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1.
Perfluoroalkyl substances were determined in liver tissues and blood of polar bears (Ursus maritimus) from five locations in the North American Arctic and two locations in the European Arctic. Concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate, heptadecafluorooctane sulfonamide, and perfluoroalkyl carboxylates with C(8)-C(15) perfluorinated carbon chains were determined using liquid chromatography tandem mass spectrometry. PFOS concentrations were significantly correlated with age at four of seven sampling locations, while gender was not correlated to concentration for any compound measured. Populations in South Hudson Bay (2000-2730 ng/g wet wt), East Greenland (911-2140 ng/g wet wt), and Svalbard (756-1290 ng/g wet wt) had significantly (P < 0.05) higher PFOS concentrations than western populations such as the Chukchi Sea (435-729 ng/g wet wt). Concentrations of perfluorocarboxylic acids (PFCAs) with adjacent chain lengths (i.e., C9:C10 and C10:C11) were significantly correlated (P < 0.05), suggesting PFCAs have a common source within a location, but there were differences in proportions of PFCAs between eastern and western location sources. Concentrations of PFOS in liver tissue at five locations were correlated with concentrations of four polychlorinated biphenyl congeners (180, 153, 138, and 99) in adipose tissue of bears in the same populations, suggesting similar transport pathways and source regions of PFOS or precursors.  相似文献   

2.
Perfluoroalkyl substances are globally distributed anthropogenic contaminants. Their production and use have increased dramatically from the early 1980s. While many recent publications have reported concentrations of perfluorooctane sulfonate (PFOS) and other perfluoroalkyl acids (PFAs) in biotic and abiotic samples, only limited work has addressed temporal trends. In this study we analyzed archived polar bear(Ursus maritimus) livertissue samples from two geographic locations in the North American Arctic, collected from 1972 to 2002. The eastern group, taken from the vicinity of northern Baffin Island, Canada, comprised 31 samples, and the western group, from the vicinity of Barrow, Alaska, comprised 27 samples. Samples were analyzed for perfluorocarboxylic acids (PFCAs) from carbon chain length C8 to C15, perfluorohexane sulfonate, PFOS, the neutral precursor perfluorooctane sulfonamide (PFOSA), as well as 8:2 and 10:2 fluorotelomer acids and their alpha,beta unsaturated acid counterparts. Concentrations of PFOS and PFCAs with carbon chain lengths from C9 to C11 showed an exponential increase between 1972 and 2002 at both locations. Doubling times ranged from 3.6 +/- 0.9 years for perfluorononanoic acid in the eastern group to 13.1 +/- 4.0 years for PFOS in the western group. PFOSA showed decreasing concentrations over time at both locations, while the remaining PFAs showed no significant trends or were not detected in any sample. The doubling time for PFOS was similar to the doubling time of production of perfluoroctylsulfonyl-fluoride-based products during the 1990s.  相似文献   

3.
The source of involatile, anthropogenic perfluorocarboxylate anions (PFCAs) in biota from remote regions is of heightened interest due to the persistence, toxicity, and bioaccumulation of these materials. Large-scale production of fluorinated compounds is carried out primarily by one of two methods: electrochemical fluorination (ECF) and telomerization. Products of the two processes may be distinguished based on constitutional isomer pattern as ECF products are characteristically comprised of a variety of constitutional isomers. The objective of this research was to develop a method for identifying the constitutional isomer profile of PFCAs in environmental samples and to apply the method to polar bear livers from two different locations. Resolution of constitutional isomers of derivatized PFCAs (8-13 carbons) was accomplished via GC-MS. Seven isomers of an authentic ECF perfluorooctanoate (PFOA) standard were separated. The linear isomer comprised 78% of this standard. Isomer profiles of PFCAs in liver samples of 15 polar bears (Ursus maritimus) from the Canadian Arctic and eastern Greenland were determined by GC-MS. The PFOA isomer pattern in Greenland polar bear samples showed a variety of branched isomers while only the linear PFOA isomer was determined in Canadian samples. Samples of both locations had primarily (>99%) linear isomers of perfluorononanoate and perfluorotridecanoate. Branched isomers of perfluorodecanoate, perfluoroundecanoate, and perfluorododecanoate were determined in the polar bear samples. Unlike the PFOA isomer signature, only a single branched isomer peak on the chromatograms was observed for these longer chain PFCAs. The presence of branched isomers suggests some contribution from ECF sources. However, in comparison to the amount of branched isomers in the ECF PFOA standard, such minor percentages of branched PFCAs may suggest additional input from an exclusively linear isomer source.  相似文献   

