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 31 毫秒
1.
Lai Y  Pan W  Ni S  Zhang D  Zhan J 《Chemosphere》2011,85(3):412-417
Though polychlorinated biphenyls (PCBs) have distributed as threats in the environment to human beings for several decades, monitoring of trace level PCBs in-field is still a challenge. As a potential method for monitoring PCBs at trace levels, Raman spectroscopy has been used to detect several PCBs in the laboratory. To facilitate the development of rapid detection of PCBs by Raman spectroscopy, it is essential to investigate the Raman spectra of all PCB congeners. Herein, the stable configurations and vibrational spectra of all the PCB congeners were calculated by Gaussian 03 program package. Based on molecular symmetry, PCBs are classified into seven groups. The structural features and the normal vibration modes for each group are discussed. Taking the C(2)-2 group as an example, the wavenumber ranges of the various normal vibration modes in the Raman spectra of PCBs were analyzed. The accuracy of calculated results was verified by experimental Raman spectra of PCB77 standard. This study can elucidate further information to promote the development of Raman spectroscopy in environmental monitoring.  相似文献   

2.
Dalian is a seaside city situated in the northeastern monsoon area of China. For the first time, levels of PCDD/F and PCB congeners in pine (Cedrus deodara) needles of Dalian urban areas were investigated. Two sampling campaigns with 17 sampling points were performed in 2002. The summation of tetra- to octachlorinated PCDD/Fs and summation of 209 PCB congeners in Dalian pine needles averaged 127+/-40 ng/kg (dry) and 4389+/-1575 ng/kg (dry), respectively. Average toxic equivalence (TEQ) for PCDD/Fs and PCBs are 2.1 and 0.4 ng/kg (dry), respectively. The pine needles can differentiate spatial variation of the pollutants. The PCDD/F and PCB levels in Dalian pine needles are low or comparable with other international regions that were not impacted by evident point sources. The data can serve as a base for long-term spatial and temporal studies of PCDD/Fs and PCBs in China.  相似文献   

3.
We measured the concentration of each polychlorinated biphenyl (PCB) congener in whole blood, plasma and blood cells, and investigated the distribution of PCBs in human blood using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). The PCB concentrations in plasma and whole blood in terms of lipid concentrations were almost equal, with a correlation coefficient of r = 0.972. In the blood, the ratio of PCBs in blood cells to those in plasma was generally about 1:9 and the congener distribution patterns in blood cells and plasma were similar.We performed verification of a simple mass screening method by obtaining information on the main PCB congeners for investigations on human accumulation and exposure. The total concentration of the seven PCB congeners (UNEP-7) proposed to the United Nations Environment Programme (UNEP) by Muir and Morita was about 50% of the total concentration of all PCB congeners, and UNEP-30 was about 80%. The seven main congeners in the blood (MCB-7) showed a value that was about 60%, and MCB-30 showed a value that was about 90%. Determinations with the main congeners in the blood showed a correlation of r = 0.990 or more between the main eight congeners (MCB-7 plus #74) and the total PCB concentration for all congeners. The results suggest that, although total PCB concentration can be effectively estimated from the main seven congeners, the main eight congeners would be preferable, and that the use of these congeners in the simple mass screening method would be effective for populations in areas uncontaminated by PCBs.  相似文献   

4.
Air concentrations of polychlorinated biphenyls (PCBs) in both gas and particle phases were measured in an urban site (BUTAL-Merinos) of the city of Bursa, Turkey between August 2004 and May 2005. The mean of total (particle+gas) PCB concentrations was about 491.8+/-189.4pg/m(3). The main contributors for PCBs in the sampling site were the local sources and long-range atmospheric transport supported by back trajectory analysis. Lower molecular weight PCB congeners generally dominated in the samples. The particle phase of the measured PCBs accounted for 15% of the total PCB concentrations. Gas/particle distribution was investigated using different approaches such as log K(P)-log P(L)(o), log K(P)-log K(OA) and the Junge-Pankow model. Regression analysis among log K(P), log P(L)(o) and log K(OA) exhibited significant correlation at p<0.05. Correlation between PCB homologs and meteorological parameters was formed to investigate the possible relationships.  相似文献   

