Formation mechanism of condensates,waxy and heavy oils in the southern margin of Junggar Basin,NW China

It is a challenge to determine the source and genetic relationship of condensate, waxy and heavy oils in one given complicated petroliferous area, where developed multiple sets of source rocks with different maturity and various chemical features.The central part of southern margin of Junggar Basin, NW China is such an example where there are condensates, light oils, normal density oils, heavy crude oils and natural gases. The formation mechanism of condensates has been seriously debated for long time;however, no study has integrated it with genetic types of waxy and heavy oils. Taking the central part of southern margin of Junggar Basin as a case, this study employs geological and geochemical methods to determine the formation mechanism of condensates,waxy and heavy oils in a complicated petroliferous area, and reveals the causes and geochemical processes of the co-occurrence of different types of crude oils in this region. Based on detailed geochemical analyses of more than 40 normal crude oils, light oils,condensates and heavy oils, it is found that the condensates are dominated by low carbon number n-alkanes and enriched in light naphthenics and aromatic hydrocarbons. Heptane values of these condensates range from 19% to 21%, isoheptane values from1.9 to 2.1, and toluene/n-heptane ratios from 1.5 to 2.0. The distribution of n-alkanes in the condensates presents a mirror image with high density waxy crude oils and heavy oils. Combined with the oil and gas-source correlations of the crude oils, condensates and natural gas, it is found that the condensates are product of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils which were derived from mature Cretaceous lacustrine source rocks in the relatively early stage. The waxy oils are the intermediate products of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils, while the heavy oils are in-situ residuals. Therefore, evaporative fractionation and/or phase-controlled fractionation would account for the formation of the condensate, light oil, waxy oil and heavy oil in the central part of southern margin of Junggar Basin, resulting in a great change of the content in terms of light alkanes, naphthenics and aromatics in condensates, followed by great uncertainties of toluene/n-heptane ratios due to migration and re-accumulation. The results suggest that the origin of the condensate cannot be simply concluded by its ratios of toluene/n-heptane and n-heptane/methylcyclohexane on the Thompson's cross-plot, it should be comprehensively determined by the aspects of geological background, thermal history of source rocks and petroleum generation,physical and chemical features of various crude oils and natural gas, vertical and lateral distribution of various crude oils in the study area.     

Differentiating depositional environments and maturity of crude oils using GC-AED benzothiophenic spectra

Organosulfur compounds of crude oils and light oils (condensates), collected from ten Chinese petroleumbearing basins and representing different sedimentary environments, were analyzed and identified using a newly-developed GC-AED technique. The results show that the distributions of organosulfur compounds of crude oils from different sedimentary environments are of obvious difference. The crude oils from marine carbonates are rich in organosulfur compounds and those from the source rocks in an ocean-land interchanging facies and a littoral facies have a high abundance of organosulfur compounds, while no or less organosulfur compounds of crude oils from a fresh-water lacustrine facies and a swamp facies were detected in the detectable abundance range of the instrument. This analysis gives a new effective method for oil-source correlation. We also tried to relate the various parameters of benzothiophenic compounds of crude oils with the methane carbon isotope of associated natural gases to discuss the thermoevolutionary degree of crude oils and natural gases.     

Survival of two species of amphipods in aqueous extracts of petroleum oils

Aqueous extracts of two petroleum oils, No. 2 fuel oil and Southern Louisiana crude, were tested on two amphipods, Gammarus muccronatus and Amphithoe valida, for survival. The oils were toxic at concentrations of 0.8 ppm (fuel oil) and 2.4 ppm (S. Louisiana crude). Mortalities increased with the concentration and length of exposure. Few or no young were produced at these and higher concentrations (breeding adults were decreasing rapidly in numbers). The amphipods are more sensitive to aqueous extracts of these oils than benthic polychaetes and shrimp, for which data are available.     

