第 44 卷第 6 期 Vol.44, No.6, 536~ 年 11 月 GEOCHIMICA Nov., 2015 曹新星 1,2*, 李艳 1,2, 王丽 1, 尹琴 3, 宋之光 1, 赵迪斐 (1., ; 2., ; 3., ; 4.,

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1 第 44 卷第 6 期 Vol.44, No.6, 536~ 年 11 月 GEOCHIMICA Nov., 2015 曹新星 1,2*, 李艳 1,2, 王丽 1, 尹琴 3, 宋之光 1, 赵迪斐 (1., ; 2., ; 3., ; 4., ) 摘要 : (K 2 n 3 )(K 2 n 4 ), (TOC) 1.37%~2.52% 0.12%~0.82%, > > >, 21.1%~54.9%, 15.4%~27.8%, 12.7%~19.2% 1.7%~11.0%, (Fla)(Py)(Bflas) a (BaAn) e (BePy) (Cor) (Inpy) (P) [g, h, i] 苝 (BghiP) 䓛 (Chry) (MP) (Ret) 苝 (Pery);, 䓛, a e ; [g, h, i] 苝 a e, [g, h, i] 苝, 苝,, 关键词 : ; ; ; 中图分类号 : P593 文献标识码 : A 文章编号 : (2015) The distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments from Upper Cretaceous Nenjiang Formation of Songliao Basin and its paleoclimate significance CAO Xin-xing 1,2*, LI Yan 1,2, WANG Li 1, YIN Qin 3, SONG Zhi-guang 1 and ZHAO Di-fei 4 1. State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou , China; 2. University of Chinese Academy of Sciences, Beijing , China; 3. Research Institute of Petroleum Exploration and Production, SINOPEC Henan Oilfield Branch Company, Zhengzhou , China; 4. Key Laboratory of Coalbed Methane Resources and Reservoir Formation Process, the Ministry of Education, China University of Mining and Technology, Xuzhou, Jiangsu , China Abstract: The core samples from the members 3 and 4 of Nenjiang Formation (K 2 n 3 and K 2 n 4 ) in the Songliao Basin have been analysed for organic matter abundance and the composition and distribution of polycyclic aromatic hydrocarbons (PAHs). The results show that the TOC content of sediments in K 2 n 3 (member 3) and K 2 n 4 (member 4) is in the range of 1.37% to 2.52% and 0.12% to 0.82%, respectively. The relative abundance of soluble organic matter fractions is in an order of aromatic hydrocarbons < aliphatic hydrocarbons < polar compounds < asphaltene, their relative percentage being in the range of 21.1% to 54.9% (asphaltene), 15.4% to 27.8% (polar compounds), 12.7% to 19.2% (aliphatic hydrocarbons) and 1.7% to 11.0% (aromatic hydrocarbons), respectively. 4 收稿日期 (Received): ; 改回日期 (Revised): ; 接受日期 (Accepted): 基金项目 : ( ) 作者简介 : (1989 ),,, * 通讯作者 (Corresponding author): CAO Xin-xing, caoxinxing@gig.ac.cn, Tel: Geochimica Vol. 44 No. 6 pp. 536~545 Nov., 2015

2 第 6 期曹新星等 : 松辽盆地上白垩统嫩江组三四段沉积有机质及多环芳烃化合物组成分布与古气候意义 537 A large number of PAH compounds are detected in the sediments, including fluoranthene (Fla), pyrene (Py), benzofluoranthene (Bflas), benzo[a]anthracene (BaAn), benzo[e]pyrene (BePy), coronene (Cor), indeno[1, 2, 3-cd]pyrene (Inpy), phenanthrene (P), benzo[ghi]perylene (BghiP), methylphenanthrene (MP), chrysene (Chry), retene (Ret) and perylene (Pery). Among these PAH compounds, the P, MP, Chry and Ret are mainly derived from the original organic matter input and its diagenetic transformation. The ratios of PAH compounds suggest that the Fla, Py, Bflas, BaAn, and BePy in the sediments of K 2 n 3 were largely originated from the combustion of biomass, and the Inpy and BghiP perhaps generated from the diagenetic transformation of original organic matter. While the Fla, Py, Bflas, BaAn and BePy in the K 2 n 4 were mainly derived from the combustion of biomass, and the Inpy and BghiP in the K 2 n 4 were originated from the mix sources (the combustion of biomass and the diagenesis process). The high abundance of Pery in the K 2 n 4 was likely related to the specific terrigenous organic matter input. Finally, vertical variations in the relative abundance of these PAH compounds in the sediments of K 2 n 3 and K 2 n 4 suggest that the Songliao Basin may experience a climatic shift from relative warm-humid to arid during the sedimentation period of K 2 n 3 and K 2 n 4. Key words: polycyclic aromatic hydrocarbons; paleoclimate and paleoenvironment; Cretaceous Nenjiang Formation; Songliao basin 0, [1 5] [6], -,, Song et al. [7] Pr/Ph /,, [8], ( ),,, [9], 1, ;,, ; [9] (SK-1)SK-1 ( 1) -, [10] m, ~ m;, m, ~ m;, ;, ( 2) 2 100, 50 g, +( 91) 72 h, ; + Cao Xin-xing et al.: Distribution of PAHs in Upper Cretaceous sediments of Songliao Basin and its paleoclimate significance