5.
Lake sediments contaminated with polychlorinated biphenyls (PCBs) were purged using a gas stripping technique to estimate desorption rate constants. Desorption profiles and modeling of the data clearly show a two-step release of PCBs from sediment suspensions that can be described as a labile (fast) release followed by a non-labile (slow) release. Data are summarized by labile and non-labile rate constants and by mass in each phase as a function of suspended solids concentration for twelve pure congeners and nine co-eluting data sets (twenty-one chromatograph peaks total). Labile desorption rate constants range from 113 days(-1) to 1.43 days(-1) for the 100 mg/l sediment suspension, from 67.7 days(-1) to 2.45 days(-1) for the 1000 mg/l sediment suspension, and from 8.41 days(-1) to 0.946 days(-1) for the 5000 mg/l sediment suspension. Labile rate constants consistently decreased with increasing suspended solids, and, in general, decreased with increasing degree of chlorination (reflected in increasing retention time in the chromatogram). No consistent trend was observed for the non-labile rate constants with suspended solids concentration or degree of chlorination. The average non-labile rate constant for the PCB congeners studied here was 0.154 days(-1) (s.d.=0.158; n=63). The distribution between the labile and non-labile phases also failed to indicate dependence on suspended solids concentration, chlorine substitution pattern, or molecular weight of the congener, although the data from the 5000 mg/l suspension consistently contained less labile components. The average distributions (n=63) were 60.1% in the labile phase and 39.9% in the non-labile phase.  相似文献   

6.
Jiang Y  Wang X  Zhu K  Wu M  Sheng G  Fu J 《Chemosphere》2011,83(6):767-773
Surface soil samples taken from 55 sampling sites at the urban areas of Shanghai were collected and analyzed for the occurrence of 144 polychlorinated biphenyls (PCBs) by GC-μECD. The results showed that totally 74 PCB congeners were identified and the mean concentration of total PCBs was 3057 ng kg−1 with a range of 232 to 11325 ng kg−1. Compared with the related reports, the level of PCBs contamination in this study was approximately equal to the global background value in soils, but higher than Chinese background for rural and urban soils. According to the compositional profiles of PCBs homologues, a higher proportion of low chlorinated (from tri-CBs to hexa-CBs) was observed. The results indicated that PCB15 + 13, PCB18, PCB28, PCB104 + 47 and PCB153 were the most dominant congeners among the identified PCBs. Through homologues analysis, cluster analysis and principal component analysis (PCA), it was found that PCBs were stretched from mixed local sources, and appeared to be mostly originated by Aroclor 1260- and 1254-like mixtures as well as some samples influenced by Aroclor 1232 and 1242. The correlation analysis showed the relatively good correlation among the PCB homologues and soil total organic carbon (TOC), suggesting important influence of soil TOC on PCBs contamination in soil matrix in Shanghai region. The toxic equivalency (TEQ) concentrations of these six dioxin-like PCBs detected in urban soil samples range from 2.71 to 24.9 pg kg−1-PCDDeq with a mean 8.18 pg kg−1-PCDDeq.  相似文献   

7.
Wang DG  Yang M  Jia HL  Zhou L  Li YF 《Chemosphere》2008,73(1):38-42
Surface soil (0-5cm) samples from 14 sampling sites including rural and urban areas of Dalian, a coastal city in Liaoning Province, China, were collected and analyzed for 84 polychlorinated biphenyls (PCBs). Total 57 PCB congeners were identified and mean concentration of total PCBs among all the sites was 2.8mugkg(-1) dry weight (dw) with a range of 1.3 (rural site) to 4.8mugkg(-1)dw (urban site). For the urban sites, total PCB concentrations in the soil samples collected in industrial area are highest, followed by those from business/residential sites and the garden sites, but the differences are not significant. Higher percentage of lighter weighted molecular PCBs were found in the rural site than urban sites in Dalian, possibly indicating the "urban fractionation effect". Total seven dioxin-like PCBs (CB-77, 81, 105, 114, 118, 123, and 126) have been found in Dalian soils and the mean concentration (in mugkg(-1)dw) among all the sites of CB-105 (0.17) is higher than any other dioxin-like PCBs, followed by that for CB-81 (0.14) and for 118 (0.06). No significant correlation relationship between the concentrations of dioxin-like PCBs and those of total PCBs was found. The toxic equivalency (TEQ) concentrations (in ngkg(-1)dw) of these seven dioxin-like PCBs in 14 soil samples range from 0.006(7) to 4.885(7) (with a mean 1.372(7)) for humans and mammals, from 0.001(7) to 0.37(7) (with a mean 0.14(7)) for fish, and from 0.01(7) to 31.47(7) (with a mean 17.23(7)) for birds.  相似文献   

