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1.
Size-classified ice crystal samples were collected during the Spring of 1998, at the Jungfraujoch High-Alpine Research Station (3454 m), located in Switzerland. A procedure modified from the Guttalgor method, originally developed for size-selective sampling of raindrops by Bächmann et al. (Atmos. Environ. 26A (1992) 1795) was used to sample ice crystals during precipitation events. The size-classified ice crystal samples were analyzed using ion chromatography to determine the concentrations of Na+, NH4+, K+, Ca2+, Mg2+, Cl, NO3, and SO42− in each size class. For ions associated with coarse mode aerosol, Na+, K+, Ca2+, Mg2+, and Cl, concentration increased with decreasing ice crystal size, suggesting scavenging by nucleation. For the remaining ions, mixed behavior was observed suggesting a combination of gas phase scavenging and scavenging via riming.  相似文献   

2.
Results are reported for a series of migration experiments performed in a hydraulically characterized, single, natural fracture in a block of granite with overall dimensions of 1 × 1 × 0.7 m (all approximate), using the conservative, poorly sorbing and strongly sorbing radionuclides 3H20, 131I, 22Na, 85Sr, 137Cs, 60Co, 154,155Eu, 237Np, and 238Pu. The volumetric flow velocity of the transport solution was 3 ml h−1, giving a residence time in the fracture of approximately 50 h. Elution profiles were obtained for 3H20, 131I, 22Na, 85Sr and 137Cs but no evidence of the other radionuclides was observed in the eluent. Results from supporting static sorption measurements on crushed geological materials and granite coupons showed in general higher sorption on alteration minerals than on granite. Sorption was lowest for 22Na and 85Sr.The migration of 131I, 22Na, 85Sr through the fracture in real time was followed using end-window Geiger-Müller probes located in unused boreholes. Additional information, obtained by alpha and gamma scanning of the fracture surfaces after separating the block along the fracture, confirmed that transport had occurred along the flow path predicted from the hydraulic characterization of the fracture and that, over a 5.5 month period, the bulk of the injected 137Cs had migrated only 75 cm along the flow path. The 60Co, the rare earths and the actinides had not moved beyond the location of the injection borehole, suggesting that fracture infilling minerals played a major role in retarding radionuclide transport. Additional confirmation of the role of secondary minerals in radionuclide retardation was obtained using selective sequential extraction on the fracture surfaces. These observations support the inclusion of sorption data for fracture infilling minerals in the sorption database developed for the geosphere model for the Canadian Nuclear Fuel Waste Management Program.  相似文献   

3.
This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH? · pH?1. The sediments were spiked with atrazine at 7.25-36.23 mg kg?1 (6.21 × 10?7–3.09 × 10?6 mol atrazine · g?1 sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 × 10?2?7.04 × 10?2 d?1 for the atrazine-spiked sediments.  相似文献   

4.
Diffusion coefficients (T=23±2 °C) and accessible porosities for HTO, 36Cl and 125I were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na+ and Cl as the main components (I=0.42 M).The measured values of the effective diffusion coefficients (De) and rock capacity factors (α) are: De=1.2–1.5×10−11 m2 s−1 and α=0.09–0.11 for HTO, De=4.0–5.5×10−12 m2 s−1 and α=0.05 for 36Cl and De=3.2–4.6×10−12 m2 s−1 and α=0.07–0.10 for 125I. For non-sorbing tracers (HTO, 36Cl) the rock capacity factor α is equal to the diffusion-accessible porosity . The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of 17% for HTO, 28% for 36Cl and 30% for 125I. Moreover, the diffusion coefficients for 36Cl and 125I are smaller than for HTO, which is consistent with an effect arising from anion exclusion.The diffusion coefficients of HTO and 125I measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.  相似文献   

