Hydrogen isotope of individual n-alkanes from modern sediments and their application to environments

Hydrogen isotopes are commonly fractionated to a much greater extent and as a result display larger variations in δ values, In terms of the hydrogen isotope ratios of individual n-alkanes of 16 samples of modern sediments selected from four different locations in the southern part of Gansu, China, the δD values for most of the n-alkanes varied from -150‰-300‰, Variations in δD also occurred between different ranges of n-alkanes, effects of environmental changes on the hydrogen isotopic compositions of individual n-alkanes have been detected. Besides the δD values of n-alkanes, the δD values of lipids including pristane （Pr）, phytane （Ph） were also examined, by the combination of D/H ratios with molecular fingerprinting, Our results further support the notion that hydrogen isotopes of n-alkanes from modern sediments can act as paleoclimatic and paleoenvironmental proxies and provide invaluable new sources of information in the research of paleoenvironment reconstruction.     

利用两种指纹因子判别小流域泥沙来源

为精确识别黄土高原丘陵沟壑区典型小流域泥沙来源,分析了流域内“源-汇”地区土壤的理化性质及生物标志物（正构烷烃）作为潜在指纹识别因子,并建立了复合指纹模型。结果显示:单独的土壤理化指纹及正构烷烃均不能有效识别泥沙来源;土壤理化指纹和正构烷烃分别在林地、农地及沟道的辨别上显示出其局限性。多元化的复合指纹（碳优势指数CPI、Ca、TP、C₂₀、C₂₉、Fe）则能辨别90.5%的泥沙来源。模型结果显示沟道是该流域泥沙的主要来源,占60.8%,其次为农地占20.7%,林地占11.3%,草地占7.2%。研究表明,结合生物标志物的复合指纹法能更精确地反映泥沙来源,适用于各泥沙源头的地质条件差异较小的流域,对黄土高原小流域水土流失治理具有指导意义。     

南海现代沉积物中正构烷烃碳分子组合特征及其指示意义

利用1998年6~9月南海海洋环境调查及1987年SO-50中德联合调查中所取得的资料,对南海沉积物中正构烷烃碳分子组合特征进行分析和研究,并将南海与渤海、黄海、东海现代沉积过程中的正构烷烃碳分子组合特征进行对比,结果表明:(1)南海北部沉积物中正构烷烃碳分子分布范围为nC15~nC33,双峰群,居前的低碳数主峰碳为nC19~nC22,居后的高碳数主峰碳为nC27,nC24以后奇碳的优势明显,OEP为2.13,nC23-/nC24 值平均为1.53,沉积物中陆源输入居多;南海南部沉积物中正构烷烃碳分子分布范围为nC15~nC33,呈双峰群,居前的低碳数峰群以nC19~nC23为主峰碳,居后的高碳数峰群以nC27或nC29为主峰碳,OEP为1.58,nC23-/nC24 值平均为2.15,沉积物中海洋生物来源居多。南海沉积物中正构烷烃碳分子为海洋和陆源两种有机质来源。(2)南海南部处于典型热带海洋环境,生物生产力较高,大量硅质、钙质生物在海域繁殖,生物效应降低了陆源物质的丰度。物源效应和生物效应的差异是南海南、北部现代沉积物的碳分子组合分布变化的主要原因。(3)南海现代沉积物各站位沉积物中正构烷烃的P r/Ph值基本小于1,说明沉积物沉积时为缺氧还原的沉积环境,但局部海域沉积环境具有较强的氧化性,沉积物在沉积过程中一定程度上受到涌升的南极底层水的影响。(4)南海与东海、黄海、渤海不同海域沉积物中正构烷烃碳分子组合特征对比可知,各海域沉积物均显示出物源效应。     

Stable Carbon Isotope and Long-Chain Alkane Compositions of the Major Plants and Sediment Organic Matter in the Yellow River Estuarine Wetlands

