Evolution of polycyclic alkanes in the Espirito Santo Basin

The distributions of polycyclic alkanes were monitored in a Neocomian sequence (well 1-ESS-34) from the Espirito Santo Basin, southeast Brazil. The profiles included, apart from regular hopanes, significant concentrations of 18α(H), 28,30-bisnorhopane and subordinate amounts of gammacerane. Sterane concentrations, normally with hopane/sterane <5, were compatible with other geochemical data indicating a predominantly planktonic/microbial source of the deposited organic matter. Sample maturities ranged from very immature to the onset of oil generation, allowing biomarker distributions to be followed along a broad maturation range. The ability of certain molecular ratios (e.g. C₂₇ 17α(H)/17β(H)hopanes) to reflect a maturity sequence with depth in the closely-spaced strata of the immature upper levels (Jiquiá Stage) showed the value of molecular techniques over classical geochemical methods (e.g. vitrinite reflectance) for the study of immature sequences. The presence in the oils of southern Espirito Santo of 28,30-bisnorhopane, gammacerane and methyl steranes in similar concentrations as in extracts of the deepest levels of the 1-ESS-34 well qualify the Jiquia Stage as the probable source rock of oils accumulated in the basin.     

Sesquiterpenoids in sediments of a hypersaline lagoon: A possible algal origin

Core samples were collected in Lagoa Vermelha, a hypersaline lagoon located about 100 km east of Rio de Janeiro (Brazil). The sediment composition is predominantly carbonate in amounts up to 93%. Analysis of δ¹³C of the total organic matter in the sediments showed that marine organic matter predominates throughout the core (δ¹³C ranges from −15.84 to −22.64‰ vs. PDB). Organic carbon contents (TOC) ranged from 0.81 to 13.28%. A series of cadinane-type sesquiterpenoids can be recognized in the gas chromatography-mass spectrometry data. Essentially the same components are present in all the samples, with variations only in their relative abundances. The most abundant compounds are α- and β-cubebene, α- and β-cedrene, cadinenes (different isomers), α-curcumene and calamenene, with minor amounts of calarene, humulene, calacorene and cadalene. Since this lagoon is surrounded by dunes with only minor vegetation typical of this environment (grasses, small non-resinous shrubs and no forest) with no potential source for sesquiterpenoids, a terrestrial origin for these compounds is excluded and an algal origin is more consistent with the locale and the recognition of sesquiterpenoids (including cadinol) in microbial mats from the lagoon. Only the natural product precursor sesquiterpenoids are present in the microbial mats with no detectable diagenetic derivatives (e.g. calamenene and cadalene). This indicates that the compounds in the mats are from recent input and those found in the sediments are most likely derived from former algal biomass in this lagoon, a fact confirmed by the recognition of a series of diagenetic aromatic components in the sediments. Surface sediments contain n-alkanes with no even-to-odd predominance indicating that microbial activity is higher in shallower sediments. Moreover, mass fragmentograms (m/z 191) of biomarkers revealed the presence of 17α(H),21β(H)-hopanes, the mature isomers, together with their ββ precursors and low amounts of the intermediates with the βα configuration (moretanes). This indicates a contribution of mature organic matter to these immature sediments.     

Organic geochemistry of Cuban oils—I. The northern geological province

The isoprenoid, hopanoid and steroid compositions of 15 oils from the most productive oil fields in Cuba were studied to determine source-rock depositional environments and organic matter sources. The oils, which are from the northern geological province of Cuba and can be defined by the position with respect to the overthrust belt, can be grouped into two families: those from the Remedios (1) and those from the Placetas (2) tectonostratigraphic units.Remedios oils contain 17α(H)-diahopane, high relative amounts of 18α(H)-22,29,30-trisnorneohopane and diasteranes, which is indicative of generation from clay-rich source rocks. The crude oils of the Placetas Unit exhibit a sterane/hopane composition consistent with a carbonate origin. Nevertheless, these polycyclic hydrocarbons exhibit significant changes in composition, indicating that several organic matter sources, e.g. a carbonate/evaporitic origin of Varadero and Varadero Sur oils, have contributed to the oils from this Unit. The Remedios oils are more mature [evaluated from the and sterane indices] than the Placetas oils.A wide range of biodegradation levels are encountered in these oils (from 0 to 7–8 using the scale derived by Volkman et al. (1983). The high relative abundance of 25-norhopanes is a distinctive feature of Remedios oils. The presence of these compounds in lightly biodegraded or nondegraded oils corresponds to a mixing of paleobiodegraded oil with more recently sourced nondegraded oil in the reservoir. The most biodegraded oil, Cantel, exhibits and sterane ratios, and hopane ratios that have been altered by microbial attack.     

