Stable carbon and hydrogen isotopes of gases from the large tight gas fields in China

By the end of the year 2010,a total of 15 large tight gas fields have been found in China,located in the Ordos,Sichuan,and Tarim basins.The annual production and total reserves of these fields in 2010 were 222.5×108and 28657×108m3,respectively,accounting for 23.5%and 37.3%,respectively,of the total annual production and reserves of natural gases in China.They took a major part of all natural gas production and reserves in China.According to the analyses of 81 gas samples,the stable carbon and hydrogen isotopic compositions of tight gases in China have following characteristics:(1)Plots of 13C1-13C2-13C3,13C1-C1/C2+3and 13C1-13C2demonstrate the coal-derived origin of tight gases in China;(2)For the primary alkane gases,both carbon and hydrogen isotopic values increase with increasing molecular mass,i.e.,13C113C213C313C4and2H12H22H3;(3)The isotopic differences of 13C2-13C1,13C3-13C1,2H2-2H1and 2H3-2H1decrease with increasing Ro(%)and C1/C1–4;(4)There are seven causes for the carbon and hydrogen isotopic reversal,however,the carbon and hydrogen isotopic reversal of tight gases in China is caused mainly by multiple stages of gas charge and accumulation.     

Geochemical characteristics and origin of gases from the Upper,Lower Paleozoic and the Mesozoic reservoirs in the Ordos Basin,China

The Ordos Basin,the second largest sedimentary basin in China,contains the broad distribution of natural gas types.So far,several giant gas fields have been discovered in the Upper and Lower Paleozoic in this basin,each having over 1000×10 8 m 3 of proven gas reserves,and several gas pools have also been discovered in the Mesozoic.This paper collected the data of natural gases and elucidated the geochemical characteristics of gases from different reservoirs,and then discussed their origin.For hydrocarbons preserved in the Upper Paleozoic,the elevatedδ13C values of methane,ethane and propane indicate that the gases would be mainly coal-formed gases;the singular reversal in the stable carbon isotopes of gaseous alkanes suggests the mixed gases from humic sources with different maturity.In the Lower Paleozoic,theδ13C 1 values are mostly similar with those in the Upper Paleozoic,but theδ13C 2 andδ13C 3 values are slightly lighter,suggesting that the gases would be mixing of coal-type gases as a main member and oil-type gases.There are multiple reversals in carbon isotopes for gaseous alkanes,especially abnormal reversal for methane and ethane(i.e.δ13C 1 >δ13C 2 ),inferring that gases would be mixed between high-mature coal-formed gases and oil-type gases.In the Mesozoic,the δ13Cvalues for gaseous alkanes are enriched in 12C,indicating that the gases are mainly derived from sapropelic sources;the carbon isotopic reversal for propane and butane in the Mesozoic is caused by microbial oxidation and mixing of gases from sapropelic sources with different maturity.In contrast to the Upper Paleozoic gases,the Mesozoic gases are characterized by heavier carbon isotopes of iso-butane than normal butane,which may be caused by gases generated from different kerogen types. Finally,according toδ13C 1 -Ro relationship and extremely low total organic carbon contents,the Low Paleozoic gases would not be generated from the Ordovician source as a main gas source,bycontrast, the Upper Paleozoic source as a main gas source is contributed to the Lower Paleozoic gases.     

The components and carbon isotope of the gases in inclusions in reservoir layers of Upper Paleozoic gas pools in the Ordos Basin,China

The components and carbon isotope of gases in inclusions are one of the most important geochemical indexes for gas pools.The analysis results of the components and carbon isotope of gases from inclusions in reservoir layers of Upper Palaeozoic gas pools in the Ordos Basin show that most inclusions grown in reservoir sandstone are primary inclusions.There is only a little difference about the components and carbon isotope between the well gases and the secondary inclusions gases.This indicated that the epigenetic change of gas pools is little.This difference between the well gases and the secondary inclusions gases is caused by two reasons:(i)The well gases come from several disconnected sand bodies buried in a segment of depth,while the inclusion gases come from a point of depth.(ii)The secondary inclusions trapped the gases generated in the former stage of source rock gas generation,and the well gases are the mixed gases generated in all the stages.It is irresponsible to reconstruct the palaeo-temperature and palaeo-pressure under which the gas pool formed using carbon dioxide inclusions.     

