Application of backflush and micro-flow techniques to the analysis of C5—C13 hydrocarbons in crude oils and its geochemical significance

An Agilent 6890N GC equipped with both FID and Agilent 5975 MSD analyzer has been employed to analyze C₅—C₁₃ hydrocarbon fractions of crude oils. A technical combination of program temperature volatilizer injection, backflush and micro-flow controller afforded a fine separation of C₅—C₁₃ compounds on a PONA column with the heavy part of crude oils being cut off before entering the analytical column. Both GC-FID chromatogram and GC-MS mass chromatograms (MID and full scan) could be obtained at the same time. The retension time differences of nC₆—nC₁₃ alkanes between GC and TIC were in the range of 0.02—0.58 minutes. Totally 286 peaks have been assigned group compositions. Results on 8 typical oil samples from CNPC Key Laboratory Crude Oil Library showed that the characteristics of C₆—C₁₃ hydrocarbon group composition could be used in oil-oil correlation studies.     

Application of backflush and micro-flow techniques to the analysis of C5—C13 hydrocarbons in crude oils and its geochemical significance

An Agilent 6890N GC equipped with both FID and Agilent 5975 MSD analyzer has been employed to analyze C₅—C₁₃ hydrocarbon fractions of crude oils. A technical combination of program temperature volatilizer injection, backflush and micro-flow controller afforded a fine separation of C₅—C₁₃ compounds on a PONA column with the heavy part of crude oils being cut off before entering the analytical column. Both GC-FID chromatogram and GC-MS mass chromatograms (MID and full scan) could be obtained at the same time. The retension time differences of nC₆—nC₁₃ alkanes between GC and TIC were in the range of 0.02—0.58 minutes. Totally 286 peaks have been assigned group compositions. Results on 8 typical oil samples from CNPC Key Laboratory Crude Oil Library showed that the characteristics of C₆—C₁₃ hydrocarbon group composition could be used in oil-oil correlation studies.     

Pool-formation and secondary change of biodegraded viscous oils: Case study of reservoir section in the Zhengjia-Wangzhuang Oilfield, Jiyang Depression

It is demonstrated by various geochemical indexes that the Zhengjia-Wangzhuang Oilfield with viscous crude oil in the Jiyang Depression has been sourced from the contribution of matured source rocks in the upper Es4. The principal cause leading to the densification of crude oils would be biodegradation, with the degradation level of crude oils being ranked as 2-8; vertically, the biodegradation level increases from the top to bottom of the oil column, with a distinctive biodegradation gradient occurring. Calculated parameters of sterane, terpane and methyl-phenanthrene have indicated that the source-rock's maturity of crude oils and asphaltic sands ranges from 0.7 to 0.9, and based on the calculation of Easy Ro model, the temperature of hydrocarbon generation in the source rock would be within 120-140℃, which coincides with the measurements of reservoir inclusions. The measured homogenization temperature would represent the generation temperature of the source rock, and be fairly different from that of reservoir while being charged with hydrocarbons, which reflects the hydrocarbon-charging to be a fast process, and the period of pool-formation to be consistent with that of peaked generation. According to the evaluation of generation history, the pool-formation could have been occurring in 7-15 Ma. And the biodegradation of crude oils in the study area would be considered to take place in 4-15 Ma based on the examination of biodegradation order and dynamic calculations.     

Application of C5—C13 light hydrocarbons in depositional environment diagnosis

Based on the geological background and Gammacerane/C31H（S ＋ R） ratios, source rock depositional environments of the studied oil samples （194） from 13 oilfields were classified into three groups according to salinity： saline-lacustrine facies, fresh to brackish lacustrine facies （including limnetic facies）, and semi-saline to saline facies （including marine facies of the Tarim Basin）. C5-C13 compound groups in the crude oils were separated by GC, and about 286 compounds were qualitatively analyzed. The geochemical application of the C6- C13 compound groups and their ratios between each group with individual carbon number was investigated. Our studies show that （1） C6-C13 compound groups and their ratios in the crude oils could serve as new reliable parameters for oil-oil correlation because the C6- C13 light fractions are the major oil component, especially in light oil or condensate, in which they account for almost 90% of the whole oil; （2） the compound groups of C7 light hydrocarbons in oils derived from different depositional environments with different salinity have different characteristics; （3） C6-C13 compound groups and ratios may be affected by other factors such as maturity, but they are mainly controlled by salinity of depositional waters.     