8.
Desorption of PCBs from sediment can significantly affect the ultimate fate and effects of PCBs in aquatic systems. Using a gas purging technique to strip soluble and sorbed polychlorinated biphenyls (PCBs) from solutions and sediment suspensions, Henry's law constants, approach to equilibrium, and desorption rate constants for four PCB congeners were measured. Henry's law constants were on the order of 10−4 m3 atm mole−1. Desorption rate constants measured for a predominantly kaolinitic, low-organic carbon sediment were on the order of 0.03–0.1 days−1. In contrast, desorption rate constants measured for a sediment composed of montmorillonite with a 3% organic carbon content were on the order of 0.009–0.04 days−1. Desorption data suggest that equilibration times for PCBs with low chlorine content are on the order of six weeks, and months to years for PCBs with a significantly higher chlorine content.  相似文献   

9.
This study characterizes the levels of polychlorinated biphenyls (PCB) congeners PCB 77, PCB 81, PCB 126, and PCB 169, in a group of 150 men and women with no documented exposure to PCBs. Its purpose is to provide current referent levels of coplanar PCBs in Missouri residents and to compare those levels to levels reported in the literature from the United States and other countries. Although this study used an extensive questionnaire assessing potential sources of exposure, no positive relations were found between these exposure sources and participants' PCB levels. The PCB levels for the four congeners measured were lower than any reported in the literature. PCBs 126 and 169 are only two of the dioxin-like congeners; however, their contribution makes up 11% of the total TEQ. Age was significantly related to PCB 126 and PCB 169. For every one-year increase in age, both PCB congeners increased by approximately 0.4 parts per trillion (ppt). There was no gender difference for PCB 126; however, PCB 169 levels were 3 ppt higher in males than females.  相似文献   

10.
Various tissues from a deceased Yucheng (oil disease) patient were analyzed for individual polychlorinated biphenyl (PCB) and dibenzofuran (PCDF) congeners. With a few exceptions, PCBs with 5 or less chlorine atoms were almost completely excreted from the patient's tissues about two years after the ingestion of the toxic oil. In contrast, most PCB congeners with 6 or more chlorine atoms were retained in the tissues. The intestinal fat contains the highest level of PCBs while the liver contains the highest concentration of PCDFs. The major PCDF congeners retained in the tissues were 1,2,3,4,7,8-hexaCDF, 2,3,4,7,8-pentaCDF, and 1,2,4,7,8-pentaCDF. The former two congeners, especially 2,3,4,7,8-pentaCDF, are very toxic PCDFs; they may play important roles in the etiology of Yucheng.  相似文献   

11.
Fu S  Yang ZZ  Li K  Xu XB 《Chemosphere》2008,73(6):962-966
Sandstorms, which distribute many particles, are a special atmospheric occurrence and are frequent in northern China. We conducted this study to determine, for the first time, the concentration of polychlorinated biphenyls (PCBs) in sandstorm depositions. We collected 13 samples from urban areas of Beijing, and we measured a total of 144 PCB congeners. Thirteen samples all contained PCB residues. The total PCB concentration ranged from 1.6 to 15.6ngg(-1) (median, 4.8ngg(-1), dry weight), with trichlorinated biphenyls as the predominant homologue (>50.4%). Furthermore, we observed increasing PCB contamination from northwest to east Beijing. We later explored possible factors affecting contamination of the sandstorm depositions, which revealed a significant correlation between SigmaPCBs and the minimum particle size of the sandstorm deposition samples. Principal-component analysis revealed that the major source of PCBs in Beijing may be potentially associated with the number-one commercial PCB through the long-range transmission. In previous results, PCBs were not a severe component of contamination in sandstorm depositions of Beijing. However, this study suggested that sandstorm deposition may be a potential source of exposure to PCBs for the residents of Beijing, China.  相似文献   