Natural gas origins of large and medium-scale gas fields in China sedimentary basins

China sedimentary basins present abundant natural gas resource thanks to its unique geological settings.Marine highly-matured hydrocarbon source rocks,widespread coal-measure strata and low temperature Quaternary saline strata,etc.,indicate the wide foreground of China natural gas resources. Up to now,most of the petroliferous basins have been discovered to have wholesale natural gas accumulation from Precambrian,Paleozoic,Mesozoic to Cenozoic in the east,the central,the west and the coast of China.These large and medium-scale gas reservoirs are mainly composed of hydrocarbon gas with big dry coefficient,tiny non-hydrocarbon,wide carbon isotope distribution and varying origin types,the hydrocarbon gas includes coal-formed gas,oil-formed gas,biogenic gas and inorganic gas, etc.Coal-formed gas is the main type of China natural gas resources,in particular several explored large-scale gas fields(>100 billion cubic meter)of Kela 2,Sulige and Daniudi,etc.,they all belong to coal-formed gas fields or the gas fields consisting mostly of coal-formed gas.Oil-formed gas is also abundant in China marine basins,for example marine natural gas of Sichuan Basin generated from crude oil cracking gas.Primary and secondary biogenic gas fields were discovered respectively in the Qaidam Basin and Western Slope of Songliao Basin.In addition,inorganic gases are mainly distributed in the eastern China,in particular the Songliao Basin with abundant carbon dioxide accumulation,indicating that the eastern China present large exploration potential of inorganic gas.     

Carbon isotope characteristics,origin and distribution of the natural gases from the Tertiary salty lacustrine facies in the West Depression Region in the Qaidam Basin

Since the Meso-Cenozoic, controlled by paleoclimate, a series of fresh to brackish water basins and salt to semi-salt water basins were developed in wet climatic zones and in dry climate zones in China, respectively[1]. The geological and geochemical char…     

Natural gas leakage of Mizhi gas reservoir in Ordos Basin, recorded by natural gas fluid inclusion

Abundant natural gas inclusions were found in calcite veins filled in fractures of Central Fault Belt across the centre of Ordos Basin. Time of the calcite veins and characteristics of natural gas fluid inclusion were investigated by means of dating of thermolum luminescence (TL) and analyzing stable isotope of fluid inclusion. Results show that natural gas inclusion formed at 130―140℃ with salinity of 5.5 wt%―6.0 wt% NaCl. It indicates that natural gas inclusion is a kind of thermal hydrocarbon fluid formed within the basin. Method of opening inclusion by heating was used to analyze composition of fluid inclusion online, of which the maximal hydrocarbon gas content of fluid inclusion contained in veins is 2.4219 m3/t rock and the maximal C1/Σci ratio is 91%. Laser Raman spectroscopy (LRS) was used to analyze chemistry of individual fluid inclusion in which the maximal hydrocarbon gas content is 91.6% compared with little inorganic composition. Isotope analysis results of calcite veins show that they were deposited in fresh water, in which the δ13CPDB of calcite veins is from -5.75‰ to 15.23‰ andδ18OSMOW of calcite veins is from 21.33‰ to 21.67‰. Isotope results show thatδ13C1 PDB of natural gas fluid inclusion is from -21.36‰ to -29.06‰ and δDSMOW of that is from -70.89‰ to -111.03‰. It indicates that the gas of fluid inclusion formed from coal source rocks and it is the same as that of natural gas of Mizhi gas reservoir. Results of TL dating show that time of calcite vein is (32.4±3.42)×104 a, which is thought to be formation time of gas inclusion. It indicated that natural gas inclusion contained in calcite veins recorded natural gas leakage from Mizhi gas reservoir through the Central Fault Belt due to Himalayan tectonic movement.     

Abiogenic hydrocarbons in commercial gases from the Songliao Basin, China

This paper discusses the kinetic fractionation, composition and distribution characteristics of carbon and hydrogen isotopes for various alkane gases formed in different environments, by different mecha- nisms and from different sources in nature. It is demonstrated that the biodegradation or thermode- gradation of complex high-molecule sedimentary organic material can form microbial gas or thermogenic gas. The δ 13C1 value ranges from -110‰ to -50‰ for microbial gases but from -50‰ to -35‰ (even heavier) f...     

