辽河西部凹陷低熟油的高分辨质谱特征及其成因机制

doi:10.19657/j.geoscience.1000-8527.2023.116

摘要/Abstract

摘要：

辽河西部凹陷低熟油资源丰富,不同类型稠油的成因机制差异尚不清楚,解决上述问题对辽河稠油的勘探工作具有指导意义。本文采用色谱/质谱(GC/MS)结合傅里叶变换离子回旋共振质谱(FT-ICR MS)技术对辽河西部凹陷北部高升和牛心坨油田低熟油的特征及其成因机制进行研究。高升原油形成于强还原咸水水体,有机质为菌藻类低等生物与陆源的双重贡献。牛心坨原油形成于还原性半咸水水体,有机质来源为低等微生物和陆源有机质双重输入,具有高蜡特征。成熟度参数表明二者均为低熟油。两种低熟油中均检测到N₁、N₁O₁、N₁O₂、O₁、O₂、O₃、O₄化合物,高升低熟油以N₁类为主,牛心坨低熟油以O₂类为主;前者富含脂肪酸和藿烷酸,后者富含脂肪酸,藿烷酸含量较低,反映两种原油成因机制的差异。高升低熟油中大量的藿烷酸表明其生烃母质在早期成岩作用阶段经历了细菌改造作用,低熟油为细菌改造有机质低温生烃和藻类类脂低温生烃混合成因机制。牛心坨低熟油富含脂肪酸和高等植物蜡质,成因机制为生物类脂物早期低温生烃。两种低熟油的成因机制,为低熟油成因理论提供了研究方法,有助于完善低熟油成因理论并指导类似盆地低熟油油气勘探。

关键词: 辽河西部凹陷, 低熟油, 成因机制, 杂原子化合物, 高分辨率质谱

Abstract:

The Liaohe Western Depression is enriched in low-maturity oil resources, however the formation mechanism of its hydrocarbon remains unclear.GC/MS combined with ESI FT-ICR MS approaches are used to study the characteristics and formation mechanisms of low-maturity oil in the Gaosheng and Niuxintuo areas.The Gaosheng crude oil originated in a strongly reduced saline water environment, with its organic matter sourced from bacteria, algae, and terrestrial sources.The Niuxintuo crude oil originated in a reducing brackish water environment, with its organic matter primarily derived from a combination of microorganisms and terrestrial sources.Notably, the Niuxintuo crude oil exhibits a high wax content.The maturity parameters of the saturated hydrocarbons suggest that both sites contain low-maturity oils.Both low-maturity oils exhibited the presence of N₁, N₁O₁, N₁O₂, O₁, O₂, O₃, and O₄ compounds.The Gaosheng low-maturity oil predominantly consists of N₁ class compounds, while the Niuxintuo low-maturity oil is primarily composed of O₂ class compounds.The former contains an abundance of fatty acids and hopanoic acid, whereas the latter is characterized by high levels of fatty acids and notably lower hopanoic acid content.This divergence underscores the differences in the formation mechanisms of the two crude oils.The significant presence of hopanoic acid in the Gaosheng low-maturity oil suggests that the hydrocarbon source material underwent reformation by bacterium during the early diagenetic stage.The Gaosheng low-maturity oil results from a combined genetic mechanism involving early hydrocarbon generation from the biological lipids and bacterial reformation of the hydrocarbon source materials.The Niuxintuo low-maturity oil is abundant in fatty acids and higher plant waxes.Its formation mechanism involves early hydrocarbon generation from a significant quantity of biological lipids.Research into the genetic mechanisms of these two types of low-maturity oils provides a methodological approach for studying low-maturity oil genesis.This endeavor enhances our understanding of the genesis of low-maturity oils and provides guidance for exploring low-maturity oil in analogous basins.

