西藏纳木错表层沉积物中正构烷烃的来源与空间分布特征

通过测定纳木错现代植物和表层沉积物样品中的正构烷烃,结合主成分分析方法,明确了表层沉积物中烷烃的主要来源,并初步分析了它们在湖泊中的空间分布特征.研究结果显示,沉水植物所含烷烃以n-C21-C25为主,具有n-C23的峰值;陆生植物主要含n-C27-C33烷烃,具有n-C29或n-C31的峰值;但垫状点地梅(Androsace tapete)和香柏(Sabina pingii)的主峰碳却是n-C33烷烃,这在以往研究中鲜有报道.在纳木错表层沉积物中,正构烷烃具有典型的n-C31和n-C23双峰分布形式,来源于低等菌藻类、沉水植物以及陆生植物,其中碳数小于C20的短链烷烃主要来源于低等菌藻类,其空间分布均一,由低等菌藻类的浮游生活型所决定;长链烷烃主要来源于高等植物,含量从滨岸到湖中心逐渐减少,这与其在运移和沉积过程中受微生物的持续降解作用有关,此外,来源于陆生植物的n-C27-C33烷烃因河流汇水面积和流量不同而存在空间差异,这值得重视和进一步研究.     

GC profiles of oils reflect organic maturity rather than depositional environment of parent source rock: examples from Central Australia

Abstract

Review and analysis of 1332 gas chromatography (GC) n-alkane traces of oils from the Cooper and Eromanga basins indicate the shape of any GC trace profile is primarily controlled by the degree of organic maturity (early, peak or late) at which the oils were expelled from the parent source rock, rather than indicating the depositional environment, and hence organic composition, of that source rock. The depositional environment of a source rock may still be inferred, however, from the position of the n-alkane maximum on the GC traces of early expulsion oils in association with the pour point of the oil. Departures of GC trace profiles from the standard early, peak or late expulsion profiles can indicate mixing of oils of different maturities, while variations in the GC trace profiles of oils within adjacent reservoir units may indicate phase separation of the parent liquid, or possible seal breach by an accumulation that exceeds the capacity of its overlying seal.

1. KEY POINTS

2. GC trace profiles of 1332 oils from across the Cooper and Eromanga basins of central Australia have been reviewed.

3. Organic maturity, rather than organic composition, of the parent source rock controls the shape of any GC trace profile.

4. All early maturity oils display a consistent GC trace profile shape that is different from all peak maturity oils and different again from all late maturity oils.

5. Depositional environment of the source rocks within a basin can be inferred from the relative pour points of the resultant oils.

     

不同纬度地区植物中正构烷烃及其同位素组成

本文应用GC-MS和GC-TC-IRMS同位素分析技术,对我国北部柴达木盆地花土沟至南部广西南宁5个地区草、芦苇和树叶3类植物中正构烷烃及其碳氢同位素进行了分析.结果显示了不同纬度地区植物中正构烷烃碳数分布在C15～C30之间,呈单峰型分布,主峰碳数为C27、C29和C31;CPI值分布在3.49～17.25之间,平均值是草＜芦苇＜树叶;ACL值为26.24～30.26,平均值是草＞芦苇＞树叶.研究发现,随着植物生长地区纬度的增高和年平均气温的降低,植物中正构烷烃主峰碳数、CPI值、ACL值都降低,并且纬度每增加1.,草、芦苇和树叶中ACL值分别减少0.08、0.22和0.36;气温每增加1℃,草、芦苇和树叶中ACL值分别增加0.04、0.24和0.20.研究样品中C27和C29正构烷烃的δ13C值分布在-25.3‰～-35.5‰之间,草具有相对轻的碳同位素组成;C27和C29正构烷烃碳同位素组成与环境因子(如纬度和温度)之间的相关性,在这次研究中没有观察到.样品中C27和C29正构烷烃δD值分布在-132.1‰～-192.6‰之间,草具有相对轻的氢同位素组成.随着纬度增加和气温降低,草和树叶中C27和C29正构烷烃富集轻同位素.因此,可以应用草、芦苇和树叶中正构烷烃主峰碳数、CPI值和ACL值以及草、树叶中C27、C29正构烷烃δD值指示环境特征.     

Biodegraded Oil and Its High Molecular Weight (C_(35+)) n-alkanes in the Qianmiqiao Region in the Bohai Bay Basin, Northern China

With a production of 208.2 m3/d, heavy oil was produced by drill stem test (DST) from three shallow reservoirs in Sand Group Nos. Ⅰ and Ⅲ of the Neogene Guantao Formation (NgⅠ and NgⅢ) and the Eogene Dongying Formation (Ed) in an exploratory well Ban-14-1 within the Qianmiqiao region, Bohai Bay Basin, northern China. Based on the GC and GC-MS data of the NgⅠ and NgⅢ heavy oil samples, all n-alkanes and most isoprenoid hydrocarbons are lost and the GC baseline appears as an evident "hump", implying a large quantity of unresolved complex mixture (UCM), which typically revealed a result of heavy biodegradation. However, there still is a complete series of C14-C73 n-alkanes in the high-temperature gas chromatograms (HTGC) of the heavy oil, among which, the abundance of C30- n-alkanes are drastically reduced. The C35-C55 high molecular weight (HMW) n-alkanes are at high abundance and show a normal distribution pattern with major peak at C43 and an obvious odd-carbon-number predominance with CPI37-55 and     

