumulation mainly occurred at sites in the western shallow water areas and east channel, which reflected the hydraulic conditions and influence from riparian anthropogenic activities. Heavy metals in the enrichment sections were evaluated by a sequential extraction method for possible chemical forms in sediments. Since the residual, Fe/Mn oxides and organic/sulfide fractions were dominant geochemical phases in the enriched sections, the bioavailability of heavy metals in sediments was generally low. The 206Pb/207Pb ratios in the metal-enriched sediment sections also revealed the influence of anthropogenic sources. The spatial distribution of cumulative heavy metals in the sediments suggested that the Zn and Cu mainly originated from point sources, while the Pb probably came from non-point sources in the estuary.  相似文献   

12.
The distribution and speciation of heavy metals in five agricultural soils of Piedmont Region (north-western Italy) were investigated. Ten metals, namely Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Ti and Zn were considered. Analytical determinations were performed by atomic emission or atomic absorption spectroscopy after microwave sample dissolution in acid solution. Total metal concentrations fit in the typical concentration ranges for unpolluted soils, with the exception of cadmium and lead content in some horizons. The effect of sampling depth on concentrations was discussed. Speciation studies were carried out by applying Tessier's procedure, which allows to subdivide the total metal content into five fractions, representing portions bound to different components of the soil. Moreover, the element labilities in two soils were evaluated by extraction with EDTA. Correlations among the variables and/or similarities among the sampling points were identified by principal component analysis and hierarchical cluster analysis.  相似文献   

13.
A study was conducted to evaluate the effect of long-term irrigation of sewage contaminated with heavy metals like Cd, Cr, Cu and Pb on microbial and biochemical parameters of soils of West Bengal, India. The microbial parameters included microbial biomass carbon (MBC), microbial metabolic quotient; the biochemical parameters included fluorescein diacetate hydrolyzing activity, beta-glucosidase, urease, phosphatase, and aryl sulphatase activities. A sequential extraction technique was used to quantify water soluble, exchangeable, carbonate bound, Fe/Mn-oxide bound, organically bound, and residual metal fractions. Metal concentrations in the two most labile fractions (i.e., water soluble and exchangeable fractions) were generally low. Total metal concentrations at each site seemed to be associated with soil amorphous Fe and Al minerals. The MBC and the enzymes studied were significantly and negatively correlated with water soluble and exchangeable metals but not significantly correlated with other forms, indicating that water soluble and exchangeable forms exerted a strong inhibitory effect on the soil microbial and biochemical parameters. It was concluded that irrigating soils with metal contaminated sewage seemed to damage soil quality in the long term.  相似文献   

14.
Metal (Pb, Cu and Zn) partitioning in six separated sediment size fractions (<8, 8-12, 12-19, 19-31, 31-42, 42-60 microm) of river bed sediment have been analyzed by sequential extraction. The concentrations of some major elements (Si, Al, Ca, Mg, K, Na, Fe, Mn and P), and organic and inorganic C were determined to correlate the elemental composition of the sediment with metal speciation and grain size. Results show that Zn and Pb concentrations increase with decreasing grain size. For Big Creek and Big Otter Creek, respectively, the highest concentrations of Zn (326 and 230 mg kg(-1)) and Pb (158 and 67 mg kg(-1)) were found in the smallest (<8 microm) fraction, whereas the Cu levels (619 and 1281 mg kg(-1)) were most abundant in the second smallest (8-12 microm) fraction. The major accumulative phases for Cu, Zn and Pb were carbonates, Fe/Mn oxides and organic matter, but the relative importance of each phase varied for individual metals and grain sizes. The extraction data show increasing potential bioavailability of metals with decreasing grain size. Estimates of metal yields in the study catchments suggest that over 80% of the metal yield in sediment smaller than 63 microm is associated with solids smaller than 31 microm.  相似文献   

15.
Amendment of agricultural soils with municipal sewage sludges provides a valuable source of plant nutrients and organic matter. Nevertheless, addition of heavy metals and risks of eutrophication continue to be of concern. Metal behaviour in soils and plant uptake are dependent on the nature of the metal, sludge/soil physico-chemical properties and plant species. A pot experiment was carried out to evaluate plant production and heavy metal uptake, soil heavy metal pools and bioavailability, and soil P pools and possible leaching losses, in agricultural soils amended with sewage sludge for at least 10 years (F20) compared to non-amended soils (control). Sewage sludge application increased soil pH, N, Olsen-extractable-P, DOC and exchangeable Ca, Mg and K concentrations. Total and EDTA-extractable soil concentrations of Cu and Zn were also significantly greater in F20, and soil metal (Cu, Mn and Zn) and P fractionation altered. Compared to the control, in F20 relative amounts of acid-extractable (Mn, Zn), reducible (Mn, Zn) and oxidisable (Cu, Zn) metal fractions were greater, and a dominance of inorganic P forms was observed. Analyses of F20 soil solutions highlighted risks of PO4 and Cu leaching. However, despite the observed increases in metal bioavailability sewage sludge applications did not lead to an increase in plant shoot concentrations (in wild plants or crop species). On the contrary, depending on the plant species, Mn and Zn tissue concentrations were within the deficiency level for most plants.  相似文献   

16.
In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m?2 day?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.  相似文献   