12.
Computerized methodologies for the quantification of total PCBs, PCB in Aroclor mixtures and individual PCB congeners in environmental samples are presented. The method for total PCBs is based on a multiple-linear regression analysis using data from capillary gas chromatography of Arocolor standards. PCB congeners were identified and their weight percentages determined in Aroclor mixtures by GC/MS. PCB congeners and total PCBs were accurately quantified in predetermined test data and environmental samples.  相似文献   

13.
Li Z  Kong S  Chen L  Bai Z  Ji Y  Liu J  Lu B  Han B  Wang Q 《Chemosphere》2011,85(3):494-501
A total of 82 surface soil samples collected from central urban sites, surrounding rural sites, coastal sites and background sites in Tianjin were analyzed for 84 PCB congeners. The mean values of total PCBs concentrations for surrounding rural sites, central urban sites, coastal sites, background sites and the whole Tianjin region were 4.45, 3.20, 12.65, 1.96 and 4.02 ng g(-1), respectively. No "urban fractionation effect" was found in Tianjin, which reflected the influence of local emission sources for PCBs such as industries and township enterprises in surrounding rural sites. In contrast, a "primary fractionation effect" was found in Tianjin region. The PCBs concentrations for whole Tianjin region showed a strong east-west gradient and the percentages of lighter molecular weight PCBs homologs (sum of di- to tetra-PCBs) to the total PCBs concentrations increased from east to west. The seven indicator PCBs concentrations were well correlated with the total PCBs concentrations with the correlation coefficients as 0.76 for Tianjin region and 0.74 for central urban sites, respectively. Predominant PCB homolog groups were penta- and tri-PCBs for Tianjin region. 10 dioxin-like PCBs concentrations were well correlated with total PCBs concentrations for all the sampling sites (R=0.79, P<0.0001). The TEQ concentrations for 10 dioxin-like PCBs were 5.3424 ng kg(-1) for Tianjin region and showed a strong east to west gradient. The spatial distribution of PCBs levels, homolog composition patterns and TEQ concentrations were all obviously influenced by local emission sources for PCBs in the east part of Tianjin region.  相似文献   

14.
Polychlorinated biphenyl (PCB) patterns were interpreted in two radioisotopically constrained sediment cores from the Arctic ocean in order to seek clues about their large-scale environmental fates. Low but clearly measurable fluxes of individual PCB congeners were observed in deeper layer sediments, corresponding to the past 170 years, in a single dated core from the Baffin Bay shelf. Fluxes of the dominant individual congeners in the surface sediments were 20-100 pg m(-2) d(-1). Combining these data with the sediment data from the Arctic Monitoring and Assessment Program, it appears that the PCB distribution in Arctic surface sediments is governed by the organic carbon (OC) content of the sediments. The historical development of the PCB congener fingerprint suggests that the modern sediments are enriched in medium-chlorinated congeners, implying that there are at least two significant, but distinctly different, sink processes acting on the PCB pool. The relative abundance of light-to-heavy congeners, in mid-shelf marine sediments of similar ages, between 40 degrees N and 76 degrees N latitude suggests a northward dilution of PCBs which is stronger attenuated for heavier congeners, consistent with a temperature-driven global fractionation process. The significant presence of PCB in historical archives pre-dating the organochlorine society, as observed in this and several previous studies, awaits a fuller explanation.  相似文献   