4.
Polybrominated diphenyl ethers (PBDEs) were determined in adipose tissue of adult and subadult female polar bears sampled between 1999 and 2002 from sub-populations in Arctic Canada, eastern Greenland, and Svalbard, and in males and females collected from 1994 to 2002 in northwestern Alaska. Only 4 congeners (BDE47, 99, 100, and 153) were consistently identified in all samples. BDE47 was the major PBDE congener representing from 65% to 82% of the sum (sigma) PBDEs. Age was not a significant covariate for individual PBDEs or sigmaPBDE. Higher proportions of BDE 99, 100, and 153 were generally found in samples from the Canadian Arctic than from Svalbard or the Bering-Chukchi Sea area of Alaska. Geometric mean sigmaPBDE concentrations were highest for female polar bear fat samples collected from Svalbard (50 ng/g lipid weight (lw)) and East Greenland (70 ng/g lw). Significantly lower sigmaPBDE concentrations were found in fat of bears from Canada and Alaska (means ranging from 7.6 to 22 ng/g lw).  相似文献   

5.
Polar bears (Ursus maritimus) are being impacted by climate change and increased exposure to pollutants throughout their northern circumpolar range. In this study, we quantified concentrations of total mercury (THg) in the hair of polar bears from Canadian high- (southern Beaufort Sea, SBS) and sub- (western Hudson Bay, WHB) Arctic populations. Concentrations of THg in polar bears from the SBS population (14.8 ± 6.6 μg g(-1)) were significantly higher than in polar bears from WHB (4.1 ± 1.0 μg g(-1)). On the basis of δ(15)N signatures in hair, in conjunction with published δ(15)N signatures in particulate organic matter and sediments, we estimated that the pelagic and benthic food webs in the SBS are ~ 4.7 and ~ 4.0 trophic levels long, whereas in WHB they are only ~ 3.6 and ~ 3.3 trophic levels long. Furthermore, the more depleted δ(13)C ratios in hair from SBS polar bears relative to those from WHB suggests that SBS polar bears feed on food webs that are relatively more pelagic (and longer), whereas polar bears from WHB feed on those that are relatively more benthic (and shorter). Food web length and structure accounted for ~ 67% of the variation we found in THg concentrations among all polar bears across both populations. The regional difference in polar bear hair THg concentrations was also likely due to regional differences in water-column concentrations of methyl Hg (the toxic form of Hg that biomagnifies through food webs) available for bioaccumulation at the base of the food webs. For example, concentrations of methylated Hg at mid-depths in the marine water column of the northern Canadian Arctic Archipelago were 79.8 ± 37.3 pg L(-1), whereas, in HB, they averaged only 38.3 ± 16.6 pg L(-1). We conclude that a longer food web and higher pelagic concentrations of methylated Hg available to initiate bioaccumulation in the BS resulted in higher concentrations of THg in polar bears from the SBS region compared to those inhabiting the western coast of HB.  相似文献   

6.
The tissue-specific composition of sum classes of brominated and chlorinated contaminants and metabolic/degradation byproducts was determined in adult male and female polar bears from East Greenland. Significantly (p < 0.05) higher concentrations of sigma-PCBs, various other organochlorines such as sigma-CHL, p,p'-DDE, sigma-CBz, sigma-HCHs, octachlorostyrene (OCS), sigma-mirex, dieldrin, the flame retardants sigma-PBDEs, and total-(alpha)-hexabromocyclododecane (HBCD), sigma-methylsulfonyl (MeSO2)-PCBs and 3-MeSO2-p,p'-DDE, were found in the adipose and liver tissues relative to whole blood and brain. In contrast, sigma-hydroxyl (OH)-PCB, 4-OH-heptachlorostyrene and sigma-OH-PBDE concentrations were significantly highest (p < 0.05) in whole blood, whereas the highest concentrations of sigma-OH-PBBs were found in the adipose tissue. Based on the total concentrations of all organohalogens in all three tissues and blood, the combined body burden was estimated to be 1.34 +/- 0.12 g, where > 91% of this amount was accounted for by the adipose tissue alone, followed by the liver, whole blood, and brain. These results show that factors such as protein association and lipid solubility appear to be differentially influencing the toxicokinetics, in terms of tissue composition/ localization and burden, of organohalogen classes with respect to chemical structure and properties such as the type of halogenation (e.g., chlorination or bromination), and the presence or absence of additional phenyl group substituents (e.g., MeO and OH groups). The tissue- and blood-specific accumulation (or retention) among organohalogen classes indicates that exposure and any potential contaminant-mediated effects in these polar bears are likely tissue or blood specific.  相似文献   