Biodegradation of heavy oils by halophilic bacterium

A halophilic bacterial strain TM-1 was isolated from the reservoir of the Shengli oil field in East China. Strain TM-1, which was found to be able to degrade crude oils, is a gram-positive non-motile bacterium with a coccus shape that can grow at temperatures of up to 58℃ and in 18% NaCl solution. Depending on the culture conditions, the organism may occur in tetrads. In addition, strain TM-1 produced acid from glucose without gas formation and was catalase-negative. Furthermore, strain TM-1 was found to be a facultative aerobe capable of growth under anaerobic conditions. Moreover, it produced butylated hydroxytoluene, 1,2-benzenedicarboxylic acid-bis ester and dibutyl phthalate and could use different organic substrates. Laboratory studies indicated that strain TM-1 affected different heavy oils by degrading various components and by changing the chemical properties of the oils. In addition, growth of the bacterium in heavy oils resulted in the loss of aromatic hydrocarbons, resins and asphaltenes, and enrichment with light hydrocarbons and an overall redistribution of these hydrocarbons.     

Groundbreaking gas source rock correlation research based on the application of a new experimental approach for adsorbed gas

Many years of experimentation have led to the development and improvement of equipment and methods used to make gas source rock correlations.By crushing samples using a ball mill and directly collecting adsorbed gases in the absence of aqueous media under high vacuum conditions,most possible interference factors,such as atmospheric pollution,crushing-induced pyrolysis,and gas collection by aqueous media are eliminated.This greatly enhances the volume percentage of hydrocarbon gas in the acquired adsorbed gases,with maxima up to more than 80%.The actual measurement of carbon isotopic series can be carried out to such an extent as to be δ13C1-δ13C5.A preliminary study using newly established equipment and methods has indicated the following.(1) The carbon isotopic composition of ethane in adsorbed gases on hydrocarbon source rocks can be used to distinguish the types of source rocks.This is consistent with results obtained by using organic geochemical parameters for source rocks,and illustrates that it is highly feasible to use the carbon isotopic composition of ethane in natural gases as a parameter for distinguishing the types of source rocks.(2) The thermal evolution degree(Ro) of hydrocarbon-source rocks calculated in terms of the carbon isotopic composition of methane in adsorbed gases on hydrocarbon source rocks agrees well with the vitrinite reflectance actually measured in the source rocks.This confirms the reliability of the relationship between the carbon isotopic composition of methane in natural gases and the thermal evolution degree determined using statistics.(3) Finally,a direct gas source correlation method for natural gases has been established,and the expression of log Ro vs.δ13C1 established in terms of actually measured δ13C1 values of methane in absorbed gases.Ro values of hydrocarbon source rocks have been established as well,thus creating favorable conditions for precise oil-and-gas source correlations in exploration areas.     

The zircon SHRIMP chronology and trace element geochemistry of the Carboniferous volcanic rocks in western Tianshan Mountains

The genesis of the Carboniferous volcanic rocks in the Dahalajunshan group, mainly consisting of trachytes and trachy-andesites and distributing widely in western Tianshan Mountains, remains to be controversial. It has been proposed to be relevant to “rift” or “plume”. Detailed petrology and geochemical data presented in this paper show that these volcanic rocks represent typical continental arc magmatism. The volcanic rocks are mainly trachy-andesitic, and the magma source is enriched in LILE, Th and Pb, and depleted in HFSE and Ce. Trace element geochemical study suggests that the basalts could be modeled by 7% -11% partial melt of garnet Iherzolite. The volcanic rocks in the Dahalajunshan group are neither the products of “rift” nor so-called “plume”but represent the continental island arc of the Paleo-Southern Tianshan Ocean. The mantle wedge had been modified by the melt generating in subduction zone during a long evolution history of this island arc. The continental crust materials （i.e. mainly sediment on ocean floor） had been added into island arc through melt in subduction zone. Volcanic rocks occurring in different regions might represent magma eruption in different time. The zircon SHRIMP dating indicates that the ages of the basalt varies between 334.0 Ma and 394.9 Ma. The 13 analyses give an average age of 353.7±4.5 Ma （MSWD = 1.7）. The apparent ages of zircons in trachy-andesite vary between 293.0 Ma and 465.4 Ma. All analyses fall on the U-Pb concordant line and are divided into two groups. 8 analyses produce an average age of 312.8±4.2 Ma （MSWD = 1.7）, which represents the crystallizing age of zircon rims in trachy-andesite. The acquired two ages （i.e. 354 and 313 Ma） belong to the Early Carboniferous and Late Carboniferous epochs, respectively. Thus, the Dahalajunshan group would be separated into several groups with the accumulation of high-quality age dating and data of trace element and isotopic geochemistry, in our opinion.     

