分子地层学的原理、方法及应用实例

当前分子地层学研究已涉及蛋白质、核酸、碳水化合物、类脂物和木质素等多种生物化学组分。在地层中,分子化石具有分布的广泛性、定量的准确性、应用的指纹性和信息的多样性等特点,其地层学应用的主要原理是依据分子化石的生物源信息和其离开生物体后发生的一系列转化途径来实现的,其表述方法可以是含量、相对丰度、碳数分布和单体同位素特征等。在各类年代学框架下,由这些分子化石参数所揭示的各类生物事件和环境事件可以成为区域性乃至全球性地层对比的主要依据。分子地层学与分子古生物学、生物地球化学、有机地球化学密切相关,它与传统三大地层学分支学科明显不同,目前还没有明确的分子地层单位,也没有进行广泛的分子地层划分与对比工作。对各类生物事件与环境事件有重要指示作用的分子地层学,与生态地层学、事件地层学等地层学分支学科类似,其主要任务是在传统生物地层学或其他年代学框架下,提高地层划分和对比的精度。以浙江长兴煤山二叠纪-三叠纪界线地层和第四纪泥炭为例,以高分辨率的生物事件与环境事件为切入点,分别探讨在生物地层学或其他年代学框架下的分子地层工作,由此提出了分子地层学的分类单位——分子化石带。     

生物标志化合物碳同位素地球化学研究的几个相关问题

生物标志化合物稳定碳同位素地球化学是８０年代末期新兴的研究领域。单个生物标志化合物碳同位素组成的成因解释是该领域至关重要的问题。本文综合讨论了与此有关的生物合成过程中脂类化合物碳同位素变化、细菌生物合成过程中碳同位素分馏及其脂类化合物碳同位素组成特征，从而为我国的生物标志化合物碳同位素地球化学研究提供了新的理论依据     

Carbon and oxygen isotope compositions of the carbonate facies in the Vindhyan Supergroup, central India

The Vindhyan sedimentary succession in central India spans a wide time bracket from the Paleoproterozoic to the Neoproterozoic period. Chronostratigraphic significance of stable carbon and oxygen isotope ratios of the carbonate phase in Vindhyan sediments has been discussed in some recent studies. However, the subtle controls of facies variation, depositional setting and post-depositional diagenesis on stable isotope compositions are not yet clearly understood. The Vindhyan Supergroup hosts four carbonate units, exhibiting a wide variability in depositional processes and paleogeography. A detailed facies-specific carbon and oxygen isotope study of the carbonate units was undertaken by us to investigate the effect of these processes and to identify the least altered isotope values. It is seen that both carbon and oxygen isotope compositions have been affected by early meteoric water diagenesis. The effect of diagenetic alteration is, however, more pronounced in case of oxygen isotopes than carbon isotopes. Stable isotope compositions remained insensitive to facies only when sediments accumulated in a shallow shelf setting without being exposed. Major alteration of original isotope ratios was observed in case of shallow marine carbonates, which became exposed to meteoric fluids during early diagenetic stage. Duration of exposure possibly determined the magnitude of alteration and shift from the original values. Moreover, dolomitization is found to be accompanied by appreciable alteration of isotope compositions in some of the carbonates. The present study suggests that variations in sediment depositional settings, in particular the possibility of subaerial exposure, need to be considered while extracting chronostratigraphic significance from δ¹³C data.     