5.
The fate of 14C-labeled sulfadiazine (14C-SDZ) residues was studied in time-course experiments for 218 days of incubation using two soils (Ap horizon of loamy sand, orthic luvisol; Ap horizon of silt loam, cambisol) amended with fresh and aged (6 months) 14C-manure [40 g kg?1 of soil; 6.36 mg of sulfadiazine (SDZ) equivalents per kg of soil], which was derived from two shoats treated with 14C-SDZ. Mineralization of 14C-SDZ residues was below 2% after 218 days depending little on soil type. Portions of extractable 14C (ethanol-water, 9:1, v/v) decreased with time to 4–13% after 218 days of incubation with fresh and aged 14C-manure and both soils. Non-extractable residues were the main route of the fate of the 14C-SDZ residues (above 90% of total recovered 14C after 218 days). These residues were high immediately after amendment depending on soil type and aging of the 14C-manure, and were stable and not remobilized throughout 218 days of incubation. Bioavailable portions (extraction using CaCl2 solution) also decreased with increasing incubation period (5–7% after 218 days). Due to thin-layer chromatography (TLC), 500 μg of 14C-SDZ per kg soil were found in the ethanol-water extracts immediately after amendment with fresh 14C-manure, and about 50 μg kg?1 after 218 days. Bioavailable 14C-SDZ portions present in the CaCl2 extracts were about 350 μg kg?1 with amendment. Higher concentrations were initially detected with aged 14C-manure (ethanol-water extracts: 1,920 μg kg?1; CaCl2 extracts: 1,020 μg kg?1), probably due to release of 14C-SDZ from bound forms during storage. Consistent results were obtained by extraction of the 14C-manure-soil samples with ethyl acetate; portions of N-acetylated SDZ were additionally determined. All soluble 14C-SDZ residues contained in 14C-manure contributed to the formation of non-extractable residues; a tendency for persistence or accumulation was not observed. SDZ's non-extractable soil residues were associated with the soluble HCl, fulvic acids and humic acids fractions, and the insoluble humin fraction. The majority of the non-extractable residues appeared to be due to stable covalent binding to soil organic matter.  相似文献   

6.
磷酸铵镁沉淀法处理废水时常受众多因素影响,其中重金属类杂质对该过程影响较大。实验研究了Mn2+、Cu2+杂质存在条件下,用该法去除制药废水中PO43-、NH4+污染物,同时,用XRD、XRF、SEM等手段研究了所得鸟粪石晶体特征。结果表明,pH为9.5时,Mn2+、Cu2+杂质存在条件下,PO43-去除率分别为88%和85%,投加晶种有利于回收特定晶形鸟粪石,Cu2+对磷酸铵镁结晶过程的影响较Mn2+存在时显著。  相似文献   

7.
The aim of the present work was to establish the kinetics for the degradation of doxycycline in the aquatic environment with a view to arriving at a kinetic model that can be used to predict the persistence of antibiotic with confidence. The degradation of doxycycline in both water and sediment phases of aquatic microcosm experiments, as well as in distilled water control experiments, was studied over a period of 90 days. An initial 21% loss due to adsorption by the sediment was observed in the microcosm experiment soon after charging. Biphasic zero-order linear rates of degradation, attributed to microbial degradation of the free and sediment or colloidal particle-adsorbed antibiotic, were observed for both water phase (2.3 × 10?2 and 4.5 × 10?3 μgg?1 day?1) and sediment phase (7.9 × 10?3 and 1.5 × 10?3 μgg?1 day?1) of the microcosm experiment. The covered distilled water control experiment exhibited a monophasic zero-order linear rate (1.9 × 10?3 μgg?1 day?1) attributed to hydrolysis, while the distilled water experiment exposed to natural light exhibited biphasic liner rates attributed to a combination of hydrolysis and photolysis (2.9 × 10?3 μgg?1 day?1) and to microbial degradation (9.8 × 10?3 μgg?1 day?1). A kinetic model that takes into account hydrolysis, photolysis, microbial degradation as well as sorption/desorption by colloidal and sediment particles is presented to account for the observed zero-order kinetics. The implications of the observed kinetics on the persistence of doxycycline in the aquatic environment are discussed.  相似文献   

8.
Since the development of the TIE (Toxicity Identification and Evaluation) in 1988 it has been assumed that the capacity of EDTA and sodium thiosulfate to complex some metals, and thus remove their toxicity, can be applied to both freshwater and seawater ecotoxicological tests and the results subsequently interpreted. However, it is now known that there is a wide variability in the extent of this complexation. In this context, the removal of toxicity caused by the presence of Hg2+, Cd2+, Cu2+, Cr6+, Zn2+, Ni2+, Pb2+, Ag1+ and Se2+, through metal complexation by EDTA and sodium thiosulfate, in relation to the performance of embryo-larval tests with the sea urchin Arbacia lixula was investigated. It was observed that EDTA was capable of removing the toxicity of Pb2+, Zn2+ and Cu2+ while sodium thiosulfate only reduced the toxicity of Ag1+. Compared to the complexation observed in freshwater ecotoxicological tests, the complexing agents used in this study (EDTA and sodium thiosulfate) have a lower capacity to complex metals in the marine ecotoxicological test with A. lixula.  相似文献   

