The effects of biodegradation on the compositions of aromatic hydrocarbons and maturity indicators in biodegraded oils from Liaohe Basin

By aid of gas chromatogram/mass spectrometry (GC-MS), the distributions and the compositions of biomarkers in a set of sequentially biodegraded oils from Liaohe Basin, China, have been quantitatively analyzed, and it has been found that during the biodegradation process of crude oils, the molecular maturity parameters such as Ts/Tm, homohopane C₃₁ 22S/(22S+22R) and sterane C₂₉ 20S/(20S+20R) ratios will be affected to different extent. The results show that except homohopane C₃₁ 22S/(22S+22R) ratio, Ts/Tm ratio will decrease with increasing biodegradation, but for C₂₉ 20S/(20S+20R) ratio, it will almost remain constant in slightly and moderately biodegraded oils, and then will increase quickly in severely biodegraded oils. The main reason is that there are some differences in the ability of resistant biodegradation for different isomer of biomarkers with different stereo configuration, resulting in the fact that destroying rate by bacteria for those biomarkers with weak ability will be higher than those with strong ability in resistant biodegradation. For example, 18α(H)-22,29,30-trisnorhopanes (Ts) will be destroyed more quickly than 17α(H)-22,29,30-trisnorshopanres (Tm), and 20R isomer is more quickly than 20S isomer for C₂₉ sterane, resulting in the relative ratios changed with increasing biodegradation. Therefore, much more attention should be paid to the biodegradation extent of crude oils and the type of biomarker maturity indicators, when the distributions and the compositions of biomarkers in biodegraded oils are used to determine the maturity of biodegraded oils.

     

The effects of biodegradation on biomarker maturity indicators in sequentially biodegraded oils from Liaohe Basin,China

By aid of gas chromatogram/mass spectrometry (GC-MS), the distributions and the compositions of biomarkers in a set of sequentially biodegraded oils from Liaohe Basin, China, have been quantitatively analyzed, and it has been found that during the biodegradation process of crude oils, the molecular maturity parameters such as Ts/Tm, homohopane C₃₁ 22S/(22S+22R) and sterane C₂₉ 20S/(20S+20R) ratios will be affected to different extent. The results show that except homohopane C₃₁ 22S/(22S+22R) ratio, Ts/Tm ratio will decrease with increasing biodegradation, but for C₂₉ 20S/(20S+20R) ratio, it will almost remain constant in slightly and moderately biodegraded oils, and then will increase quickly in severely biodegraded oils. The main reason is that there are some differences in the ability of resistant biodegradation for different isomer of biomarkers with different stereo configuration, resulting in the fact that destroying rate by bacteria for those biomarkers with weak ability will be higher than those with strong ability in resistant biodegradation. For example, 18α(H)-22,29,30-trisnorhopanes (Ts) will be destroyed more quickly than 17α(H)-22,29,30-trisnorshopanres (Tm), and 20R isomer is more quickly than 20S isomer for C₂₉ sterane, resulting in the relative ratios changed with increasing biodegradation. Therefore, much more attention should be paid to the biodegradation extent of crude oils and the type of biomarker maturity indicators, when the distributions and the compositions of biomarkers in biodegraded oils are used to determine the maturity of biodegraded oils.     

The effects of biodegradation on the compositions of aromatic hydrocarbons and maturity indicators in biodegraded oils from Liaohe Basin

By the aid of GC-MS technique, a series of sequentially biodegraded oils from Liaohe Basin have been analyzed. The results show that the concentrations and relative compositions of various aromatic compounds in the biodegraded crude oils will change with increasing biodegradation degree. The concentrations of alkyl naphthalenes, alkyl phenanthrenes, alkyl dibenzothiophene are decreased, and the concentration of triaromatic steroids will increase with increasing biodegradation degree in biodegraded oils. Those phenomena indicate that various aromatic compounds are more easily biodegraded by bacteria like other kinds of hydrocarbons such as alkanes, but different series of aromatic compounds have a varied ability to resistant to biodegradation. The ratios of dibenzothiophene to phenenthrene (DBTH/P) and methyl dibenzothiophene to methyl phenanthrene (MDBTH/MP) are related to the features of depositional environment for source rocks such as redox and ancient salinity. However, in biodegraded oils, the two ratios increase quickly with the increase of the biodegradation degree, indicating that they have lost their geochemical significance. In this case, they could not be used to evaluate the features of depositional environment. Methyl phenanthrene index, methyl phenanthrene ratio and methyl dibenzoyhiophene ratio are useful aromatic maturity indicators for the crude oils and the source rocks without vitrinite. But for biodegraded oils, those aromatic maturity indicators will be affected by biodegradation and decrease with the increase of the biodegradation degree. Therefore, those aromatic molecular maturity indicators could not be used for biodegraded oils.     