若尔盖高原湖沼沉积剖面饱和烃组分特征及地球化学意义

利用GC-MS技术对若尔盖高原一湖沼沉积剖面（深346 cm）沉积有机质的饱和烃馏分进行了分析,结合已有的AMS 14C年代、剖面岩性和TOC资料,探讨了该剖面分子化石分布特征及其相关参数对有机物来源、微生物活动和气候变化等环境信息的指示意义。分析表明,中高碳数占绝对优势的正构烷烃反映了有机物主要来源于高等植物,且草本高等植物输入丰富;岩相、TOC和Pr/Ph比值很好地指示了该剖面沉积物从早全新世（约11.4~7.3 cal ka BP,深度346~203 cm）强还原深湖条件到中全新世（约7.3~4.5 cal ka BP,>203 cm）弱还原沼泽条件的演化过程,正构烷烃参数奇偶优势（OEP1和OEP2）、C25/C31和轻烃/重烃比值（∑C21-/∑C22+）详细反映了这种水文演变过程中生物源的变化,尤其剖面120 cm以上很可能有泥炭藓(Sphagnum)的重要输入,而且敏感地指示了剖面120 cm以上有机物遭受了明显的微生物改造作用,从而引起正构烷烃组分的改变。另外,在约9.8~8.6 cal ka BP（深度286~240 cm）期间剖面岩性及其以上各项代用指标发生明显快速变化,说明早全新世若尔盖高原气候相对暖湿阶段具有不稳定性。     

可可西里古湖泊沉积物有机碳δ13C变化特征及其影响因素

文章选择青藏高原腹地可可西里边缘地区古湖泊为研究对象,通过对湖泊沉积物有机碳、氮和粒度等分析,对中更新世以来BDQ06孔湖泊沉积物有机碳同位素的波动特征及其影响因素进行了分析。结果表明:湖泊沉积物有机质以湖泊自生植物为主,有机碳同位素的大小主要指示挺水植物与沉水植物的比例,进而指示湖泊水体大小的变化。沉积物C/N值较低时;碳同位素偏重阶段,湖泊沉积物以沉水植物为主,植物主要利用水中溶解的CO₂进行光合作用,因此有机碳同位素偏正,指示湖泊水体较大,环境条件较好;碳同位素偏负阶段,湖泊沉积物以挺水植物和浮游生物为主,植物主要利用大气中CO₂作为碳源,类似于C3植物,碳同位素偏轻,指示湖泊水体较小,气候偏干。其中在岩芯的部分层位有机碳δ13C曲线出现几个明显偏低的位置,对应的C/N>10,说明此时段有大量陆源高等植物进入湖泊,并不是由挺水植物和浮游植物所造成的。     

Matrix protected organic matter in a river dominated margin: A possible mechanism to sequester terrestrial organic matter?

The provenance of organic matter in surface sediments from the northern Gulf of Mexico was investigated by analyzing the compositions of lipid biomarkers (n-alkanes, fatty acids, sterols) liberated after a series of chemical treatments designed to remove different organo-mineral matrix associations (i.e. freely extractable, base-hydrolyzable, unhydrolyzable). Bulk analyses of the organic matter (carbon content, carbon:nitrogen ratios, stable and radiocarbon isotopic analyses) were also performed on the intact sediments and their non-hydrolyzable, demineralized residue. We found recognizable lipids from distinct sources, including terrestrial vascular plants, bacteria and marine algae and zooplankton, within each of the isolated fractions. Based on the lipid signatures and bulk compositions, the organic matter within the unhydrolyzable fractions appeared to be the most diagenetically altered, was the oldest in age, and had the highest abundance of terrigenous lipids. In contrast, the base-hydrolyzable fraction was the most diagentically unaltered, had the youngest ages and was most enriched in N and marine lipids. Our results indicate that fresh, autochthonous organic matter is the most important contributor to base-hydrolyzable lipids, whereas highly altered allochthonous sources appear to be predominant source of unhydrolyzable lipids in the surface sediments from the Atchafalaya River shelf. Overall, the lipid biomarker signatures of intact sediments were biased towards the autochthonous source because many of the organic compounds indicative of degraded, terrigenous sources were protected from extraction and saponification by organo-mineral matrices. It is only after these protective matrices were removed by treatment with HCl and HF that these compounds became evident.     