9.
Abstract

Toxicity of heavy metals to living organisms is a worldwide research topic. Although, much has been discovered about cadmium and nickel impact on biological systems, a lot still remains unclear. We used inductively coupled plasma – optical emission spectroscopy to address the question of the effect of two different heavy metals nickel, and cadmium on intracellular ion balance. Increase or decrease of the content of several essential cations including Ca2+, Na+, K+, Mg2+, Cu2+, Fe3+ in the yeast Schizosaccharomyces pombe was determined. Our results revealed that the cell exposure to high nickel and cadmium concentrations led to significant elevation of Ca2+, Na+, Mg2+, Cu2+, Fe3+ levels in the yeast cell, while the content of K+ decreased. Correlation analyses showing in the presence of nickel and cadmium strong positive correlation among each tested element (Ca2+, Na+, Cu2+, Mg2+ and Fe3+) except for K+, demonstrate the significant impact of heavy metal treatment to ion homeostasis of the cell. Our data indicate that acute nickel and cadmium contamination leads to substantial ionome misbalance in yeast.  相似文献   

10.
The interactions between metals (Ca2+ and Hg2+) and extracellular polymeric substances (EPS) extracted from the aerobic and anaerobic sludge in wastewater treatment reactors were investigated using a combination of zeta potential measurement and 3-dimensional excitation–emission matrix (EEM) fluorescence spectroscopy with parallel factor (PARAFAC) analysis. Results show that Ca2+ had no substantial effects on the EEM fluorescence spectra of the EPS, but their zeta potentials increased with the increasing Ca2+ dosage. However, Hg2+ had a significant effect on the EEM fluorescence spectra of the EPS, while their zeta potentials seemed not to be affected by the dose of Hg2+. The interactions between Hg2+ and EPS were elucidated using the fluorescence quenching with PARAFAC analysis, while the interactions between Ca2+ and EPS were evaluated by the zeta potential technique. The binding constants for Hg2+ and EPS were two orders of magnitude higher than those for Ca2+ and EPS, suggesting that the binding mechanisms between Ca2+ and EPS were different from those between Hg2+ and EPS. The results might be useful for understanding the roles of EPS in bacterial self-protection against heavy metals and the aggregate formation mechanisms through ionic bridging interactions.  相似文献   

11.
Tagetes erecta has a high potential for cadmium (Cd) phytoremediation. Through several hydroponic experiments, characteristics of 108Cd distribution and accumulation were investigated in T. erecta with split -roots or removed xylem/phloem. The results showed that 108Cd transport from roots to aboveground tissues showed the homolateral transport phenomenon in split-root seedlings. 108Cd content of leaves on the +108Cd side and the −108Cd side was not significantly different, which implied that there was horizontal transport of 108Cd from the +108Cd side to the −108Cd side in cut-root seedlings. Like 108Cd transport, the transport of 70Zn was homolateral. Reduction of water consumption in the removed xylem treatment significantly decreased 108Cd accumulation; whereas, the removed phloem treatment had no significant effect on water consumption, but did decrease 108Cd accumulation in leaves of the seedlings. The removal of phloem significantly reduced distal leaf 108Cd content, which was significantly lower than that in the basal leaves in both the split-root and unsplit-root seedlings. Overall, the results presented in this study revealed that the root to aboveground cadmium translocation via phloem is as an important and common physiological process as xylem determination of the cadmium accumulation in stems and leaves of marigold seedlings.  相似文献   

12.
A relative rate procedure was used to measure hydroxyl rate constants at room temperature in the presence of oxygen. The photolysis of methyl nitrite in the presence of nitric oxide was used to generate OH radicals. The rate of loss of the test compounds was measured relative to that of ethane (kOH = 2.74 × 10-13 cm3 molec-1 s-1). The rates obtained at 297 ± 2 K are: acetylene = (7.8 ± 1.6) × 10-13 cm3 molec-1 s-1,1,2-dichloroethane (2.8 ± Q.6) × 10-13 cm3 molec-1 s-1, 1,2-dibromoethane (2.4 ± 0.5) × 10-13 cm3 molec-1 s-1, p-dichlorobenzene (4.3 ± 0.9) × 10-13 cm3 molec-1 s-1 and carbon disulfide (29 ± 6) × 10-13 cm3 molec-1 s-1. Under a proposed EPA rule, this OH rate determination procedure could be used to determine if a given volatile organic will be subject to control for reduction of photochemical ozone.  相似文献   

