Molybdenum Isotopic Compositions and Significance of Bitumen at Different Geological Periods in Shangsi Section, Guangyuan, Sichuan
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摘要: 对四川广元地区寒武纪、二叠纪和石炭纪部分海相碳酸盐岩地层中沥青的Mo同位素和微量元素进行了测定.结果表明, 该区不同时期沥青的δ98Mo有较大的变化范围(+0.34‰~+1.71‰), 总体上, 接近缺氧沉积岩δ98Mo的范围.寒武纪海相地层中沥青具有明显的δEu正异常(0.75~1.68), 其Mo、Ni、V等氧化还原敏感元素含量相对较高, 且具有明显偏重的δ98Mo(1.17‰~1.71‰), 特别是下寒武统筇竹寺组的一个样品(Hs-qzs)出现明显的δEu正异常(1.68), 可能与同期强烈的海底热液活动有关.热液喷发过程中产生的大量硫化氢, 导致偏重δ98Mo以及Mo、Ni、V等元素的富集.虽然该区不同时期的海相碳酸盐岩中沥青的TMV与TMNi没有明显的相关性, 但是不同时期(寒武纪、二叠纪和石炭纪)沥青的δ98Mo与V/Ni比值的分布区域存在一定的差异, 有可能与来源不同有关, 暗示δ98Mo有可能仍然保存着部分源岩的性质, 特别是下寒武统筇竹寺组(Hs-qzs)的TMV与TMNi相对偏高, 可能与海底热液作用及后期相对较强的降解作用有关.Abstract: In this research, new Molybdenum isotopic compositions of the bitumen, in the Gaungyuan section, Sichuan, as well as trace elements are determined. The results show that it has a large variation of δ98Mo (+0.34‰~+1.71‰) in this region, reaching the range of anoxic sediments δ98Mo in general. The slightly positive δEu anomaly has been shown in the Cambrian interval (0.75-1.68), specially, with a sample from Qiongzhusi Formation (Hs-qzs) with a significant positive δEu anomaly (1.68), corresponding to the enrichment of redox-sensitive trace elements (such as Mo, Ni, V), with the positive δ98Mo (1.17‰-1.71‰). These characteristics might be related to local intense hydrothermal erupting, corresponding to the large quantity of H2S and HS- into the contemporaneous seawater. Introduction of these sulfide gases would cause MoO42- to be transferred into MoS42-, favoring the preferential deposition of the heavy Mo isotope as MoS42- and thus leaving a positive Mo isotope value. Although no much good correlation between TMV and TMNi has been shown in this area, the distinct fields from difference interval of bitumen is observed by the plot of δ98Mo against V/Ni ratios, it implies the possible stability of δ98Mo by local mobilization during diagenesis/early catagenesis.
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Key words:
- Molybdenum isotope /
- bitumen /
- marine sediment /
- geochemistry
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图 1 四川广元上寺剖面地质示意(据Isozaki et al., 2007修改)
Fig. 1. Geological map of Guangyuan Shangsi section, Sichuan
表 1 四川广元地区不同时期海相碳酸盐岩中沥青的δ98Mo、TOC和微量元素数据
Table 1. The δ98Mo, TOC and trace element data of the bitumen from marine carbonate rock in Guangyuan section