Key words: Liaohe Basin, low-mature oil, formation mechanism, heteroatomic compound, high-resolution mass spectrometry

中图分类号:

P618.1

邓硕, 李素梅, 曹敬涛, 黄太明, 刘佳, 张建淼, 施倩倩. 辽河西部凹陷低熟油的高分辨质谱特征及其成因机制[J]. 现代地质, 2024, 38(05): 1354-1369.

DENG Shuo, LI Sumei, CAO Jingtao, HUANG Taiming, LIU Jia, ZHANG Jianmiao, SHI Qianqian. High-Resolution Mass Spectrum Characteristics and Formation Mechanism of Low Maturity Oil in the Liaohe Western Depression[J]. Geoscience, 2024, 38(05): 1354-1369.

图/表 13

图1 辽河西部凹陷构造位置图(a)、构造特征示意图(b)和构造剖面图(c)

Fig.1 Structural location map of the Western Liaohe Depression (a), comprehensive map of structural characteristics (b), and structural section (c)

表1 原油物理性质与族组分组成[7]

Table 1 Physical properties and group composition of oils from Gaosheng and Niuxintuo[7]

井号	油田	层位	深度 (m)	降解程度	密度 (g/cm³)	黏度 (mPa·s)	凝固点 (℃)	含蜡量 (%)	含硫量 (%)	饱和烃 (%)	芳烃 (%)	非烃 (%)	沥青质 (%)	非烃+ 沥青质(%)	饱/芳
Z17-23	高升	Es₄中	1753.00	未	0.89	414	31	11.45	0.48	35.90	20.70	28.60	14.90	43.50	1.58
G1-5-13	高升	Es₄中	1337.00	轻微	0.90	1935	26	10.00	0.63	37.80	18.50	26.80	16.90	43.70	2.04
G3-6-25	高升	Es₃下	1788.00	中等	0.94	3524	6	5.10	0.53	27.50	21.10	29.30	22.10	51.40	1.31
G3-6-0151	高升	Es₃下	1641.95	中等	0.93	2585	9	6.68	0.51	24.00	19.60	30.90	25.50	56.40	1.23
T37-29	牛心坨	Es₄下	1909.55	未	0.88	1178	39	13.43	0.40	37.80	17.20	24.80	20.20	45.00	2.20
T35-29	牛心坨	潜山	2170.00	未	-	-	-	-	-	37.25	9.02	40.39	13.33	53.73	4.13

图2 原油饱和烃总离子流图(a)、m/z =217质量色谱图(b)和 m/z =191质量色谱图(c)

Fig.2 TIC (a), m/z=217 (b) and m/z=191 (c) mass chromatograms of saturated hydrocarbon fractions from selected oils

表2 高升、牛心坨原油常规地球化学参数

Table 2 Basic geochemical parameters of oils from Gaosheng and Niuxintuo

井号	深度 (m)	Pr/ Ph	Pr/ C₁₇	Ph/ C₁₈	CPI	OEP	C₂₇ (%)	C₂₈ (%)	C₂₉ (%)	C₂₇/C₂₉ 规则甾烷	4-甲基甾烷/ C₂₉规则甾烷	伽马蜡烷/C₃₀ 藿烷	甾烷/ 藿烷	C₂₉甾烷 20S/ (S+R)	C₂₉甾烷 αββ/ (ααα+ αββ)	C₂₁₊₂₂/ C₂₉ 甾烷	三环萜烷/五环萜烷	DBT/ P
Z17-23	1753.00	0.68	1.00	2.35	2.28	1.21	21.86	35.49	42.65	0.51	0.46	0.41	0.62	0.22	0.22	0.01	0.03	0.13
G1-5-13	1337.00	0.52	0.77	2.47	-	-	22.06	37.19	40.75	0.54	0.30	0.38	0.40	0.24	0.23	0.01	0.02	0.10
G3-6-25	1788.00	0.50	5.22	24.29	-	-	22.98	36.80	40.22	0.57	0.31	0.25	0.32	0.31	0.27	0.03	0.02	0.06
G3-6-0151	1641.95	0.50	5.22	18.77	-	-	22.90	36.64	40.46	0.57	0.31	0.25	0.34	0.29	0.28	0.02	0.02	0.06
T37-29	1909.55	0.78	1.22	1.98	2.43	1.34	33.60	29.89	36.51	0.92	0.47	0.18	0.68	0.23	0.21	0.01	0.02	0.13
T35-29	2170.00	0.71	1.24	2.17	2.36	1.31	28.65	35.90	35.45	0.81	0.44	0.22	0.86	0.24	0.22	0.01	0.02	0.16