Elemental(TOC,TN,C/N)and stable carbon isotopic(δ^13C)compositions and long-chain alkane(n C16-38)concentrations were measured for eight major plants and a sediment core collected from the Yellow River estuarine wetlands.Our results indicate that both C3(-25.4‰to-29.6‰)and C4(-14.2‰to-15.0‰)plants are growing in the wetlands and C3 plants are the predominant species.The biomass of the wetland plants had similar organic carbon(35.5-45.8%)but very different organic nitrogen(0.35-4.15%)contents.Both C3 and C4 plants all contained long-chain alkanes with strong odd-to-even carbon numbered chain predominance.Phragmites australis,a dominant C3 plant contained mainly n C29 and n C31 homologues.Aeluropus littoralis,an abundant C4 plant were concentrated with n C27 and n C29 homologues.Organic matter preserved in the Yellow River estuarine sediments showed strong terrestrial signals(C/N=11-16,δ^13C=-22.0‰to-24.3‰).The distribution of long-chain n-alkanes in sediments also showed strong odd-to-even carbon chain predominance with n C29 and n C31 being the most abundant homologues.These results suggest that organic matter preserved in the Yellow River estuarine sediments were influenced by the wetland-derived organic matter,mainly C3 plants.The Yellow River estuarine wetland plants could play important role affecting both the carbon and nutrient cycling in the estuary and adjacent coastal waters.     

Characteristics and origin of carbon isotopes of n-alkanes in crude oils from the western Pearl River Mouth Basin,South China sea

The quantitative characterization of carbon isotopes of n-alkanes is commonly carried out in organic geochemical studies. Possible controls on carbon isotopes include source organic matter, maturity, fractionation during oil expulsion and migration, and the mixing of different oils. In this study of the origin of crude oils in the western Pearl River Mouth Basin, the influences of all of these factors have been considered in reaching a conclusion. Carbon isotopes of n-alkanes in the crude oils, and the extracts of the two effective source rocks (the Wenchang and Enping formations) in the basin, exhibit clear differences. The Wenchang source rocks have heavy δ¹³C values that remain almost constant or become slightly heavier with increasing carbon number. The Enping source rocks have light δ¹³C values that become lighter with increasing carbon number. Two groups of oils in this area were identified based on the carbon isotopes of the n-alkanes; groupIoils are similar to extracts of the Wenchang source rocks. However, the groupIIoils are different from both the Wenchang and Enping source rocks and the carbon isotopic profiles of their n-alkanes exhibit a “V” feature with increasing carbon number. The results of artificial thermal maturation experiments indicate that, from the early stage to the peak stage of oil generation (with EasyRo between 0.64% and 1.02%), the δ¹³C values of n-alkanes in the pyrolysis oils become heavier by about 3‰ with increasing thermal maturity, but the shape of the carbon isotopic profiles are not significantly changed. Calculated δ¹³C values of n-alkanes in “mixed” artificial pyrolysis oils indicate that the mixture of oils generated from the same source rocks with different maturities could not change the carbon isotopic profile of the n-alkanes, however, a mixing of the Wenchang and Enping oils could give the “V” feature in the profiles, similar to the groupIIoils in this area. The groupIIoils appear to be mixed Wenchang and Enping oils, the latter being the dominant component in the mixture. We conclude that the source organic matter and the degree of mixing are the main factors controlling the carbon isotopic characteristics of n-alkanes in crude oils in the western Pearl River Mouth Basin.     

Last glacial terrestrial vegetation record of leaf wax n-alkanols in the northern South China Sea: Contrast to scenarios from long-chain n-alkanes