http://www.sciencedirect.com/science/article/pii/S1674987111001083

Stable carbon isotope geochemistry provides important information for the recognition of fundamental isotope exchange processes related to the movement of carbon in the lithosphere and permits the elaboration of models for the global carbon cycle.Carbon isotope ratios in fluid-deposited graphite are powerful tools for unravelling the ultimate origin of carbon（organic matter,mantle,or carbonates） and help to constrain the fluid history and the mechanisms involved in graphite deposition.Graphite precipitation in fluid-deposited occurrences results from CO₂- and/or CH₄-bearing aqueous fluids.Fluid flow can be considered as both a closed（without replenishment of the fluid） or an open system（with renewal of the fluid by successive fluid batches）.In closed systems,carbon isotope systematics in graphite is mainly governed by Rayleigh precipitation and/or by changes in temperature affecting the fractionation factor between fluid and graphite.Such processes result in zoned graphite crystals or in successive graphite generations showing,in both cases, isotopic variation towards progressive ^l3C or ¹²C enrichment（depending upon the dominant carbon phase in the fluid.CO₂ or CH₄,respectively）.In open systems,in which carbon is episodically introduced along the fracture systems,the carbon systematics is more complex and individual graphite crystals may display oscillatory zoning because of Rayleigh precipitation or heterogeneous variations of 5’ C values when mixing of fluids or changes in the composition of the fluids are the mechanisms responsible for graphite precipitation.     

轮南14井原油正构烷烃和类异戊二烯单体碳同位素研究

通过对轮南14井正构烷烃和类异戊二烯烃的单体碳同位素分析,证实该井奥陶系和石炭系油藏具有相同或相似的油源,而三叠系油藏与奥陶系、石炭系油藏具有较大的碳同位素差异,反映其油源不同.在奥陶系、石炭系和三叠系油藏中,均呈现出类异戊二烯烃碳同位素值略重于同碳数正构烷烃的特征,结合前人研究成果,从生物合成途径及分子内碳同位素的分布角度出发得到合理的解释.     

长江三角洲晚新生代沉积物有机碳、总氮和碳酸盐组成及古环境意义

长江三角洲地区埋深达320m的PD钻孔揭示了上新世以来河湖相、滨海相和三角洲相的沉积环境特征。钻孔沉积物中有机碳、总氮和碳酸盐组成变化较大,但具有一定的规律性。上新世东部地区气候较暖湿,古湖泊发育,化学风化强烈,有机质保存率较低;早更新世气候波动较大,相对温湿气候下高等植被发育;中、晚更新世长江流域气候逐渐变冷干,晚第四纪气候变化较显著,流域植被类型发生明显变化;全新世气候转暖,有机质保存率高。有机碳、总氮和碳酸盐组成揭示的古气候变化与孢粉、沉积地层等资料相当吻合,与相邻内陆地区的第四纪古环境研究认识也具有明显的可比性。本研究也揭示,运用有机碳、总氮和碳酸盐组成重建我国东部地区第四纪古环境和季风演化史具有相当的难度,必须充分考虑沉积地层不连续性、粒度、有机质来源、埋藏成岩环境以及陆海相互作用等多因素的复杂影响,同时需要结合有机碳同位素等分析来深化古环境研究。     

Recharge sources and hydrogeochemical evolution of groundwater in semiarid and karstic environments: A field study in the Granada Basin (Southern Spain)

The objective of this study is to refine the understanding of recharge processes in watersheds representative for karstic semiarid areas by means of stable isotope analysis and hydrogeochemistry. The study focuses on the Granada aquifer system which is located in an intramontane basin bounded by high mountain ranges providing elevation differences of almost 2900 m. These altitude gradients lead to important temperature and precipitation gradients and provide excellent conditions for the application of stable isotopes of water whose composition depends mainly on temperature. Samples of rain, snow, surface water and groundwater were collected at 154 locations for stable isotope studies (δ¹⁸O, D) and, in the case of ground- and surface waters, also for major and minor ion analysis. Thirty-seven springs were sampled between 2 and 5 times from October 2004 to March 2005 along an altitudinal gradient from 552 masl in the Granada basin to 2156 masl in Sierra Nevada. Nine groundwater samples were taken from the discharge of operating wells in the Granada basin which are all located between 540 and 728 masl. The two main rivers were monitored every 2–3 weeks at three different altitudes. Rainfall being scarce during the sampling period, precipitation could only be sampled during four rainfall events. Calculated recharge altitudes of springs showed that source areas of mainly snowmelt recharge are generally located between 1600 and 2000 masl. The isotope compositions of spring water indicate water sources from the western Mediterranean as well as from the Atlantic without indicating a seasonal trend. The isotope pattern of the Quaternary aquifer reflects the spatial separation of different sources of recharge which occur mainly by bankfiltration of the main rivers. Isotopic signatures in the southeastern part of the aquifer indicate a considerable recharge contribution by subsurface flow discharged from the adjacent carbonate aquifer. No evaporation effects due to agricultural irrigation were detected.     