17.
Qiao XL  Luo YM  Christie P  Wong MH 《Chemosphere》2003,50(6):823-829
An incubation experiment was conducted to study the chemical speciation and extractability of three heavy metals in two contrasting biosolids-amended clay soils. One was a paddy soil of pH 7.8 and the other was a red soil of pH 4.7 collected from a fallow field. Anaerobically digested biosolids were mixed with each of the two soils at three rates: 20, 40 and 60 g kg(-1) soil (DM basis), and unamended controls were also prepared. The biosolids-amended and control soils were incubated at 70% of water holding capacity at 25 degrees C for 50 days. Separate subsamples were extracted with three single extractants and a three-step sequential extraction procedure representing acetic acid (HOAc)-soluble, reducible and oxidisable fractions to investigate the extractability and speciation of the heavy metals. As would be expected, there were good relationships between biosolids application rate and metal concentrations in the biosolids-amended soils. The three heavy metals had different extractabilities and chemical speciation in the two biosolids-amended soils. Ethylene diamine tetraacetic acid extracted more Cu, Zn and Cd than did the other two single extractants. The oxidisable fraction was the major fraction for Cu in both biosolids-amended soils and the HOAc-soluble and reducible fractions accounted for most of the Zn. In contrast, Cd was present mainly in the reducible fraction. The results are discussed in relation to the mobility and bioavailability of the metals in polluted soils.  相似文献   

18.
Introduction In this work, sediments of the River Tisa (Tisza) are studied to assess their environmental pollution levels for some major heavy metals, as well as to predict the investigated elements’ mobility on the basis of their association type with the substrate. The Tisa River catchments area is a subbasin of the River Danube. Part of this river, 166 km long, belongs to the Serbian province of Vojvodina, before it flows into the Danube. It has been chosen for our investigation, because it has been exposed to intense pollution in the last decades. Materials and Methods The river sediment samples were collected at 32 locations. The proportions of sand, silt and clay fractions were determined. The sequential extraction procedure following a modified Tessier method was applied for speciation of the metal forms in the collected samples. The metal concentrations of Zn, Cd, Pb, Ni, Cu, Cr, Fe and Mn in extracts were determined by atomic absorption spectroscopy. Results and Discussion Granulometric analysis showed that some 50% of the Tisa River sediments were silt and clay, while the rest was sand with quartz, as the main constituent. The average metal content of the surface river sediment samples for every fraction of sequential extraction was presented and discussed in relation to pH, Eh and metal fractionation. The average metal content from the Tisa River sediments, obtained as an average of the metal’s concentration released in all five sequential extraction fractions was compared with: average metal contents of the Tisa River sediments in Hungary, metal content in soils formed on the Tisa River alluvium of Vojvodina, average metal content in soils of Vojvodina, and average metal content in soils of Hungary. An assessment of metal pollution levels in Tisa River sediments was made by comparing mean values for obtained results for the Tisa River sediments with the freshwater sediment’s Quality Guidelines as published by US EPA, Environment Canada and soil standards for Serbia. Conclusion According to US EPA and Canadian Quality Guidelines for freshwater sediments, the concentration of heavy metals in Tisa sediments were: (a) much higher than defined concentrations below which harmful effects on river biota are unlikely to be observed, (b) below defined concentrations above which harmful effects on river biota are likely to be observed. The concentration levels of Pb, Ni, Cu and Cr in Tisa River sediments are safe when compared with Serbian MAQ (Maximum Allowed Quantity) standards for soils, but they are unsafe in the case of Zn and Cd. Recommendations and Outlook The quality of sediments in the Tisa River was on the border line between potentially polluted and polluted. This line could very easily be exceeded since the quality of sediments in the Tisa River in Hungary was already worse than in Serbia. These results indicated the need for further monitoring of heavy metals in that locality.  相似文献   

19.
This study was designed to evaluate the impact of sewage sludge spreading on tropical soilborne heavy metal speciation. Sludgeborne heavy metal speciation was also assessed, and the potential mobility of the elements was classified as follows: Zn>Ni>Cu approximately Cr. Two sequential extraction procedures were applied to study Cr, Cu, Ni and Zn speciation in control soils and sludge-amended soils. We demonstrated that sewage sludge spreading over a 2-year period did not have an impact on soilborne heavy metal concentrations but affected speciation of the most mobile fractions of Ni and Zn. Both protocols were consistent for the organic matter fractions, with an increase in Cu, Zn and Cr concentrations in the amended soil as compared to the control soil. In addition, we highlighted that the two protocols characterized different pools of organic matter and that organic compounds remained in the solid matrix after extraction. With respect to the reducible fraction, completely opposite results were obtained with the two protocols and the solid residue study revealed that the two schemes were ineffective in characterizing iron and manganese fractions.  相似文献   

20.
We evaluated the distribution of 15 metal ions, namely Al, Cd, Cu, Cr, Fe, La, Mn, Ni, Pb, Sc, Ti, V, Y, Zn and Zr, in the soil of a contaminated site in Piedmont (Italy). This area was found to be heavily contaminated with Cu, Cr and Ni. The availability of these metal ions was studied using Tessier’s sequential extraction procedure: the fraction of mobile species, which potentially is the most harmful for the environment, was much higher than that normally present in unpolluted soils. This soil was hence used to evaluate the effectiveness of treatment with vermiculite to reduce the availability of the pollutants to two plants, Lactuca sativa and Spinacia oleracea, by pot experiments. The results indicated that the addition of vermiculite significantly reduces the uptake of metal pollutants by plants, confirming the possibility of using this clay in amendment treatments of metal-contaminated soils. The effect of plant growth on metal fractionation in soils was investigated. Finally, the sum of the metal percentages extracted into the first two fractions of Tessier’s protocol was found to be suitable in predicting the phytoavailability of most of the pollutants present in the investigated soil.  相似文献   

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