538 2015 年 Fig.1 1 1 Map showing the structure of Songliao Basin and the location of SK-1 drilling hole ( 41)+(11), Rock-Eval 6 Plus ( 1) (GC) Agilent 7890A, (FID), JW-DB-5 30 m 0.25 mm 0.

3 年 Fig Map showing the structure of Songliao Basin and the location of SK-1 drilling hole ( 41)+(11), Rock-Eval 6 Plus ( 1) (GC) Agilent 7890A, (FID), JW-DB-5 30 m 0.25 mm 0.25 µm ; ,, 80, 2 min 20 /min 130, 3 /min min; 80, 2 min 4 /min min GC-MS Thermo GC Ultra Trace-DSQ, (70 ev), HP-5 60 m 0.25 mm 0.25 µm,, 290, GC, 50~650 u , t max 450, 443, R o 0.71~1.05,, TOC 1.37%~2.52%, Geochimica Vol. 44 No. 6 pp. 536~545 Nov., 2015

第 6 期曹新星等 : 松辽盆地上白垩统嫩江组三四段沉积有机质及多环芳烃化合物组成分布与古气候意义 539 Fig.2 2 Photo images of the core samples from the third and fourth members of Nenjiang Formation (K 2 n 3 and K 2 n 4 ) TOC 1%, 21.1%~54.9%, 15.

4 第 6 期曹新星等 : 松辽盆地上白垩统嫩江组三四段沉积有机质及多环芳烃化合物组成分布与古气候意义 539 Fig.2 2 Photo images of the core samples from the third and fourth members of Nenjiang Formation (K 2 n 3 and K 2 n 4 ) TOC 1%, 21.1%~54.9%, 15.4%~27.8%, 12.7%~19.2%, 1.7%~11.0%,, 3,, nc 16 nc 15 ;,, nc 15 nc 17 nc 19 ;,,,, [11] ; [12],, CPI , 4, TOC Pr/Ph, ( ), Pr/Ph 2.06~4.20 ;, Pr/Ph 0.95~2.35 (> 3), Pr/Ph 0.8~2.5, [13] Pr/Ph 2~3, Pr/Ph 3;, (), Pr/Ph 0.95~2.35, TOC, 3.2 3~6 ( 5), Table 1 表 1 嫩三段和嫩四段样品热解参数 Sampling information and pyrolysis parameters of the core samples from Nenjiang Formation d (m) t max () TOC (%) HI (/TOC)(mg/g) OI (/TOC)(m/g) R o N N N N N N N N N N N N N Cao Xin-xing et al.: Distribution of PAHs in Upper Cretaceous sediments of Songliao Basin and its paleoclimate significance

5 年 Fig.3 3 The chromatograms of aliphatic hydrocarbon fractions in the core samples of Nenjiang Formation Geochimica Vol. 44 No. 6 pp. 536~545 Nov., 2015

6 第 6 期曹新星等 : 松辽盆地上白垩统嫩江组三四段沉积有机质及多环芳烃化合物组成分布与古气候意义 541, 苝 2, Fla/(Py+Fla) 0.5, 0.44~0.69, 0.36[g, h, i] 苝, InPy/(BghiP+InPy) 0.2; [g, h, i] 苝, InPy/(BghiP+InPy) 0.23~0.33, a 䓛,, BaAn/(BaAn+ Chry) 0.35, CPI TOCPr/Ph Fig.4 Profile variation of CPI, TOC and Pr/Ph ratio in the core samples of Nenjiang Formation (P)(MP)(Ret) 苝 (Pery)(Fla) (Py) a (BaAn) 䓛 (Chry)(Bflas) e (BePy) a (BaPy)(InPy) [g, h, j] 苝 (BghiP)(Cor),, [g, h, i] 苝, ; 苝苝, (m/z=252) ( 5b); [g, h, i] 苝, [g, h, i] 苝 ;, [g, h, i] 苝 5~6 a e a [g, h, j] 苝, [14], Fla/(Py + Fla) 0.5, Fla Py (), Fla/(Py + Fla) 0.4, 0.4~0.5 [15 17] Fla/(Py + Fla) 0.5, ; Fla/(Py + Fla) 0.49, 2, , Yunker et al. [14] BaAn/(BaAn + Chry) 0.35 a, BaAn/(BaAn + Chry) Fla/(Py + Fla) BaAn/(BaAn + Chry) 0.35, BaAn/(BaAn + Chry) Fla/(Py + Fla) ( 6),,, a 表 2 多环芳烃化合物比值表 Table 2 Ratios of polycyclic aromatic hydrocarbon compounds Ratio () () N875 N885 N917 N964 N985 N1004 N1026 N1038 N1111 N1135 N1145 N1155 Fla/Py Fla/(Py+Fla) InPy/(BghiP+InPy) BaAn/ : , BaAn + Chry Cao Xin-xing et al.: Distribution of PAHs in Upper Cretaceous sediments of Songliao Basin and its paleoclimate significance

