Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogen precursors

A series of kerogens and kerogen precursors isolated from DSDP samples, oil shales and Recent algal mats have been examined by Curie point pyrolysis-high resolution gas chromatography and gas chromatography-mass spectrometry. This study has shown that the three main types of kerogens (marine, terrestrial and mixtures of both) can be characterized using these techniques. The marine (algal) kerogens yield principally aliphatic products and the terrestrial kerogens yield more aromatic and phenolic products with some n-alkanes and n-alkenes. The yields of n-alkanes and n-alkenes increase and phenols decrease with increasing geologic age, however, pyrolysis-GC cannot be used to characterize the influence of short term diagenesis on the kerogen structure.     

Surface geochemical methods used for oil and gas prospecting — a review

The majority of the world's oil and gas deposits have been discovered by drilling in the vicinity of natural petroleum seeps, and to date the most successful geochemical prospecting methods still rely upon the surface detection of hydrocarbons. Gas chromatographic techniques are now commonly used in the analysis of hydrocarbon gases for prospecting both onshore (analysis of soils and rocks) and offshore (analysis of near-bottom waters and sediments). Detection of helium fluxes has been partially successful as a geochemical prospecting technique. Many indirect techniques such as the determination of isotope and metal-leaching anomalies in surface rocks and the measurement of radon fluxes have not been widely used.Onshore geochemical prospecting appears to have more problems associated with it than offshore prospecting due to the more complex migration mechanism of near-surface waters containing dissolved gases. No onshore prospecting studies have been published which thoroughly consider this factor and the success of onshore prospecting remains equivocal. In offshore prospecting “sniffers” have been used to detect hydrocarbon anomalies in near-bottom waters, and coring equipment has been used for the detection of hydrocarbons in near-surface sediments. Success is claimed using these techniques.Geochemical prospecting methods are complementary to the widely used geophysical methods. Geochemical methods can provide direct evidence for the presence of petroleum accumulations and are relatively cheap and rapid. Failures in prospecting to date are attributable to the simplistic manner in which data have been interpreted; insufficient attention has been paid to the hydrological and geological factors which modify the upward migration of indicator species to the surface. As oil and gas deposits become more difficult to locate, greater attention should be paid to geochemical prospecting techniques, especially as a regional exploration tool.     

Monitoring In Situ Biodegradation of MTBE Using Multiple Rounds of Compound‐Specific Stable Carbon Isotope Analysis

At a large industrial facility, methyl tert‐butyl ether (MTBE) was released to the subsurface and dispersed into the light, non‐aqueous phase liquids (LNAPL), in the first aquifer, with the LNAPL serving as a continuous source of MTBE in groundwater. Compound‐specific isotope analysis was conducted on both MTBE and tert‐butyl alcohol (TBA) in groundwater samples collected in 2008, 2011, and 2013 from wells located along and off the center line of the MTBE plume. The study demonstrated the onset and progress of biodegradation of MTBE between 2008 and 2013. The TBA observed in 2008 appears to be derived only in part from MTBE transformation while a significant portion of TBA might be contributed directly from LNAPL sources. In 2011 to 2013, the dominant source of TBA in the mid‐gradient plume was MTBE transformation. A contribution of an offsite LNAPL source, in particular to the down‐gradient area of the plume, is possible but could not be unequivocally confirmed. The time series provided direct evidence for MTBE biodegradation, but also a valuable insight on the sources of TBA.     

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.     

Identification of steranes and tritepanes in geolipid extracts by high-resolution gas chromatography and mass spectrometry

One method for the analysis of complex organic mixtures from geological sources is the use of high-resolution gas chromatographic data together with mass spectra obtained by combined gas chromatography-mass spectrometry (gc-ms). The present study involved examination of a variety of authentic triterpenoid alkanes (triterpanes) and steroid alkanes (steranes) for reference purposes, by measurement of their Kovats indices on OV-101 and Dexsil 300 liquid phases, and by the recording of their low-resolution mass spectra by gc-ms. These measurements provide reference data for analysis of the triterpenoid alkanes in geological samples and show that mass spectrometry is a valuable technique for triterpane analysis, permitting in many cases gross structural assignments which may be refined by a comparison of Kovats indices with those of authentic standards.     