Marine organic geochemistry of the Eastern Mediterranean: 1. Aliphatic and polyaromatic hydrocarbons in Cretan Sea surficial sediments

As part of a lipid biogeochemical study, aliphatic and polyaromatic hydrocarbons were determined in surficial sediments from the Cretan Sea (South Aegean Sea) in the Eastern Mediterranean. Total concentrations of both aliphatic (AHC) and polyaromatic (PAH) hydrocarbons were low (562–5697 and 14.6–158.5 ng/g, respectively) with respect to other coastal sediments worldwide and compare with concentrations found in open sea areas. The composition of AHC was dominated by unresolved complex mixture (UCM) indicating the presence of petroleum-related hydrocarbon inputs as confirmed by the detection of specific α,β-hopanes. PAH consisted mainly of pyrolytic four- to five-ring compounds. UCM and PAH amounts revealed that Cretan Sea receives low supply of anthropogenic material compared to NW Mediterranean. The spatial distributions of AHC and PAH indicated that urban run-off and transport from the continental self are the major input pathway of anthropogenic and biogenic hydrocarbons from terrestrial sources in the near shore area, whereas atmospheric transport might be the significant source of hydrocarbons in the deep area.     

原油热模拟实验中重排藿烷类变化特征及其意义

通过对TZ62井原油进行热模拟实验,探讨热演化程度对原油中重排藿烷类化合物形成分布的影响及其地球化学意义。实验发现：在400～500 ℃阶段,随着热演化程度的增加,原油中高碳数微晶蜡类长链化合物热裂解和原油中的沥青质热降解作用对重排藿烷的形成具有贡献作用。在500～550 ℃对应的原油裂解高峰阶段,藿烷类化合物浓度明显降低,且17α(H)-藿烷比重排藿烷类化合物具有更快的热裂解速率。在温度为550～600 ℃阶段,较高的热演化程度对17α(H)-藿烷甲基重排作用形成重排藿烷具有贡献作用。重排藿烷参数(17α(H)-重排藿烷/17α(H)-藿烷、Ts/Tm)在400～500 ℃变化较弱,几乎不受热演化程度的影响;在500～550 ℃的原油裂解高峰阶段,逐渐增大;在550～600 ℃发生反转,逐渐减小。重排藿烷参数可作为高成熟阶段原油成熟度判识的有效参数,其有效应用范围是生油窗晚期至原油裂解高峰期。     

Characterization of model evaporitic environments through the study of lipid components

A saline circuit has been studied as a model of coastal evaporite system. The lipid composition of diverse salt ponds encompassing calcite, gypsum and halite domains has been determined. Most of the lipid materials has been found in the carbonate samples and is related to algal/cyanobacterial debris. Lipids in the gypsum domain are of heterotropic microbialorigin and extreme halophilic bacteria constitute the main lipid contribution in the halite samples. n-Alkane distributions with high predominance of n-docosane constitute a previously described feature of sedimentary evaporitic conditions that is charateristics of the intermediate calcite/gypsum samples. In the calcite domain, the presence of C20 highly branched isoprenid olephines, tetrahymanol and the large amounts of phytol constitute likely precursors of lipids usually found in evaporitic environments (i.e. C20 highly branched isoprenoid alkanes, gammacerane and high phytane/pristane ratios). Their occurence point to dehydration and hydrogenations as two main diagenetic processes leading to the formation of “evaporitic molecular markers”.     

