Geochemical Characteristics of the Meso-Neoproterozoic Source Rocks and Oil-Source Correlations in the Yanshan Area
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摘要: 燕山地区中-新元古界的油气富集情况一直以来都是学者们关注的热点.运用总有机碳（TOC）测试、热解、气相色谱（GC）、气相色谱质谱（GC-MS）等方法，对其有机地球化学特征，特别是生物标志化合物、有机质来源和沉积环境进行了详细的讨论，对比油苗/沥青与烃源岩中生物标志化合物组成特征，识别燕山地区中-新元古界地层中的主力烃源岩.研究得出，下马岭组、洪水庄组烃源岩有机碳含量高，生烃潜力大，热演化程度适中，为好-极好的烃源岩，铁岭组烃源岩为差-中等烃源岩，高于庄组烃源岩热演化程度过高，已不能判断烃源岩类型.根据研究区的生物标志化合物特征，可以将其划分为两类，其中洪水庄组、铁岭组及下马岭组为第Ⅰ类烃源岩，以无环类异戊二烯姥鲛烷（Pr）和植烷（Ph）的相对含量极低，具有一定丰度的C20规则三环萜烷（C20TT）和C19TT以及特殊的13α（正烷基）-三环萜烷系列化合物，富含四环萜烷（C24TeT）、降新藿烷（Ts和C29Ts）和重排藿烷（C30Dia），缺失甾烷化合物为特征，揭示了第Ⅰ类烃源岩具有较高的热演化程度，缺氧的沉积环境以及特殊的成烃生物.高于庄组为第Ⅱ类烃源岩，以高丰度的C23~C25TT以及规则藿烷，普遍存在C27~C29规则甾烷，低丰度的C24四环萜、降新藿烷和重排藿烷，未检测到补身烷和13α（正烷基）-三环萜系列化合物为特征，呈现出典型海相碳酸盐岩沉积环境下的原油特征以及指示了较为多样的生物来源.油源对比表明，第Ⅰ类油苗/沥青主要来源于洪水庄组烃源岩，而第Ⅱ类沥青砂岩的有机地球化学组成特征和高于庄组烃源岩十分相似.Abstract: The enrichmentof Meso-Neoproterozoic oil and gas in Yanshan area has been the hot topic focused on by scholars. Total Organic Carbon (TOC) test, pyrolysis, gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS) and other methods are applied in this paper to discuss organic geochemical characteristics of samples. Especially, the biomarker compounds, organic matter sources and sedimentary environment are discussed in detail. The geochemical and biomarker characteristics of oil seepage/asphalt and source rocks are compared to identify the major source rocks of Meso-Neoproterozoic strata in Yanshan Region. The results show that the source rocks of the Xiamaling and Hongshuizhuang formations, featured with high content of organic carbons, great hydrocarbon generation potential and moderate degree of thermal evolution, are good and supreme source rocks.The source rocks of Tieling Formation are poor-medium source rocks, and the degree of thermal evolution of Gaoyuzhuang Formation is excessively high to determine the type of source rocks. According to the characteristics of biomarkers in the researched area, the source rocks are divided into two categories. Wherein, the source rocks of Hongshuizhuang, Tieling and Xiamaling Formations are classified into Category Ⅰ. The relative contents of acyclic isoprene pristane (Pr) and phytane (Ph) are very low, with certain abundance of regular C20 tricyclic terpane (C20TT), C19TT and special 13α (n-alkyl) - tricyclic terpanes, rich in tetracyclic terpane (C24TeT), norneohopane (Ts and C29Ts) and rearranged hopanes (C30Dia), and are characterized by the absence of sterane compound.Revealing moderate degree of thermal evolution, anoxic sedimentary environment and a special hydrocarbon generating organism of Category Ⅰ source rocks. Gaoyuzhuang Formation, provided with Category Ⅱsource rocks, is characterized with high abundance of C23-C25TT and regular hopane, common C27-C29 regular steranes, low abundance of C24 tetracyclic terpane, norneohopane and rearranged hopane, and no drimane and 13α (n-alkyl)-featured with tricyclic terpene serial compound is detected, showing the characteristics of crude oil in typical marine carbonate sedimentary environment and indicating various biological sources. The oil and source rock correlation shows that Category Ⅰ oil seepage/asphalt mainly originates from the source rocks of Hongshuizhuang Formation, while the organic geochemical composition characteristics of CategoryⅡasphalt sandstone are extremely similar to the source rocks of Gaoyuzhuang Formation.
