双壳类分子生物标志物对海水重金属的响应评述

海洋双壳类动物的组织和器官对微量重金属具有高富集能力,诱导机体内的某些分子生物标志物(molecular biomarkers,MBMs)发生变化,可用于指示海水中的重金属污染水平。近10年来,许多学者在双壳类MBMs对海水重金属的响应规律方面进行了研究,其中,金属硫蛋白(MTs)、热激蛋白70(HSP70)、抗氧化防御系统等受到了较多的关注。本文在介绍这些MBMs结构和功能的基础上,重点评述了各种MBMs对海水重金属的响应特征,并提出了影响双壳类MBMs应用于海水重金属监测的因素及进一步研究的方向。     

Characterization of high molecular weight biomarkers in crude oils

High-temperature gas chromatography (HTGC) has enhanced our ability to characterize hydrocarbons extending to C₁₂₀ in crude oils. As a result, hydrocarbons in waxes (> C₂₀) have been observed to vary significantly between crude oils, even those presumed to originate from the same source. Prior to this development, microcrystalline waxes containing hydrocarbons above C₄₀ were not characterized on a molecular level due to the analytical limitations of conventional gas chromatography. Routine screenings of high pour-point crude oils by high-temperature gas chromatography has revealed that high molecular weight hydrocarbons (> C₄₀) are very common in most oils and may represent 2% of the crude oil. Precise structures, origins, and significance of these high molecular weight compounds remain elusive. As a preliminary step to expand our knowledge of these compounds their general molecular structures and formulas have been investigated in this study. Initial results suggest that the major high molecular weight compounds include a homologous series of n-alkanes, methylbranched alkanes, alkylcyclopentanes, alkylcyclohexanes, alkylbenzenes and alkylcycloalkanes.     

柴达木盆地石炭系烃源岩和煤岩生物标志物特征及其地球化学意义

采自柴达木盆地东北部石炭系烃源岩和煤岩的生物标志化合物研究表明,研究样品的有机质演化已达高成熟阶段,其母质来源以水生生物为主,同时有较丰富的陆源物质输入。除煤岩的沉积古环境较氧化且经历过较强的降解过程外,其余样品的沉积古环境均属于较还原环境,沉积介质为咸水环境,有机质总体丰度高。因此该区石炭系海陆交互相含煤沉积是一套较一般侏罗系为好的烃源岩系,有较好的生烃潜力。     

新元古界生物多样性及上元古系的命名

针对目前全球上远古系命名上存在的分歧,从整个元古界系级单位划分命名的基本原则出发,结合未元古纪全球生物多样性的特点,提出了交示上远古用多细胞后生生物（包括各种微体和宏体的多细胞、植物）首次大量的,以多样化和物色化形式广布全球这一重要事件给予正式命名,称其为“后生生物系（纪）”,简称为“后生系”（Ｍｅｔａｂｉｏｔｉａｎ）这一新的命名方案不仅符合国际地层季员会１９８９年通过的前寒武系划分方案中关于元古界系级单位划分命名的基本精神,而且充分体现了未元古纪全球生物发展演化的重要特色,同时有利于消除目前世界许多国家争用各自的地名来命名上元古系所造成的分坡。     

Sources and preservation of organic matter in the Cretaceous Toolebuc Formation, eastern Australia

The organic matter-rich Toolebuc Formation of eastern Australia was deposited in a Lower Cretaceous epicontinental sea. Parameters from biological marker studies indicate that the organic matter is immature to marginally mature for hydrocarbon generation. The occurrence of abundant coccoliths and the distribution of alkane biomarkers suggest that the organic matter (Type II) is largely of planktonic origin and only in the southeastern part of the depositional area can a terrestrial influence be discerned. Variations in kerogen composition can be attributed to the extent of the oxidation of the source materials and the degree of incorporation of sulphur. The atomic H/C ratios (c. 1.1) are remarkably constant for most of the Toolebuc Formation. Atomic O/C ratios vary from 0.1 and 0.4 and can be related both to depth and paleogeographic position. Kerogen sulphur contents range up to 7%, and the highest values occur in the most carbonate-rich sediments. Total sulphur (inorganic + organic) to carbon ratios in the sediments vary from 1 to <0.2 and are a function of paleogeographic position and lithology. Most of the sulphur in the sediments is in the form of pyrite, but the proportion of sulphur in organic form increases as the total sulphur content decreases. The evidence for oxidation of the organic matter and incorporation of sulphur into it during deposition suggests that bituminite, which is the dominant organic maceral in the Toolebuc Formation, was formed from an organic gel derived by decay of predominantly algal material. These data support a modified gyttja model (Kauffman, 1981) for the deposition of organic matter in the Toolebuc Formation.     