图3 高升、牛心坨原油的母质类型[25-26]

Fig.3 Cross plots of biomarker parameters indicate different facies in the Gaosheng and Niuxintuo oils[25-26]

图4 高升、牛心坨原油C27-C28-C29规则甾烷三角图[27]

Fig.4 Ternary plot showing the relative distribution of C27, C28 and C29 steranes in the oils from Gaosheng and Niuxintuo[27]

图5 高升(a)和牛心坨(b)原油中杂原子化合物类型及其相对丰度

Fig.5 Relative abundance of heteroatom class species in Gaosheng (a) and Niuxintuo (b) crude oil

表3 高升、牛心坨原油负离子ESI FT-ICR MS参数

Table 3 Basic parameters of Gaosheng and Niuxintuo crude oil analyzed by negative-ion ESI FT-ICR MS

井号	N₁ (%)	N₁O₁ (%)	N₁O₂ (%)	O₁ (%)	O₂ (%)	O₃ (%)	O₄ (%)	N₁ (%)				O₁ (%)			O₂ (%)			A	B	C	D
井号	N₁ (%)	N₁O₁ (%)	N₁O₂ (%)	O₁ (%)	O₂ (%)	O₃ (%)	O₄ (%)	DBE₉	DBE₁₂	DBE₁₅		DBE₄	DBE₅		DBE₁	DBE₅	DBE₆	A	B	C	D
Z17-23	40.86	6.99	5.82	25.79	19.83	0.00	0.71	22.34	14.19	5.25	37.20		20.61	34.20		15.34	11.64	1.38	1.04	0.24	0.75
G1-5-13	36.07	3.60	3.72	21.78	27.87	6.29	0.67	19.80	12.15	4.77	44.21		19.07	22.15		17.73	14.41	0.73	1.08	0.32	0.93
G3-6-25	54.22	5.76	2.23	23.11	14.12	0.00	0.55	17.50	12.62	5.84	34.36		19.36	19.80		17.27	14.21	0.73	1.35	0.33	0.90
G3-6-0151	50.46	4.42	1.49	22.45	20.06	0.00	1.12	17.73	12.64	5.70	36.74		19.43	34.24		14.50	11.24	1.45	1.52	0.51	1.04
T37-29	23.32	6.72	7.04	18.98	35.79	6.17	1.99	28.23	14.84	4.66	46.67		18.40	48.21		21.75	7.34	1.75	0.70	0.50	1.76
T35-29	17.62	1.15	0.45	16.01	63.92	0.71	0.14	30.69	12.45	3.49	61.03		18.07	85.16		3.38	2.75	13.41	0.80	1.08	1.86

图6 原油中N1、O1和O2类化合物DBE的分布特征

Fig.6 Relative abundance of N1, O1 and O2 class species with various DBE values in the crude oils detected by negative-ion ESI FT-ICR MS

图7 原油中N1类化合物碳数、DBE及其强度关系(左)和原油中不同DBE系列的N1类化合物碳数分布特征(右)

Fig.7 Plots of DBE versus carbon number for N1 class species for the selected oils (left), and carbon curve of N1 class species with DBE=9, 12 and 15 in the selected oils (right)

