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1.
For modelling isotopic variations in oils it is convenient to differentiate the effects of oil generation ( 100–150°C) from the effects of oil to gas cracking ( 150–180°C). During generation, δ13C of kerogen may increase by up to 1% due to release of isotopically light oil and gas, although most kerogens show little or no chan δ13C of the generated oil increases by between 0 and 1% (av. 0.5%) due to mixing of isotopically heavy oil with an initial isotopically light unbound fraction, possibly of bacterial origin. The change occurs mostly over the first 20% of generation. During oil to gas cracking, kinetic isotope effects become important and the effect on δ13C of the remaining oil can be modelled as a Rayleigh process. δ13C increases by 1.5% by 50% cracking. Insufficient data are available to calibrate the effects at higher levels of cracking, and modelling these variations is hindered by a lack of understanding of the mechanism of pyrobitumen formation. However, increases greater than about 4% are unlikely to be observed. With increasing maturity, the low molecular weight fractions become isotopically heavy faster than the high molecular weight fractions. As a result, any separation of the low molecular weight fraction into a gas phase (“condensate formation”) will produce an isotopic difference between oil and condensate that depends on maturity. In the early stages of generation the condensate may be up to 1% lighter than the remaining oil. With increasing maturity, this difference at first decreases and then increases in the opposite sense. By half way through oil to gas cracking the condensate may be 1.5% heavier than the residual liquid. More subtle rearrangement reactions may result in small, but significant, changes to the shape of the isotope “type-curves” when different oil fractions are compared.  相似文献   

2.
Jurassic coals, coaly shales, shales and claystones from the Eastern Pontides in NE Turkey have been investigated using microscopical, petrophysical and detailed organic geochemical methods in order to determine their catagenetic stage, to reveal the composition of the organic matter and to discuss the depositional environment. The Liassic–Dogger period in the Eastern Pontides was characterised by the presence of a rift system which resulted in rock units of very variable lithology and facies. Coal seams, ranging from a few centimetres to several decimetres and intercalated with shales, claystones and sandstones occur within the basal part (the Aggi Formation) as well as in the uppermost part (the Hamurkesen Formation) of the rift deposits. All coal seams investigated are at a catagenetic maturation stage corresponding to subbituminous B up to low volatile bituminous ranks. They represent a depositional environment of short-lived swamp areas with intense aerobic reworking of the higher plant detritus by heterotrophic bacteria, but with possible anaerobic microenvironments at deeper levels. At least some coal seams were influenced temporarily by marine ingressions. Most samples are impure humic coals with highly variable chemical compositions as indicated by the broad range of their hydrogen contents. This variation in hydrogen content is partly attributed to variable contributions of algal material. On the other side, considering several analytical results, the hydrogen variation is primarily due to bacterial reworking that affected the composition of the organic matter to variable extent and resulted especially in an enrichment of bacterial lipids. Bacterial reworking by an active microbial community within the upper layer of the peat swamp is inferred from elevated concentrations of iso-alkanes even exceeding those of the corresponding n-alkanes in several samples which, to the best of our knowledge, have not been observed with coals before.  相似文献   

3.
塔里木盆地克拉通区天然气碳同位素与成熟度关系探讨   总被引:4,自引:5,他引:4  
周兴熙  王红军 《地球化学》1999,28(6):571-579
气藏中天然气碳同位素的轻重不仅反映了母质继续效应和成熟效应,同时也取决于累积、散失、混合效应。塔里木盆地3个古隆起(中、 塔北和巴楚)区的天然气均主要来自寒武系一下奥陶统烃财。塔中地区保存条件好,天然气聚集时期长,为连续聚气区,其累积效应强,碳同位素普遍偏轻;塔北和 扎塔格地区保存状况相对较差,天然气聚集期短,累积效应弱,碳同位素值重了区。塔中北皮一些奥陶第 藏由于有中上奥陶统生成的低熟气-生物气  相似文献   