New aromatic biomarkers and possible maturity indicators found in New Albany Shale extracts

Aromatic hydrocarbons from benzene extracts of New Albany Shale were characterized. A biomarker that has a molecular weight of 546 and a structural configuration consistent with that of an alkyl-aromatic hydrocarbon (C₄₀H₆₆) was tentatively identified. It was found that the relative concentrations of the biomarker are indicative of differing levels of thermal maturity of the shale organic matter. A 40-carbon bicyclic carotenoid (C₄₀H₄₈) is proposed as the geochemical precursor of this biomarker. Thermal maturity of the shale organic matter can also be differentiated by observing differences in “fingerprints” as obtained by field-ionization mass spectrometry on the aromatic hydrocarbon fraction. Using this technique, we found that the more mature shale samples from southeastern Illinois contain more low molecular weight extractable aromatic hydrocarbons and the less mature shale samples from northwestern Illinois contain more high molecular weight extractable aromatic hydrocarbons. It was demonstrated that field-ionization and tandem mass spectrometric techniques through fingerprint and individual compound identification, are useful for shale aromatic hydrocarbon fraction characterization and for thermal maturation interpretation.     

Sulfides in petroleum

The homologous series of terpenoid sulfides previously reported to be present in Athabasca bitumen have been detected in a variety of petroleums from the Western Hemisphere. All 22 samples examined, ranging in age from Devonoan to Cretaceous, contained the terpenoid sulfides. A method is described for the isolation of sulfides from petroleums based on the selective oxidation of sulfides to more polar sulfoxides which are easily removed from the mixture and their subsequent reduction to sulfides. The sulfide content in the petroleum maltenes examined ranged from 0.3 to 16.1% w/w. In addition to the bicyclic and tetracyclic terpenoid sulfides a new series of tricyclic terpenoid sulfides has been identified, and the details of the isoprenoid side chain have been elucidated for all three homologous series. The distributions by carbon number of the bicyclic and tetracyclic homologous series of terpenoid sulfides show pronounced variations which are attributed to thermal maturity and degree of water washing of the petroleum, thus the ability to identify terpenoid sulfides should provide a useful tool for oil-oil and oil-source rock correlation studies. The bicyclic and tricyclic terpenoid sulfides have the same carbon framework as the carotenoids which suggest that these sulfides were accessory pigments in photosynthesis.     

Origin of Oils in “Subtle pools” in the Dongying Depression, Bohai Bay Basin, China

Subtle traps or oil pools have become an important exploration play in the Dongying Depression, Bohai Bay Basin, east China. Despite recent successes in exploration, the formation mechanisms of subtle traps are still not well understood. The majority of subtle oil pools in the Dongying Depression are developed in the middle interval of the Es3 Member of the Paleogene Shahejie Formation with the subtle traps being primarily of lenticular basin-floor turbidite sands encompassed in mudstones. Oil in the subtle traps was previously thought to have migrated directly from the surrounding source rocks of the same formation （Es3）. Detailed geochemical investigation of 41 oils and 41 rock samples from the depression now indicates that the oils from the subtle traps cannot be correlated well with the surrounding Es3 source rocks, which are characterized by high Pr/ Ph （〉1）, low Gammacerane/C30hopane, representing a freshwater lacustrine setting. In contrast the oils features low Pr/Ph （〈1） and relatively high Gammacerane content, showing a genetic affinity with the underlying Es4 source rocks, which also have the same qualities, indicating a brackish lacustrine setting. Oils in the Es3 subtle traps are probably derived from mixed sources with the contribution from the upper Es4 source rocks predominating. Therefore unconventional oil migration and accumulation mechanisms need to be invoked to explain the pooling of oils from the ES4 source rocks, which probably came through a thick low interval of the Es3 source rocks with no apparent structural or stratigraphic pathways. We suggest that the subtle oil migration pathway probably plays an important role here. This finding may have significant implications for future exploration and the remaining resource evaluation in the Dongying Depression.     

莺琼盆地中新统海相烃源岩地球化学特征及生烃潜力评价

通过有机碳测定、岩石热解分析、显微组分定量分析、饱和烃色谱、色谱-质谱等实验分析,对莺琼盆地中新统海相烃源岩的地球化学特征进行了研究,探讨了不同层位烃源岩的生烃潜力。结果表明：莺琼盆地中新统海相烃源岩有机质丰度总体较低,大部分烃源岩为中等烃源岩,有机质类型以Ⅱ2型和Ⅲ型为主,有机质热演化主要处于成熟阶段。烃源岩显微组分组成具有富含镜质组、壳质组+腐泥组次之、贫含惰性组的特征。烃源岩沉积环境主要为弱氧化-弱还原环境,具有陆生高等植物和低等水生生物生源混合输入的特征。莺歌海盆地梅山组烃源岩综合评价为中等烃源岩,生烃潜力相对较好,三亚组烃源岩综合评价为较差—中等烃源岩,具有一定的生烃潜力。琼东南盆地梅山组和三亚组烃源岩综合评价为中等烃源岩,具有相当的生烃潜力。