Characteristics and indication of terrestrial biomarkers of crude oil in different local structures of Xihu Depression, East China Sea Basin
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摘要: 利用地球化学分析手段，对西湖凹陷黄岩构造带、平北地区以及宁波构造带的16个轻质油样品进行了分析。原油中富含反映陆源高等植物输入的生物标志化合物，尤其是源于被子植物、裸子植物及蕨类植物的三环、四环二萜类及其芳构化产物，而反映水生低等植物输入的生物标志化合物含量较低。不同构造带间原油中这些化合物的分布特征具有明显差异，如异海松烷/nC20、异海松烷/（异海松烷+16β（H）扁枝烷）、1，2，5-三甲基萘/1，3，6-三甲基萘、1，7-二甲基菲/（惹烯+1，7-二甲基菲）等。这些差异指示了宁波构造带与平北地区原油裸子植物输入较多，蕨类植物及被子植物输入较少，而黄岩构造带原油蕨类植物输入较多，被子植物与裸子植物较少的特点。研究中利用全油色谱-质谱将原油饱和烃与芳烃组分建立联系，提出（异海松烷+1，7-二甲基菲）/（惹烯+16β（H）扁枝烷）作为反映西湖凹陷轻质原油生源构成的指标，而该参数与全油碳同位素值的正相关关系证明了裸子植物树脂对西湖凹陷轻质油的重要成烃贡献。Abstract: Sixteen light oil samples from Huangyan structural belt, Pingbei area and Ningbo structural belt in Xihu Depression were analyzed by geochemical analysis. The crude oil samples are rich in biomarkers related to the input of terrestrial higher plants, especially the tricyclic and tetracyclic diterpenes and their aromatization compounds derived from angiosperm, gymnosperms, and pteridophytes, while the content of biomarkers reflecting the input of aquatic plants are relatively low. The distribution of these high plant biomarkers between different local structures is obviously different, such as isopimarane/nC20, isopimarane/(isopimarane+16β(H)-phyllocladane), 1, 2, 5-trimethyl naphthalene/1, 3, 6-trimethyl naphthalene, and 1, 7-dimethyl phenanthrene/(retene+1, 7-dimethyl phenanthrene). These differences indicate that there are high contents of gymnosperms input, and low contents of pteridophytes and angiosperms input of crude oil from the Ningbo structural belt as well as the Pingbei area. However, crude oil from the Huangyan structural belt has more pteridophytes input and fewer angiosperms and gymnosperms input. In this study, whole oil gas chromatography-mass spectrometry analysis was used to develop a relationship between saturated hydrocarbons and aromatic hydrocarbons. The ratio of (isopimarane+1, 7-dimethyl phenanthrene)/(retene+16β(H)-phyllocladane) was proposed as an index to reflect the provenance of organic matter of light oil in Xihu Depression, and the positive correlation between the parameter values and whole oil carbon isotope values proves that the gymnosperms have the most important hydrocarbon-generating contribution to the crude oil in Xihu Depression.
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Key words:
- diterpenoids /
- biomarkers /
- provenance of organic matter /
- light oil /
- evaporative fractionation
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图 1 西湖凹陷构造单元划分与原油取样井位置
Figure 1. Local structures of Xihu Depression and sampling wells location
图 2 西湖凹陷典型原油饱和烃气相色谱图
Figure 2. Gas chromatogram of saturated hydrocarbon of typical crude oil samples in Xihu Depression
图 3 西湖凹陷原油正构烷烃摩尔浓度分布特征
Figure 3. Molarity distribution of n-alkanes of crude oil samples in Xihu Depression
图 4 西湖凹陷原油Pr/nC17与Ph/nC18关系图
Figure 4. Cross plot of Pr/nC17 and Ph/nC18 of crude oil in Xihu Depression
图 5 西湖凹陷典型原油二萜类化合物分布特征
1~3.降海松烷；4.8β(H)-半日花烷；5.4β(H)-19-降异海松烷；6.朽松木烷；7.芮目泪烷；8.海松烷；9.异海松烷；10.16β(H)扁枝烷；11.16β(H)贝壳杉烷；12.16α(H)扁枝烷；13.16α(H)贝壳杉烷