7.
Mercury concentrations in hair from 397 Greenland polar bears (Ursusmaritimus) sampled between 1892 and 2001 were analyzed for temporal trends. In East Greenland the concentrations showed a significant (p < 0.0001, n = 27) increase of 3.1%/year in the period 1892-1973. In Northwest Greenland, a similar (p < 0.0001, n = 69) increase of 2.1%/year was found, which continued until 1991, when the most recent samples were obtained. In East Greenland, a significant (p = 0.009, n = 322) decrease of 0.8%/year was observed after 1973. Two Northwest Greenland samples from 1300 A.D. had a mean value of 0.52 mg/kg of dry weight, which can be considered as a baseline level. The Hg concentration during 1985-1991 from Northwest Greenland (mean value of 7.45 mg/kg of dry weight) was more than 14-fold higher than the assumed baseline level from 1300 A.D. from the same region (i.e., about 93% anthropogenic). Although a decrease was found in East Greenland after 1973, the concentration is still ca. 11-fold higher than the baseline level (i.e., about 90% anthropogenic).  相似文献   

8.
Reproductive organs from 55 male and 44 female East Greenland polar bears were examined to investigate the potential negative impact from organohalogen pollutants (OHCs). Multiple regressions normalizing for age showed a significant inverse relationship between OHCs and testis length and baculum length and weight, respectively, and was found in both subadults (dichlorodiphenyl trichloroethanes, dieldrin, chlordanes, hexacyclohexanes, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs)) and adults (hexachlorobenzene [HCB]) (all p < 0.05). Baculum bone mineral densities decreased with increasing chlordanes, DDTs, and HCB in subadults and adults, respectively (all p < 0.05). In females, a significant inverse relationship was found between ovary length and sigma PCB (p = 0.03) and sigma CHL (p < 0.01), respectively, and between ovary weight and sigma PBDE (p < 0.01) and uterine horn length and HCB (p = 0.02). The study suggests thatthere is an impact from xenoendocrine pollutants on the size of East Greenland polar bear genitalia. This may pose a riskto this polar bear subpopulation in the future because of reduced sperm and egg quality/quantity and uterus and penis size/robustness.  相似文献   

9.
Little is known about the reproductive endocrinology of the male polar bear, Ursus maritimus, except that serum testosterone concentrations are high in April and May during the mating season and are low from August to November during the non-mating season. The objective of this study was to describe the relationship between seasonal changes in testicular size and serum concentrations of testosterone, LH and prolactin. Blood samples and testicular measurements were obtained from free-ranging male polar bears in Canada in April (n = 5) and May (n = 15) near Resolute Bay, Northwest Territories and near Churchill, Manitoba in July (n = 15) and October (n = 22). Testis size was greater in May (39.4 +/- 3.5 cm(2)) than in October (27.3 +/- 2.0 cm(2)) (P = 0.002). Serum testosterone concentrations were approximately three-fold higher in April (5.8 +/- 0.8 ng ml(-1)) than in May (1.7 +/- 0.5 ng ml(-1)), July (0.6 +/- 0.2 ng ml(-1)) and October (1.1 +/- 0.2 ng ml(-1)). Similarly, serum LH concentrations were high in April (0.14 +/- 0.04 ng ml(-1)) and low in May (0.09 +/- 0.01 ng ml(-1)), July (0.10 +/- 0.02 ng ml(-1)) and October (0.08 +/- 0.00 ng ml(-1)). Serum prolactin concentrations were high in April (1.9 +/- 0.3 ng ml(-1)), highest in May (2.5 +/- 0.2 ng ml(-1)), lower in July (1.3 +/- 0.1 ng ml(-1)) and lowest in October (0.8 +/- 0.07 ng ml(-1)). The present study demonstrates a positive relationship between testicular size and serum concentrations of LH, prolactin and testosterone in the male polar bear and confirms the previously reported seasonal changes in serum testosterone concentrations. Data from the present study provide important baseline and comparative endocrine information that can be used to aid captive breeding programmes in zoos and to further ecological-behavioural studies of polar bears.  相似文献   