Advances in Glycerol Dialkyl Glycerol Tetraethers and Long-Chain Alkyl Diols in the Marine Sediments: Implications for Paleoclimatic and Paleoenvironmental Changes

Lipid biomarkers widely dotted in marine sediments, as their distribution characteristics accurately record huge information on the metabolism of the original organisms and migration and transformation of these organic components, are often used to reconstruct the paleoclimatic and paleoenvironmental conditions. This paper reviewed the progress in the study of paleoclimatic-environmental changes during the late Quaternary using abundant core lipids Glycerol Dialkyl Glyceryl Tetraethers (GDGTs) and long-chain alkyl diols in marginal sea sediments. It is pointed out that clarifying the “source-sink” process of lipid biomarkers buried in marine sediments is a prerequisite for paleoclimatic-environmental reconstruction. It is believed that the use of multiple indicators that are less affected by early diagenesis can increase the accuracy of reconstructing paleoclimatic changes. In the large-river dominated marginal seas, the mechanism of land-sea climate coupling evolution stimulated by the paleoclimatic-environmental changes can be elucidated based on paleoclimatic records reconstructed from core lipids GDGTs and long-chain alkyl diols in marine sediments. It is hoped that this paper can provide reliable technical means and a solid theoretical basis for predicting future temperature and rainfall changes.     

Isotopic order, biogeochemical processes, and earth history: Goldschmidt lecture, Davos, Switzerland, August 2002

The impetus to interpret carbon isotopic signals comes from an understanding of isotopic fractionations imposed by living organisms. That understanding rests in turn on studies of enzymatic isotope effects, on fruitful concepts of isotopic order, and on studies of the distribution of ¹³C both between and within biosynthetic products. In sum, these studies have shown that the isotopic compositions of biological products are governed by reaction kinetics and by pathways of carbon flow.Isotopic compositions of individual compounds can indicate specific processes or environments. Examples include biomarkers which record the isotopic compositions of primary products in aquatic communities, which indicate that certain bacteria have used methane as a carbon source, and which show that some portions of marine photic zones have been anaerobic. In such studies, the combination of structural and isotopic lines of evidence reveals relationships between compounds and leads to process-related thinking. These are large steps. Reconstruction of the sources and histories of molecular fossils redeems much of the early promise of organic geochemistry by resolving and clarifying paleoenviron-mental signals. In turn, contemplation of this new information is driving geochemists to study microbial ecology and evolution, oceanography, and sedimentology.     

植硅体稳定同位素生物地球化学研究进展

植硅体形态鉴定与组合分析广泛应用于古环境重建和农作物起源分析等.鉴于植硅体的抗腐蚀、抗降解,易保存,锢囚的碳不易污染,且保存了植物的原始信息等特性,其有机地球化学研究日益被重视.植硅体稳定同位素分析表明植硅体是植物通过吸收单硅酸,以蒸腾作用为主要动力,在植物的不同部位发生同位素分馏淀积形成,其稳定同位素组成具有丰富的植物生理和环境信息.植物不同部位植硅体稳定同位素组成具有差异,其含量和硅、氧同位素值沿蒸腾流通常有增加的趋势.沉积物植硅体碳同位素分析不仅可以用于恢复草本的C3、C4植物生物量的比例,并且有可能重建古大气的碳同位素构成,是三者中最具有潜力的考古学、古环境研究的指标.植硅体有机化学组成分析,特别是类脂物分析,有利于认识植硅体碳同位素值相对于总有机碳偏负,C3、C4草本植硅体同位素差值范围缩小的原因.     