7 年 Fig.5 5 (m/z = ) Mass chromatograms of PAHs (m/z ) in the third and fourth members of Nenjiang Formation Geochimica Vol. 44 No. 6 pp. 536~545 Nov., 2015

8 第 6 期曹新星等 : 松辽盆地上白垩统嫩江组三四段沉积有机质及多环芳烃化合物组成分布与古气候意义 a ( Yunker et al. [14] ) Fig. 6 Cross plot of BaAn/(BaAn+Chry) vs. Fla/(Fla+Py) for source determination (referred to Yunker et al. [14] ), InPy/(BghiP + InPy) [g, h, i] 苝, 0.5 (), 0.2, 0.5~0.2 [18] InPy/(BghiP + InPy) 0.2, ; 0.5~0.2, [g, h, i] 苝, e [19], e, [20 21], [19],, [22], 䓛 [23], 䓛,, [24], [25 26] 5,, ;,,,,, () [27], 苝 [28], [29], 苝苝, 苝 [30 31] 苝, 苝, 苝 ; 苝 ( 5),, : a e ; 䓛 [g, h, i] 苝 ; 苝 ; [g, h, i] 苝 Cao Xin-xing et al.: Distribution of PAHs in Upper Cretaceous sediments of Songliao Basin and its paleoclimate significance

9 年 3.4,, [32],, [27],, a,, [18] ;, a,,,,,, [27],, 4, TOC 1.37~2.52%, TOC 1%,,, a e [g, h, i] 苝䓛苝 BaAn/(BaAn + Chry) > 0.35Fla/(Py + Fla) > 0.5 InPy/(BghiP + InPy) < 0.2; BaAn/(BaAn + Chry) > 0.35Fla/(Py + Fla) > 0.4 InPy/(BghiP + InPy) 0.5~0.2 a e ; 䓛苝 [g, h, i] 苝 ; 苝 ; [g, h, i] 苝参考文献 (References): [1],,,,. -[J]., 2008, 25(3): Xi Dang-peng, Yin Xiu-zhen, Cui Ying, Jin Xia, Wang Xiao-qiao. Paleolimnology and paleocimate from the upper Qingshankou to the lower Yaojia Formations in central Songliao Basin [J]. Acta Micropalaeontol Sinica, 2008, 25(3): (in Chinese with English abstract). [2],,,,,. [J]., 1998, 15(4): Huang Qing-hua, Chen Chun-rui, Wang Ping-zai, Han Min-xin, Li Xing-jun, Wu Da-qing. The late Cretaceous bio-evolution and anoxic events in the ancient lake in the Songliao Basin [J]. Acta Micropalaeontol Sinica, 1998, 15(4): (in Chinese with English abstract). [3],,,,,,,. [J]., 2004, 23(5): Wan Chuan-biao, Qiao Xiu-yun, Lü Qian, Jin Yu-dong, Wang Ping, Chi Huan-yuan, Jiao Yu-guo, Zhang Guo-bin. Spore and pollen, alga fossil assemblage of Nenjiang Formation in the western part of Daqing Placanticline [J]. Pet Geol Oilfield Develop Daqing, 2004, 23(5): (in Chinese with English abstract). [4]. 1 [D]. : (), Liu Mei-yu. Late Cretaceous Lake environmental change revealed by biomarkers from SK-1, Songliao Basin [D]. Beijing: China University of Geosciences (Beijing), 2014 (in Chinese with English abstract). [5] Chamberlain C P, Wan X Q, Graham S A, Carroll A R, Doebbert A C, Sageman B B, Blisniuk P, Kent-Corson M L, Wang Z, Wang C S. Stable isotopic evidence for climate and basin evolution of the Late Cretaceous Songliao basin, China [J]. Palaeogeogr Palaeoclimatol Palaeoecol, 2013, 385: [6],,,,,,. [J]., 2002, 29(4): Ma An-lai, Li Xian-qing, Xiong Bo, Wang Tie-guan, Feng Zi-hui, Kong Qing-yun, Li Shao-hua. Organic petrology of the source rocks in Qijia-Gulong region, Songliao basin [J]. Pet Explor Geochimica Vol. 44 No. 6 pp. 536~545 Nov., 2015

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