spectrum of pore types and networks in mudrocks and a descriptive classification for matrix related mudrock pores matrix related pore networks in mudrocks are composed of nanometer to micrometer size pores in shale gas systems these pores along with natural fractures form the flow path permeability network that allows flow of gas from the mudrock to induced fractures during production a pore classification consisting of three major matrix related pore types is presented that can be used to quantify matrix related pores and relate them to pore networks two pore types are associated with the mineral matrix the third pore type is associated with organic matter om fracture pores are not controlled by individual matrix particles and are not part of this classification pores associated with mineral particles can be subdivided into interparticle interp pores that are found between particles and crystals and intraparticle intrap pores that are located within particles organic matter pores are intrap pores located within om interparticle mineral pores have a higher probability of being part of an effective pore network than intrap mineral pores because they are more likely to be interconnected although they are intrap om pores are also likely to be part of an interconnected network because of the interconnectivity of om particles in unlithifed near surface muds pores consist of interp and intrap pores and as the muds are buried they compact and lithify during the compaction process a large number of interp and intrap pores are destroyed especially in ductile grain rich muds compaction can decrease the pore volume up to 88 by several kilometers of burial at the onset of hydrocarbon thermal maturation om pores are created in kerogen at depth dissolution of chemically unstable particles can create additional moldic intrap pores

heterogeneity of the lower silurian longmaxi marine shale in the southeast sichuan basin of china this study characterizes the vertical heterogeneity of the lower silurian longmaxi marine shale in the southeast sichuan basin based on core description thin sections observation geological chemistry data interrogation and qemscan image analysis lithofacies associations mineralogy graptolite species occurrence rock fabrics as well as toc total organic carbon and gas content change noticeably and regularly in the lower silurian longmaxi marine shale within sequence stratigraphic framework lithofacies associations mainly include in situ graptolite rich and siliceous shale in the transgressive systems tract tst micro offsite graptolite rich shale and shale interbedded with siltstone laminaes in the early highstand systems tract ehst and micro offsite graptolite rich and carbonate rich shale in the late highstand systems tract lhst the tst has a greater abundance of diplogratus than ehst and lhst and has a lesser level of monograptus which is conversely higher in the ehst and lhst the tst shale is silica rich while the lhst shale is generally clay rich the ehst shale is more balanced in its silica and clay content than the tst and lhst are the sedimentary structure and fabric of shale shows that shale is homogenous in the tst with laminaes well developed in the ehst but decreasing in the lhst toc and gas content are highest in the tst and decrease upward the tst with high toc high gas content high brittle minerals silica rich and anoxic suboxic to dysoxic sedimentary environment is the most potential shale gas target interval in the study area our research also shows that the toc mainly controls shale gas accumulation and that the redox conditions mainly control the preservation of organic matter the silica also plays a significant role in shale gas content due to its contribution to hydraulic fracturing finally the study proposes a depositional and heterogeneity model for the lower silurian longmaxi marine shale in the study area

evolution of methane sorption capacity of coal seams as a function of burial history a case study from the campine basin ne belgium based on extensive data sets of high pressure sorption isotherms and canister desorption data from two central european coal basins campine and ruhr basins a computational scheme has been developed to calculate the maximum coal bed methane cbm sorption capacity of coal seams as a function of pressure temperature and coal rank in addition the effects of in situ moisture content and maceral composition have been tentatively implemented using this algorithm it is possible to explicitly take into account variations in sorption capacity of the coal seams in sedimentary basins over geologic time as a function of burial history and thermal evolution the procedure has been applied to model the evolution and the present day coal bed methane content of the campine basin ne belgium it is demonstrated how the present day gas content of the campine basin is controlled by the burial history of the coal layers throughout geologic time the maximum gas sorption capacity typically occurs at a depth range between 500 and 1000 m during periods of uplift and erosion 250 and 90 ma before present the uppermost coal layers have lost methane due to a reduction of gas storage capacity while their storage capacity has increased during periods of burial 300 and 180 ma ago and present additionally the present day gas content is controlled by the gas generation history coal layers which have lost storage capacity during geologic time will stay undersaturated if not replenished by late stage e g microbial gas the gas content profile of test well kb206 in the ne campine basin established from canister desorption tests can be reproduced by assuming that undersaturation of the coals is due to erosion and re burial and that no significant gas generation e g microbial gas has taken place after the time of maximal burial isotopic data d 178 13c 59 indicate the presence of a small portion of microbial gas the absolute gas contents in this well are lower than the calculated maximum present day sorption capacity this may be due to an underestimation of the effect of water content on sorption capacity or result from degassing via nearby faults enforced by fluid circulation

the importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs abstract the effect of shale composition and fabric upon pore structure and ch 4 sorption is investigated for potential shale gas reservoirs in the western canadian sedimentary basin wcsb devonian mississippian d m and jurassic shales have complex heterogeneous pore volume distributions as identified by low pressure co 2 and n 2 sorption and high pressure hg porosimetry thermally mature d m shales 1 6 2 5 vro have dubinin radushkevich d r co 2 micropore volumes ranging between 0 3 and 1 2 cc 100 g and n 2 bet surface areas of 5 31 m 2 g jurassic shales which are invariably of lower thermal maturity ranging from 0 9 to 1 3 vro than d m shales have smaller d r co 2 micropore volumes and n 2 bet surface areas typically in the range of 0 23 0 63 cc 100 g co 2 and 1 9 m 2 g n 2 high pressure ch 4 isotherms on dried and moisture equilibrated shales show a general increase of gas sorption with total organic carbon toc content methane sorption in d m shales increases with increasing toc and micropore volume indicating that microporosity associated with the organic fraction is a primary control upon ch 4 sorption sorption capacities for jurassic shales however can be in part unrelated to micropore volume the large sorbed gas capacities of organic rich jurassic shales independent of surface area imply a portion of ch 4 is stored by solution in matrix bituminite solute ch 4 is not an important contributor to gas storage in d m shales structural transformation of d m organic matter has occurred during thermal diagenesis creating and or opening up microporosity onto which gas can sorb as such d m shales sorb more ch 4 per weight percent wt toc than jurassic shales inorganic material influences modal pore size total porosity and sorption characteristics of shales clay minerals are capable of sorbing gas to their internal structure the amount of which is dependent on clay type illite and montmorillonite have co 2 micropore volumes of 0 78 and 0 79 cc 100 g n 2 bet surface areas of 25 and 30 m 2 g and sorb 2 9 and 2 1 cc g of ch 4 respectively dry basis a reflection of microporosity between irregular surfaces of clay platelets and possibly related to the size of the clay crystals themselves mercury porosimetry analyses show that total porosities are larger in clay rich shales compared to silica rich shales due to open porosity associated with the aluminosilicate fraction clay rich sediments low si al ratios have unimodal pore size distributions

geochemistry of the extremely high thermal maturity longmaxi shale gas southern sichuan basin abstract the marine shale of the silurian longmaxi formation in southern sichuan basin china is characterized by its huge thickness 100 600 m high toc values 0 35 18 4 favorable types of organic matter i and ii1 high ro values 1 8 4 2 abundant brittle minerals average 56 3 and strong gas generation intensity particularly its bottom section which has toc 2 and thickness of 20 70 m has recently been a main target for shale gas exploration and development geochemical parameters of 13 gas samples from longmaxi shale from 10 wells were analyzed in this study wetness of the gas molar fraction of ethane through pentanes in total gaseous hydrocarbon is only 0 24 0 70 making the longmaxi shale gas among the driest in the world carbon isotopic compositions of the alkane gases from longmaxi shale are characterized by 13c1 13c2 13c3 with the most positive 13c1 values in the world a positive relationship was observed between its 13c1 and 13c2 values reflecting the extremely high thermal maturity of the source rock 2hch4 values range from 140 to 151 and the 2hc2h6 values range from 130 to 173 the hydrogen isotopic compositions were mainly characterized by 2hch4

barnett shale gas production fort worth basin issues and discussion newark east barnett shale field fort worth basin texas is currently the most productive gas field in texas in terms of daily production and is growing at an annual rate of more than 10 however despite the fact that the barnett play has been studied intensely by very capable geologists and engineers from several companies over a period of many years there continues to be several misunderstandings concerning fundamental factors controlling the success of the barnett play of north texas barnett gas production is poorer in areas near faults and structural flexures anticlines and synclines fractures which are most abundant in these structural settings are detrimental to barnett production open natural fractures are rare in the barnett and have little or nothing to do with barnett productivity in areas where barnett shale is thermally mature with respect to gas generation it is slightly overpressured about 0 52 psi ft 11 76 kpa m limestone beds within the barnett formation are the product of debris flows that originated on a carbonate shelf to the north of the present basin center it appears that the barnett can be used as an exploration model for other basins especially analogous basins of the ouachita trend the history of the development of the barnett reservoir in north texas provides an excellent example of how persistence can lead to success in nonconventional gas plays