Design and Implementation of Distributed Numerical Control in Flexible Manufacturing System

To monitor, control and manage the work process of computer numerical control machine tools in a flexible manufacturing system (FMS) effectively, the distributed numerical coutrol (distributed-NC) software should be innovated with the characteristics of modularization and reconfiguration. In this paper, firstly, distributed-NC functions in the FMS environment are described. Then, we present a design and development method of the real time distributed-NC that is on the basis of the re-coufigurable software and hardware platform and with an object-oriented model concept. Finally, to verify the proposed method, the distributed-NC software has been implemented in VC++ 6.0 and has been tested in connection with the different physical flexible manufacturing shops.     

Macromolecules Mimicking Backbones of Nucleic and Teichoic Acids.Synthesis,Some Properties and Applications

1 Results Several methods have been elaborated in this laboratory allowing preparation of macromolecules with phosphodiester bonds,and having sequence of atoms similar as in the chains of biomacromolecules - nucleic or teichoic acids (TA),namely:-(C)n-O-PO-,where n=2 (for teichoic acids) or 3.These methods,to be discussed in the lecture,are based on the ring-opening polymerization,transesterification,and recently elaborated direct addition of phosphoric acid to diepoxides.For the first time an attempt has been made to directly reacting phosphoric acid with diols in the presence and absence of catalysts.The major side reaction,preventing high molar mass polymers formation,results from dealkylation,i.e.nucleophilic attack of the OH groups on the C atom,instead attack on the P atom.The other two methods allowed reaching high molar mass macromolecules,with Mn up to 105.Following these studies phosphorylation of polymers with side groups containing -OH groups were studied and a series of diblock copolymers with ionic and nonionic blocks were prepared.     

Synthesis and Spectrum Properties Studies of Tropolone Azo

1 Results Tropolone,2-hydroxy-2,4,6-cycloheptatrienone,an isomer of benzoic acid,a seven-membered,non-benzenoid aromatic molecule possessing three double bonds conjugated with a carbonyl group.The studies of tropolone forms complexes[1] with many metals became more important because of their potential application in the field of material science,agriculture and medicine.In the course of our studies on the chemistry of 5-substituted tropolone derivatives[2],the synthesis of new tropolone azo derivatives through the coupling of diazotized 2-amino-4-nitropheno-6-sulfoacidphenol and tropolone is described.it's structures were confirmed by elemental analysis,IR and 1H NMR,13C NMR and chromogenic properties and UV-Vis absorption spectra were investigated under different pH condition.Experimental results show that the synthesized derivatives can be used as new indicators and host molecules.Tropolone-azo (A)was prepared by reacting tropolone and 2-amino-4-nitropheno-6-sulfoacidphenol in a 1:1 molar ratio in water.See Fig.1.     

Efficient photo-assisted Fenton oxidation treatment of multi-walled carbon nanotubes

In this paper,a new and efficient way to oxidize and functionalize the multi-walled carbon nanotubes (MWNTs) has been developed by using a combination of ultraviolet (UV) irradiation and Fenton oxida-tion process,namely UV/Fenton oxidation treatment. Comparing with conventionally individual Fenton oxidation treatment of MWNTs,UV/Fenton combined treatment improved the etching rates and effi-ciencies and hence reduced the time for surface modification of MWNTs,which was proved to be an effective method in etching and functionalizing CNTs. The formation of new functional groups,struc-tural changes and thermal stability during oxidation period were characterized by Fourier transform infrared spectroscopy (FTIR),Raman spectroscopy and could be clarified by thermogravimetric analy-sis (TGA),which showed that it was under UV irradiation conditions that MWNTs could be rapidly functionalized with hydroxyl,carbonyl and carboxyl groups in the presence of Fenton reagents,origi-nating from the increase in the gross HO· concentration and the existent synergetic effect when using UV irradiation combing with Fenton oxidation process. Introduction of such new oxygen-containing functional groups was attributed to attacks of HO· on defect sites and unsaturated bonds of C=C in the MWNTs sample,which should play an important role in accounting for the FTIR and Raman spectral changes.     

Synthetic Application of Indium Hydride

1 Results Recently much interest was focused on the indium chemistry. Barbier and, Reformatsky types of reactions are main streams of the chemistry. The synthetic application of indium hydride (HInCl2), however, has been just started in contrast to the chemistry of the same 13th group of elements such as aluminum and boron hydrides. At first we generated the hydride by the transmetallation between Bu3SnH and InCl3, and then found it has both considerable stability and reactivity, and the hydride could be applied to a variety of hydroindation in the both of ionic and radical manners. In particular, it was found to act as an interesting radical reagent generated from a variety of the hydride sources, The reactions proved to be strongly depend on the hydride source as shown in the equations.See Fig.1,Fig.2.     