De-A-steroids in immature marine shales

Three series of de-A-diasterenes have been observed in a variety of immature marine shales. Two of them have been identified by comparison with authentic standards and the structures of the third assigned by extrapolation. The greater complexity in the number of series compared with diasterenes indicates that the ring A degradation occurred to differing extents. The rate of C-20 diagenetic isomerisation in the de-A-diasterenes proceeds at a similar rate to that in diasterenes. Two series of B-ring monoaromatic de-A-steroid hydrocarbons have also been found. Comparison with the B-ring monoaromatic anthrasteroids indicates that the de-A-compounds are 14α(H) and 14β(H) isomers. Diagenetic isomerisation of the 14α(H) isomers to the more stable 14β(H) isomers occurs at a rate similar to that in the B-ring monoaromatic anthrasteroid series.     

冀中凹陷文安油田双环倍半萜的分布及其意义

基于全油气相色谱/质谱联用定量分析技术,分析了冀中凹陷文安油田原油中双环倍半萜在空间分布上的非均质性特征及其变化规律,并讨论了其非均质性特征的地质-地球化学意义。结果表明：微生物的降解作用对双环倍半萜的影响并不明显,文安油田原油含有丰富的双环倍半萜;文安油田原油中双环倍半萜的总体分布特征是C14倍半萜化合物相对丰度最小,C15倍半萜化合物相对丰度居中,C16倍半萜化合物相对丰度最高;文安油田南区与北区原油存在明显非均质性;重排补身烷与8β（H）-补身烷、C30重排藿烷与C30藿烷、C27重排甾烷与C27甾烷的相对丰度比值具有显著相关性,反映重排补身烷的形成机理与重排甾烷、重排藿烷的形成具有相似性;原油分子组成上的非均质性预示着文安油田原油可能存在两种不同的成因类型,文安油田南区和北区可能存在着2个油气富集体系。     

柯克亚油田原油地球化学特征和油源研究

应用GC/MS、GC/MS/MS分析技术,剖析了塔西南地区侏罗系和二叠系两套烃源岩生物标志物组合特征,建立了区分的指标体系,即二叠系源岩重排藿烷、C30-未知萜烷含量丰富,侏罗系源岩重排藿烷含量较低,但检测到二萜类化合物,而在二叠系源岩中未检测到该类化合物。柯克亚原油重排藿烷、C30-未知萜烷发育。精细油-岩对比结果表明,柯克亚原油主要来源于二叠系烃源岩,同时原油中检测出微量的二萜类化合物,说明侏罗系烃源岩也有一定的贡献。     

利用芳烃参数研究煤系烃源岩中重排藿烷成因

研究发现鄂尔多斯盆地部分地区上古生界煤系烃源岩存在较高丰度的17α(H)-重排藿烷和早洗脱重排藿烷,在对重排藿烷分布、组成特征及生标组成特征研究的基础上,应用芳烃参数对高丰度重排藿烷的成因进行了探讨。饱和烃生物标志物组成特征显示,高重排藿烷与陆源高等植物生源关系密切,主要在弱氧化沉积环境下演化形成。具有高-异常高丰度17α(H)-重排藿烷和早洗脱重排藿烷(C₃₀*/C₃₀H>0.2、C₃₀E/C₃₀H>0.1)的烃源岩二环+三环芳烃相对含量一般大于50%,四环、五环芳烃含量相对较低,普遍低于35%,未见芳香甾萜类,研究认为其生源主要为陆生高等植物;甲基菲指数MPI₁、MPI₂和甲基菲比值F1研究结果显示,Pr/Ph>1的弱氧化环境烃源岩17α(H)-重排藿烷和早洗脱重排藿烷在进入成熟阶段后开始大量形成,并随成熟度升高而增大;Pr/Ph<1还原环境下的烃源岩重排藿烷丰度相对较低,但在进入成熟阶段后仍有随成熟度升高而增大的趋势;三芴系列化合物参数表明,沉积环境的弱氧化性质对17α(H)-重排藿烷和早洗脱重排藿烷的形成有较大的影响,沼泽相沉积环境最有利于重排藿烷的形成。