图8 原油中O1类化合物碳数、DBE及其强度关系(左)和原油中不同DBE系列(DBE为4和5)的O1类化合物碳数分布特征(右)

Fig.8 Plots of DBE versus carbon number for O1 class species in the selected oils (left), and carbon curve of O1 class species with DBE=4 and 5 in the selected oils (right)

图9 原油中O2类化合物碳数、DBE及其强度关系(左)和原油中不同DBE系列(DBE为1、5和6)的O2类化合物碳数分布特征(右)

Fig.9 Plots of DBE versus carbon number for O2 class species in the selected oils (left), and carbon curve of O2 class species with DBE=1, 5 and 6 in the selected oils (right)

图10 基于负离子ESI FT-ICR MS的参数与常规地球化学参数的相互关系

Fig.10 Cross plots of negative-ion ESI FT-ICR MS indices for condensation of O2 species versus GC-MS parameters for the oils

参考文献 81

[1]	李素梅, 庞雄奇, 金之钧, 等. 未熟-低熟油研究现状与存在的问题[J]. 地质论评, 2003, 49(3): 298-304.
[2]	毛光周, 刘池洋, 高丽华. 中国未熟-低熟油的基本特征及成因[J]. 山东科技大学学报(自然科学版), 2012, 31(6): 76-85.
[3]	王铁冠, 钟宁宁, 候读杰, 等. 中国低熟油的几种成因机制[J]. 沉积学报, 1997(2): 75-83.
[4]	黄第藩, 李晋超. 陆相沉积中的未熟石油及其意义[J]. 石油学报, 1987, 8(1): 1-9. DOI
[5]	葛海霞, 张枝焕, 闵伟, 等. 济阳坳陷青东凹陷低熟油生烃机理研究[J]. 现代地质, 2016, 30(5): 1105-1114.
[6]	史建南, 邹华耀, 郝芳. 辽河坳陷西部凹陷低熟油成藏机理[J]. 油气地质与采收率, 2007, 14(1): 36-39.
[7]	李素梅, 庞雄奇, 高先志, 等. 辽河西部凹陷稠油成因机制[J]. 中国科学(地球科学), 2008, 38(增): 138-49.
[8]	LI S M, PANG X Q, SHI Q, et al. Geochemical characteristics of crude oils from the Tarim Basin by Fourier transform ion cyclotron resonance mass spectrometry[J]. Energy Exploration & Exploitation, 2011, 29(6): 711-741.
[9]	李素梅, 孟祥兵, 张宝收, 等. 傅里叶变换离子回旋共振质谱的地球化学意义及其在油气勘探中的应用前景[J]. 现代地质, 2013, 27(1): 124-132.
[10]	李素梅, 徐田武, 史权, 等. 东濮凹陷盐湖相原油氮/氧化合物分布特征及其应用[J]. 现代地质, 2019, 33(6): 1137-1150.
[11]	李素梅, 张宝收, 张海祖, 等. 塔中原油超高二苯并噻吩硫特征及其控制因素[J]. 现代地质, 2011, 25(6): 1108-1120.
[12]	朱芳冰. 辽河盆地西部凹陷源岩特征及低熟油分布规律研究[J]. 地球科学, 2002, 27(1): 25-29.
[13]	史权, 张亚和, 徐春明, 等. 石油组分高分辨质谱分析进展与展望[J]. 中国科学(化学), 2014, 44(5): 694-700.
[14]	漆家福, 邓荣敬, 周心怀, 等. 渤海海域新生代盆地中的郯庐断裂带构造[J]. 中国科学(地球科学), 2008, 38(增): 19-29.
[15]	漆家福, 李晓光, 于福生, 等. 辽河西部凹陷新生代构造变形及“郯庐断裂带” 的表现[J]. 中国科学(地球科学), 2013, 43(8): 1324-1337.
[16]	李明刚, 漆家福, 童亨茂, 等. 辽河西部凹陷新生代断裂构造特征与油气成藏[J]. 石油勘探与开发, 2010, 37(3): 281-288.
[17]	冷济高, 庞雄奇, 李晓光, 等. 辽河断陷西部凹陷油气成藏主控因素[J]. 古地理学报, 2008, 10(5): 473-480.
[18]	胡英杰, 王延山, 黄双泉, 等. 辽河坳陷石油地质条件、资源潜力及勘探方向[J]. 海相油气地质, 2019, 24(2): 43-54.
[19]	王延山, 胡英杰, 黄双泉, 等. 渤海湾盆地辽河坳陷天然气地质条件、资源潜力及勘探方向[J]. 天然气地球科学, 2018, 29(10): 1422-1432. DOI
[20]	惠沙沙, 庞雄奇, 柳广弟, 等. 辽河西部凹陷沙河街组烃源岩特征及油源精细对比[J]. 地球科学, 2023, 48(8): 3081-3098.
[21]	周晓龙. 辽河西部凹陷雷家—高升地区原油物性特征及影响因素[J]. 石油地质与工程, 2017, 31(1): 22-25.
[22]	李秀娟. 国内外稠油资源的分类评价方法[J]. 内蒙古石油化工, 2008, 34(21): 61-62.
[23]	PETERS K E, WALTERS CC, MOLDOWAN J M. The Biomarker Guide[M]. Cambridge: Cambridge University Press, 2004.
[24]	SINNINGHE DAMSTE J S, KENIG F, KOOPMANS M P, et al. Evidence for gammacerane as an indicator of water column stratification[J]. Geochimica et Cosmochimica Acta, 1995, 59(9): 1895-1900. PMID