Long-chain n-alkanols and n-alkanes in core sediments from the northern South China Sea (SCS) were measured to make a comparison during terrestrial vegetation reconstruction from ~42 ka to ~7 ka. The results showed that terrestrial vegetation record from long-chain n-alkanes matched well with previous studies in nearby cores, showing that more C₄ plants developed during the Last Glacial Maximum (LGM) and C₃ plants dominated in the interglacial period. However, these scenarios were not revealed by terrestrial vegetation reconstruction using long-chain n-alkanols, which showed C₃ plant expansion during the LGM. The discrepancy during the interglacial period could be attributed to the aerobic degradation of functionalized long-chain n-alkanols in the oxygen-rich bottom water, resulting in poor preservation of terrestrial vegetation signals. On the other hand, the different advantages of functionalized n-alkanols and non-functional n-alkanes to record local and distal vegetation signals, respectively, may offer a potential explanation for the contradiction during the LGM when the SCS was characterized by low-oxygen deep water. Nevertheless, large variations on n-alkyl lipid compositions in C₃/C₄ plants could play a part in modulating sedimentary long-chain n-alkanols and n-alkanes toward different vegetation signals, thereby suggesting that caution must be taken in respect to the terrestrial vegetation reconstruction using long-chain n-alkanes and long-chain n-alkanols.     

东北地区五大连池湖相沉积物正构烷烃和单体碳同位素特征及其古植被意义

对中国东北地区小兴安岭与松嫩平原过渡带五大连池青石钻孔湖相沉积物进行了有机地球化学分析,检测出丰富的正构烷烃生物标志化合物.本文主要讨论了正构烷烃的分布及其单体碳同位素组成特征.正构烷烃具有前峰型和双峰型两种分布特征,表明其有机质为混合来源,包括低等菌藻类生物和陆生高等植物输入.正构烷烃的分布特征表明,自35.2ka B.P.以来,nC27/nC31和ACL指标共同记录了东北地区小兴安岭与松嫩平原过渡带的植被以草本为主.对C27、C29和C31长链正构烷烃进行了单体碳同位素测定,并利用二元模式估算了C3和C4植物相对生物量,结果表明,自35.2ka B.P.以来,研究区的植被以C3植物为主.期间在典型冷暖气候事件中,受温度变化的影响,C3/C4植物的相对生物量有明显的变化,在全新世大暖期(6.0ka B.P.),受温度升高影响,C3植物的生物量显著减少,C4植物的生物量则明显增加;而在两次典型冷气候事件(中全新世降温事件8.2ka B.P.和新仙女木事件12.9ka B.P.)时期,受温度降低影响,C3植物的生物量有增加的趋势,C4植物的生物量则相对呈减少的趋势;在末次冰盛期21.0ka B.P.时,受明显低温特征的影响,C3植物生物量高达80.0％,这可能是当时低温的气候特征抑制了C4植物的生长.研究结果对探索我国东北地区C3/C4植物分布格局,并为评估未来气候演化对该地区植被格局和农业生产的影响提供科学依据.     

The spatial distribution of sedimentary compounds and their environmental implications in surface sediments of Lake Khar Nuur (Mongolian Altai)

Lake sediments are valuable natural archives to reconstruct paleoclimate and paleoenvironmental changes which consist of inorganic and organic sediment compounds of allochthonous origin from the catchment and of autochthonous production in the lake. However, for robust paleo-reconstructions it is important to develop a better understanding about sedimentation processes, the origin of inorganic and organic sediment compounds and their distribution within the lake. In this context, modern process studies provide important insights, although environmental and anthropological changes can affect the spatial distribution of sediment compounds through time. Therefore, in this study the spatial distribution of grain size and geochemical proxies in 52 surface sediment samples from Lake Khar Nuur, a small high-altitude lake in the Mongolian Altai with a small and anthropogenically used hydrological catchment, is investigated. The results show a distinct sediment focussing in the two deep basins of the lake, which therefore act as accumulation zones. In those accumulation zones, total organic carbon (TOC), total nitrogen (N) and their isotopic composition (δ¹³C_TOC, δ¹⁵N) as well as n-alkanes indicate that organic sediment compounds are a mixture of both allochthonous and autochthonous origin. While the recent catchment vegetation consists of grasses/herbs and the shrub Betula nana (L.) with distinct differences in their n-alkane homologue patterns, those differences are not reflected in the sediment surface samples which rather indicates that grass-derived n-alkanes become preferentially incorporated in the lake. Extensive anthropogenic activity such as grazing and housing in the southern part of the catchment causes soil erosion which is well reflected by high TOC, N and sulphur (S) contents and ¹⁵N depleted δ¹⁵N values at the central southern shore, i.e. increased allochthonous sediment input by anthropogenically-induced soil erosion. Overall, the surface sediments of Lake Khar Nuur origin from allochthonous and autochthonous sources and are focussed in the accumulation zones of the lake, while their distribution is both environmentally and anthropogenically driven.     