4.
A maturity indexing procedure based on the isotopic difference between the total accumulated methane produced by exhaustive pyrolysis and the kerogen (Δ13C) and the mole ratio of methane to kerogen carbon (CMR), has been tested by applying a standardized technique, i.e. exhaustive pyrolysis (600°C for 120 hr) of extracted-powdered samples and measurement of the amounts and isotopic composition of the methane and kerogen carbon, on a suite of 15 Bakken shale samples.A linear relation was found between the carbon mole ratio of pyrolysis-derived methane and total organic carbon and the δ13C difference between the pyrolysis-derived methane and total organic carbon (r = −0.79); and between the amount of CH4 generated from exhaustive pyrolysis and H/C atomic ratios (r = +0.91).  相似文献   

5.
Thermal maturity was determined for about 120 core, cuttings, and outcrop samples to investigate the potential for coalbed gas resources in Pennsylvanian strata of north-central Texas. Shallow (< 600 m; 2000 ft) coal and carbonaceous shale cuttings samples from the Middle-Upper Pennsylvanian Strawn, Canyon, and Cisco Groups in Archer and Young Counties on the Eastern Shelf of the Midland basin (northwest and downdip from the outcrop) yielded mean random vitrinite reflectance (Ro) values between about 0.4 and 0.8%. This range of Ro values indicates rank from subbituminous C to high volatile A bituminous in the shallow subsurface, which may be sufficient for early thermogenic gas generation. Near-surface (< 100 m; 300 ft) core and outcrop samples of coal from areas of historical underground coal mining in the region yielded similar Ro values of 0.5 to 0.8%. Carbonaceous shale core samples of Lower Pennsylvanian strata (lower Atoka Group) from two deeper wells (samples from ~ 1650 m; 5400 ft) in Jack and western Wise Counties in the western part of the Fort Worth basin yielded higher Ro values of about 1.0%. Pyrolysis and petrographic data for the lower Atoka samples indicate mixed Type II/Type III organic matter, suggesting generated hydrocarbons may be both gas- and oil-prone. In all other samples, organic material is dominated by Type III organic matter (vitrinite), indicating that generated hydrocarbons should be gas-prone. Individual coal beds are thin at outcrop (< 1 m; 3.3 ft), laterally discontinuous, and moderately high in ash yield and sulfur content. A possible analog for coalbed gas potential in the Pennsylvanian section of north-central Texas occurs on the northeast Oklahoma shelf and in the Cherokee basin of southeastern Kansas, where contemporaneous gas-producing coal beds are similar in thickness, quality, and rank.  相似文献   

6.
Purification protocols to extract pollen from lake sediments contain chemicals that alter the carbon and oxygen pollen-isotope values according to pollen characteristics and family affiliation. Modern (raw) pollen of broad-leaved (Alnus glutinosa, Betula pendula, Carpinus betulus, Corylus avellana, Fagus sylvatica and Quercus robur) and coniferous tree species (Picea abies and Pinus sylvestris) were treated with potassium hydroxide (KOH), hydrofluoric acid (HF), sodium hypochlorite (NaClO) and sulphuric acid (H2SO4) to test the impact on δ13Cpollen and δ18Opollen and assess the applicability in purification protocols. Pollen of broad-leaved and coniferous trees reacted differently to chemical exposure, but response patterns are generally alike. Alterations of δ13Cpollen values vary between + 1.0‰ (B. pendula, NaClO-treatment) and −5.0‰ (P. sylvestris, H2SO4-treatment). The δ13Cpollen values of raw and chemically treated samples seem to be related after treatments with KOH, NaClO and HF, whereas the application of H2SO4 led to inconsistent changes among species. The impact of chemicals on δ18Opollen are more diverse and offsets range between +1.1‰ (C. avellana, NaClO-treatment) and −17.9‰ (P. sylvestris, H2SO4-treatment). In general, the use of isotope-altering chemicals in purification protocols should be brought to a minimum, but the application of KOH and NaClO seems mostly unproblematic before δ13Cpollen and δ18Opollen analysis.  相似文献   