Using the biomarker bonded on the asphaltenes for biodegraded oil-source correlation

Ruthenium-ion-catalyzed oxidation(RICO)has been used to investigate asphaltenes from three oils with the same origin in the Juquan Basin and three oils with the same origin but with different degree of biodegradation in the Turpan Basin,Northwest China.The preliminary results showed that the biomarkers bonded on the asphaltenes with the same origin is similar and is correlated with the free biomarker in saturates.The bonded biomarkers have no relationship with the biodegradation.An application on the severely biodegraded oils is reported here.The biomarker and benznecarboxylic methyl esters reflecting t eh structure of the asphaltenes after RICO should provide a new way for oil-source correlation and it should be specially useful for severely biodegraded oil-source correlation.     

β_2-Adrenoceptor affinity chromatography and its application in the screening of the active compounds from Semen Armeniacae Amarum

β2-Adrenoceptor (β2-AR) was purified from the rabbit lung tissue by sepharose-salbutamol affinity chromatographic column. To prepare the β2-AR stationary phase, β2-AR was evenly immobilized on the surface of macro-pore silica with a mild chemical coupling method through covalent bond. The reten- tion properties of β2-AR stationary phase were characterized by four ligands, salbutamol sulfate, noradrenaline bitartrate, adrenaline hydrochloride and propranolol hydrochloride, to establish the β2-AR affinity chromatography. Then, the method was used to screen the active compounds from the total extracts of Semen Armeniacae Amarum. The results showed that β2-AR on the surface of the sta- tionary phase could keep its original bioactivity and selectivity. Amygdalin retained in the chroma- tographic column was proved to be the active compound of the total extracts of Semen Armeniacae Amarum. Compared with the existing chromatographic screening approaches, this method showed a good stability and high selectivity. The active compounds which could interact with β2-AR in traditional Chinese medicine (TCM) could be screened efficiently by this method, providing a new way to screen the active compounds in complicated samples such as TCM.     

Ramet population ecology of Panicum virgatum in the field —Competitively random growth of ramets and foraging behavior of ramet populations

The authors investigated the heterogeneous size patterns and dynamic growth of the ramet population of Panicum virgatum, a clonal caespitose plant, limited to the space occupied by a ramet bunch and the time of the ramet yearly life cycle, to understand the ecology of clonal caespitose plants in the field, where the ramet bunch generally consisted of more than one genet. Dynamic life tables for ramet populations were established by the replacement of living ramets at the present time with ＂dead＂ ones in past time. These tables revealed stable coexisting patterns of isometric and allometric growing processes of ramets in mass and height respectively, which approximately followed the historic trajectory of a density-independent population. The ecology of clonal caespitose plants is further discussed based on the competitively random growth of ramet individuals, including the scale of foraging behavior. In the field, the ramet population ecology of switchgrass may be a statistical result of competitively random growth of ramet individuals. The foraging behavior of a ramet population could then be presented as a process in which ramet individuals competed with each other for light and grew randomly, while at the same time a relatively stable dynamic growth pattern was apparent at the level of the ramet population, and the functional leaves were placed properly in time and space.     

A breakthrough of researching reservoir adsorption gas and its significance

GC-C-MS on linear isotope analysis equipment makes it possible to measure the hydrocarbon gases at the level of 10 -3-10 -2 μL- By applying this technique the carbon isotopes of C1-C3 of the adsorbed gas from the Triassic oil sand bed of the Aican-l Well in the Turpan-Hami basin were analysed. The δ13C values of C1-C3, are -55.1‰, -38.6‰ and -35.0‰ respectively. In terms of geochemical characteristics of natural gases and crude oils, in combination with basinal geological backgrounds, it is considered that the reservoir adsorbed gas was formed by crude-oil biodegradation, absorbed by reservoir rocks and its oil-gas source is related with the Permain (perhaps including the Carboniferous). The adsorbed gas is obviously different from the Jurassic coal-generated oil and gas.     

Indicators of δ13C and δ18O of gas hydrate-associated sediments

The analyses of δ13C and δ18O of gas hydrate-associated sediments from two cores on Hydrate Ridge in Cascadia convergent margin offshore Oregon, eastern North Pacific show the values of d 13C from -29.81‰ to -48.28‰ (PDB) and d 18O from 2.56‰ to 4.28‰ (PDB), which could be plotted into a group called typical carbonate minerals influenced by the methane in cold venting. Moreover, the values of d 13C and d 18O show a consistent trend in both cores from top to bottom with increasing of d 13C and decreasing of d 18O. This trend could be explained as an effect caused by the anaerobic oxidation of methane (AOM) in depth and the oxygen fraction during the formation of gas hydrate in depth together. These characteristics of d 13C and d 18O indicate that the gas hydrate-associated sediments are significantly different from the normal marine carbonates, and they are deeply influenced by the formation and evolution of gas hydrate. So, the distinct characteristics of d 13C and d 18O of gas hydrate-associated sediments could be undoubtedly believed as one of parameters to determine the presence of gas hydrates in other unknown marine sediment cores.     