geochemical characteristics and origin of natural gas from wufeng longmaxi shales of the fuling gas field sichuan basin china abstract as the first giant shale gas field in china the fuling gas field has recently been regarded as one of the most important regions for natural gas exploration and production in the sichuan basin however the origin of natural gas from upper ordovician wufeng and the bottom of lower silurian longmaxi wl shales in the fuling gas field is poorly understood to limit a comprehensive understanding of gas generation accumulation and exploration in this work based on molecular and stable carbon isotopic composition of a total of 24 gas samples from five shale gas wells in the fuling field we analyzed the geochemical characteristics and gas origin and discussed the cause for the geochemical anomalies carbon isotopic reversals molecular composition results show that gases from the fuling gas field are dry and mainly composed of methane 97 9 98 9 with a very low level of ethane c2h6 propane c3h8 and non hydrocarbon gases mainly co2 and n2 these dry gases are classified as oil associated gas and mainly derived from secondary cracking due to the lack of gas samples across a maturation gradient from immature to late mature the wl gases in the fuling field show an unclear evolution trend between the 13c2 and wetness values however all these samples are located in the isotopic reversal zone carbon isotopes of gaseous alkanes clearly display full isotopic reversals 13c1 13c2 13c3 which is indicative of a relatively high thermal maturity and consistent with the measured vitrinite reflectance and modeled values 3 0 ro the observed complete carbon isotopic reversals in the wl gases are caused by a combination of several mechanisms in which isotope exchange at high temperature is the primary controlling factor other secondary factors include rayleigh type fractionation of c2h6 and c3h8 secondary cracking and gas diffusion mixing of gases at different thermal maturity levels

change in composition and pore structure of longmaxi black shale during oxidative dissolution abstract owing to the presence of chemically unstable compositions e g clay minerals carbonate pyrite and organic matter om which are closely related to shale structure failures or dissolution pores the methods to increase gas well long term productivity from tight shale matrix need to take into account the chemical interaction of shale with injected fluid in this study black shale samples obtained from lower silurian longmaxi formation in sichuan basin china were treated with 15 wt hydrogen peroxide h2o2 for the comprehensive understanding of the change in shale composition and the associated dissolution structures the measurements of mass loss total organic carbon content and mineralogical composition showed that carbonate reductive inorganic minerals containing ferrous iron e g pyrite and chlorite and om in samples exhibited strong dissolution however the other minerals behaved in a non reactive manner at the experimental time scale after the oxidative treatment for 240 h a large amount of oxidation induced fractures and dissolution pores were observed by field emission scanning electron microscopy the fractures mainly oriented parallel to lamination were attributed to the dissolution of om and structural alteration of clay minerals all the dissolution pores seemed to be strongly dependent on the loss of dolomite pyrite and om results from high pressure mercury intrusion and low pressure nitrogen adsorption analysis showed that these dissolution pores ranging from 10 to 500 nm in diameter exhibited a significant increase in pore volume due to the removal of interconnected pore filling om while the volume of pores 1 m in size exhibited a minor increase because the micrometer size dissolved particles appeared to be discrete or unconnected thus the oxidative dissolution could lead to the higher porosity and better connectivity of nanometer size pore networks in shale samples the induced fractures reduced the size of diffusion dominant zones in shale matrix and the dissolution pores increased the size of gas transport pathways into fractures these results indicate that the injection of h2o2 may play an important role in shale matrix stimulation by oxidative dissolution which is likely to improve matrix diffusivity