Natural gas geochemistry and its origins in Kuqa depression

According to gas compositional and carbon isotopic measurement of 114 gas samples from the Kuqa depression,accumulation of the natural gases in the depression is dominated by hydrocarbon gases, with high gas dryness(C1/C1-4)at the middle and northern parts of the depression and low one towards east and west sides and southern part.The carbon isotopes of methane and its homologues are relatively enriched in 13 C,and the distributive range ofδ13C 1 ,δ13C 2 andδ13C 3 is-32‰―-36‰,-22‰―-24‰and-20‰―-22‰,respectively.In general,the carbon isotopes of gaseous alkanes become less negative with the increase of carbon numbers.Theδ13C CO2 value is less than-10‰in the Kuqa depression,indicating its organogenic origin.The distributive range of 3 He/ 4 He ratio is within n×10-8 and a decrease in 3 He/ 4 He ratio from north to south in the depression is observed.Based on the geochemical parameters of natural gas above,natural gas in the Kuqa depression is of characteristics of coal-type gas origin.The possible reasons for the partial reversal of stable carbon isotopes of gaseous alkanes involve the mixing of gases from one common source rock with different thermal maturity or from two separated source rock intervals of similar kerogen type,multistages accumulation of natural gas under high-temperature and over-pressure conditions,and sufficiency and diffusion of natural gas.     

Geological characteristics of large gas provinces and large gas fields in China

Based on the examination of the global researches on oil and gas provinces and large gas fields and the analysis of the features,attributes and distribution of large gas provinces and gas fields,this paper puts forward three indicators of determining large oil and gas provinces:spatial indicator,reservoir-forming indicator and resource indicator.It classifies the gas accumulated areas and large gas provinces in China and analyzes the controlling factors on the distribution of large gas provinces and large gas fields:the lateral distribution is mainly controlled by high-energy sedimentary facies and constructive diagenetic facies,palaeo-highs and their periclinal zones,deep faults,etc,and the vertical distribution is mainly controlled by unconformities,series of evaporates and deep low-velocity highly-conductive beds,etc.It also reveals the main geological characteristics of large gas provinces and large gas fields in China.Large gas fields in four-type basins have their own characteristics and onland large gas fields are dominantly developed in foreland basins and craton basins;there are three types of gas sources,of which,coal is the main source with high gas generating intensity and varying origins;reservoir rocks of the large gas fields(provinces)are of various types and dominated generally by low-middle permeability and porosity pore-type reservoirs;structural traps and litho-stratigraphic traps coexist in Chinese large gas fields and form dense high abundance and large-area low and middle-abundance large gas fields;most of the large gas fields have late hydrocarbon-generation peaks and reservoir formation,and experienced the process of multiple-stage charging and late finalization; large gas provinces(fields)have good sealing and preservation conditions,and evaporates seals are largely developed in large and extra-large gas fields.This paper intends to shed light on the exploration and development of large gas fields(provinces)through analyzing their geological characteristics.     

Ternary geochemical-tracing system in natural gas accumulation

The establishment of geochemical-tracing system of gas generation and accumulation is helpful to re-elucidating the gas migration and accumulation in time and space. To deduce the complex process of gas accumulation, a ternary geochemical-tracing system is set up, according to stable isotope inheritance of source rocks, kinetic fractionation of stable isotopes, time-accumulating effect of noble gas isotopes, mantle-derived volatile inheritance, and organic molecule inheritance of light hydrocarbons and thermally kinetic fractionation in their generation, in combination with the previous achievements of gas geochemistry and geochemical parameters of gas-source correlation. There are tight interactions for the geochemical parameters with much information about parent inheritance and special biomarkers, in which they are confirmed each other, reciprocally associated and preferentially used for the requirement so that we can use these geochemical parameters to effectively demonstrate the sources of natural gas, sedimentary environments and thermal evolution of source rocks, migration and accumulation of natural gas, and rearrangement of natural gas reservoirs. It is necessary for the ternary geochemical-tracing system to predict the formation of high efficient gas reservoir and their distribution in time and space.     

Geochemical characteristics of pyrolysis gas from epimetamorphic rocks in the northern basement of Songliao Basin,Northeast China

The Xushen gas field,located in the north of Songliao Basin,is a potential giant gas area for China in the future.Its proved reserves have exceeded 1000×10 8 m 3 by the end of 2005.But,the origin of natural gases from the deep strata is still in debating.Epimetamorphic rocks as a potential gas source are widely spreading in the northern basement of Songliao Basin.According to pyrolysis experiments for these rocks in the semi-confined system,gas production and geochemistry of alkane gases are discussed in this paper.The Carboniferous-Permian epimetamorphic rocks were heated from 300℃to 550℃,with temperature interval of 50℃.The gas production was quantified and measured for chemical and carbon isotopic compositions.Results show thatδ13C 1 is less than?20‰,carbon isotope trend of alkane gas isδ13C 1 <δ13C 2 <δ13C 3 orδ13C 1 <δ13C 2 >δ13C 3 ,these features suggest that the gas would be coal-type gas at high-over maturity,not be inorganic gas with reversal trend of gaseous alkanes (δ13C 1 >δ13C 2 >δ13C 3 ).These characteristics of carbon isotopes are similar with the natural gas from the basin basement,but disagree with gas from the Xingcheng reservoir.Thus,the mixing gases from the pyrolysis gas with coal-typed gases at high-over maturity or oil-typed gases do not cause the reversal trend of carbon isotopes.The gas generation intensity for epimetamorphic rocks is 3.0×10 8 ―23.8×10 8 m 3 /km 2 ,corresponding to Ro from 2.0%to 3.5%for organic matter.     