云南错恰湖两百年来气候环境变化与重金属污染

高海拔地区由于特殊的自然环境对气候变化和营养输入的响应十分敏感.在人类活动逐渐加强的背景下,高山湖泊高分辨率的沉积物记录了人与自然相互作用的演变过程.选取云南西北部典型高山湖泊——错恰湖,获取长度37 cm的连续湖泊沉积序列,基于铅铯测年法得到年代深度模型,并对湖芯样品进行总有机碳、总氮及正构烷烃的多指标测定和元素测量,结合气象监测数据探讨分析错恰湖的有机质来源和流域环境演化特征.根据气候代用指标的变化,两百年来错恰湖泊环境及区域气候演化可以分成4个主要阶段：1807-1900年：湖泊水位上升、湖面扩大,有机质丰度下降,有机质以外源贡献为主,内源比例上升;1900-1950年：湖泊水位开始下降、湖面收缩,有机质丰度下降,外源有机质来源增加;1950-1982年：湖泊水位下降、湖面进一步收缩,有机质丰度下降,外源输入比例继续增加;1982-2007年：湖泊水位下降、湖面收缩,有机质含量上升且以陆源输入为主,同时内源贡献比例开始增加.在元素测定结果中,人类活动对应了湖泊沉积重金属含量变化的3个阶段：1950年以前,重金属含量低且稳定,可视作自然背景阶段,人类影响忽略不计;1950年以后,湖泊流域工农业逐渐发展,人为干扰凸显;直到1982年以后,冶炼工业的进步加强了重金属的污染态势,并通过大气传输沉降被湖泊沉积物记录.错恰湖沉积记录的分析讨论在总结该区域气候环境演化历史的同时,加深了对气候人类活动湖泊生态系统相互作用过程的理解,为高山湖泊响应人类活动影响提供了证据.     

Geochemical evolution during the cracking of crude oil into gas under different pressure systems

Two comparative simulation experiments(a normal atmospheric-pressure opening system and a 20 MPa closed system)were conducted to study the geochemical evolution of n-alkane,sterane,and terpane biomarkers in the process of oil cracking into gas under different pressures.With an initial experimental temperature set at 300°C,the temperature was increased to 650°C at a heating rate of 30°C/h.The products were tested every 50°C starting at 300°C,and a pressure of 20 MPa was achieved using a water column.The low-maturity crude oil sample was from the Paleogene system in the Dongying sag in eastern China.The threshold temperature obtained for the primary oil cracking process in both pressure systems was 450°C.Before the oil was cracked into gas,some components,including macromolecular n-alkanes,were cracked into medium-or small-sized n-alkanes.The secondary oil cracking of heavy hydrocarbon gases of C2–5to methane mainly occurred between 550°C to 650°C,and the parameters Ln(C1/C2)and Ln(C1/C3),as well as the dry coefficients,increased.Overpressure inhibited the oil cracking process.In the 20 MPa system,the oil conversion rate decreased,the temperature threshold for gas generation rose,and oil cracking was inhibited.Compared with the normal pressure system,high-carbon n-alkanes and other compounds in the 20 MPa pressure system were reserved.Furthermore,the parameters∑C21-/∑22+,Ln(C1/C2),and Ln(C1/C3),as well as the dry coefficients,decreased within the main temperature range.During secondary oil cracking(550°C to 600°C),the Ph/nC18and Pr/nC17decreased.High pressure influenced the evolution of the biomarkers Ts and Tm,C31homohopane,C29sterane,and their related maturity parameters to different extents during oil cracking under different temperature ranges.