Botryococcus—A planktonic green alga, the source of petroleum through the ages: Transmission electron microscopical studies of oil shales and petroleum source rocks

The hydrocarbon secreting alga Botryococcus has been identified in organic remains of sediments ranging from Precambrian to Recent, and is believed to have been a major source material for petroleum generation throughout the geological time. In some petroleum source rocks of Lower Palaeozoic and Precambrian age, identification of the alga is only possible by electron microscopy. Transmission electron microscopy (TEM) has been used in the present study to identify microstructures of the algal remains in a range of oil shales and petroleum source rocks. It has been established that Botryococcus is the predominant alga in the Kukersite oil shale of Estonia. Similarly, the alga has been shown to be a major contributor to petroleum source rocks in Cambrian and Precambrian sedimentary basins in Australia. TEM has been applied to observations of Botryococcus in torbanites and to products from simulated maturation experiments on torbanite. A comparison with algal remains from Cambrian and Precambrian sediments ranging from undermature to overmature, enabled the distinction of organic matter in various stages of oil generation. Maturation/thermal effects on alginite have been established by reflectance and fluorescence, and compared with experimental results.     

黑龙江依兰煤田达连河组油页岩生物 标志化合物特征及地质意义

采用气相色谱、气相色谱-质谱技术开展了依兰煤田达连河组油页岩的生物标志化合物特征研究.饱和烃气相色谱显示,达连河组油页岩有机质具有混合来源.中部厚层油页岩样品奇偶优势(OEP)值普遍大于2.4,表明其成熟度相对较低,而煤层间厚层油页岩的OEP均小于2.4,表明随深度的增加其成熟度相对较高.中部厚层油页岩段样品的Pr/Ph值均大于0.8,含煤段油页岩样品的Pr/Ph值均大于2.8.综合分析认为,达连河组下部含煤段油页岩层有机质丰度高,水生低等生物对有机质贡献较大,有机质类型主要为Ⅱ1型,具有姥鲛烷优势,为弱氧化—弱还原、淡水湖沼相沉积;中部厚层油页岩段有机质类型主要为Ⅱ1型、Ⅱ2型,具有姥植均势,反映了淡水—微咸水深湖相环境.     

Phytoliths as indicators of pedogenesis and paleoenvironmental changes in the Brazilian cerrado

This paper presents the preliminary results of phytolith analyses of a peat located in the cerrado of the Uberaba municipality, State of Minas Gerais, Brazil. The phytolith soil sequence is discussed by comparison with phytolith assemblages extracted from dominant plants (Cyperaceae and Poaceae). Increasing mean age of phytolith assemblages with depth is assumed. Poaceae Cuneiform bulliform cell, Parallelepiped bulliform cell and Elongate smooth long cell types dominate up to 80 cm, rapidly drop to 42% at 80 cm and regularly decrease from 42% to 2% upwards. Cyperaceae Rondel concave type shows the inverse trend, being dominant in the upper part of the profile. This pattern can be assigned to increasing selective dissolution of the Cyperaceae phytolith type with depth, or/and to a decrease of water stress suffered by the grasses, leading to a decrease of bulliform cell silicification. Soil processes and paleo-environmental changes hypotheses are discussed.     

西藏尼玛盆地古近纪湖相油页岩正构烷烃特征及其古环境与古气候意义

尼玛盆地地处青藏高原中部特殊区域,自新生代以来沉积了大套连续的湖相暗色油页岩,其富含生物分子化石,对重建青藏高原古气候和古环境具有重要意义。本文通过对尼玛盆地古近系牛堡组康嘎勒剖面正构烷烃及相关参数分布特征进行研究,结果显示,剖面油页岩正构烷烃分布从底到顶由单峰前峰型向单峰后峰型过渡,具2个旋回周期;碳优势指数相对稳定,但TAR、ACL、P_aq及nC_≤21/nC_≥25变化较大,表明湖泊沉积有机质由内源为主的低等藻类向高等水生植物和外源陆生高等植物转变,且区域气候环境由温凉湿润向炎热干旱逐步演化。综合分析认为,尼玛盆地在始新世的气候变化在很大程度上是受西风环流和季风系统的共同影响。且西风环流和季风的强度变化与全球气候存在一定的关系。即全球变暖时,西风环流势力减弱,西风环流和残余洋水汽为高原中部提供的有效降水减少,气候相对干旱;而在全球降温时,西风环流和印度季风增强,残余洋水汽的叠加又为高原中部提供了充足的有效降水,气候湿润。

     

Spread of oil from theTenyo Maru,off the Southwest coast of Vancouver Island

We provide background oceanography and observations and hindcast simulations of spreading oil leaked from the wreck of theTenyo Maru, a fishing vessel that sank off the western entrance to Juan de Fuca Strait in July 1991. The vessel sank in the region of the Tully Eddy on the continental shelf. Although this eddy is normally present in summer, its location shifts and its trapping time varies considerably. The spread of theTenyo Maru oil is represented reasonably well by assuming the eddy to be a littler further to the east and north of its position as observed during drifter studies in 1986. Observations in 1985 showed that the preferred exit route of surface water from the eddy was toward the southeast, the direction followed by theTenyo Maru oil in 1991; however, other drift paths are possible, and under different weather conditions the oil could have drifted toward the Vancouver Island coast.     

Equation of state,structural behaviour and phase diagram of synthetic MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, as a function of pressure and temperature

The behaviour of synthetic Mg-ferrite (MgFe₂O₄) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K₀=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa^–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by _a0+_a1*(T–298)+_a2/(T–298)², where _a0=9.1(1) 10^–6 K^–1, _a1=4.9(2) 10^–9 K^–2 and _a2= 5.1(5) 10^–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol^–1 and =–17.6(± 1.2) kJ mol^–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe₂O₄, which shows that the high-pressure transition from spinel to orthorombic CaMn₂O₄-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe₂O₃.     