10.
11.
Glaucous gulls (Larus hyperboreus) and their eggs from Svalbard (Norwegian Arctic) have been used as biomonitors of contaminants in the marine environment. In this study, the enantiomer fractions (EFs) of chiral chlordanes and atropisomeric polychlorinated biphenyl (PCB) congeners were determined in the blood plasma of adult male and female glaucous gulls from three breeding colonies in Svalbard. Plasma EFs were similar in magnitude and direction to EFs previously reported in glaucous gulls from other arctic food webs, suggesting overall similarities in the biochemical processes influencing the EFs of bioaccumulated organochlorine (OC) contaminants within the food webs at those locations. Additionally, EFs in yolk of eggs collected concurrently from within the same nesting colonies varied with location, laying date, and OC concentrations, and may be influenced by changes in the local feeding ecology between those colonies. No differences were found between the EFs for any analyte in female gulls compared to those found in egg yolk, indicating that processes involved in the maternal transfer of chlordanes and PCBs to eggs do not modulate the stereochemical ratio between enantiomers. Therefore, the use of eggs as a valuable and noninvasive means of OC biomonitoring may also extend to enantiomer compositions in glaucous gulls, and perhaps also in other seabird species from arctic regions.  相似文献   

12.
ABSTRACT

The contamination of groundwater and surface water from previous uses of perfluoroalkyl substances (PFASs), particularly products containing the contaminants perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA), has become a concern for drinking water and as a potential exposure route to the food supply. In 2016, the Food and Drug Administration (FDA) was asked to investigate a bog in Massachusetts where the surface water was believed to be contaminated with PFASs. As a result, a method was developed for the analysis of PFASs in cranberries, and water and fruit from the affected bog were evaluated. A QuEChERS method was developed and validated for PFOA, PFOS, and six additional shorter-chain PFASs. Method recoveries ranged from 60% to 115% for validation spikes performed at 10, 20 and 40 ng g?1 and method detection limits ranged from 0.2 to 5.6 ng g?1. Bog water samples were analysed using Environmental Protection Agency (EPA) method 537 for PFOA, PFOS and four additional short-chain PFASs. Surface water concentrations for PFOS ranged from 16 to 122 ng L?1 and input water concentrations were 132 ng L?1 and 206 ng L?1. Of the eight water samples, seven had water concentrations that exceeded the EPA health advisory level for PFOS of 70 ng L?1. Of the 42 cranberry samples analysed, none had detects of PFOA or PFOS above their method detection limits (0.4 and 0.5 ng g?1, respectively), nor any of the other short-chain PFASs.  相似文献   

13.
To ensure selection of appropriate materials for industrial use in terms of toxicity, a procedure to estimate a health index (HI) that can be used for prioritizing less hazardous components of consumer products is described. The HI is based on the occupational exposure limits (OELs) of organic substances that compose the products. To calculate the HI of a product, it is often necessary to predict OEL values for the substances for which an OEL value has not yet been promulgated. We developed a method to estimate the OEL values from median lethal dose (LD50) data of rodent. A good correlation between known OEL values and the LD50 data was obtained by a multivariate regression analysis by introducing organic compensation coefficients, which were caluculated as 10 to the Bth power where B is the regression coefficient of dummy variables denoting the characteristics of the organic compounds such as functional groups, molecular structures, and so on. We believe that the use of the present method should be limited to predicting unknown OEL values for the HI and used for material prioritization. It should not be extended to determinations of regulatory OELs.  相似文献   