[25]	CONNAN J, CASSOU A M. Properties of gases and petroleum liquids derived from terrestrial kerogen at various maturation levels[J]. Geochimica et Cosmochimica Acta, 1980, 44(1): 1-23.
[26]	HUGHES W B, HOLBA A G, DZOU L I P. The ratios of dibenzothiophene to phenanthrene and pristane to phytane as indicators of depositional environment and lithology of petroleum source rocks[J]. Geochimica et Cosmochimica Acta, 1995, 59(17): 3581-3598.
[27]	HUANG W Y, MEINSCHEIN W G. Sterols as ecological indicators[J]. Geochimica et Cosmochimica Acta, 1979, 43(5): 739-745.
[28]	HUGHEY C A, RODGERS R P, MARSHALL A G, et al. Identification of acidic NSO compounds in crude oils of different geochemical origins by negative ion electrospray Fourier transform ion cyclotron resonance mass spectrometry[J]. Organic Geochemistry, 2002, 33(7): 743-759.
[29]	HUGHEY C A, RODGERS R P, MARSHALL A G, et al. Acidic and neutral polar NSO compounds in Smackover oils of different thermal maturity revealed by electrospray high field Fourier transform ion cyclotron resonance mass spectrometry[J]. Organic Geochemistry, 2004, 35(7): 863-880.
[30]	QIAN K N, ROBBINS W K, HUGHEY C A, et al. Resolution and identification of elemental compositions for more than 3000 crude acids in heavy petroleum by negative-ion microelectrospray high-field Fourier transform ion cyclotron resonance mass spectrometry[J]. Energy & Fuels, 2001, 15(6): 1505-1511.
[31]	JI H, LI S M, GREENWOOD P, et al. Geochemical characteristics and significance of heteroatom compounds in lacustrine oils of the Dongpu Depression (Bohai Bay Basin, China) by negative-ion Fourier transform ion cyclotron resonance mass spectrometry[J]. Marine and Petroleum Geology, 2018, 97: 568-591.
[32]	CLEGG H, WILKES H, HORSFIELD B. Carbazole distributions in carbonate and clastic source rocks[J]. Geochimica et Cosmochimica Acta, 1997, 61(24): 5335-5345.
[33]	张宝, 包建平. 有机含氮化合物研究新进展[J]. 天然气地球科学, 2004, 15(2): 182-186. DOI
[34]	李素梅, 王铁冠, 张爱云, 等. 原油中吡咯类化合物的地球化学特征及其意义[J]. 沉积学报, 1999, 17(2): 312.
[35]	WAN Z H, LI S M, PANG X Q, et al. Characteristics and geochemical significance of heteroatom compounds in terrestrial oils by negative-ion electrospray Fourier transform ion cyclotron resonance mass spectrometry[J]. Organic Geochemistry, 2017, 111: 34-55.
[36]	KIM S, STANFORD L A, RODGERS R P, et al. Microbial alteration of the acidic and neutral polar NSO compounds revealed by Fourier transform ion cyclotron resonance mass spectrometry[J]. Organic Geochemistry, 2005, 36(8): 1117-1134.
[37]	LIAO Y H, SHI Q, HSU C S, et al. Distribution of acids and nitrogen-containing compounds in biodegraded oils of the Liaohe Basin by negative ion ESI FT-ICR MS[J]. Organic Geoche-mistry, 2012, 47: 51-65.