Possible algal origin of long chain odd n-alkanes in immature sediments as revealed by distributions and carbon isotope ratios

A Pliocene oil shale (Pula, Hungary), a C₃ plant Triticum aestivum and a C₄ plant Zea mays were compared using isotopic composition of bulk organic matter, along with distributions and individual carbon isotope ratios of n-alkanes from organic extracts. The microalga Botryococcus braunii (A race) was thus shown to be the main source of the predominant 27, 29 and 31 n-alkanes of Pula sediment Therefore, the dominance of odd carbon-numbered n-alkanes in the range C₂₅–₃₅ in extracts from immature sediments shall not be systematically assigned to higher plant contribution but algal input is also possible. In fact, the long chain n-alkanes with an odd predominance previously observed in extracts of various immature sediments are likely to be derived at least partially, from algae.     

Pyrolytic and spectroscopic study of a sulphur-rich kerogen from the “Kashpir oil shales” (Upper Jurassic, Russian platform)

The kerogen of an organic-rich sample, termed f top, from the Gorodische section (Russian platform) was studied using a combination of microscopic, spectroscopic and pyrolytic methods so as to examine its chemical structure, source organisms and formation pathway(s). This kerogen, which is mainly composed of orange gel-like, nanoscopically amorphous organic matter, exhibits a relatively high aliphatic character; organic sulphur is mainly present as di(poly)sulphides and alkylsulphides. The f top kerogen was chiefly formed via intermolecular incorporation of sulphur in algal or cyanobacterial lipids and carbohydrates. However, its formation also involved oxidative condensation via ether linkages. Comparison of f top sample with other S-rich kerogens points to a closer similarity with Monterey kerogens rather than with a kerogen from the bituminous laminites of Orbagnoux.     

High-resolution last deglaciation record from the Congo fan reveals significance of mangrove pollen and biomarkers as indicators of shelf transgression

High abundances of mangrove pollen have been associated with transgressive cycles on tropical margins, but the detailed relations between systems tracts and the taphonomy of the pollen are unclear. We report here the occurrence and high abundance of Rhizophora pollen, in association with taraxerol, a Rhizophora-sourced biomarker, from a high-resolution Congo fan core covering the last deglaciation. An age model based on ¹⁴C dates enables the temporal changes in taraxerol content and the percentage frequencies and flux (pollen grains (pg) cm⁻² (10³ yr)⁻¹) of mangrove pollen to be compared quantitatively with the lateral rate of transgression across the flooding surface (derived from glacio-hydro-isostatic model output and the bathymetry of the margin). Rhizophora pollen concentrations and taraxerol content of the sediment are very strongly positively correlated with the lateral rate of transgression and indicate, independently of any sequence stratigraphic context, that mangrove pollen spikes are associated with the transgressive systems tract rather than the highstand systems tract or maximum flooding surface. Lower-resolution longer-term records from this margin indicate an association between taraxerol concentrations and transgressive rather than regressive phases. The flux of these materials to the Congo fan is interpreted as a function of the erosion of flooded mangrove swamp on the shelf and, less importantly, changing extent of mangrove habitat, during sea-level rise. Congo River palaeoflood events also result in reworking of mangrove pollen and supply to the fan, but this mechanism is subdominant. Rhizophora pollen has been underestimated in many palynological studies undertaken on cores from the African margin because of inappropriate sieve mesh size used during laboratory preparation.     

Origin of the Cenozoic–Mesozoic magnetite-series and ilmenite-series granitoids in East Asia

Among the Phanerozoic granitoids of East Asia, the most prevailing Cenozoic–Mesozoic rocks are reviewed with respect to gabbro/granite ratio, bulk composition of granitoids, redox state, and O- and Sr-isotopic ratios. Quaternary volcanic rocks, ranging from basalt to rhyolite, but typically felsic andesite in terms of bulk composition in island arcs, are oxidized type, possibly due to oxidants from subducting oceanic crust into the source regions. Miocene plutonic rocks in the back-arc of Japan could be a root zone for such volcanism but are more felsic in composition. Cenozoic–Mesozoic plutonic zones are classified by (1) the redox state (magnetite/ilmenite series), and (2) average bulk composition (granodiorite/granite). The granodioritic magnetite series occur with fairly abundant gabbro and diorite in the back-arc of island arcs (Greentuff Belt) and intercontinental rapture zones (Yangtze Block). These rocks are mostly juvenile in terms of the ⁸⁷Sr/⁸⁶SrI and δ¹⁸O values.The granitic magnetite series with some gabbroids occur in rapture zones along the continental coast (Gyeongsang Basin, Fujian Coast) and the back-arc of island arc (Sanin Belt). They were generated mostly in felsic continental crust, with the help of heat and magmas from upper mantle. The generated granitic magmas had little interaction with C- and S-bearing reducing materials, due probably to extensional tectonic settings. The δ¹⁸O value gives narrow ranges but the ⁸⁷Sr/⁸⁶SrI ratio varies greatly depending upon the age and composition of the continental crust. Granitic ilmenite-series are characterized by high δ¹⁸O values, implying much contribution of sediments. The ⁸⁷Sr/⁸⁶SrI ratios are low in island arcs but very high in continental interior settings. Amount of mafic magmas from the upper mantle seems a key to control the composition of granitoid series in island arc settings, while original composition of the protolith may be the key to control granitoid composition in continental interiors.     

Carbon isotopic composition of individual n-alkanes in asphaltene pyrolysates of biodegraded crude oils from the Liaohe Basin, China

Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C₁₆–C₂₉ range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.