样品编号 Pgy-wjp-100 Gy-qx-c Pgy-mo-43 Pgy-qx-22 Pgy-17 Pgy-mo-3 C2-fs-5 Hs-clp Hs-cl Hs-qzs 时代 二叠纪 二叠纪 二叠纪 二叠纪 二叠纪 二叠纪 石炭纪 寒武纪 寒武纪 寒武纪 样品描述 黑色泥质层 方解石脉与沥青共生 干沥青较多,选干沥青 黑色灰岩夹干沥青 泥质灰岩夹干沥青 干沥青 藻纹层沥青层共生 中粗粉砂岩夹沥青 粉砂岩中夹干沥青 沥青带,较厚 V(μg/g) 759.7 698.0 918.8 140.6 319.0 274.3 57.27 83.81 438.0 132.6 Co(μg/g) 42.72 3.64 20.65 2.23 3.08 5.06 6.20 0.85 14.98 1.90 Ni(μg/g) 616.0 143.7 168.49 40.71 74.51 40.19 58.02 51.56 132.3 293.9 Cu(μg/g) 185.8 51.42 68.19 17.55 10.52 39.68 36.91 7.22 3408 7.47 Zn(μg/g) 727.3 86.18 104.1 92.20 64.21 50.52 18.34 13.20 77.12 20.20 Ga(μg/g) 23.88 14.18 25.46 2.37 3.88 3.53 10.01 1.42 5.37 0.78 Zr(μg/g) 352.6 147.0 227.9 23.08 34.65 29.28 114.3 18.09 82.92 6.25 Mo(μg/g) 121.7 79.56 68.46 16.67 120.9 7.15 3.89 3.38 77.84 21.32 La(μg/g) 34.06 11.13 22.92 2.57 5.20 6.33 9.47 2.84 11.11 1.30 Ce(μg/g) 63.45 17.91 34.59 4.23 9.45 9.24 13.94 5.25 17.02 2.21 Pr(μg/g) 9.10 2.07 3.86 0.51 1.16 1.32 1.49 0.68 2.26 0.28 Nd(μg/g) 40.17 7.15 12.97 1.93 4.30 5.02 4.77 2.82 8.87 1.06 Sm(μg/g) 9.46 1.26 2.13 0.44 0.90 1.16 0.81 0.77 1.79 0.23 Eu(μg/g) 2.14 0.20 0.36 0.10 0.14 0.25 0.15 0.21 0.50 0.13 Gd(μg/g) 9.71 1.02 1.71 0.52 0.78 1.34 0.74 0.99 1.89 0.22 Tb(μg/g) 1.33 0.17 0.29 0.09 0.13 0.22 0.13 0.18 0.30 0.03 Dy(μg/g) 7.03 1.18 1.75 0.61 0.78 1.23 0.83 1.10 1.83 0.18 Ho(μg/g) 1.40 0.27 0.43 0.15 0.16 0.27 0.21 0.24 0.41 0.04 Er(μg/g) 3.97 0.92 1.40 0.42 0.46 0.76 0.72 0.64 1.24 0.12 Tm(μg/g) 0.60 0.16 0.26 0.07 0.08 0.12 0.13 0.09 0.20 0.02 Yb(μg/g) 3.46 1.13 1.86 0.48 0.51 0.70 0.94 0.50 1.22 0.12 Lu(μg/g) 0.49 0.18 0.29 0.07 0.07 0.11 0.14 0.07 0.19 0.02 La/Sm 2.33 5.72 6.94 3.80 3.72 3.53 7.56 2.38 4.01 3.57 Gd/Yb 2.32 0.74 0.76 0.91 1.26 1.58 0.65 1.65 1.29 1.52 La/Yb 7.06 7.06 8.85 3.87 7.32 6.46 7.19 4.11 6.56 7.67 ∑L/∑H 2.37 2.81 3.37 1.54 2.71 1.99 2.77 1.37 2.24 2.89 ∑REE 750.8 169.4 313.5 52.49 91.97 117.9 131.3 73.52 199.4 24.33 δCe(‰) 0.87 0.85 0.82 0.85 0.90 0.74 0.82 0.90 0.79 0.86 δEu(‰) 0.68 0.51 0.56 0.63 0.51 0.62 0.57 0.75 0.83 1.68 V/Ni 1.23 4.86 5.45 3.45 4.28 6.83 0.99 1.63 3.31 0.45 δ98Mo(‰) 0.58 1.02 1.5 1.1 0.59 0.34 1.5 1.17 1.24 1.71 TOC(%) 25.34 13.60 11.40 1.91 2.47 5.04 9.08 75.59 57.97 65.64 EFV 3.02 6.65 5.64 8.53 12.89 13.11 0.70 6.49 7.39 29.69 EFNi 6.67 3.73 2.82 6.73 8.21 5.24 1.94 10.88 6.09 179.4 EFCu 2.21 1.47 1.26 3.19 1.27 5.69 1.36 1.68 172.6 5.02 EFZn 5.10 1.45 1.13 9.87 4.58 4.26 0.40 1.80 2.30 7.98 EFU 8.50 39.70 5.93 46.83 16.72 27.98 2.84 1.24 5.61 4.22 EFMo 72.47 113.66 63.08 151.65 733.04 51.29 7.15 39.27 197.1 716.20 EFCo 1.11 0.23 0.83 0.88 0.81 1.58 0.50 0.43 1.65 2.77 注:δCe=2(Ce样品/Ce球粒陨石)/(La样品/La球粒陨石+Nd样品/Nd球粒陨石);δEu=2(Eu样品/Eu球粒陨石)/(Sm样品/Sm球粒陨石+Tb样品/Tb球粒陨石);EF为元素富集因子,TM为微量元素的浓度.EF=TM/Zr*=TM/Zrsample: TM/Zraverage shale,即利用锆扣除陆源碎屑影响( Wilde et al., 2004 ).平均页岩数据据Wedepohl(1971, 1991). -
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