[38]	LIU Y, WAN Y Y, ZHU Y J, et al. Impact of biodegradation on polar compounds in crude oil: Comparative simulation of biodegradation from two aerobic bacteria using ultrahigh-resolution mass spectrometry[J]. Energy & Fuels, 2020, 34(5): 5553-5565.
[39]	BAKR M M Y, WILKES H. The influence of facies and depositional environment on the occurrence and distribution of carbazoles and benzocarbazoles in crude oils: A case study from the Gulf of Suez, Egypt[J]. Organic Geochemistry, 2002, 33(5): 561-580.
[40]	ZHANG C M, ZHANG Y Q, ZHANG M, et al. Carbazole distributions in rocks from non-marine depositional environments[J]. Organic Geochemistry, 2008, 39(7): 868-878.
[41]	SCHIMMELMANN A, WINTSCH R, LEWAN M. From mo-dern chitin to thermally mature kerogen: Lessons from nitrogen isotope ratios[M]// Proceedings of the Abstracts of Papers of the American Chemical Society. Washington: Amer Chemical Soc,20036.
[42]	LI M W, FOWLER M G, OBERMAJER M, et al. Geochemical characterisation of Middle Devonian oils in NW Alberta, Canada: Possible source and maturity effect on pyrrolic nitrogen compounds[J]. Organic Geochemistry, 1999, 30(9): 1039-1057.
[43]	LI M W, LARTER S R, STODDART D, et al. Fractionation of pyrrolic nitrogen compounds in petroleum during migration: Deri-vation of migration-related geochemical parameters[J]. Geological Society, London, Special Publications, 1995, 86(1): 103-123.
[44]	SNYDER L R. Distribution of benzcarbazole isomers in petro-leum as evidence for their biogenic origin[J]. Nature, 1965, 205: 277.
[45]	BENNETT B, CHEN M, BRINCAT D, et al. Fractionation of benzocarbazoles between source rocks and petroleums[J]. Organic Geochemistry, 2002, 33(5): 545-559.
[46]	SHI Q, HOU D J, CHUNG K H, et al. Characterization of heteroatom compounds in a crude oil and its saturates, aroma-tics, resins, and asphaltenes (SARA) and non-basic nitrogen fractions analyzed by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry[J]. Energy & Fuels, 2010, 24(4): 2545-2553.
[47]	SHI Q, ZHAO S Q, XU Z M, et al. Distribution of acids and neutral nitrogen compounds in a Chinese crude oil and its fractions: Characterized by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry[J]. Energy & Fuels, 2010, 24(7): 4005-4011.
[48]	POETZ S, HORSFIELD B, WILKES H. Maturity-driven generation and transformation of acidic compounds in the organic-richposidonia shale as revealed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry[J]. Energy & Fuels, 2014, 28(8): 4877-4888.
[49]	KAMGA A W, BEHAR F, HATCHER P G. Quantitative ana-lysis of long chain fatty acids present in a type I kerogen using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry: Compared with BF₃/MeOH methylation/GC-FID[J]. Journal of the American Society for Mass Spectrometry, 2014, 25(5): 880-890.
