Organic Geochemistry and Elements Distribution in Dahuangshan Oil Shale, Southern Junggar Basin: Origin of Organic Matter and Depositional Environment
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International Journal of Coal Geology 115 (2013) 41–51 Contents lists available at SciVerse ScienceDirect International Journal of Coal Geology journal homepage: www.elsevier.com/locate/ijcoalgeo Organic geochemistry and elements distribution in Dahuangshan oil shale, southern Junggar Basin: Origin of organic matter and depositional environment Shu Tao a,b,⁎, Dazhen Tang a, Hao Xu a, Jianlong Liang a, Xuefeng Shi c a Coal Reservoir Laboratory of National CBM Engineering Center, School of Energy Resources, China University of Geosciences (Beijing), Beijing 100083, China b Coalbed Methane Resources and Reservoir Formation Process Key Laboratory of Ministry of Education, China University of Mining and Technology, Xuzhou 221116, China c CNOOC Energy Technology & Services-Oilfield Engieering Research Institute, Tianjin 300452, China article info abstract Article history: The Dahuangshan oil shale, located in the northern Bogda Mountain, on the southern margin of the Junggar Received 3 March 2013 Basin, was deposited in a Late Permian lacustrine environment. A combined investigation of element and Received in revised form 14 May 2013 organic geochemistry was performed to define the source rock potential, the paleoenvironment, and source Accepted 16 May 2013 of the organic matter. Thick sequences of oil shales with an average thickness of 638 m were deposited in Available online 25 May 2013 Lucaogou Formation which mainly consists of oil shale, argillaceous dolomite, silty claystone, tuff, limestone, and dolomitic marl. A spot of plant stem fossils and abundance of pyrite crystals, fishtail and fish skeleton can Keywords: Geochemistry also be found there. Rare earth elements Analyzed oil shale samples from Dahuangshan area are characterized by high total organic carbon (TOC) con- Paleoenvironment tents (5.6–34.75%), S2 (22.65–199.25 mg HC/g rock), hydrogen index (HI, 359–1068 mg HC/g TOC), and oil Oil shale yield (4.9–26.6%), indicating the oil shales have excellent source rock potential. Tmax values (433–453 °C) Dahuangshan show an early to medium maturation stage of organic matter, which is supported by organic geochemical maturation parameters. All of the obtained kerogen types are types II and I, with oil prone source rock potential. Dahuangshan oil shale samples are rich in SiO2 (68.59%), followed by Al2O3 (10.18%) and Fe2O3 (5.43%). Com- pared with average shale and North American Shale Composite (NASC), analyzed oil shale samples are obviously enriched in P (0.71%). There is a significant correlation between Al2O3 and Fe2O3,MgO,K2O, MnO, Cu, Ba, Co, and Ni for their association with clay minerals. Besides, the significant correlations between Fe2O3 and MnO, Co, and Ni are considered to result from their similarity on geochemical behavior. All selected oil shales are characterized by distinctly sloping light rare earth elements (LREE) trends (LaN/SmN = 2.70–5.95) accompanied by flat heavy rare earth elements (HREE) trends, with distinct Eu negative anomalies (0.60–0.73). Two slightly different pat- terns of REEs in the oil shale samples are distinguished by the difference in Ce depletion and Nd anomaly. In addition, Dahuangshan oil shale samples are characterized by short- to middle-chain n-alkanes, low carbon preference index (CPI) values (0.93–1.24), single peak composed of nC20 or nC22,lowPr/Ph(0.41–0.91), relatively high Homohop index (0.061–0.99), and high concentrations of C27 sterane, indicating reducing, deep-water, and moderate saline environment with prevalent contribution of algae and microorganisms to organic matter accumulation. © 2013 Elsevier B.V. All rights reserved. 1. Introduction fossil resources that can be produced and converted to liquid fuels, has received increasing attention. The Third Chinese Oil and Gas Resource As- With rapid increases in consumption of energy and chemicals, oil sessment and the 2007 World Energy Survey showed that a total oil shale supply and demand imbalances are intensifying so as to become resource of some 720 Gt is located across 22 provinces, 47 basins, and 80 a restraining factor on economic growth in China. China had imported deposits. The shale oil resource has been estimated at some 48 Gt, which about 179 million (Fu et al., 2010) tons of crude oil in 2008 and over is highly significant for alleviating the pressure of petroleum supplies (Liu 250 million tons in 2011. Oil shale, one of the substantial unconventional et al., 2007; WEC, 2007). At present, retorting and combustion for power generation are the main patterns of oil shale application. In 2011, shale oil production by retorting technology was about 1.46 million tons all ⁎ Corresponding author at: Coal Reservoir Laboratory of National CBM Engineering over the world, of which about 650,000 t were produced in China, includ- Center; School of Energy Resources, China University of Geosciences (Beijing), Beijing 100083, China. Tel.: +86 10 82322011. ing 7 oil shale retorting plants located in 5 