15.
We conducted a congener-specific analysis of non-dioxin-like polychlorinated biphenyls (non-dioxin-like PCBs) in blood collected between July 2002 and July 2004 from 195 pregnant women living in Sapporo City of Hokkaido Prefecture, Japan. The present study is one of the few studies in which full congener concentrations of non-dioxin-like PCBs have been measured in the blood of pregnant women. Of the 195 pregnant women, 101 were primipara (mean: 28.8 years, median: 28.0 years) and 94 were multipara (mean: 32.3 years, median: 33.0 years). Among the 197 non-dioxin-like PCB congeners, 58 congeners were identified in the blood of pregnant women. The arithmetic mean total concentrations of 58 non-dioxin-like PCB congeners in the blood of primiparous and multiparous mothers in Sapporo City were 42.2-329.3 (mean: 114.5, median: 98.6) and 31.5-258.0 (mean: 100.3, median: 91.4)ngg(-1)lipid, respectively. The results show that the contamination of non-dioxin-like PCBs in the blood of women has decreased compared to past levels in other domestic areas, in which the subject age was similar to that in this study. The results of the present study indicate that current levels of non-dioxin-like PCBs in the blood of Japanese women and can be used as baseline data for future temporal trends. The sums of the ratios of the concentrations of hexaCBs and heptaCBs to the total concentrations of 58 non-dioxin-like PCB congeners in the blood of primiparous and multiparous mothers were 78.5% and 77.7%, respectively. The hexaCBs ratios in the blood of primiparous and multiparous mothers were 45.4% and 44.7%, respectively. HexaCB-153 among hexaCBs congeners, the most abundant congener in the blood of primiparous and multiparous mothers, contributed approximately 22.0% and 21.8% to the total concentrations of 58 non-dioxin-like PCBs congeners that were measured in the blood, respectively. Among the non-dioxin-like PCB congeners measured in the present study, hexaCB-138, heptaCB-170, heptaCB-180, and heptaCB-182/heptaCB-187 also showed high ratios to total concentrations of 58 non-dioxin-like PCB congeners detected in the blood of primiparous and multiparous mothers. With regard to the relationship between the total concentrations of 58 non-dioxin-like PCB congeners in maternal blood and the number of deliveries or the age of primiparous and multifarious mothers, the total levels of these PCB congeners tended to decreases with increases in the number of deliveries and significantly increased with increasing maternal age in both groups. Furthermore, significant correlations were observed between the total concentrations of these PCB congeners in blood and the age of primiparae and multiparae. The concentrations of hexaCB-153 in the blood of primiparous and multiparous mothers showed a close correlation to the total concentrations of these PCBs, suggesting that hexaCB-153 could be an indicator of total concentrations of non-dioxin-like PCB congeners in the blood of pregnant women.  相似文献   

16.
Chen IM  Chang FC  Wang YS 《Chemosphere》2001,45(2):223-229
To understand the dechlorination ability of chlorobenzenes (CBs) and polychlorinated biphenyls (PCBs) by untamed microorganisms under anaerobic condition and to correlate gas chromatographic properties with the occurrence of reductive dechlorination, introduction of CBs and PCBs in the culture medium inoculated with microorganisms from sludge and sediment, respectively, were performed. Three kinds of culture media preparing from sludge, river water and a synthetic medium were used in the experiments. HCB was degraded to 1,3,5-trichlorobenzene (1,3,5-TCB) and 1,3-dichlorobenzene (1,3-DCB) in both sludge medium and synthetic medium with inoculated microorganisms. Three PCB congeners including 2,3,4-, 3,4,5- and 2,3,4,5-CBp (chlorinated biphenyl) were not found to be dechlorinated in the river water medium with inoculation culture but to be dechlorinated in the synthetic medium. MNDO methodology was used to compute theoretical dechlorination reaction heats and GC-ECD techniques were used to estimate chromatographic data of CB and PCB congeners. Both CB and PCB congeners showed that dechlorination by untamed microorganisms under anaerobic mixed cultures were more likely to occur when larger amounts of energy were released and greater deltaln RRT value between the parent congener and the daughter product was observed. Deltaln RRT provided a more precise information on the singularity of PCBs ortho-dechlorination in an aspect of thermodynamic favorable rule.  相似文献   

17.
A. Perdih  J. Jan 《Chemosphere》1994,28(12):2197-2202
In silicone rubber crosslinked with bis(2,4-dichlorobenzoyl) peroxide (DCBP) as initiator about 0.1% of DCBP is converted into polychlorobiphenyls (PCBs). The PCB content in silicone rubber determined by high resolution gas chromatography (HRGC) after its destruction by HF is around 10 mg/kg. 29 PCB congeners were detected. Instead of the expected PCB-47, lower chlorinated congeners are predominant. Some possible pathways of their origin are presented.  相似文献   