青藏高原东北部尕海湖沉积物中正构烷烃及其氢同位素组成与有机质源指示意义

系统采集了位于青藏高原东北部的尕海湖淡水湖泊沉积物,对沉积物中正构烷烃及其氢同位素进行了分析,研究了沉积物中正构烷烃及其氢同位素组成,探讨了它们的来源。研究结果表明,尕海湖沉积物中正构烷烃分布反映了它们来自水生和陆生植物。尕海湖沉积正构烷烃氢同位素组成平均值为-221.9‰~-190.5‰。C_(21)~C_(33)奇碳数正构烷烃δD值明显地将样品划分为两种类型。类型Ⅰ样品的C_(21)~C_(33)奇碳数正构烷烃平均δD值明显地高于类型Ⅱ样品。类型Ⅰ沉积正构烷烃δD值分布特征反映了它们主要来自尕海湖水生植物;类型Ⅱ沉积物中正构烷烃δD值特征指示了它们主要来自研究区陆生草本植物。提出了具有δD值低、丰度高和CPI值低的中等链长正构烷烃起源于改造陆源草本植物的细菌。研究成果证实了沉积正构烷烃δD值可以作为指示有机质源的地球化学指标。     

Paleohydrological Changes in the Western Tibetan Plateau over the Past 16,000 years Based on Sedimentary Records of n‐Alkanes and Grain Size

Both monsoons and westerlies have exerted influence on climate dynamics over the Tibetan Plateau (TP) since the last deglaciation, producing complex patterns of paleohydroclimatic conditions. Diverse proxy records are essential to forge a robust understanding of the climate system on the TP. Currently, there is a general lack of understanding of the response of inland lakes over the TP to climate change, especially glacier‐fed lakes. Paleohydrological reconstructions of such lakes could deepen our understanding of the history of lake systems and their relationship to regional climate variability. Here we use records of n‐alkanes and grain size from the sediments of Bangong Co in the western TP to reconstruct paleohydrological changes over the past 16,000 years. The Paq record (the ratio of non‐emergent aquatic macrophytes versus emergent aquatic macrophytes and terrestrial plants) is generally consistent with the variations in summer temperature and precipitation isotopes. The changes in grain‐size distributions show a similar trend to Paq but with less pronounced fluctuations in the early‐middle Holocene. The new data combined with previous results from the site demonstrate that: 1) Bangong Co experienced relatively large water‐level fluctuations during the last deglaciation, with a steadily high lake‐level during the early‐middle Holocene and a decreasing lake‐level in the late Holocene; 2) The lake level fluctuations were driven by both high summer temperatures via the melting water and monsoon precipitation. However, the dominant factor controlling lake level changed over time. The lake‐level history at Bangong Co deduced from the n‐alkanes and grain‐size records reveals the past hydrological changes in the catchment area, and stimulates more discussion about the future of glacier‐fed lakes under the conditions of unprecedented warming in the region.     

Composition and Evolution of Hydrogen Isotopes of n-Akanes Generated from Anhydrous Pyrolysis of Sediments from Lake Gahai,Gannan, China

To understand the thermal evolution of lacustrine sedimentary n-alkane hydrogen isotopic composition (δD), especially bacterially derived n-alkanes, anhydrous thermal simulation experiments were performed with sediments from Lake Gahai (Gannan, China). We analyzed the original and pyrolysis-generated n-alkanes and their δD values. The results showed that thermal maturity and n-alkane origins significantly affected the distribution of pyrolysis-generated n-alkanes. In immature to post-mature sediments, the bacterial-derived medium-chain n-alkanes generally had depleted δD values. The maximum difference in average δD values between the bacterial-and herbaceous plant-derived medium-chain n-alkanes was 32‰, and the maximum difference in δD values among individual n-alkanes was 59‰. We found that the average δD value of pyrolysis-generated n-alkanes from different latitude was significantly different in immature to highly mature sediments, but similar in post-mature ssediments. The hydrogen isotopes of sedimentary n-alkanes can be used as indicators for paleoclimate/paleo-environment conditions only when sediments are immature to highly mature. During thermal evolution, the δD value of generated individual n-alkanes and the average δD value increased with thermal maturity, indicating that hydrogen isotopes of sedimentary n-alkanes can be used as an index of organic matter maturity. We established mathematical models of average δD values of generated n-alkanes from immature to post-mature sediments using nC21?/nC21+ and average chain lengths. These results improve our understanding of the distribution and δD value of sedimentary n-alkanes derived from herbaceous plants in mid-latitude plateau cold regions.     