7.
Stable carbon isotopic composition of organic matter (δ13Corg) and compound-specific δ13C values of biomarkers from 15 lacustrine source rocks were analyzed to identify the original paleoenvironment and source organisms. The δ13C values of hopanes (δ13Chop) ranged from −68.7‰ to −32‰ and exhibit strongly 13C-depleted values in the lower part of Member 1 of the Nenjiang Formation (K2n1, up to −68.7‰), suggesting an origin from predominantly methanotrophic bacteria. 13C-enriched δ13CGa values and significantly 13C-depleted δ13Chop in K2n1, which coincide with water stratification and an intermittent anoxic photic zone, represents a shallow chemocline. The presence of an intermittent anoxic photic zone, which means that the anoxia expanded into the euphotic zone, is beneficial for OM preservation and results in high values of TOC and HI in this section. However, the absence of gammacerane and 13C-enrichment of δ13Chop in Member 2 of Nenjiang Formation (K2n2) reflect a deeper chemocline, corresponding to relatively oxidizing conditions and low values of TOC and HI. Moreover, the negative correlation of TOC vs δ13Corg and HI vs δ13Corg reflects the control of OM formation by sedimentary environments rather than productivity in the water column. Thus, the depth of the chemocline not only controls the abundance of OM but also affects the development of the microbial community, such as chemoautotrophic bacteria in the deep chemocline and chemoautotrophic and methanotrophic bacteria in the shallow chemocline. Moreover, δ13CGa and δ13C values for 4-methyl steranes are related to water salinity, with a higher salinity accompanied by 13C-enrichment in gammacerane and 4-methyl steranes.  相似文献   

8.
中国煤和烃源岩镜质组的激光诱导荧光显微特征及其应用   总被引:1,自引:1,他引:1  
应用自行组装的激光诱导荧光显微光度计(LIFM)系统地研究了中国煤和烃源岩中镜质组的荧光强度及荧光变化,建立了镜质组的荧光变化与成熟度之间的相关模式图(R-I-VRo),该图可解决镜质组反射率抑制问题,并将烃源岩成熟度评价范围扩展到VRo达2.0%左右,该方法对于正确评价烃源岩成熟度具有广泛的应用前景。  相似文献   

9.
In order to investigate the distribution characteristics of stable carbon isotope ratios (δ 13C) in the desert plant Reaumuria soongorica, the δ 13C values of leaves were measured in 407 individuals of 21 populations. Soil physicochemical properties including soil water content, soil total dissolved solids, soil total nitrogen, soil total phosphorus and soil organic content were also analyzed in order to survey the major factors influencing δ 13C values on spatial variation. Leaves and soil samples were simultaneously collected from the ten major distribution areas in Northwest China at altitudes from 394 m to 1 987 m above sea level, at latitudes from 36°10′N to 44°33′N, and at longitudes from 81°43′E to 106°37′E. These ten areas include Shihezi, Baicheng, Yiwu areas in Xinjiang Uygur Autonomous Region; Anxi, Zhangye, Baiyin, Lanzhou areas in Gansu Province; Shapotou, Yinchuan areas in Ningxia Hui Autonomous Region; and Alashan County in Inner Mongolia Autonomous Region. The results show that the δ 13C value of R. soongorica ranges from −22.77‰ to −29.85‰ with an average of −26.52‰. Foliar d13C values in R. soongorica are not significantly correlated with altitude, latitude or longitude, and a spatial distribution trend of d13C values of R. soongorica is not obvious on a large scale. However, when d13C values of two R. soongorica populations under the same climate conditions are compared, δ 13C values increase obviously from east to west and from north to south. As none of the soil total dissolved solids, soil total nitrogen, soil total phosphorus, and soil organic content shows a uniform trend from east to west and from north to south, we suppose that the small-scaled spatial distribution pattern of δ 13C values of R. soongorica is mainly controlled by the soil water content. Translated from Quaternary Sciences, 2006, 26(6): 947–954 [译自: 第四纪研究]  相似文献   