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图 2 燕山地区中‒新元古界沉积地层柱状图（Song et al., 2021）
Fig. 2. Histogram of Meso-Neoproterozoic sedimentary strata in the Yanshan area
图 3 燕山地区中元古界油苗/沥青取样层段
a.兴隆1井雾迷山组；b.韩1井骆驼岭组；c.冀浅1井铁岭组和雾迷山组；d.冀浅2井铁岭组；e.龙潭沟古油藏下马岭组；f.双洞古油藏铁岭组
Fig. 3. Meso-Neoproterozoic sampling layer of oil seepages/asphalt in Yanshan area
图 4 燕山地区中元古界油苗/沥青样品展示
1/2.韩1井，骆驼岭组，砂岩；3/4.兴隆1井，雾迷山组，灰岩；5/6.冀浅1井，铁岭组，灰岩；7/8.冀浅2井，雾迷山组，灰岩；9/10.双洞，铁岭组，固体沥青；11/12.龙潭沟，下马岭组，沥青砂岩
Fig. 4. Meso-Neoproterozoic oil seepages/asphalt sample display in Yanshan area
图 5 燕山地区中元古界烃源岩样品采样层位
a.宣龙坳陷下马岭组；b.冀浅1井洪水庄组；c.冀浅3井高于庄组；d.冀北坳陷铁岭组
Fig. 5. Meso-Neoproterozoic source rock samples layer in Yanshan area
图 6 燕山地区中元古界烃源岩样品展示
a.冀浅3井，高于庄组，泥晶白云岩；b.塌山剖面铁岭组，黑色泥岩；c.夏家沟下马岭组，黑色页岩；d.冀浅1井洪水庄组，黑色泥岩；e.孙家庄剖面洪水庄组，黑色泥岩；f.老黄庄剖面洪水庄组，黑色泥岩
Fig. 6. Meso-Neoproterozoic source rock samples display in Yanshan area
图 7 燕山地区中元古界烃源岩评价相关图
Fig. 7. Correlation diagram of Meso-Neoproterozoic source rock evaluation in Yanshan area
图 8 燕山地区中元古界两类烃源岩TIC分布特征
Fig. 8. Distribution characteristics of TIC of Meso-Neoproterozoic two types of source rocks in Yanshan area
图 9 燕山地区中元古界两类烃源岩Pr/nC17和Ph/nC18相关图
Fig. 9. Correlation between Pr/nC17 and Ph/nC18 of Meso-Neoproterozoic two types of source rocks in Yanshan area
图 10 燕山地区中元古界两类烃源岩m/z 191萜烷分布特征
Fig. 10. Distribution characteristics of m/z 191 terpane of Meso-Neoproterozoic two types of source rocks in Yanshan area
图 11 燕山地区中元古界两类烃源岩m/z 191地化参数相关图
Fig. 11. Correlation diagram of m/z 191 geochemical parameter of Meso-Neoproterozoic two types of source rocks in Yanshan area
图 12 燕山地区中元古界两类烃源岩m/z 123分布特征
Fig. 12. Distribution characteristics of m/z 123 of Meso-Neoproterozoic two types of source rocks in Yanshan area
图 13 燕山地区中元古界两类烃源岩m/z 217分布特征
Fig. 13. Distribution characteristics of m/z 217 of Meso-Neoproterozoic two types of source rocks in Yanshan area
图 14 燕山地区中元古界第Ⅰ类烃源岩和油砂分布特征对比
Fig. 14. Comparison of distribution characteristics of Meso-Neoproterozoic type Ⅰ source rocks and oil sands in Yanshan area
图 15 燕山地区中元古界第Ⅱ类烃源岩和油砂分布特征对比
Fig. 15. Comparison of distribution characteristics of Meso-Neoproterozoic type Ⅱ source rocks and oil sands in Yanshan area
图 16 燕山地区中元古界油源对比相关参数
Fig. 16. Related parameters of Meso-Neoproterozoic oil source comparison in Yanshan area
表 1 燕山地区中元古界部分烃源岩地球化学参数统计
Table 1. Statistics table of geochemical parameters of some Meso-Neoproterozoic source rock samples in Yanshan area