Figure 5. Diterpenoids distribution characteristics of typical crude oil samples in Xihu Depression
图 6 西湖凹陷典型原油五环三萜烷与甾烷分布特征
Figure 6. Pentacyclic triterpanes and steranes distribution of typical crude oil samples in Xihu Depression
图 7 西湖凹陷典型原油芳烃萘系列与菲系列化合物分布特征
a.萘系列质量色谱图，峰侧所标的数字为萘上甲基取代位置；2.2-甲基萘；1.1-甲基萘; 1, 7.1, 7-二甲基萘；1, 2, 5.1, 2, 5-三甲基萘；1, 2, 5, 6 & 1, 2, 3, 5.1, 2, 5, 6+1, 2, 3, 5-四甲基萘；b.菲系列质量色谱图，在峰上标的数字为菲上甲基取代位置，2.2-甲基菲；3.3-甲基菲；9.9-甲基菲; 1.1-甲基菲; 1, 7.1, 7-二甲基菲
Figure 7. Naphthalene and phenanthrene compounds distribution characteristic of typical crude oil samples in Xihu Depression
图 8 原油高等植物生源输入指标关系图
Figure 8. Cross plots of different higher plants input index of crude oil
表 1 原油样品基本信息及物性数据
Table 1. Basic information and physical property data of crude oil samples
井号 深度/m 层段 构造位置 密度/(g·cm-3) 含蜡量/% 含硫量/% Rc/% H1 2 704.3~2 719.0 E3h上 黄岩构造带 0.79 0.68 0.05 1.34 H1 2 805.8~2 811.3 E3h上 黄岩构造带 0.81 0.33 N.A. 1.37 H1 2 984.5~2 989.5 E3h下 黄岩构造带 0.81 0.41 0.02 1.32 H2 2 512.5~2 519.5 E3h上 黄岩构造带 0.77 1.92 0.05 1.42 H2 3 031.5~3 039.0 E3h下 黄岩构造带 0.80 3.69 0.06 1.29 H3 3 350.0~3 361.0 E3h上 黄岩构造带 0.78 0.79 0.04 1.41 H4 3 416.2~3 437.4 E3h上 黄岩构造带 0.79 1.46 0.01 1.51 P1 4 150.0~4 169.0 E2p下 平北地区 0.84 2.11 0.10 1.57 P2 4 107.5~4 111.0 E2p上 平北地区 0.79 1.62 0.05 1.25 P2 4 186.7~4 202.5 E2p中 平北地区 0.82 3.08 0.07 1.26 P3 4 183.0~4 196.0 E2p上 平北地区 0.82 3.27 0.04 1.29 P3 4 548.7~4 566.2 E2p中 平北地区 0.86 10.54 0.07 1.20 P4 4 359.0~4 382.0 E2p下 平北地区 0.84 8.18 0.06 1.30 P4 4 580.0~4 620.0 E2p中 平北地区 0.80 20.00 0.05 1.24 N1 3 709.0~3 739.0 E3h上 宁波构造带 0.80 5.84 0.08 1.61 N1 3 769.0~3 799.0 E3h上 宁波构造带 0.84 7.75 0.02 1.59 注：Rc=2.432 2×MDI(甲基双金刚烷指数)+0.438 9；MDI=4-MD(甲基双金刚烷)/(1-MD+3-MD+4-MD)[15] 
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表 2 西湖凹陷原油样品地球化学参数
Table 2. Geochemical parameters of crude oil samples in Xihu Depression
井号 层段 A B C D E F G H I J K H1 E3h上 11.11 1.29 0.16 0.61 0.16 0.32 0.12 0.35 0.87 4.69 2.23 H1 E3h上 8.44 1.26 0.16 0.57 0.15 0.24 0.13 0.34 0.89 5.21 2.30 H1 E3h下 8.82 1.34 0.17 0.63 0.12 0.21 0.14 0.37 0.89 4.15 2.63 H2 E3h上 9.48 0.2 2.12 0.43 0.02 0.22 0.19 0.81 1.11 0.61 0.68 H2 E3h下 7.69 1.64 0.2 0.38 0.02 0.22 0.20 0.74 0.94 0.84 0.71 H3 E3h上 8.19 0.98 0.13 0.67 0.10 N.A. 0.16 0.54 1.02 4.19 2.80 H4 E3h上 8.51 1.08 0.14 0.61 0.16 0.18 0.19 0.66 0.92 3.95 1.85 P1 E2p下 10.16 0.21 0.03 0.76 0.05 N.A. 0.18 0.55 0.96 5.08 6.09 P2 E2p上 6.68 0.95 0.15 0.84 0.63 0.77 0.09 0.30 1.31 9.30 6.58 P2 E2p中 8.15 0.83 0.13 0.83 0.62 N.A. 0.09 0.30 1.30 10.06 6.60 P3 E2p上 7.55 1.46 0.2 0.84 0.46 0.24 0.11 0.33 1.20 8.72 6.50 P3 E2p中 6.79 0.83 0.13 0.74 0.61 0.24 0.11 0.51 1.56 7.23 3.94 P4 E2p下 5.06 1.04 0.14 0.78 0.86 0.48 0.10 0.32 1.28 6.65 4.09 P4 E2p中 5.63 1.04 0.14 0.84 0.54 0.38 0.04 0.15 1.57 7.52 6.51 N1 E3h上 6.94 0.55 0.09 0.98 0.18 0.25 0.08 0.27 0.85 25.09 41.91 N1 E3h上 7.43 0.58 0.09 0.98 0.14 N.A. 0.08 0.27 0.80 31.97 45.67 A.Pr/Ph；B.Pr/nC17；C.Ph/nC18；D.异海松烷/(异海松烷+16β(H)扁枝烷)；E.异海松烷/nC20；F.Ts/Tm；G.(1, 2, 5, 6-四甲基萘+1, 2, 3, 5-四甲基萘)/四甲基萘系列；H.1, 2, 5-三甲基萘/1, 3, 6-三甲基萘；I.1-甲基菲/9-甲基菲；J.1, 7-二甲基菲/惹烯；K.(异海松烷+1, 7-二甲基菲)(扁枝烷+惹烯)
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