Improved approaches to ecotoxicity testing of petroleum products

Crude oils produced in the North West shelf of Western Australia are highly volatile, a characteristic not shared by most of the Northern Hemisphere crude oils on which internationally accepted toxicity test protocols were developed. Because of this volatility and some other factors, the LC50 and EC50 values obtained from acute toxicity tests will be significantly affected by the changes of toxicant concentration in test solutions during the period of exposure. To address these issues all steps of a standard protocol for crude oil toxicity testing have been revised. A systematic study has been performed on factors which affect petroleum hydrocarbon solubilisation in aqueous systems during test solution preparations. The influence of mixing time, agitation energy and volume/interface ratio on a hydrocarbon concentration in a water-soluble fraction (WSF) was studied for heavy, medium and light crude oils. A study of the sensitivity of marine unicellular algae to WSF of crude oils was conducted with Isochrysis sp., Nannochloropsis-like sp. and Nitzchia closterium. Total concentrations of hydrocarbons dissolved in test solutions were estimated by UV-spectrometry and GC/FID chemical analyses. When the toxicant concentration decreased during the exposure period, the EC50 values derived from initial or final concentrations either underestimate or overestimate toxicity, respectively. Therefore, weighted average concentrations (WAC) calculated for the whole test period were recommended for expressing hydrocarbon concentrations in test solutions of crude oils. Toxicity indices calculated from WAC of total hydrocarbons for different crude oils can be compared regardless of the rates of hydrocarbon loss.     

Large-scale cold water dispersant effectiveness experiments with Alaskan crude oils and Corexit 9500 and 9527 dispersants

There continues to be reluctance in some jurisdictions to use chemical dispersants as a viable countermeasure for accidental oil spills. One argument used by some opponents to dispersant use is that “chemical dispersants do not work effectively in cold water”. To address this issue, the U.S. Minerals Management Service (MMS) funded and conducted two series of large-scale dispersant experiments in very cold water at Ohmsett - The National Oil Spill Response Test Facility, located in Leonardo, New Jersey in February-March 2006 and January-March 2007. Alaska North Slope, Endicott, Northstar and Pt. McIntyre crude oils and Corexit 9500 and Corexit 9527 dispersants were used in the two test series. The crude oils were tested both when fresh and after weathering. Results demonstrated that both Corexit 9500 and Corexit 9527 dispersants were 85-99% effective in dispersing the fresh and weathered crude oils tested at cold temperatures. The MMS expects that results from these test series will assist government regulators and responders in making science based decisions on the use of dispersants as a response tool for oil spills in the Arctic.     

Compound-specific stable carbon isotopic composition of petroleum hydrocarbons as a tool for tracing the source of oil spills

With the increasing demand for and consumption of crude oils, oil spill accidents happen frequently during the transportation of crude oils and oil products, and the environmental hazard they pose has become increasingly serious in China. The exact identification of the source of spilled oil can act as forensic evidence in the investigation and handling of oil spill accidents. In this study, a weathering simulation experiment demonstrates that the mass loss of crude oils caused by short-term weathering mainly occurs within the first 24h after a spill, and is dominated by the depletion of low-molecular weight hydrocarbons (相似文献   

Identification of fuel samples from the Prestige wreckage by pattern recognition methods

A set of 34 worldwide crude oils, 12 distilled products (kerosene, gas oils, and fuel oils) and 45 oil samples taken from several Galician beaches (NW Spain) after the wreckage of the Prestige tanker off the Galician coast was studied. Gas chromatography with flame ionization detection was combined with chemometric multivariate pattern recognition methods (principal components analysis, cluster analysis and Kohonen neural networks) to differentiate and characterize the Prestige fuel oil. All multivariate studies differentiated between several groups of crude oils, fuel oils, distilled products, and samples belonging to the Prestige's wreck and samples from other illegal discharges. In addition, a reduced set of 13 n-alkanes out of 36, were statistically selected by Procrustes Rotation to cope with the main patterns in the datasets. These variables retained the most important characteristics of the data set and lead to a fast and cheap analytical screening methodology.     

Effects of surface and sunken crude oil on the behaviour of a sea urchin

Studies have been made of the effects of exposure to various forms of crude oil on the righting behaviour of Paracentrotus lividus and its reactions towards the presence of oil. Prolongation of the righting response was recorded in animals exposed to contact with surface or sunken fresh crude oil or to their water soluble fractions. No such effect was recorded on exposure to weathered oils and results indicate that the more volatile components of crude oil were responsible for this effect. Paracentrotus showed no avoidance reaction to the presence of sunken oil in its vicinity. The likely ecological significance of these results is discussed.     