organic matter hosted pore system marcellus formation devonian pennsylvania the marcellus formation of pennsylvania represents an outstanding example of an organic matter om hosted pore system most pores detectable by field emission scanning electron microscopy fe sem are associated with om instead of mineral matrix in the two wells studied here total organic carbon toc content is a stronger control on om hosted porosity than is thermal maturity the two study wells span a maturity from late wet gas vitrinite reflectance ro 1 0 to dry gas ro 2 1 samples with a toc less than 5 5 wt display a positive correlation between toc and porosity but samples with a toc greater than 5 5 wt display little or no increase in porosity with a further increasing toc in a subset of samples 14 across a range of toc 2 3 13 6 wt the pore volume detectable by fe sem is a small fraction of total porosity ranging from 2 to 32 of the helium porosity importantly the fe sem visible porosity in om decreases significantly with increasing toc diminishing from 30 of om volume to less than 1 of om volume across the range of toc the morphology and size of om hosted pores also vary systematically with toc the interpretation of this anticorrelation between om content and sem visible pores remains uncertain samples with the lowest om porosity higher toc may represent gas expulsion pore collapse that was more complete as a consequence of greater om connectivity and framework compaction whereas samples with higher om porosity lower toc correspond to rigid mineral frameworks that inhibited compactional expulsion of methane filled bubbles alternatively higher toc samples may contain om low initial hydrogen index relatively unreactive that is less prone to development of fe sem detectable pores in this interpretation om type controlled by sequence stratigraphic position is a factor in determining pore size distribution

geological controls on matrix permeability of devonian gas shales in the horn river and liard basins northeastern british columbia canada abstract controls of matrix permeability are investigated for devonian gas shales from the horn river and liard basins in northeastern british columbia canada mineralogy is varied with high carbonate high quartz and moderate quartz carbonate and clay rich strata quartz content varies between 2 and 73 carbonate varies between 1 and 93 and clay varies between 3 and 33 the toc content ranges between 0 3 and 6 wt and porosity varies between about 1 and 7 for horn river basin samples quartz is mainly biogenic in origin derived from radiolarians toc content increases with the quartz content suggesting the toc and quartz both are derived from siliceous phytoplankton a positive relationship between porosity and quartz content is due to the positive relationship between quartz and toc matrix permeability parallel to bedding varies between 7 5e 02 and 7 1e 07 md at an effective stress of 15 mpa variation in permeability is due to a complex combination of factors that includes origin and distribution of minerals pore size distribution and fabric mercury intrusion capillary curves indicate that the higher matrix permeability values 2e 03 md occurs in samples that contain interconnected pore apertures greater than 16 m even when these samples may contain less macropores than low permeability samples the fabric of high permeability samples can be either isotropic or anisotropic however permeability of anisotropic samples is more sensitive to changes in effective stress than isotropic samples more highly anisotropic samples contain moderate amounts of quartz carbonate and in some clay high permeability samples that contain a more balanced ratio between micro meso and macroporosity would not only have faster flow rates but also greater access to sorbed gas within the microporosity compared to samples that lack mesopores several muskwa samples compared to evie and besa river samples contain higher quartz moderate clay and high toc content coupled with high permeability less sensitivity to effective stress and balanced ratios between micro meso and macroporosity would be a lower exploration risk due a greater propensity to fracture the ability to produce and store hydrocarbons due to higher toc contents and greater communication between macropores and micropores in the organic and clay fractions

pore types and pore size distributions across thermal maturity eagle ford formation southern texas pore types pore size and pore abundance vary systematically across thermal maturity in the eagle ford formation maverick basin southern texas scanning electron imaging of 20 samples from four wells is used to assess the complex response of pores to chemical and mechanical processes entailing both destruction of primary porosity and generation of secondary pores primary mineral associated pores are destroyed by compaction cementation and infill of secondary organic matter whereas secondary pores are generated within organic matter om destruction of primary pores during early burial to 0 5 occurs by compaction of ductile detrital om and clays and to a lesser degree as a result of cementation and infill of secondary om larger pores are associated with coccolith debris the dominant om is spatially isolated detrital om stringers porosity is volumetrically dominated average 6 2 by relatively large mostly interparticle mineral associated pores median size 51 6 nm 0 000002 in detection limit near 3 4 nm 0 00000012 0 00000015 in at low maturity porosity and pore size correlate directly with calcite abundance and inversely with om volumes at higher maturity further destruction of primary pores occurs through cementation secondary om infill and greater compaction mineral associated pores are present at high maturity 1 2 1 3 but are smaller median size 30 2 nm 0 0000011 in and less abundant average of 2 5 than at low maturity a large portion of om within high maturity samples is diagenetic in origin and has pervaded into primary pore space coating cement crystals and filling intraparticle pores substantial mineral associated porosity is locally present in samples where incursion of primary pore space by secondary om has not occurred abundant secondary porosity is generated as om matures into the wet gas window porosity in most high maturity samples is volumetrically dominated average of 1 3 by smaller om hosted pores median size 13 2 nm 0 00000051 in