Effect of different wetness conditions on Sphagnum lipid composition in the Erxianyan peatland,central China

Samples of Sphagnum palustre and peat from the Erxianyan peatland, central China, were analyzed for lipids and their carbon isotopes to investigate how lipid distributions respond to hydrological change and to evaluate the importance of the contribution of microbial lipids to the peat moss. The lipids in samples collected from different hydrological settings in and around a pond and in the central part of the bog show clear variation along the hydrological gradient, with higher n-C₂₃/n-C₂₅ alkane ratio values and lower ACL (average chain length) values of long chain n-alkanes, n-fatty alcohols and n-fatty acids at the wetter sites. Although the relationship between the S. palustre lipids and the hydrological conditions can be partially overprinted in peat by an input from vascular plants, lipid ratios such as P_aq and ACL can provide useful qualitative information about Sphagnum contributions. In addition, lipid composition and carbon isotope values provide information about microbial activity associated with S. palustre. The occurrence of a high abundance of 7-methylheptadecane in submerged S. palustre is an indication of cyanobacteria in the living peat moss. The relatively ¹³C-depleted carbon isotope values of the n-C₂₃ alkane could result from the influence of symbiotic methanotrophs on the carbon available for assimilation by S. palustre.     

南海北部有孔虫碳氧同位素特征与晚第四纪水合物分解的响应关系

为探寻晚第四纪以来水合物分解事件在南海北部甲烷渗漏环境下有孔虫中的记录,对南海北部陆坡2个区块的沉积柱状样有孔虫碳氧同位素组成和测年分析发现,底栖有孔虫Uvigerina spp.碳同位素值为-2.12‰～-0.21‰,浮游有孔虫Globigerinoides ruber.氧同位素值为-3.11‰～-0.60‰,ZD3、ZS5 2个柱状样孔底年龄分别为26 616、64 090 a,对应了氧同位素Ⅲ、Ⅳ期末期,有孔虫碳同位素负偏的层位与氧同位素Ⅱ、Ⅳ期(冷期)层位相对应,负偏程度达到了-2‰,与布莱克海台和墨西哥湾等地区晚第四纪沉积层中有孔虫碳氧同位素组成相似。分析认为:研究区是典型的甲烷渗漏环境,该区在氧同位素Ⅱ、Ⅳ期,由于全球海平面下降,导致海底压力减小,天然气水合物分解释放,具轻碳同位素的大量甲烷释放进入海底溶解无机碳(DIC)池并记录在有孔虫壳体内,造成有孔虫碳同位素负偏;同时在有孔虫负偏层位黄铁矿和自生碳酸盐较发育,进一步证实了有孔虫碳同位素受甲烷影响较大,而海洋生产力的降低和早期成岩作用对有孔虫碳同位素负偏的影响较小。     

A Review of Magnesium Isotope System in Rivers

In recent years, a series of important progresses have been made in the aspect of magnesium isotopes behavior in weathering processes. These progresses are not only favorable to understand the change of the magnesium isotopic compositions in rivers, but also establish the foundation to further reveal the magnesium isotope geochemical cycle. The magnesium in rivers is both magnesium sink for weathering and magnesium source for the ocean. The Mg isotopic compositions in rivers are dominated by the magnesium sources and Mg isotope fractionations processes. The sources of magnesium in rivers originate mainly from draining rocks, as well as less contribution from the eolian deposition, groundwater, plant debris, and precipitation. The Mg isotope fractionations in rivers are mainly related to precipitation and dissolution of carbonate minerals, silicate mineral hydrolysis, adsorption on mineral or colloidal matter surface, and plant uptake. Generally, the contribution of carbonate minerals dissolution or precipitation is equal to add or reduce magnesium from carbonate endmember, which has a remarkably negative δ²⁶Mg value. Based on the fact that most clay minerals are rich in ²⁶Mg during nature silicate mineral hydrolysis, then it is possible to infer that residual weathering products enrich in ²⁶Mg. However, there is no significant Mg isotope fractionation causing by the adsorption on mineral or colloidal matter surface during river water migration. For the plant uptake, the root prefers to have ²⁶Mg, leading the plant itself rich in heavier Mg isotopic composition. In addition, formation of secondary minerals in rivers could also reflect the changes of chemical parameters in rivers (such as major elements, CO₂ solubility, pH, etc.). Hence, Mg isotopic composition in rivers and associated isotope fractionations are not only the basis for the application of magnesium isotope to trace surface material cycle, but also have important significance for the further understanding the geochemical cycle of magnesium isotopes.     