18.
Kim M  Kim S  Yun S  Lee M  Cho B  Park J  Son S  Kim O 《Chemosphere》2004,54(10):1533-1538
The risk assessment of polychlorinated biphenyls (PCBs) is difficult since complex congeners were used in many industrial applications for a long period of time and the residue monitoring in foods of animal origin and the environment were not established in comparable systems. The relationships of determined concentrations in indicator PCB congeners (mono- and di-ortho PCBs) and coplanar PCB congeners (non-ortho PCBs) in livestock products are presented in this study. The concentrations of seven indicator PCBs were compared with three coplanar PCBs in beef, pork, and chicken fat. Distributions of concentration for the indicator PCBs in three different animal species were similar except for that of PCB-118 (2,3',4,4',5-pentachlorobiphenyl) in pork fat. The congeners with the highest concentration were PCB-138 (2,2',3,4,4',5'-hexachlorobiphenyl) in beef and pork fat and PCB-28 (2,4,4'-trichlorobiphenyl) in chicken fat. The bioaccumulation and metabolism of PCBs in animal species represent different congener profiles in livestock products. The percentage of the total concentration of three coplanar PCBs was about 2% of the total concentration of the seven indicator PCBs. Relatively high concentration of mono-ortho and di-ortho PCBs in fat samples of livestock products may be calculated with the concentration of coplanar PCBs that can be usually determined on a sequential procedure with dioxin analysis. Therefore, the relationship of the amounts between seven indicator PCBs and three coplanar PCBs may be useful to derive the composition and level of contaminants in beef, pork, and chicken.  相似文献   

19.
Polychlorinated biphenyls (PCBs) are persistent and hazardous environmental contaminants, which tend to bioaccumulate in the food chain. In the present report the long-term effect of low-level dietary PCB concentrations was studied on performance, egg quality, apparent PCB digestibility, apparent PCB retention and PCB accumulation in laying hens that were fed experimental diets for 41 weeks. The tested dietary concentrations of supplemented PCBs, based on the sum of seven reference congeners, were 0, 1.5 and 6 ng/g. PCB ingestion did not significantly affect performance or egg quality parameters. The PCB concentration in egg yolk reached a nearly constant level after approximately 40 and 70 days of consumption of the diets containing 1.5 and 6 ng PCBs/g, respectively. Apparent faecal PCB digestibility and apparent retention were not influenced by dietary levels of added fat varying between 1.5% and 4.5%, but were significantly higher in hens fed diets containing added PCBs. Moreover, apparent PCB digestibility and retention increased significantly with age. Among the seven individual PCB congeners, no systematically significant differences with regard to apparent faecal digestibility were observed throughout the experiment. Accumulation of PCBs in the fat fraction of egg yolk, abdominal adipose tissue and thigh and breast muscle greatly depended upon PCB intake, but never exceeded the maximally allowed concentration of 200 ng/g. As PCBs 52 and 101 were hardly found in egg yolks and hen tissues, it was concluded that both congeners were greatly metabolised. Comparison of relative contents of individual PCB congeners revealed that PCBs 118, 138 and 153 were preferentially incorporated in yolk and body tissues.  相似文献   

20.
Park H  Lee SJ  Kang JH  Chang YS 《Chemosphere》2007,68(9):1699-1706
The objective of this study was to evaluate all congeners of polychlorinated biphenyls (PCBs) in human serum samples. Concentrations of all PCB congeners in the serum of 87 volunteers were determined by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). The participants consisted of 47 males and 40 females, including 25 men working at municipal solid waste incinerators (MSWIs). The mean concentrations of total PCBs and dioxin-like PCBs were 242.77ng/g lipid (median: 180.17ng/g lipid) and 18.57ng/g lipid (median: 15.34ng/g lipid), respectively. Penta-, hexa-, and heptachlorinated biphenyls contributed more than 80% of the total PCBs detected in human serum. Congener-specific analysis indicated that PCB153, PCB138, PCB180, PCB187, and PCB118 contributed 57.3% of the total PCBs detected in human serum samples. A statistical analysis was performed to determine whether there were significant correlations between PCB concentrations and specific variables such as age, gender, smoking habits, occupation, and body mass index (BMI). However, serum PCB concentrations correlated only with age. In addition, we found that total PCBs and dioxin-like PCBs highly correlated with PCB153 (correlation coefficient r=0.93, p<0.01) and PCB118 (correlation coefficient r=0.98, p<0.01), respectively. Thus these two congeners could be satisfactory indicators for total PCBs and dioxin-like PCBs in human serum.  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