Unusual N—Alkane Distributions in Extracts from Marine Carbonate Rocks at High Levels of Maturity and Overmaturity

N-alkanes in extracts from possible carbonate source rocks of the Lower Ordovician Majiagou Formation in the central gas field of the Shanganning Basin and the Upper Sinian Dengying Formation in the Weiyuan gas field of the Sichuan Basin, are characterized by bimodal distributions with the dominant carbon numbers in the range C₁₇-C₂₁ and C₂₅-C₂₉. In most samples, the lower carbon number components are present in greater abundance than the higher carbon number ones. Most samples contain significant concentrations of waxy hydrocarbons (C₂₂₊) with C_21-/C₂₂₊ ratios between 0.50 to 3. 16, and an average value of 1. 34. The n-alkanes in extracts of outcrops and shallow core samples of Upper Proterozoic and Lower Palaeozoic carbonate rocks in the western and southern parts of the North China Basin are of unimodal distributions dominated by n-alkanes maximizing in the C₂₅-C₂₉ range. These extracts have very high concentrations of waxy hydrocarbons with C_21-/C₂₂₊ ratios all < 1. 0, ranging from 0. 14 to 0. 90 and averaging 0. 36. All of the extracts have a marked odd/even predominance in the high molecular weight n-alkane range regardless of whether they are from shallow or deep cores or out-crop samples. Simulation experiments were performed using typical sapropelic-type kerogens from the immature Sinian Lower Xiamalin Formation carbonate-rich shales collected at Jixian, Hebei Province, North China Basin, and the contemporary microplanktonic blue-green algaeSpirulina subsala. Results indicate that the unusual distribution of n-alkanes in the extracts of Upper Proterozoic and Lower Palaeozoic carbonate rocks possibly originated from algae in the source rocks at high levels of maturity and overmaturity. This research project was financially supported by the Chinese Academy of Sciences (Grant No. KZCX2-111 ).     

四川盆地海、陆相烃源岩有机质稳定碳同位素组成变化及其地球化学意义

采用质谱和色谱-同位素质谱技术,测定了500余个干酪根及饱和烃、芳烃组份、正构烷烃的δ13C值,以此揭示了四川盆地海、陆相烃源岩有机碳同位素组成随地质时代的变化特点及其在高成熟阶段的演化特征,并结合其他相关分析资料,应用碳同位素剖析了不同类型海、陆相烃源岩的有机质生源及沉积环境。研究结果表明,该盆地从震旦系灯影组到中三叠统雷口坡组的海相地层中,干酪根的碳同位素组成随层位变新呈逐渐变重的趋势,可能的原因之一是浮游植物的进化作用;而上三叠统须家河组至中侏罗统千佛崖组的陆相有机质碳同位素组成则有反向的年代变化,主要与生源构成和沉积环境性质有关。这些海、陆相烃源岩的有机源难以用干酪根δ13C值进行区分,而可用饱和烃与芳烃组份的δ13C及其CV值来区别。海洋和湖泊不同沉积相带烃源岩的干酪根具有明显不同的δ13C值,结合其他相关资料可识别其有机质来源。煤系地层中煤与泥岩在干酪根碳同位素组成上没有可区分性,而两者有不同的正构烷烃碳同位素分布曲线。从成熟晚期到高-过成熟阶段,海、陆相干酪根的碳同位素均变重1~2‰,煤系泥岩的正构烷烃碳同位素分布曲线由负向线型分布向平直型演变。这些碳同位素的变化特征为油气源对比和烃源识别提供了依据。     

黄土高原西部地区现代植被及其表土正构烷烃分布模式研究

由于现代木本、草本植物正构烷烃主峰分布的研究结果存在一定的差异,从而导致黄土沉积中利用正构烷烃主峰分布进行古植被恢复时存在较大争议,尤其是松科植物主峰分布的不同。因此,采集黄土高原西部地区常见木本和草本植物及其表土,包括研究区常见松科植物,利用GC分析,开展现代植物及其表土正构烷烃主峰分布的研究。结果发现,黄土高原西部地区常见10种木本植物正构烷烃的主峰分布均以C27或C29为主峰,3种草本植物以C31为主峰,与分子有机地球化学研究结果一致,研究区3种常见松科植物均以C29为主峰,并无C31为主峰的分布; 研究区现代表土正构烷烃的结果显示,表土正构烷烃主峰分布与上覆植被输入量有直接关系,对于不同景观的采样点,由于其木本、草本植物输入量的差异而导致正构烷烃分布存在差异,对于有机质来源较为多元化的地区,分析要十分慎重。同一种植物腐叶与新鲜叶片正构烷烃主峰分布是一致的,说明植物叶片的腐烂过程对其正构烷烃主峰分布没有产生影响。对同一种植物不同地区的对比分析发现,木本植物正构烷烃主峰分布特征受生长环境影响较小,主峰分布不变,但是对于草本植物受生长环境影响较大,主峰分布会产生变化。因此,对于黄土沉积中利用正构烷烃主峰分布特征进行的古植被恢复在开展现代过程研究的基础上是较为可靠准确的。