14.
This report describes the development of a method for the determination and quantification of perfluoroalkyl substances (PFASs) in beer. A total of 93 beer samples were analyzed for the presence of PFASs by means of liquid chromatography tandem mass spectrometry. The results of this study have made it possible to calculate possible PFAS uptake via beer as well as the potential PFAS-related health risk as a result of beer consumption with regard to the tolerable daily intake (TDI) of perfluoro-n-octanoic acid (PFOA) (1,500 ng/kg bodyweight and day) and perfluorooctane sulfonate (PFOS) (150 ng/kg bodyweight and day). PFOS concentrations above the limit of quantification were detected in 50 % of the samples. The highest PFOS concentration detected in any of the beers was 18.4 ng/L, and the highest PFOA concentration was 56.9 ng/L. The calculated maximum uptake of both substances for which a TDI level exists were 2.44 ng/kg bodyweight/day for PFOA and 0.79 ng/kg bodyweight/day for PFOS assuming that an adult consumed his/her total daily liquid uptake exclusively by drinking 3 L of beer, equivalent to the maximum measured concentration (worst-case scenario). In regard to the model calculations made here, the maximum uptake of PFOA and PFOS via consumption of beer can be considered negligible at 0.85 % of the concentration that would be required to reach the TDI for PFOS and 0.16 % for PFOA.  相似文献   

15.
Metabolic footprinting coupled with statistical analysis was applied to multiple, chemically stressed activated sludge cultures to identify probable biomarkers that indicate community stress. The impact of cadmium (Cd), 2,4-dinitrophenol (DNP), and N-ethyl-maleimide (NEM) shock loads on the composition of the soluble fraction of activated sludge cultures was analyzed by gross biomolecular analyses and liquid chromatography-mass spectrometry (LC-MS). Fresh mixed liquor from four distinct treatment plants was each divided in four different batches and was subjected to no chemical addition (control) and spike additions of the stressors Cd, DNP, or NEM. The results indicate that chemical stress caused a significant release of proteins, carbohydrates, and humic acids from the floc structure into the bulk liquid. Using discriminant function analysis (DFA) with genetic algorithm variable selection (GA-DFA), the samples subjected to the different stress conditions plus control could be differentiated, thereby indicating that the footprints of the soluble phase generated by LC-MS were different for the four conditions tested and, therefore, were toxin-specific but community-independent. These footprints, thus, contain information about specific biomolecular differences between the stressed samples, and we found that only a limited number of m/z (mass to charge) ratios from the mass spectra were needed to differentiate between the control and each stressed sample. Since the experiments were conducted with mixed liquor from four distinct wastewater treatment plants, the discriminant m/z ratios may potentially be used as universal stress biomarkers in activated sludge systems.  相似文献   

16.
PCB and endosulfan concentrations in the chorioallantoic membrane (CAM) of white leghorn chickens (Gallus domesticus) were evaluated as indicators of hepatic cytochrome P450 isozyme activity in hens and chicks as well as toxicant concentrations in eggs and hens. Sixteen hens were randomly divided into four groups of four and dosed with a mixture of PCB105 (2,3,3',4,4'-pentachlorobiphenyl), PCB156(2,3,3',4,4',5-hexachlorobiphenyl), PCB189 (2,3,3',4,4',5,5'-heptachlorobiphenyl), and technical grade endosulfan (3:1 ratio of alpha and beta isomers) at three different dose groups. The first 10 fertile eggs laid by each hen were collected, the even-numbered eggs incubated until hatched, and the odd numbered eggs were analyzed for test chemicals. Strong (r2), significantly positive (p value) relationships were found between total PCB mass (ng) in CAMs and both total PCB concentrations (ng/g wet wt) in adults (r2 = 0.91, p = 0.0001) and eggs (r2 = 0.87, p = 0.0001). The relationship between total PCB mass in CAMs and hepatic cytochrome p450 isozyme activity in chicks (r2 = 0.49, p = 0.0001) and hens (r2 = 0.45, p = 0.014) was also significant but not as strong. This study shows that CAMs can be used to estimate avian exposure to PCBs and resultant biological response.  相似文献   