experimental investigation of changes in methane adsorption of bitumen free woodford shale with thermal maturation induced by hydrous pyrolysis this study quantifies the effects of organic matter om thermal maturity on methane ch4 sorption on the basis of five samples that were artificially matured through hydrous pyrolysis achieved by heating samples of immature woodford shale under five different time temperature conditions ch4 sorption isotherms at 35 degrees c 50 degrees c and 65 degrees c and pressures up to 14 mpa on dry solvent extracted samples of the artificially matured woodford shale were measured the results showed that ch4 sorption capacity normalized to toc varied with thermal maturity following1 the trend maximum oil 367 degrees c oil cracking 400 degrees c maximum bitumen early oil 333 degrees c early bitumen 300 degrees c immature stage 130 degrees c the langmuir constants for the samples at maximum oil and oil cracking stages are larger than the values for the bitumen forming stages the total pore volume determined by n 2 physisorption at 77 k increases with increased maturation mesopores 2 50 nm in width were created during the thermal conversion of organic matter and a dramatic increase in porosity appeared when maximum bitumen and maximum oil generation stages were reached a linear relationship between thermal maturity and brunauer emmett teller bet surface area suggests that the observed increase in ch4 sorption capacity may be the result of mesopores produced during om conversion no obvious difference is observed in pore size distribution and pore volume for samples with pores 2 0 nm with the increase of thermal maturity based on co2 physisorption at 273 k the isosteric heat of adsorption and the standard entropy for artificially matured samples ranged from 17 9 kj mol 1 to 21 9 kj mol 1 and from 85 4 j mol 1 k 1 to 101 8 j mol 1 k 1 respectively these values are similar to the values of immature woodford kerogen concentrate previously observed but are larger than naturally matured organic rich shales high temperature hydrous pyrolysis might have induced lewis acid sites on both organic and mineral surfaces resulting to some extent in chemical interactions between the adsorption site and the methane c h bonds the formation of abundant mesopores 2 50 nm within organic matter during organic matter thermal maturation makes a great contribution to the increase in both bet surface area and pore volume and a significant increase in 2 6 nm pores occurs at maximum oil generation and oil cracking to gas ultimately controlling the methane adsorption capacity therefore consideration of pore size effects and thermal maturity is very important for gas in place gip prediction in organic rich shales c 2014 elsevier ltd all rights reserved

oligocene plant ecological strategies in low latitude asia unraveled by leaf economics abstract the oligocene represents an important epoch in the history of the stepwise global climate evolution from a warm climate to a cooler climate the change probably introduced selective pressures influencing ecological strategies and caused the past ecosystems restructured however little is known about the paleoenvironment and adaptive plant ecological strategies in the terrestrial realm of the low latitudes here based on the plant fossils from the baigang formation of the baise basin low latitude china the paleoclimate paleovegetational type and paleoecological strategy are reconstructed using leaf physiognomic analyses integrated plant record and leaf economics spectrum respectively the results show that under a warm and wet sub tropical climate with low seasonality the oligocene baise flora was dominated by slow return maximized resource retention species but mixed with a considerable proportion of fast return rapid resource acquisition species these ecological strategies might promote the community to maximize the use of limited living resources and at the same time to better tolerate potential extreme situations these results allow us to examine which ecological strategies that fossil plants selected under a given paleoclimate condition and might potentially provide a clue to predict the direction of ecological strategy changes in a future climate change scenario