Main models and distribution patterns of gas reservoirs in large-medium gas fields of China

Based on characteristics and trap types of gas reservoirs in large and medium gas fields in China, 4 gas reservoir models have been established:(i) structural trap gas reservoir model I, formed earlier than or simutaneously with generating of gases; (ii) structural trap gas reservoir model II, formed later than generating of gases; (iii) fossil weathered residuum gas reservoir model; and (iV) mud diapir abnormal temperature and pressure gas reservoir model. Distribution patterns of large-medium gas fields are described with the concept of “sealed compartment”. It is concluded that the inner-compartment area, marginal area of the compartment and the areas between two overlapped sealed compartments are the most favourable areas for discovering large-medium gas fields. Project supported by the “85–102” Chinese National Key Science and Technology Project.     

Discrimination of abiogenic and biogenic alkane gases

We have combined the analytical data of the carbon isotope distribution pattern, R/Ra and CH4/3He values of abiogenic and biogenic (referring to the thermogenic and bacterial or microbial) alkane gases in China with those of alkane gases from USA, Russia, Germany, Australia and other countries. Four discrimination criteria are derived from this comparative study: 1) Carbon isotopic composition is generally greater than -30‰ for abiogenic methane and less than -30‰ for biogenic methane; 2) Abiogenic alkane gases have a carbon isotopic reversal trend (δ 13C1> δ 13C2> δ 13C3> δ 13C4) with δ 13C1>-30‰ in general; 3) Gases with R/Ra >0.5 and δ 13C11 δ 13C2>0 are of abiogenic origin; 4) Gases (meth- ane) with CH4/3He≤106 are of abiogenic origin, whereas gases with CH4/3He≥1011 are of biogenic origin.     

Molecular and carbon isotopic compositions of gas inclusions of deep carbonate rocks in the Tarim Basin

Gaseous components of gas inclusions in deep carbonate rocks (>5700 m) from the Tacan 1 well were analyzed by online mass spectrometry by means of either the stepwise heating technique or vacuum electromagnetism crushing. The carbon isotopic compositions of gases released by vacuum electromagnetism crushing were also measured. Although the molecular compositions of gas inclusions show differences between the two methods, the overall characteristics are that gas inclusions mainly contain CO2, whilst hydrocarbon gases, such as CH4, C2H6 and C3H8, are less abundant. The content of CO is higher in the stepwise heating experiment than that in the method of vacuum electromagnetism crushing, and there are only minor amounts of N2, H2 and O2 in gas inclusions. Methane δ13C values of gas inclusions in Lower Ordovician and Upper Cambrian rocks (from 5713.7 to 6422 m; -52‰-63‰) are similar to those of bacterial methane, but their chemical compositions do not exhibit the dry character in comparison with biogenic gases. These characteristics of deep gas inclusions may be related to the migration fractionation. Some deep natural gases with light carbon isotopic characteristics in the Tazhong Uplift may have a similar origin. The δ13C1 values of gas inclusions in Lower Cambrian rocks (7117-7124 m) are heavier (-39‰), consistent with highly mature natural gases. Carbon isotopic compositions of CO2 in the gas inclusions of deep carbonate rocks are similar (from -4‰ to -13‰) to those of deep natural gases, indicating predominantly an inorganic origin.     

Main factors controlling the foundation of medium-giant gas fields in China

Medium-giant gas fields refer to those whose proved reserves are or more than 10 × 10⁹ m³. Now, 30 such fields have been found in China. The main controlling factors of their formation are as follows:gas-generating center and its surroundings; traps related to paleo-uplift in the gas-generating area; traps of medium-giant size hidden in low-medium rank coal-bearing series and those above or beneath the coal measures; late reservoir formation; poretype reservoir in gas-generating area and well-developed regional cap rock.     