10.
本文选用了镜质组反射率在0.77%-1.88%之间5 种不同成熟度的煤, 将其制成民用蜂窝煤球, 研究民用蜂窝煤燃烧排放颗粒物(PM)的化学组成, 包括元素(C、N、O、S)、有机碳(OC)、元素碳(EC)和水溶性无机离子(WSII), 稳定碳同位素组成特征和质量吸收效率值(MAE), 并讨论了它们与煤成熟度之间的关系.结果表明, 5 种原煤C、N、O、S 元素组成差别不大, 但是燃烧后排放的PM 化学组成差别比较大.无烟煤燃烧排放的PM 粒径分布呈双峰结构, 峰值分别在0.09 μm 和0.25 μm; 而烟煤PM 的峰值为0.58 μm.无烟煤排放PM 的颗粒数远小于烟煤.PM、OC 和EC 的排放受煤成熟度的影响非常大, 无烟煤排放的量最小, 分别为2.21 g/kg、0.22 g/kg 和0.004 g/kg; 成熟度最低的烟煤排放量最大, 分别为70.3 g/kg 、46.1 g/kg 和2.42 g/kg.PM、OC 和EC 的排放因子与煤的成熟度成幂指数关系.EC 的MAE 在0.17-21.9 m^2/g 之间, 与煤成熟度呈指数相关关系.燃煤WSII 的平均排放因子为801 mg/kg, WSII 当中含量最高的是NH4^+ 和24SO4^2- , 平均分别占WSII总量的23.5%和44.4%.燃煤排放PM 的δ^13C 变化范围为–24.5‰-–22.8‰, 平均值为–23.6‰.以上研究有助于人们从原煤性质的角度去考察民用燃煤对人类健康和气候变化的影响, 并为大气污染源解析提供一些科学依据.  相似文献   

11.
为探究青藏高原搭格架地热区地热水、湖水、河水、冰雪融水等天然水体的水化学组成及物质来源控制因子,于2014年8月对该地区进行了考察和取样。利用紫外-可见光分光光度计和ICP-OES测定了水样中各阴、阳离子含量,利用Gas Bench连接同位素质谱仪测定了水样中溶解无机碳(DIC)同位素比值。结果表明,地热水中总溶解固体(TDS)含量为977.13~1 279.50 mg/L,阳离子以K+和Na+为主,阴离子以HCO3-和Cl-为主,湖水的TDS含量为77.81~810.94 mg/L,阳离子以Na+和Ca2+为主,阴离子以HCO3-(CO32-)和SO42-为主,地热水和湖水的水化学类型为HCO3-Na型;河水和冰雪融水的各离子含量较低,水化学类型为HCO3-Ca型;地热水的DIC浓度范围为9.2~15.4 mmol/L,δ13CDIC值为-9.09‰~-0.95‰;湖水的DIC浓度为1.1~9.7 mmol/L,δ13CDIC值为-8.84‰~-0.27‰。根据水化学Gibbs分布模式图判断出区域水化学特征主要受硅酸盐岩风化控制,以钠长石和钾长石风化为主,但是地热水的水化学组分受到硅酸盐岩和蒸发盐岩共同控制。通过碳同位素比值分析对区域主要风化过程中CO2的来源示踪表明,湖区周围的硅酸盐风化其碳源主要为土壤CO2,热泉区硅酸盐水解其碳源为地球深部CO2输入。   相似文献   

12.
重庆地区岩溶地下河水溶解无机碳及其稳定同位素特征   总被引:3,自引:3,他引:3  
蒲俊兵 《中国岩溶》2013,32(2):123-132
稳定碳同位素是指示岩溶动力系统碳来源及转化的重要指标。为揭示重庆地区岩溶地下水中溶解无机碳基本特征和碳来源,本文对该地区63条岩溶地下河水样进行了水化学和碳同位素分析。研究结果表明,重庆地区地下河水溶解无机碳主要表现形式为HCO3-,雨季由于稀释作用其浓度低于旱季。重庆岩溶地下河水δ13C-DIC(V-PDB)旱季变化范围为-15.34 ‰~-5.89 ‰,雨季变化范围为-17.40 ‰~-4.23 ‰。根据δ13C同位素质量平衡方法,计算得到重庆地下河旱季碳酸盐岩溶蚀对DIC贡献为45.1 % ~79.7 %,雨季平均为34.6 %~82.1 % 。计算结果表明,在人类活动不断增强的情况下,岩溶水体DIC通量中碳酸盐岩溶解来源的DIC和其参与岩溶地下水δ13C值的形成并不一定是岩溶作用理论方程中所计算的50 %,而是有一定的变化范围。因此在计算岩溶作用碳汇时,建议通过δ13C值扣除碳酸盐岩溶蚀形成DIC的通量后再来推算岩溶作用形成的碳汇量。  相似文献   

13.