17.
Soybean (Glycine max (L) Merril) seeds are known to contain different proteins displaying antinutritional and/or toxic effects, such as soybean agglutinin (an N‐acetylgalactosamine‐specific lectin), proteinase inhibitors (Kunitz‐ and Bowman–Birk‐type trypsin and chymotrypsin inhibitors) and urease (seed and tissue isoforms). Two other toxic proteins were previously isolated from soybeans, soyatoxin (21 kDa) and soybean toxin (18.4 kDa), which are immunologically related to canatoxin, a toxic protein from Canavalia ensiformis (jackbean) seeds. In this work we have screened crude extracts from seeds of six different soybean cultivars, which together represent most of the crop harvested in the southern region of Brazil, for the presence of urease, trypsin inhibitory and haemagglutination activities, intraperitoneal toxicity in mice and immunoreactivity against anti‐canatoxin antibodies. Significant differences were found in the contents of proteinase inhibitors, lectin, urease activity and lethality in mice. The relevance of these findings to the agronomic qualities and to the choice of soybean cultivars to be used as food or feed is discussed. Copyright © 2004 Society of Chemical Industry  相似文献   

18.
Cu(II) is a key species with respect to the bioavailability and hence toxicity of copper. Therefore, it is important to elucidate the factors that control Cu(I) steady-state concentrations in natural waters. In this study, a solid-phase-extraction-based method was developed that allows Cu(I) measurements at ambient concentrations. Cu(I) is selectively enriched as a bathocuproine complex on a hydrophobic polymer column, whereas Cu(II), bound to ethylenediamine, is not retained on the column. After elution with acidic methanol, Cu is analyzed with graphite-furnace atomic absorption spectroscopy. The detection limit of the whole analytical procedure is below 1 x 10(-9) M, and the mean recovery of Cu(I) is approximately 70%. We then applied this method to determine Cu(I) in water samples collected from the River Scheldt estuary and the North Sea. Upon irradiation of these filtered water samples in the laboratory (with approximately 5 kW m(-2)), Cu(I) steady-state concentrations ([Cu(I)]ss) were established within a few minutes, and [Cu(I)]ss ranged from 5% to 80% of total dissolved copper, depending on the origin of the water samples. Measured [Cu(I)]ss can be interpreted by considering light-induced reduction of Cu(II) and stabilization of Cu(I) by chloride at high salinity, thermal reduction of Cu(II) by sulfide-containing compounds at low salinity, and fast reoxidation of Cu(I) due to stabilization of Cu(II) by strong organic ligands present at intermediate salinity.  相似文献   

19.
作为全球关注的新型面源污染之一,获得性抗生素抗性基因(AARGs)的水平转移成为食品安全领域近年来研究的新课题。发酵蔬菜是我国食品加工的重要组成部分,其发酵过程多样化的微生物参与为AARGs的传播和扩散转移提供了高风险的生态场所。为此,本文提出将AARGs作为威胁发酵蔬菜食品安全的一种新型污染物,对该类污染物的来源、潜在的传播途径以及国内外相关研究进行综述,并提出了当前形势下我国开展发酵蔬菜中AARGs污染研究的方向和防控建议。  相似文献   

20.
A new instrument to measure gaseous nitrous acid (HONO) in the atmosphere   总被引:1,自引:0,他引:1  
A new in situ instrument (LOPAP: long path absorption photometer) to measure gaseous nitrous acid (HONO) using wet chemical sampling and photometric detection has been developed. This instrument is aimed to overcome the known problems with current HONO measurement techniques and was designed to be a cheap, sensitive, compact, and continuouslyworking HONO monitorfor ambient air measurements in the troposphere or for measurements of higher concentrations e.g. in smog chambers, in exhaust gases, and in indoor environments. Laboratory investigations were carried outto characterize the instrument components with respect to collection efficiency, optimum dye formation, optimum detection, and interfering species. Detection limits ranging from approximately 3 to 50 pptV have been obtained with response times from 4 to 1.5 min, respectively, using different instrument parameters. The accuracy of the measurements is in the range between +/-(10-15)%. The validation of the instrument was performed in the laboratory for HONO concentrations of 3 and 30 ppbV using ion chromatography and with a DOAS (differential optical absorption spectrometer) instrument in a large outdoor smog chamber in the range from 0.1 to 20 ppbV. The deviations were well within the errors of the measurements; however, when comparing the data with the DOAS instrument systematically higher values were found with the LOPAP instrument.  相似文献   

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