Preliminary study on the origin identification of natural gas by the parameters of light hydrocarbon

The light hydrocarbon composition of 209 natural gas samples and individual light hydrocarbon carbon isotopes of 53 natural gas samples from typical humic-sourced gas and sapropelic-sourced gas in the four basins of China have been determined and analyzed.Some identification parameters for humic-sourced gas and sapropelic-sourced gas are proposed or corrected.The differences of compound-specificδ13C value of individual light hydrocarbon between humic-sourced gas and sapropelic-sourced gas have been founded.The humic-sourced gas has the distribution ofδ13C benzene > -24‰,δ13C toluene >-23‰,δ13C cyclohexane >-24‰andδ13C methyl cyclohexane >-24‰,while the sapropelicsourced gas has the distribution ofδ13C benzene <-24‰,δ13C toluene <-24‰,δ13C cyclohexane <-24‰and δ13C methyl cyclohexane <-24‰.Among the components of C7 light hydrocarbon compound,such as normal heptane(nC7),methyl cyclohexane(MCH)and dimethyl cyclopentane(ΣDMCP),etc,relative contents of nC7 and MCH are influenced mainly by the source organic matter type of natural gas.Therefore,it is suggested that the gas with relative content of nC7 of more than 30%and relative content of MCH of less than 70%is sapropelic-sourced gas,while gas with relative content of nC7 of less than 35%and relative content of MCH of more than 50%is humic-sourced gas.Among components of C5-7 aliphatics, the gas with relative content of C5-7 normal alkane of more than 30%is sapropelic-sourced gas,while the gas with relative content of C5-7 normal alkane of less than 30%is humic-sourced gas.These paremeters have been suggested to identify humic-sourced gas and sapropelic-sourced gas.     

Carbon and hydrogen isotopic characteristics of natural gases from the Luliang and Baoshan basins in Yunnan Province, China

The Luliang and Baoshan basins are two small ba- sins in Yunnan Province. In the recent ten years or so, there have been found a number of natural gas pools of commercial importance in the two basins. Although the gas pools are small in size, the natural …     

Characteristics,genesis and accumulation history of natural gas in Hetianhe gasfield,Tarim Basin,China

Hetianhe gasfield in Bachu region of the Tarim Basin is mainly composed of three reservoir-caprock assembly,namely regional caprock of upper mudstone,middle mudstone and lower mudstone of the Carboniferous and reservoir of Bachu bioclastic limestone,glutenite and the Ordovician carbonate buried hill.Natural gas in Hetianhe gasfield sourced from the Cambrian source rock.It is thought that gases in Ma4 well block in the east of Hetianhe gasfield are mainly crude-oil cracked gases,while those in Ma3 and Ma8 well blocks in the west are the mixture gases of kerogen cracked gases and crude-oil cracked gases.Natural gas is rich in H2S and accumulated in multiply stages as the result of TSR.The accumulation history is divided into three stages,namely accumulation and breakage in the late Caledonian-early Hercynian,migration and dissipation in the late Hercynian and accumulation in Himalayan. The main accumulation of reformed gas reservoir is in Himalayan.     

Natural gas diffusion model and diffusion computation in well Cai25 Bashan Group oil and gas reservoir

Natural gas diffusion through the cap rock is mainly by means of dissolving in water, so its concentration can be replaced by solubility, which varies with temperature, pressure and salinity in strata. Under certain geological conditions the maximal solubility is definite, so the diffusion computation can be handled approximately by stable state equation. Furthermore, on the basis of the restoration of the paleo-buried history, the diffusion is calculated with the dynamic method, and the result is very close to the real diffusion value in the geological history.     

Geochemical features and genesis of the natural gas and bitumen in paleo-oil reservoirs of Nanpanjiang Basin, China

Bitumen from the Nanpanjiang Basin occurs mainly in the Middle Devonian and Upper Permian reef limestone paleo-oil reservoirs and reserves primarily in holes and fractures and secondarily in minor matrix pores and bio-cavities. N2 is the main component of the natural gas and is often associated with pyrobitumen in paleo-oil reservoirs. The present study shows that the bitumen in paleo-oil reservoirs was sourced from the Middle Devonian argillaceous source rock and belongs to pyrobitumen by crude oil cracking under high temperature and pressure. But the natural gas with high content of N2 is neither an oil-cracked gas nor a coal-formed gas generated from the Upper Permian Longtan Formation source rock, instead it is a kerogen-cracked gas generated at the late stage from the Middle Devonian argilla- ceous source rock. The crude oil in paleo-oil reservoirs completely cracked into pyrobitumen and methane gas by the agency of hugely thick Triassic deposits. After that, the abnormal high pressure of methane gas reservoirs was completely destroyed due to the erosion of 2000--4500-m-thick Triassic strata. But the kerogen-cracked gas with normal pressure was preserved under the relatively sealed condition and became the main body of the gas shows.