This study uses carbon isotope chemostratigraphy to propose an age for the Success Creek Group and Crimson Creek Formation in the absence of any direct radiometric dates, palaeomagnetic or reliable palaeontological data. The δ13C values were determined for the least‐altered dolomite samples. Suitable samples were selected on the basis of grainsize, cathodoluminescence petrography, most enriched δ18O values (> 2%o) low Mn/Sr ratios and low Fe and Mn concentrations. The average least‐altered, most 13C‐enriched dolomicrite samples in the youngest (No. 1) dolomite horizon are + 4.6%o. This is typical of Neoproterozoic (but not Cambrian) carbonates. The δ13C values of all dolomite samples in the succession are significantly positive (up to + 7.5%o) and the excursion characteristic of the Proterozoic/Cambrian boundary has not been observed. The lack of negative δ13C values in all dolomite samples studied also suggests an absence of correlatives of Sturtian and Varanger tillites in the dolomite successions. The δ13C values in all three dolomite horizons suggest a Neoproterozoic age between about 820 to 570 Ma (Cryogenian to Neoproterozoic III) on the current global compilation carbon isotope curves. This age for the Success Creek Group and Crimson Creek Formation, inferred from carbon isotope chemostratigraphy, can be substantiated by other evidence. The age of the Renison dolomites is constrained by K‐Ar dates of 708 ± 6 Ma from detrital muscovite in the underlying Oonah Formation and 588 ± 8 and 600 ± 8 Ma from doleritic rock in a lithostratigraphic equivalent of the Crimson Creek Formation from the Smithton Basin. Furthermore, acritarchs and the stromatolite Baicalia cf. B. burra also suggest a Neoproterozoic rather than Cambrian age.  相似文献   

14.
贺兰山地区树轮碳氧同位素与夏季风降水的相关性讨论   总被引:1,自引:0,他引:1  
分析了贺兰山地区油松树轮的稳定碳氧同位素组成对环境因素的响应关系 , 发现树轮碳氧同位素组成均与当年 5~ 9月总降水量具有较好的响应关系 , 碳同位素组成与 5~ 9月总降水量呈负相关关系 ,而氧同位素组成与 5~ 9月总降水量呈正相关关系 ,二者都可较好地反映该地区夏季风降水量的变化.同时 ,碳氧同位素的相关性分析表明二者具有一定程度的负相关性.树轮碳氧同位素的分馏机理十分复杂,其同位素组成不仅与降水量有关,同时还受其他环境因素的影响,单纯利用一种同位素指标来提取相应的气候信息,存在很大的不确定性.在本研究中 ,同时采用两种同位素指标来研究其气候意义 ,使得出的结论更加可靠.因此 ,夏季风降水量是控制该地区树轮稳定碳氧同位素组成的主要因素.  相似文献   

15.
选取西藏冈底斯斑岩成矿带东段的邦铺矿床斑岩矿区2条勘探线上的11个钻孔,进行了详细的岩芯编录和矿物组合、脉体穿切关系研究,将该矿床内与斑岩成矿相关的脉体划分为A、B、D脉3种类型。通过对矽卡岩矿区的详细地表及平硐观察,发现了石榴子石、阳起石、绿帘石等一系列代表流体演化特征的矿物。邦铺矿床具有典型斑岩型矿床的蚀变分带特征,从中心向外依次表现为黑云母化-硅化-绢云母化-青磐岩化,泥化呈"补丁状"无规则分布在绢云母化和青磐岩化之上。矽卡岩化则以典型矽卡岩矿物的出现为特征。A脉中绝大多数包裹体均一温度为320~550℃,盐度主要集中在两个区间内,分别为17.0%~22.0%(气液两相包裹体)和30.8%~67.2%(含子晶包裹体);B脉中绝大多数包裹体均一温度为380~550℃,盐度主要集中在1.6%~10.1%、23.2%~24.5%(气液两相包裹体)和30.8%~67.2%(含子晶包裹体)3个区间内;D脉中绝大多数包裹体均一温度为213~450℃,盐度为7.3%~11.6%。流体包裹体研究表明,与斑岩成矿的相关流体具有从高温、高盐度向低温、低盐度演化的特征;形成A、B脉的流体发生了强烈的沸腾作用,由此导致的压力波动是Mo、Cu沉淀的主要原因。16件与斑岩成矿相关的石英δDV-SMOW=-107.1‰~-185.8‰,δ18OV-SMOW=9.5‰~14.5‰;15件与矽卡岩成矿相关的石榴子石、绿帘石、石英及方解石δDV-SMOW=-184.7‰~-126‰,δ18OV-SMOW=3.9‰~12.9‰;4件斑岩成矿后期的方解石δ18OV-SMOW=-1.6‰~10.4‰,δCV-PDB=-6.5‰~-3.4‰;6件与矽卡岩成矿相关的方解石δ18OV-SMOW=1.8‰~11.9‰,δCV-PDB=-5.1‰~4.6‰。C_H_O同位素分析数据表明,邦铺整个斑岩-矽卡岩成矿系统流体主要经历了岩浆脱水去气和大气降水加入这两大地质过程。  相似文献   