序号 样品编号 层位 TOC(%) Tmax(℃) S1（mg/g） S2（mg/g） S1+S2（mg/g） HI（mg/g·TOC-1） 1 XML-1 下马岭组 23.02 439 4.4 103.28 107.68 448.65 2 XML-2 下马岭组 18.81 439 3.01 85.97 88.98 457.04 3 XML-3 下马岭组 11.38 442 1.38 35.14 36.52 394.72 4 XML-A 下马岭组 16.11 432 2.65 63.59 66.24 430.21 5 XML-4 下马岭组 7.91 435 2.17 34.03 36.2 404.01 6 HSZ-1 洪水庄组 6.18 470 1.54 19.4 20.94 350.56 7 HSZ-2 洪水庄组 6.00 450 1.65 19.71 21.36 328.5 8 HSZ-3 洪水庄组 7.87 451 1.31 27.35 28.66 347.52 9 HSZ-4 洪水庄组 5.20 448 1.51 17.2 18.71 330.77 10 HSZ-5 洪水庄组 5.41 450 1.36 17.31 18.67 319.96 11 TL-1 铁岭组 1.68 443 0.26 3.48 3.74 207.02 12 TL-2 铁岭组 1.93 443 0.28 4.35 4.63 225.62 13 TL-3 铁岭组 1.7 444 0.34 3.41 3.75 200.59 14 TL-4 铁岭组 0.94 447 0.21 1.82 2.03 193.62 15 TL-5 铁岭组 0.85 446 0.23 1.71 1.94 201.18 16 GYZ-1 高于庄组 1.57 462 0.19 0.39 0.58 24.9 17 GYZ-2 高于庄组 1.87 484 0.14 0.45 0.59 24.04 18 GYZ-3 高于庄组 0.44 521 0.06 0.16 0.22 36.69 19 GYZ-4 高于庄组 1.03 517 0.14 0.38 0.52 37.04 20 GYZ-5 高于庄组 0.88 516 0.06 0.33 0.39 37.55 
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表 2 燕山地区中元古界烃源岩饱和烃地化参数统计
Table 2. Statistics of geochemical parameters of saturated hydrocarbons of Meso-Neoproterozoic source rocks in Yanshan area
序号 样品编号 层位 Pr/nC17 Ph/nC18 8β(H)-D/nC主峰碳 8β(H)-HD/nC主峰碳 13α(正烷基)-C18TT/nC主峰碳 13α(正烷基)-C19TT/nC主峰碳 C19TT/C30H C20TT/C30H C24TeT/C30H Ts/Tm 1 XML-1 下马岭组 0.06 0.08 0.05 0.12 0.04 0.12 0.22 0.23 0.17 1.08 2 XML-2 下马岭组 0.16 0.14 0.25 0.66 0.23 0.84 0.52 0.69 0.28 0.64 3 XML-3 下马岭组 0.06 0.13 0.06 0.12 0.05 0.13 0.15 0.24 0.17 1.16 4 XML-4 下马岭组 0.08 0.3 0.05 0.14 0.05 0.12 0.21 0.23 0.17 0.98 5 HSZ-1 洪水庄组 0.22 0.36 0.45 0.30 0.10 0.29 4.24 3.69 1.11 1.46 6 HSZ-2 洪水庄组 0.23 0.28 0.07 0.18 0.08 0.24 1.91 1.40 0.71 2.50 7 HSZ-3 洪水庄组 0.25 0.35 0.03 0.11 0.08 0.33 2.89 3.35 1.01 1.55 8 HSZ-4 洪水庄组 0.31 0.38 0.04 0.12 0.12 0.31 2.19 2.22 0.89 3.07 9 TL-1 铁岭组 0.15 0.16 0.02 0.06 0.03 0.08 0.76 0.85 0.64 2.41 10 TL-2 铁岭组 0.16 0.14 0.01 0.04 0.03 0.09 0.73 0.85 0.68 2.18 11 TL-3 铁岭组 0.21 0.30 0.05 0.08 0.04 0.08 1.13 1.08 0.75 1.48 12 TL-4 铁岭组 0.21 0.28 0.03 0.05 0.03 0.07 1.86 2.21 0.99 1.48 13 GYZ-1 高于庄组 0.46 0.71 - - - - - 0.19 0.15 1.40 14 GYZ-2 高宇庄组 0.45 0.64 - - - - - 0.14 0.13 1.43 15 GYZ-3 高于庄组 0.53 0.74 - - - - - 0.26 0.13 1.35 16 GYZ-4 高宇庄组 0.52 0.73 - - - - - 0.39 0.20 1.34
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表 3 燕山地区中元古界烃源岩和油砂分子标志化合物组成特征
Table 3. Composition characteristics of molecular markers of Meso-Neoproterozoic source rocks and oil sands in Yanshan area
序号 生物标志化合物 第Ⅰ类烃源岩/第Ⅰ类油苗(沥青) 第Ⅱ类烃源岩/第Ⅱ类油苗(沥青) 1 姥鲛烷‒植烷 低 高 2 C24四环萜烷 高 低 3 重排霍烷系列 高 低 4 补身烷系列 高 无 5 13α（正烷基）‒三环萜烷（C18~C23） 完整 无 6 规则甾烷（C27~C29） 无/极低 明显
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