青海湖沉积物支链和环烷烃组分中C20，C25和C30高度支链类异戊二烯烯烃

在青海湖不同盐度的四孔近代沉积物岩芯（Ｑ－１６Ａ，ＱＨ，ＱＥ和ＱＧ）（图１）抽提物支链和环烷烃组分中检出了非常丰富的Ｃ₂₀，Ｃ₂₅和Ｃ₃₀高度支链类异戊二烯烯烃（ｈｉｇｈｌｙｂｒａｎｃｈｅｄｉｓｏｐｒｅｎｏｉｄａｌｋｅｎｅｓ），简称ＨＢＩ烯烃。这是在我国近代湖泊沉积物发现这类化合物的首次详细报导。由于Ｃ₂₀，Ｃ₂₅和Ｃ₃₀ＨＢＩ烯烃比正构烷烃具有较强的抵抗生物降解的能力（ＲｏｂｓｏｎａｎｄＲｏｗｌａｎｄ，１９８８ｂ），因此，它们广泛分布于各种近代环境中，如湖泊、海洋和高盐环境的近代沉积物中（ＲｏｗｌａｎｄａｎｄＲｏｂｓｏｎ，１９９０）。并且，具有１～６个双键的Ｃ₂₀，Ｃ₂₅和Ｃ₃₀烯烃经常是现代沉积物中丰富的烃类。最近在印度洋现代沉积物中又发现了一个新的具有７个双键的Ｃ₃₅ＨＢＩ烯烃（Ｈｏｅｆｓｅｔａｌ，１９９５）。全饱和的Ｃ₂₀（Ｉ，附图）、Ｃ₂₅（Ⅱ，附图）和Ｃ₃₀（Ⅲ，附图）ＨＢＩ烷烃已通过标样的合成确切地确定了它们的结构。在青海湖ＱＧ孔（尕海，咸水）和ＱＥ孔（耳海，淡水）抽提物中发现了Ｃ₂₀单烯（１号峰，图２ａ）。Ｃ₂₅烯烃（２号峰，图２ａ、２ｂ）和Ｃ₃₀烯烃（主要是３号和８号峰，图２ａ、２ｂ）存在于所有四孔沉积物中。     

Bicyclic sesquiterpenoids and diterpenoids in Australian crude oils

Bicyclanes previously reported only in heavily biodegraded Texas Gulf Coast crudes have been found to be ubiquitous in Australian crude oils of non-marine origin from four different basins. The compounds are present in oils, thought to be derived from the same or similar sources, that have undergone varying degrees of biodegradation. They are also found to be present in oils of different geological age. In addition a series of tricyclic diterpenoid hydrocarbons was common to four oils from the Gippsland Basin. Four of these compounds had the molecular formula C₂₀H₃₄ and mass spectral fragmentation patterns suggested they were mono-unsaturated diterpenoids. The presence of unsaturated diterpenoids in crude oils appears to be a unique observation. It is proposed that the diterpenoids may be the source of the bicyclanes also observed in these oils.     

Correlation of crude oils from the San Jorges Basin,Argentina

The aliphatic hydrocarbon fractions of sixty oils from the San Jorges Basin, Argentina have been analysed by computerized-gas chromatography-mass spectrometry. The initial aim of this study was the correlation of the oils using sterane and triterpane biomarkers. The oils could be divided into four groups which were distinguished by the relative proportions of regular to demethylated hopanes. Although it has been previously suggested that the demethylated hopanes found in oils could have resulted from biotransformation of the oils in the reservoir, in this basin the possibility that these compounds originated directly from the source beds cannot be entirely eliminated since the oils do not appear to be extensively biodegraded on the basis of their aliphatic hydrocarbon distributions. An alternative theory for the hydrocarbon distributions observed in these oils, is initially biodegradation of the oils in the reservoir followed by addition of non-degraded oil to produce a mixture of degraded and non-degraded oil.     

Effect of a dolerite intrusion on triterpane stereochemistry and kerogen in Rundle oil shale,Australia

Stereochemical changes of triterpanes present in extracts from an immature oil shale sequence intruded by a 3-m dolerite sill have been studied by gas chromatography-mass spectrometry (GC-MS). The steric configuration of the hopanes was observed to change from one dominated by the thermally less stable 17β(H), 21β(H) configuration at some distance from the intrusion, to one dominated by the thermally more stable 17α(H), 21β(H) and 17β(H), 21α(H) configurating in the immediate vicinity of the intrusion. In addition, severe alteration of the kerogen appeared to have taken place as a result of the contact metamorphism, and high concentrations of extractable organic matter were observed below the intrusion. Characterization of the kerogens by Curie-point pyrolysis has enabled the effects of the intrusion on the shales to be monitored.     

Observations on temporal red shift of wheat from multi-date spaceborne MOS-B spectrometer data

High spectral resolution spectroscopy enables to have detailed information on chemical and morphological status of crop. An attempt of using space platform for detecting red edge shift during different growth stages of wheat crop is reported. Study was conducted during rabi 1996–97 season using Modular Opto-Electronic Scanner MOS-B Imaging data onboard IRS-P3 satellite. Inverted Gaussian model was fitted for satellite derived reflectances between 650 and 870 nm to derive inflection wavelength and its subsequent change with crop stages i.e. red shift. Red shift of 10 nm observed from crown root initiation stage (703.8 nm) to peak vegetative stage (714.2 nm). A comparative study on temporal behaviour of vegetative indices like NDVI and ARVI with Red edge showed that latter is more atmospherically stable parameter. It is concluded that red edge shift which hitherto has been observed from ground and airborne sensors, can also be detected from space.