13.
TSP and PM2.5 samples were collected at Xi'an, China during dust storms (DSs) and several types of pollution events, including haze, biomass burning, and firework displays. Aerosol mass concentrations were up to 2 times higher during the particulate matter (PM) events than on normal days (NDs), and all types of PM led to decreased visibility. Water-soluble ions (Na+, NH4+, K+, Mg2+, Ca2+, F?, Cl?, NO3?, and SO42?). were major aerosol components during the pollution episodes, but their concentrations were lower during DSs. NH4+, K+, F?, Cl?, NO3?, and SO42? were more abundant in PM2.5 than TSP but the opposite was true for Mg2+ and Ca2+. PM collected on hazy days was enriched with secondary species (NH4+, NO3?, and SO42) while PM from straw combustion showed high K+ and Cl?. Firework displays caused increases in K+ and also enrichments of NO3? relative to SO42?. During DSs, the concentrations of secondary aerosol components were low, but Ca2+ was abundant. Ion balance calculations indicate that PM from haze and straw combustion was acidic while the DSs samples were alkaline and the fireworks' PM was close to neutral. Ion ratios (SO42?/K+, NO3?/SO42?, and Cl?/K+) proved effective as indicators for different pollution episodes.  相似文献   

14.
The long-lived radionuclide 79Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (SeVIO42−) and selenite (SeIVO32−). Previous investigations have demonstrated, however, that SeIV and SeVI are reduced by surface-associated FeII, thereby forming insoluble Se0 and Fe selenides. Here we show that the mixed FeII/III (hydr)oxides green rust and magnetite, and the FeII sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the FeII carbonate siderite produces elemental Se. In the case of mackinawite, both S−II and FeII surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these FeII systems is controlled by the concentration of HSe; Se0 forms only at lower HSe concentrations related to slower HSeO3 reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe2+-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since FeII phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product 79Se may be much lower than previously assumed.  相似文献   

15.
Heavy metal stress in culture media is always rhizotoxic. Our study aims to investigate the role of negative potential (ψ 0) at root cell membrane surface (CMs) on modeling Zn2+ toxicity to wheat seedling roots and to examine the effects of different nitrogen forms (NH4 + and NO3 ?) on ψ 0 and Zn rhizotoxicity. Solution culture experiments were conducted to measure the root elongation and Zn accumulation under Zn2+ exposure. The role of two nitrogen forms in affecting Zn2+ toxicity was compared, giving particular consideration to ψ 0 and Zn2+ activities at CMs ({Zn2+}0). Results showed that NH4 + alleviates Zn2+ rhizotoxicity and NO3 ? increases Zn2+ rhizotoxicity. In modeling the rhizotoxicity, root length correlated better with {Zn2+}0 than {Zn2+}b, and the predictive accuracy (r 2) of NH4 + treatment increased from 0.748 to 0.917 when incorporation of {Zn2+}0 and {Ca2+}0 into analysis. Oppositely, ψ 0 played a limited role in modeling Zn2+ rhizotoxicity and bioavailability in NO3 ? treated medium (r 2 = 0.609). Moreover, higher concentration of Zn in roots was found in NO3 ? treatment, compared with the NH4 + treatment. ψ 0 rather than the rhizotoxicity data correlated better with Zn accumulation especially in the NO3 ? treatment (r 2 > 0.7), which meant the electrical driving force at CMs playing a dominant role in modeling the metal accumulation. In conclusion, the alleviatory role of NH4 + on Zn toxicity and uptake was well explained and modeled by electrostatic effects at CMs. Though our data do not explore mechanisms for the NO3 ?-Zn2+ interactions, we propose that ψ 0 worked better in affecting the driving force for root Zn uptake, than influencing metal bioavailability at CMs.  相似文献   

16.
ABSTRACT

The stoichiometry of the reaction of aqueous ozone with sodium azide was studied at pH 12 (mainly) where a yellow metastable intermediate is observed. We propose that this is hypoazidite (N3O- ), analogous to hypobromite, and that it plays a central role in the azide catalyzed decompostion of ozone. The yellow intermediate is unstable in acid, in which it rapidly decomposes, generating N2 and NO2 -.

The rate of reaction was studied at pH 2.0–3.5, with the ionic strength at 0.6 M and temperature at 3–15 ° C. The intrinsic second-order rate constants were found to be k HN3 ≤ ≈ 400 M-1sec-1 and k N3- = (8.7 ± 0.5) × 105 M-1sec-1 (3 °C, 0.6 M), both in agreement with the only other previous study. The rate constant at 25 °C was estimated using the following experimentally determined parameters: ln kN3- (M-1sec-1) = (5.73 ± 0.36) × 103/T (K) + (28.34 ± 1.27). The value of kN3- estimated in this way is (2.5 ± 0.1) × 106 M-1sec-1 at 25 °C and 0.6 M. The enthalpy of reaction (A H) is -48 ± 3 kJ mol-1.  相似文献   