[50]	AMRANI A, AIZENSHTAT Z. Photosensitized oxidation of naturally occurring isoprenoid allyl alcohols as a possible pathway for their transformation to thiophenes in sulfur rich depositional environments[J]. Organic Geochemistry, 2004, 35(6): 693-712.
[51]	ROJAS-RUIZ F A, ORREGO-RUIZ J A. Distribution of oxygen-containing compounds and its significance on total organic acid content in crude oils by ESI negative ion FT-ICR MS[J]. Energy & Fuels, 2016, 30(10): 8185-8191.
[52]	LIU W M, LIAO Y H, PAN Y H, et al. Use of ESI FT-ICR MS to investigate molecular transformation in simulated aerobic biodegradation of a sulfur-rich crude oil[J]. Organic Geochemistry, 2018, 123: 17-26.
[53]	HEADLEY J V, PERU K M, BARROW M P. Advances in mass spectrometric characterization of naphthenic acids fraction compounds in oil sands environmental samples and crude oil—a review[J]. Mass Spectrometry Reviews, 2016, 35(2): 311-328.
[54]	段毅, 周世新, 孟自芳. 塔里木盆地群5井和曲1井原油的油源研究——脂肪酸及烷基环己烷系列化合物提供的新证据[J]. 石油实验地质, 2001(4): 433-447.
[55]	PAN Y H, LIAO Y H, SHI Q, et al. Acidic and neutral polar NSO compounds in heavily biodegraded oils characterized by negative-ion ESI FT-ICR MS[J]. Energy & Fuels, 2013, 27(6): 2960-2973.
[56]	MARTINS L L, PUDENZI M A, DA CRUZ G F, et al. Asses-sing biodegradation of Brazilian crude oils via characteristic profiles of O₁ and O₂ compound classes: Petroleomics by negative-ion mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry[J]. Energy & Fuels, 2017, 31(7): 6649-6657.
[57]	BOON A R, DUINEVELD G C A. Phytopigments and fatty acids as molecular markers for the quality of near-bottom particulate organic matter in the North Sea[J]. Journal of Sea Research, 1996, 35(4): 279-291.
[58]	VOLKMAN J K, BARRETT S M, BLACKBURN S I, et al. Microalgal biomarkers: A review of recent research developments[J]. Organic Geochemistry, 1998, 29(5/6/7): 1163-1179.
[59]	MEYERS P A. Organic geochemical proxies of paleoceanogra-phic, paleolimnologic, and paleoclimatic processes[J]. Organic Geochemistry, 1997, 27(5/6): 213-250.
[60]	SINNINGHE DAMSTÉ J S, VERSCHUREN D, OSSEBAAR J, et al. A 25,000-year record of climate-induced changes in lowland vegetation of eastern equatorial Africa revealed by the stable carbon-isotopic composition of fossil plant leaf waxes[J]. Earth and Planetary Science Letters, 2011, 302(1/2): 236-246.
[61]	TIERNEY J E, RUSSELL J M, SINNINGHE DAMSTÉ J S, et al. Late Quaternary behavior of the East African monsoon and the importance of the Congo Air Boundary[J]. Quaternary Science Reviews, 2011, 30(7/8): 798-807.