16.
铁同位素的MC-ICP-MS测定方法与地质标准物质的铁同位素组成   总被引:17,自引:5,他引:17  
详细报道了在低分辨和高分辨模式下运用MC-ICP-MS进行Fe同位素比值高精度测试的方法,对Fe同位素测定过程中谱峰干扰、基质效应、浓度效应、仪器测试的长期重现性等问题进行了评估,并对两种运行模式的测试结果进行了对比.在95%的可信度范围内,所建方法的外部精度优于0.5ε/ainu,达到国际同类实验室的先进水平,并且低分辨和高分辨两种模式下获得的Fe同位素测试结果是一致的.在此基础上对国家地质标准物质GBW07105(玄武岩)和GBW 07111(花岗闪长岩)进行了Fe同位素测定.相对于Fe同位素国际标样IRMM-014,GBW07105的Fe同位素成分为:ε57Fe=1.9±0.3(20),ε56Fe=1.3±0.2(2σ),ε57/56Fe=0.6±0.1(2σ);GBW 07111的Fe同位素成分为:ε57Fe=1.8±0.4(2σ),ε56Fe=1.2±0.2(2σ),ε57/56Fe=0.6±0.1(2σ).  相似文献   

17.
本文引入一种原始有机碳恢复的新方法,即利用Mo-TOC相关性来估算海相泥质烃源岩原始有机碳。并以藏南地区白垩纪海相泥岩、页岩为例,估算其原始有机碳含量及有机碳损失率。该方法可能在我国高成熟度-过成熟烃源岩的评价和油气资源量预测中发挥重要的作用。  相似文献   

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The present work is an attempt to establish the stable isotope database for Mesozoic to Tertiary coals from the Pannonian Basin, Hungary. Maceral composition, proximate analysis, sulphur form, sulphur isotopes (organic and pyritic), and carbon isotopes were determined. This database supports the assessment of the environmental risks associated with energy generation, the characterization of the formation and the distribution of sulphur in the coals used.The maceral composition, the sulphur composition, the C, S isotopic signatures, and some of the geological evidences published earlier show that the majority of these coals were deposited in freshwater and brackish water environments, despite the relatively high average sulphur content. However, the Upper Cretaceous, Eocene, and Lower Miocene formations also contain coal seams of marine origin, as indicated by their maceral composition and sulphur and carbon chemistry.The majority of the sulphur in these coals occurs in the organic form. All studied sulphur phases are relatively rich in 34S isotopes (δ34Sorganic = + 12.74‰, δ34Spyrite = + 10.06‰, on average). This indicates that marine bacterial sulphate reduction played a minor role in their formation, in the sense that isotopic fractionation was limited. It seems that the interstitial spaces of the peat closed rapidly during early diagenesis due to a regime of high depositional rate, leading to a relative enrichment of the heavy sulphur isotopes.  相似文献   

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Radiocarbon dating of the organic-rich sediments of Lake Illisarvik in the outer Mackenzie Delta indicates that formation of the lake occurred approximately 9500yr BP, with maximum expansion around 6000 yr BP. Sedimentation rates have remained relatively constant at an average of 0.3mm/yr. 13C results on biogenic and inorganic carbonates and organics indicate a change from dominantly terrestrial organics (?27 to ?28%0) to submerged aquatic vegetation or plankton (?18 to ?23%0) upon formation of the lake (9500yr BP), and a dramatic return to dominantly terrestrial organics at 5800yr BP (δ13C = ?27 to ?30%0). This latter shift is accompanied by a drastic reduction in the macroflora and fauna populations. 18O results suggest that a warmer climate than today existed prior to the shift at 5800yr BP.  相似文献   

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