17.
Ambient aerosol samples, collected from Mangalore region in the southwest coast of India during the period of late winter (February and March) to early summer (April and May), have been analysed for water-soluble ionic species. Their abundance pattern is dominated by HCO3, SO42−, Na+, Cl, with minor contribution from NO3, Ca2+, NH4+, K+ and Mg2+ indicating the contribution from not only sea salt, but also from anthropogenic and dust sources; with pronounced seasonal variability. The suspended particulate matter concentration varied from 35 to 160 μg m−3, with consistently higher values during the late winter. Back trajectory analysis suggests the origin of the air masses shifting from Indo-Gangetic Plains (during late winter) to those from the Arabian Sea and the area around Persian Gulf during April–May. Air masses passing over Northern India (Indo-Gangetic Plains) impart characteristic contribution of ionic species from fossil fuel combustion, biomass burning and eolian dust as asserted by the factor analysis. A detailed study on characterisation of aerosols from south Asian region is rather sparse but essential for modelling the effect of tropospheric aerosols on climate.  相似文献   

18.
Degradation of bisphenol A (BPA) in aqueous solution was studied with high-efficiency sulfate radical (SO4 ), which was generated by the activation of persulfate (S2O8 2?) with ferrous ion (Fe2+). S2O8 2? was activated by Fe2+ to produce SO4 , and iron powder (Fe0) was used as a slow-releasing source of dissolved Fe2+. The major oxidation products of BPA were determined by liquid chromatography-mass spectrometer. The mineralization efficiency of BPA was monitored by total organic carbon (TOC) analyzer. BPA removal efficiency was improved by the increase of initial S2O8 2? or Fe2+ concentrations and then decreased with excess Fe2+ concentration. The adding mode of Fe2+ had significant impact on BPA degradation and mineralization. BPA removal rates increased from 49 to 97 % with sequential addition of Fe2+, while complete degradation was observed with continuous diffusion of Fe2+, and the latter achieved higher TOC removal rate. When Fe0 was employed as a slow-releasing source of dissolved Fe2+, 100 % of BPA degradation efficiency was achieved, and the highest removal rate of TOC (85 %) was obtained within 2 h. In the Fe0–S2O8 2? system, Fe0 as the activator of S2O8 2? could offer sustainable oxidation for BPA, and higher TOC removal rate was achieved. It was proved that Fe0–S2O8 2? system has perspective for future works.  相似文献   

19.
The adsorption behavior of 241Am, 60Co, 137Cs and 85Sr in the presence and absence of chelating ligands (ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, iminodiaceiticacid and methyliminodiacetic acid) was investigated. Sorption affinity in the absence of chelating ligands followed: Am(III) > Co(II) > Cs(I) > Sr(II). The presence of chelating ligands generally had little effect on sorption of 85Sr and 137Cs with Kd values 110 and 690 mL g−1, respectively. But at 0.02 M of ethylenediaminetetraacetic or hydroxyethyliminodiacetic, the Kd decreased to 5 or 63 mL g−1, respectively, where thermochemical modeling indicated almost all 85Sr is complexed with these ligands. The Kd values for 241Am and 60Co generally decreased with increasing chelating agent concentrations. In notable cases, the Kd values for Am increased at specific concentrations of 10−3 M for IDA, MIDA and 10−4 M for EDDA. This is proposed to be due to formation of a ternary surface complex.  相似文献   

20.
Osterc A  Stibilj V 《Chemosphere》2012,86(10):1020-1027
Compared to the pre-nuclear era, large amounts of 129I have been released to the marine environment, especially as liquid and gaseous discharges from two European reprocessing plants located at Sellafield and La Hague. Their liquid discharges influence Northern Europe and most research was conducted in the area of the North Atlantic Ocean and the Baltic Sea. In this article data on 129I content and 129I/127I ratios observed in the North Adriatic Sea, which is a rather enclosed basin of the Mediterranean Sea, are presented. To the best of our knowledge no data on 129I in the Mediterranean Sea have previously been reported. As this area is isolated from direct liquid discharges, the main transport pathway is probably gaseous releases from reprocessing plants. Surface sea water, the marine alga Fucus virsoides, an iodine accumulator, and the Mediterranean mussel Mytilus galloprovincialis collected in 2009 and 2010, and marine sediment collected in 2005 and 2009 were analysed. The 129I/127I isotopic ratios observed were in the range from 0.8 to 3.0 × 10−08 for seawater, from 0.06 to 0.35 × 10−08 for marine sediment, from 0.05 to 0.10 × 10−08 for F. virsoides and from 0.3 to 0.9 × 10−08 for M. galloprovincialis.  相似文献   

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