Novel C15 sesquiterpanes and their origin in different crude oils from the Pearl River Mouth Basin of China

In the saturate fractions of crude oils from the Zhu1 and Zhu2 depressions of the Pearl River Mouth Basin,two novel C_(15) sesquiterpanes have been detected except for drimanes and rearranged drimanes.By comparison with spectra and retention times in previous studies,they have been identified as 2,2,4α,7,8-pentamethyl-trans-decalin and 2,2,4α,7,8-pentamethyl-cis-decalin,respectively,which are related to the D/Eringsof18α(H)-and18β(H)-oleanane.ResultsshowthatthenovelC15sesquiterpanesarerelativelyabundantincondensateoilsthathavehighPr/PhratiosandarerichinterrigenoustriterpanessuchasoleananeandbicadinanesfromtheZhu2depression,butevidentlylowinlacustrineoilsthathavelowPr/Phratiosandarerichin4-methylsteranesfromtheZhu1depression.ThissuggeststhatthenovelC15sesquiterpanescouldberelatedtoterrigenousorganicmatterinoriginandcanhelpdistinguishtheoriginandsourceofcrudeoilsinthestudyarea.Inaddition,thereexistcompletelydifferentcorrelationsbetweentherelativeabundancesofdifferentC15sesquiterpanesthathavedifferentsourcesandthePr/Phratio,whichindicatesredoxconditionsinthecrudeoils.Forexample,thenovelC15sesquiterpanesandcadinanethatindicateterrigenousinputarepositivelycorrelatedwiththePr/Phratio,butdrimanesandrearrangeddrimaneshavingmicrobialoriginarenegativelycorrelatedwiththePr/Phratio.ThisimpliesthattheformationofthenovelC15sesquiterpanesrequiresrelativelyoxicconditions.ThenovelC15sesquiterpanesaremuchmoreabundantincarbonaceousmudstone(Pr/Ph=7.39)thanindarkmudstone(Pr/Ph=2.19)fromtheEnpingformation,althoughtheirorganicmatterishumic.However,theyarenotcommoninsapropeliclacustrinesourcerocks(Pr/Ph=2.29)fromtheWenchangFormation.Thissuggeststhatterrigenousorganicmatterisonlyasufficientcondition,butanoxicenvironmentduringdepositionanddiagenesismaybeaprerequisitefortheformationofnovelC15sesquiterpanes.     

The relationship between methylated chromans and maturity of organic matter in the source rocks from Jianghan hypersaline basin

The distribution, the relative composition, and their variation of methylated chromans (MTTC) with maturation of organic matter in the source rocks from Mingjia 1 well, Jianghan hypersaline basin, have been analyzed and studied. There is a close relationship between the distribution of methylatd chromans and paleosalinity of depositional environment. In the Eq ₁–Eq ₃ source rocks deposited under hypersaline environment with lower Pr/Ph ratio, higher gammacerane index and abundant organic sulfur-containing compounds, methyl MTTC and dimethyl MTTC are main components, but in the Eq ₄ source rocks deposited non-hypersaline environment with relatively higher Pr/Ph ratio, lower gammacerane index and organic sulfur-containing compounds, trimethyl MTTC is a major compound in methylate chromans. Obviously, the distributions and the compositions of methylated chromans in the source rocks are in harmony with biomarker indicators indicating the paleaosalinity and redox of depositional environment. The relationship between the ratio of 5,8-dimethyl MTTC to 7,8-dimethyl MTTC (dimethyl MTTC ratio) and the maturity of organic matter in the source rocks from Mingjia 1 well has been discussed. The results show that dimethyl MTTC ratio increased with the burial depth and the maturation of organic matter in the source rocks, especially in immature level. It is noteworthy that this ratio is very susceptible to small variation in the maturity of organic matter in the source rocks when vitrinite reflectance R _o is less than 0.65%. It may imply that this ratio is a good and susceptible aromatic maturity indicator for the relative maturity of organic matter in immature source rocks.     

柴达木盆地东坪地区一类新的原油及其地球化学特征

各类生物标志物的组成特征表明:柴达木盆地北缘的冷湖油田原油具有姥植比高（Pr/Ph>2.0）,重排甾烷（C₂₇重排甾烷/规则甾烷=0.5~0.7）、重排藿烷（diaC₃₀H/C₃₀H=0.2~0.4）和新藿烷（C₂₉Ts/C₂₉H=0.4~0.7）含量中等,伽马蜡烷含量低（伽马蜡烷指数<0.05）的特征,它们源于该地区发育的下侏罗统淡水湖沼相烃源岩;而柴西北区咸水湖相原油的姥植比低（Pr/Ph<0.8）,重排甾烷（C₂₇重排甾烷/规则甾烷<0.1）、重排藿烷（diaC₃₀H/C₃₀H<0.05）和新藿烷（C₂₉Ts/C₂₉H=0.2~0.4）含量低和伽马蜡烷含量高（伽马蜡烷指数=0.4~0.8）,这一系列特征与柴西地区发育的古近系-新近系咸水湖相烃源岩一致。但是,东坪地区原油呈现完全不同的生物标志物组合,主要表现为丰富的伽马蜡烷（伽马蜡烷指数=1.2~3.0）与高含量的新藿烷（C₂₉Ts/C₂₉H>1.5）、重排藿烷（diaC₃₀H/C₃₀H>0.7）和重排甾烷（C₂₇重排甾烷/规则甾烷>0.4）并存,这与地质样品中伽马蜡烷和重排类标志物的分布特征相矛盾,因为依据现有的认识无法解释这一特殊地球化学现象。生物标志物组成特征表明东坪地区原油所具有的特殊生物标志物组合并非源于不同类型原油之间的混合,而是一种客观存在,尽管其确切的地球化学意义和形成条件目前并不清楚。由此可见,东坪地区原油为柴达木盆地一个新的原油类型,推测其烃源岩可能形成于偏酸性的咸水环境。