Hydrogen isotopic compositions, distributions and source signals of individual n-alkanes for some typical crude oils in Lunnan Oilfield, Tarim Basin, NW China

Petroleum mainly comprises carbon and hydrogen elements. The stable carbon isotopic analysis for whole oil was undertaken as early as the 1930s. After decades, the stable carbon isotopic analytical methods have been developed from analysis for whole oil and oil fractions (e.g., saturated, aromatic and polar frac-tions) into compound-specific isotopic analysis with the emergence of the newly developed GC-C-IRMS analytical technique. Especially, by using com-pound-specific isotopic analytical…     

Comprehensive diag”nostic review of the (13)~C-enriched crude oils exemplified by TD2∈ and TZ62S in Tarim Basin,NW China

The crude oils typically from the CambrianLower Ordovician source rocks of Tarim Basin, NW"China, such as TD2 and TZ62S, are13C-enriched with the stable carbon isotopic ratios(VPDB) approaching-28 %.In this paper, the main research viewpoints on this issue are summarized, and combined with results from organic and inorganic carbon isotope stratum curves of the outcrop at the Ya'erdang Mountain in Tarim Basin. In addition, more alternative interpretations are discussed. On one hand, the inverse fractionation features of stable carbon and hydrogen isotopes of these crude oils may imply their protogenous nature. On the other hand, the anisotropy of source rocks and contribution from older stratum source rocks need verifying as well. For the sake of the final resolution of this issue, some further study topics are recommended.     

Origin and accumulation of the oils from Bamianhe Oilfield, Bohai Bay Basin, Eastern China

Utilizing basic principles and methodologies of geology and organic geochemistry, kinetics of hydrocarbons generation and accumulation, quantitative assessment of crude oils sourced from different source rocks, and hydrocarbons migration pathways for the oils from the Bamianhe Oilfield, the Bohai Bay Basin, Eastern China are discussed. Results of oil-rock correlation showed that the oils were mainly derived from Es4 member (with buried depth >2700 m) of Niuzhuang and Guangli Sags within normal oil window though there is a little amount of mixed immature oils. Quantification of mixed oils with different sources indicated that mature oils account for about 80% of the total oils discovered and immature oils for only 20%. Migration of the oils sourced from the sags is controlled by predominant hydrocarbons migration passages determined by faults, unformalities and favored sandstone reservoir. Results of the origin and migration models for the oils have been recently further testified by considerable quantity of oils discovered in the Bamianhe area, which is obviously playing an important role in guiding further oil exploration.     

Study of genetic evolution of oil inclusion and density of surface oil by measurement of fluorescence lifetime of crude oil and oil inclusion

By using fluorescence lifetime image microscope (FLIM) and time-correlated single photon counting (TCSPC) technique, we measured fluorescence lifetime of crude oils with density of 0.9521–0.7606 g/cm³ and multiple petroleum inclusions from Tazhong uplift of Tarim Basin. As indicated by the test results, crude oil density is closely correlated with average fluorescence lifetime following the regression equation Y=–0.0319X+0.9411, which can thus be used to calculate density of oil inclusions in relation to fluorescence lifetime and density of corresponding surface crude. For type A oil inclusions showing brown-yellow fluorescence from Tazhong 1 well in Tarim Basin, their average fluorescence lifetime was found to be 2.144–2.765 ns, so the density of surface crude corresponding to crude trapping these oil inclusions is 0.852–0.873 g/cm³, indicating that they are matured oil inclusions trapped at earlier stage of oil formation. For type B oil inclusions with light yellow-white fluorescence, their average fluorescence lifetime was found to be 4.029–4.919 ns, so the density of surface crude corresponding to crude trapping these oil inclusions is 0.784–0.812 g/cm³, indicating that they are higher matured oil inclusions trapped at the second stage of oil formation. For type C oil inclusions showing light blue-green fluorescence, their average fluorescence lifetime was found to be 5.063–6.168 ns, so the density of surface crude corresponding to crude trapping these oil inclusions is 0.743–0.779 g/cm³, indicating that they are highly-matured light oil inclusions trapped at the third stage of oil formation.     