[62]	OLDENBURG T B P, BROWN M, BENNETT B, et al. The impact of thermal maturity level on the composition of crude oils, assessed using ultra-high resolution mass spectrometry[J]. Organic Geochemistry, 2014, 75: 151-168.
[63]	HOSSEINI S H, HORSFIELD B, POETZ S, et al. Role of maturity in controlling the composition of solid bitumens in veins and vugs from SE Turkey as revealed by conventional and advanced geochemical tools[J]. Energy & Fuels, 2017, 31(3): 2398-2413.
[64]	FARRIMOND P, GRIFFITHS T, EVDOKIADIS E. Hopanoic acids in Mesozoic sedimentary rocks[J]. Organic Geochemistry, 2002, 33(8): 965-977.
[65]	任平. 高升—雷家地区未熟油藏形成条件分析[J]. 石油地质与工程, 2015, 29(2): 38-41.
[66]	曲彦胜, 钟宁宁, 刘岩, 等. 辽河西部凹陷富有机质沉积识别及控制因素探讨[J]. 长江大学学报(自然科学版), 2014, 11(5): 18-22.
[67]	WATSON J S, JONES D M, SWANNELL R P J, et al. Formation of carboxylic acids during aerobic biodegradation of crude oil and evidence of microbial oxidation of hopanes[J]. Organic Geochemistry, 2002, 33(10): 1153-1169.
[68]	黄第藩, 张大江, 张林晔. 中国未成熟石油成因机制和成藏条件[M]. 北京: 石油工业出版社, 2003.
[69]	LUCACH S O, BOWLER B F J, FREWIN N, et al. Variation in alkylphenol distributions in a homogenous oil suite from the Dhahaban petroleum system of Oman[J]. Organic Geochemistry, 2002, 33(5): 581-594.
[70]	史继扬, 向明菊, 屈定创. 未熟-低熟烃源岩中脂肪酸的热模拟实验及演化[J]. 科学通报, 2001, 46(18): 1567-1572.
[71]	张松林, 崔明中, 李振西, 等. 盐湖相低熟油脂肪酸的组成与分布特征[J]. 沉积学报, 1999, 17(1): 130-135.
[72]	SHI J Y, XIANG M J, QU D C. Simulation experiments for evolution of fatty acids in immature source rocks[J]. Chinese Science Bulletin, 2001, 46(24): 2092-2096.
[73]	TISSOT B P, WELTE D H. Petroleum Formation and Occurrence[M]. Berlin, Heidelberg: Springer,1984.
[74]	WILSON H H. The case for early generation and accumulation of oil[J]. Journal of Petroleum Geology, 1990, 13(2): 127-156.
[75]	屈定创, 史继扬, 向明菊. 一类新的藿烯化合物的发现及其在地质藿类成因上的意义[J]. 中国科学(B辑), 1995, 25(6): 665-72.
[76]	NASCIMENTO L R, REBOUÇAS L M C, KOIKE L, et al. Acidic biomarkers from albacora oils, Campos Basin, Brazil[J]. Organic Geochemistry, 1999, 30(9): 1175-1191.
[77]	INNES H E, BISHOP A N, HEAD I M, et al. Preservation and diagenesis of hopanoids in recent lacustrine sediments of Priest Pot, England[J]. Organic Geochemistry, 1997, 26(9/10): 565-576.
[78]	WATSON D F, FARRIMOND P. Novel polyfunctionalised geohopanoids in a recent lacustrine sediment (Priest Pot, UK)[J]. Organic Geochemistry, 2000, 31(11): 1247-1252.
[79]	管红香, 吴能友, 茅晟懿, 等. 南海北部冷泉碳酸盐岩中系列藿烷酸的检出及意义[J]. 地球科学, 2013, 38(5): 1014-1022.
[80]	王广源, 周心怀, 王昕, 等. 蓬莱19-3/25-6油田未熟-低熟油特征与成因[J]. 石油实验地质, 2014, 36(2): 230-237.
[81]	LIU H, LIU W G. N-Alkane distributions and concentrations in algae, submerged plants and terrestrial plants from the Qinghai-Tibetan Plateau[J]. Organic Geochemistry, 2016, 99: 10-22.