灰岩碳氧同位素特征与隐伏花岗岩的关系——以栗木水溪庙矿区为例

对栗木水溪庙矿区泥盆系上统融县组灰岩的碳氧同位素进行了研究,该地区灰岩的碳氧同位素组成可提供隐伏花岗岩隆起及其相关流体的重要信息。受隐伏花岗岩侵入驱动的流体与上覆融县组灰岩发生反应的温度在110℃左右,流体的初始同位素组成为δ18OSMOW=-3‰,δ13CPDB≤-7‰,反应的水岩比值（w/r）可能小于5。这种岩浆水与大气降水的混合流体与围岩之间的水岩反应使得地表灰岩的δ18O和δ13C值降低,产生负异常。研究表明,围岩的δ18O值降低受反应的水岩比值和温度控制;δ13C值降低主要与反应的水岩比值有关。反应的温度越高,w/r值越大,灰岩的碳氧同位素负异常越明显。因此,水溪庙矿区地表出露的碳酸盐地层中的碳氧同位素变化可在地球化学勘查中用于指示下伏花岗岩岩脊的隐伏位置。     

天然气运移的气体同位素地球化学示踪

本文通过鄂尔多斯等含油气盆地内岩石酸解烃、罐顶气和同源多产层天然气碳同位素组成的变化，从实例剖析出发，探讨了天然气运移时气体同位素组成的变化及其对天然气运移的示踪。天然气在通过沉积地层中孔隙系统和微裂隙运移时，天然气中的甲烷碳同位素会发生一定的分馏，而乙烷以上重烃碳同位素几乎不发生分馏；在天然气层所在深度，罐顶气甲烷碳同位素组成与天然气一致，在天然气层附近，罐顶气甲烷碳同位素则明显偏离了热演化趋势线；烃源岩酸解烃与其同源的天然气重烃碳同位素组成具有较好的一致性和可比性。由此，可利用气体组分碳同位素的上述变化特征，追索天然气的运移作用。     

贺兰山地区树轮碳氧同位素与夏季风降水的相关性讨论

分析了贺兰山地区油松树轮的稳定碳氧同位素组成对环境因素的响应关系 , 发现树轮碳氧同位素组成均与当年 5～ 9月总降水量具有较好的响应关系 , 碳同位素组成与 5～ 9月总降水量呈负相关关系 ,而氧同位素组成与 5～ 9月总降水量呈正相关关系 ,二者都可较好地反映该地区夏季风降水量的变化.同时 ,碳氧同位素的相关性分析表明二者具有一定程度的负相关性.树轮碳氧同位素的分馏机理十分复杂,其同位素组成不仅与降水量有关,同时还受其他环境因素的影响,单纯利用一种同位素指标来提取相应的气候信息,存在很大的不确定性.在本研究中 ,同时采用两种同位素指标来研究其气候意义 ,使得出的结论更加可靠.因此 ,夏季风降水量是控制该地区树轮稳定碳氧同位素组成的主要因素.     

类脂化合物单体碳稳定同位素在古气候环境研究中的意义

类脂化合物极大地扩展了全球变化研究的深度，尤其是单体碳稳定同位素技术在古气候、古环境重建上有着重要作用。基于近些年来国内外的最新研究成果，就类脂化合物单体碳同位素在古气候环境方面的应用研究进行了较为全面的评述。已有研究表明利用类脂化合物单体碳同位素组成可以追溯到海洋和湖泊环境中陆源有机质的物源，其母源区历史时期 C3、C4植被的变迁以及区域性的古气候、古环境重建。