Characterization and source of oil contamination on the beaches and seabird corpses, Sable Island, Nova Scotia, 1996-2005

During April 1996-May 2005, 2343 oiled seabird corpses were recorded in beach surveys conducted on Sable Island, Nova Scotia. One hundred eighty-three samples of oil were collected from the beaches and from the feathers of bird corpses. Gas chromatographic (GC/FID) analysis was used to identify generic oil type and likely marine source. During this period, at least 74 marine oil discharge events were probably responsible for beached pelagic tar and contamination of seabird corpses found on Sable Island, of which 77.0% were crude oils, 14.9% were fuel oils, and 8.1% were bilge oil mixtures. While fuel and bilge oils may be discharged by all vessel and platform types, crude oil discharges are associated with tanker operations. This study demonstrates that oiling of the sea from tankers remains a serious wildlife issue in the Northwest Atlantic.     

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.     

Effects of crude oil on the locomotory activity of Arctic marine invertebrates

The effects of exposure to seawater dispersions of northern crude oils on the locomotory activity of two Arctic marine invertebrates, the amphipod Onisimus affinis and the coelenterate Halitholus cirrattus have been examined. Low concentrations of the oils significantly impair activity in both species. The ecological implications of such sublethal effects may be important.     

Sea transport of animal and vegetable oils and its environmental consequences

The increasing production––and therefore sea traffic––of vegetable oils has regularly led to spillages during the past 40 years. The accident of Allegra, on October,1st, 1997, in the English Channel gave rise to a spillage of 900 tonnes of palm nut oil. The drift of this solid vegetable oil was followed by aerial observations. Samples of oil were collected in order to analyse its chemical evolution. This study, associated with several bibliographic cases of pollution by non-petroleum oils, shows that drifting oils can mix with floating material to sink or form a crust. They can also be oxidized or disperse and/or be degraded by bacteria. They may also polymerise. The coating properties of vegetable oils act as crude oils to affect sea life, tourism and yachting. As a result, it is necessary to quickly collect the oil after a spillage, using usual equipment (booms and pumps).     

Review of the development of laser fluorosensors for oil spill application

As laser fluorosensors provide their own source of excitation, they are known as active sensors. Being active sensors, laser fluorosensors can be employed around the clock, in daylight or in total darkness. Certain compounds, such as aromatic hydrocarbons, present in petroleum oils absorb ultraviolet laser light and become electronically excited. This excitation is quickly removed by the process of fluorescence emission, primarily in the visible region of the spectrum. By careful choice of the excitation laser wavelength and range-gated detection at selected emission wavelengths, petroleum oils can be detected and classified into three broad categories: light refined, crude or heavy refined.

This paper will review the development of laser fluorosensors for oil spill application, with emphasis on system components such as excitation laser source, and detection schemes that allow these unique sensors to be employed for the detection and classification of petroleum oils. There have been a number of laser fluorosensors developed in recent years, many of which are strictly research and development tools. Certain of these fluorosensors have been ship-borne instruments that have been mounted in aircraft for the occasional airborne mission. Other systems are mounted permanently on aircraft for use in either surveillance or spill response roles.     

Organism relics or kerogens in oils as oil-source rock correlation indicator

Organism relics or kerogens in oils are first obsenred by a confocal laser scanning microscope (CLSM) and a transmission electron microscope (TEM). The complexes of kerogens in oils are characterized by the presence of a great variety of microfossils or macerals. These kerogens in oils are mainly the residues of the original organic substances from which oil formed, and minor kerogens from enclosing rocks enter the oils, therefore, the components and types of the kerogens in crude oils can serve as an indirect indicator of oil-source rock correlation. This method was applied to Jurassic oils in the Junggar Basin and the Turpan-Hami Basin, and there are two types of the kerogens in oils: one containing a lot of macerals from terrestrial plants may derive from coals, and the other, characterized by a high content of microscopic algae, fungus spores and Acritarch, may originate from Permian organic matter. In addition, the reflectance of the vitrodetrinites in oils can be used as an indicator of oil-source rock correlation.     

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.