Measurements and analysis of force and moment of caudal fin model in C-start

The unsteady hydrodynamic forces and moments acting on caudal-fin models of fish with different shapes and different swing durations were experimentally measured to simulate the fish C-starts. The motion of models was characterized by rotating the model to a maximum deflection angle in an excursion time T_u and back to the initial position in a return time T_d around its root-axis. Studies show that the caudal-fin plays an important role in fish C-starts and the caudal-fins with different shapes and different swing durations generate different forces and moments. In addition, the hydrodynamic forces and moments acting on the models with different shapes can be normalized by the 2nd and 3rd moments of area, respectively. The forces and moments acting on the models with different swing durations, but the same ratio of T_u to Td can also be scaled.     

Population dynamics of Pygoscelis penguins(1980–2012) and penguin dropping records(1916–2001) on Ardley Island of West Antarctica,in response to ENSO

El Nio-Southern Oscillation(ENSO)has affected penguins and their habitats in the western Antarctic Peninsula.We used both historical penguin population dynamics data(1980–2012)and sedimentary lipids in penguin droppings(1916–2001)on Ardley Island to examine the responses of the Antarctic ecosystem to ENSO(El Nin o/La Nin a)events.The results showed that during the last 30 years,climate,marine food chain changes,and human activity have significantly affected penguin population sizes on Ardley Island.The Chinstrap(Pygoscelis antarctica)and Ade′lie(P.adeliae)penguin populations showed a good correlation with ENSO events.The Chinstrap penguin population decreased significantly because it was more sensitive to increasing human disturbance(e.g.,scientific activity and tourism)than Ade′lie and Gentoo(P.papua),particularly during the breeding season.Compositional features of n-alkanes in penguin dropping sediments revealed that organic matter came from lower terrestrial plants,bacteria and algae.C23was the main nalkane heavy hydrocarbon indicating mosses and lichens in the penguin’s diet.Variation in the ratio of nC23/nC17was closely correlated with ENSO events.The bacteria intrusion index(ratio of(iC15:0?aC15:0)/nC15:0for fatty acids)reflected significant increases in microorganism activity during several periods in this area.Meanwhile,the CPIA value for fatty acids decreased because micro-organisms contributed light hydrocarbon fatty acids to penguin droppings.Our results showed that the fine structure and molecular indices of fatty acids and n-alkanes in penguin dropping sediments can be used to explain climate-driven microbial processes,and to reveal the important role that microbes and bacteria play in the relatively simple Antarctic ecosystem.     

Discussion of gas enrichment mechanism and natural gas origin in marine sedimentary basin,China

There are abundant natural gas resources in Chinese marine sedimentary basin. The exploration hot shots of natural gas are the Palaeozoic marine strata here in recent years, and several large scale gas fields have been discovered. Chinese Palaeozoic high-post matured and coal measure hydrocarbon source rocks are mainly prone to gas generation in the present. This research considered that gas source rocks and TSR are the key cause of gas enrichment of marine strata. High-quality argillaceous and coal measure hydrocarbon rocks are distributed widely in the Palaeozoic marine strata, which have been in highly matured phase in the present. The argillaceous source rock generally contains various sulfates that could accelerate crude oil cracking to gas for TSR occurrence, and coal measure source rock mainly generates gas, so Chinese marine basin gives priority to accumulating gas. Marine strata have not founded oil reservoirs in the Sichuan Basin and Ordos Basin, and they consist mainly of dry gas. Marine natural gases are the mixed gases of oil cracking gas and coal-formed gas in a general way, oil cracking gases contain usually some H2S and CO2. Hydrocarbon carbon isotopes are very complicated, and methane and ethane isotopic values bear apparent reversal caused by thermal evolution and mixing among different genetic types of natural gas. Coal-formed gases are the main component of Chinese marine natural gas. The Upper Permian of the Sichuan Basin and the Carboniferous-Permian of the Ordos Basin coal measure hydrocarbon source rock present large hydrocarbon generation potential, which are the prospecting highlight of marine natural gas hereafter. Oil cracking gas exploration will be paid much attention to in the Tarim Basin because of the lack of coal measure hydrocarbon source rock.