provinces (Li, 2012). Estonia, E-mail address: [email protected] (S. Tao). the biggest electricity producer from oil shale in the world (Hamburg, 0166-5162/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.coal.2013.05.004 42 S. Tao et al. / International Journal of Coal Geology 115 (2013) 41–51 2011), whose total generating capacities reached up to 3200 MW with 2. Geological setting about 15 million tons of oil shale was used for power generation in 2011. Thick sequences of organic-rich lacustrine oil shales have been Bogda Mountain is situated in the eastern part of Tianshan Mountain reported to underlie much of the Junggar Basin in Xinjiang Uygur range and is located on the southern margin of the Junggar Basin which Autonomous Region, northwest China. Several authors have ranked is a large, organic-rich foreland basin in northwest China (Jiao et al., these organic-rich lacustrine mudstones (oil shales) among the thickest 2007; Tao et al., 2012a). Thick sequences of organic-rich lacustrine oil and richest petroleum source rock intervals in the world (e.g. Carroll shales are exposed in the foothills of Bogda Mountain (Carroll, 1998), et al., 1992; Graham et al., 1990; Watson et al., 1987). Previous researches including 13 different oil shale mining areas, and eight of them have have focused on the oil yield, deposition, development, resources, and been studied by us in recent years (Fig. 1A) (Tao et al., 2010, 2011, metallogenic characteristics of oil shale in this area (e.g. Tao et al., 2010, 2012a,b,c). Carroll et al. (1992) documented three Upper formations 2011, 2012a,b,c). Until now, however, no available publications have that contain organic-rich mudstones. From oldest to youngest, they are addressed the geochemical characteristics of oil shale in this area. the Jingjingzigou, Lucaogou, and Hongyanchi formations, among which In the current study, the petroleum potential and the thermal ma- extremely rich and oil-prone oil shales are discovered in Lucaogou turity of the organic matter contained in Dahuangshan oil shales from Formation. the southern Junggar Basin were studied by Rock-Eval pyrolysis and The Dahuangshan region is located in the eastern part of Bogda some biomarker parameters; the occurrence and distribution of the Mountain oil shale belt (Fig. 1A). The Permian Jingjingzigou, Lucaogou, major and trace elements in the oil shales were studied in order to de- and Wutonggou formations are the major outcropping seams in this termine the geochemical background of this basin; the sedimentary and area (Fig. 1B). The Lucaogou Formation consists of a sequence of dolo- organic geochemical characteristics of selected oil shale samples were mitic mudstone, dolomitic marl, argillaceous dolomite, limestone, silty examined to discuss the source of organic matter and paleoenvironment claystone, tuff, and oil shale (Fig. 2). In Dahuangshan area, the thickness of the Dahuangshan oil shales. of the Lucaogou Formation (average 845 m) is larger than that of other Fig. 1. (A) Simplified map showing geological setting of northern Bogda Mountain, and the location of the study area. (B) Simplified geological map of the Dahuangshan oil shales, showing three oil shale profiles, and two boreholes. S. Tao et al. / International Journal of Coal Geology 115 (2013) 41–51 43 3. Samples and analytical procedures Weathering is known to affect amount and quality of organic matter in petroleum source rocks (Clayton and King, 1987; Leythaeuser, 1973). Littke et al. (1991) noted that pyrite, sulfur, and organic carbon content were altered by weathering. Therefore, the profile samples were col- lected after digging about 40 cm into the rock to minimize the effects of surface weathering. All samples were carefully packed and then im- mediately sent to the laboratory for experiments. A total of 42 outcrop oil shale samples and some interbedded rocks were collected from section No.2 (Fig. 2). All of the oil shale samples were selected for total organic carbon (TOC), Rock-Eval pyrolysis, ash yield, total sulfur, organic sulfur, and Gray-King low-temperature dry distillation analyses. Then ten of them were analyzed by X-ray fluores- cence (XRF), inductively-coupled plasma mass spectrometer (ICP-MS), gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS). The samples for geochemical analysis were all crushed and ground to less than 200 mesh. TOC and organic sulfur values were deter- mined in the Geological Laboratory of Exploration and Development Research Institute of PetroChina Huabei Oilfield Company, following the Chinese National Standard methods GB/T 19145-2003 and GB/T 215-2003, respectively. Rock-Eval pyrolysis data were performed on a Rock-Eval II instrument following the guidelines established by Espitalié et al. (1985). The samples were analyzed in the Petroleum Geology Research Center, China Petroleum Exploration and Develop- ment Research Institute. Ash yield, total sulfur, and Gray-King low- temperature dry distillation were conducted at the Xinjiang Institute of Coal Science and Coal Testing Laboratory, following the Chinese National Standard methods GB/T212-2001, GB/T214-2007, and GB/T 1341-2001, respectively.