polyphase thermal evolution in the infra cambrian ara group south oman salt basin as deduced by maturity of solid reservoir bitumen petrographic and organic geochemical analyses on solid reservoir bitumen from the late precambrian to early cambrian ara group indicate polyphase thermal evolution in the south oman salt basin sosb the ara group constitutes a complex petroleum system in the deep subsurface 3 5 km of interior oman salt diapirs encase isolated partly highly overpressured carbonate bodies intra salt stringers which represent a predominantly self charging hydrocarbon system a large number of stringer cores show that reservoir quality is decreased by the presence of solid reservoir bitumen by using different microscopy techniques this solid reservoir bitumen has been identified within pores pore throats and microfractures of the carbonates solid bitumen reflectance measurements brr were converted to vitrinite reflectance vrr using a new improved calibration vitrinite reflectance geothermometry shows that maximum paleo temperatures have a highly heterogeneous distribution paleo temperatures of 380 c were obtained from coke like solid reservoir bitumen which most likely formed from thermal cracking of oil in our model this process is related to hydrothermal fluids deriving from deeper pre salt strata of the sosb which entered the intra salt carbonate stringers during times of basement tectonic activity via hydrofractures this caused the formation of high maturities pyrobitumens in close vicinity to the fractures and precipitation of migrabitumens with increasing distance to the ht source which is supported by the geochemical composition of the solid reservoir bitumens the influx of these fluids into the carbonate stringers is considered to represent a major contribution to their strong overpressures 2007 elsevier ltd all rights reserved

process based and dynamic 2d modeling of shale samples considering the geology and pore system evolution abstract accurate characterization of shale samples is of great importance for predicting and evaluating their intrinsic properties as they undergo various geological processes as such constructing shale models not only entails accounting for the numerous components and pores but also requires considering the effects of thermal maturation on the evolutions of the pore systems and components in this study a new dynamic and process based modeling for considering the geological evolutions occurred in pore systems is developed which makes a significant improvement in reproducing the complex geological features in shale samples three types of pores including organic matter om interparticle interp and intraparticle intrap pores and several other components including kerogen pyrite clay minerals globigerinids calcite feldspar quartz and petroleum products are all considered in our process based modeling in order to demonstrate the performance of our process based method two dimensional 2d dynamic shale models of multiple cases with different geological processes are constructed then to characterize the constructed samples the occurrences and distributions of all components are studied using a two point correlation function aside from statistical comparisons the gas flow in these shale models is also simulated to exhibit the permeability variations produced in the process based models moreover the degree of cementation the fractions of interp intrap and om pores are varied to mimic new geological scenarios which aims to further evaluate the performance of the proposed technique the results indicate that our process based model presents an excellent performance furthermore the presented modeling technique can be extended to investigating the effects of various components and pores on the intrinsic properties of shales in the future

coal reservoir saturation impact of temperature and pressure methane adsorption isotherms measured for a series of coals with varying rank at a wide range of temperatures and pressures allows the prediction of the change in sorption capacity as a function of tectonic history changes in sorption capacity in response to declining pressure and temperature associated with uplift may increase or decrease the capacity of the coal and if the coal is initially saturated result in excess gas or a deficiency of gas undersaturation assuming reasonable geothermal and pressure gradients our data indicate that the sorption capacity will generally decrease with uplift and associated exhumation suggesting that an initially gas saturated coal will desorb gas during uplift of the reservoir the desorbed gas would be available for migration and or potentially resaturation of an undersaturated coal our results argue against the generally accepted theory that undersaturation of coal reservoirs results from an increase in the sorption capacity with uplift except for coals at such high pressures that the isotherms are essentially flat or for very high pressure and geothermal gradients

unconventional shale gas systems the mississippian barnett shale of north central texas as one model for thermogenic shale gas assessment shale gas resource plays can be distinguished by gas type and system characteristics the newark east gas field located in the fort worth basin texas is defined by thermogenic gas production from low porosity and low permeability barnett shale the barnett shale gas system a self contained source reservoir system has generated large amounts of gas in the key productive areas because of various characteristics and processes including 1 excellent original organic richness and generation potential 2 primary and secondary cracking of kerogen and retained oil respectively 3 retention of oil for cracking to gas by adsorption 4 porosity resulting from organic matter decomposition and 5 brittle mineralogical composition the calculated total gas in place gip based on estimated ultimate recovery that is based on production profiles and operator estimates is about 204 bcf section 5 78 10 9 m 3 1 73 10 4 m 3 we estimate that the barnett shale has a total generation potential of about 609 bbl of oil equivalent ac ft or the equivalent of 3657 mcf ac ft 84 0 m 3 m 3 assuming a thickness of 350 ft 107 m and only sufficient hydrogen for partial cracking of retained oil to gas a total generation potential of 820 bcf section is estimated of this potential approximately 60 was expelled and the balance was retained for secondary cracking of oil to gas if sufficient thermal maturity was reached gas storage capacity of the barnett shale at typical reservoir pressure volume and temperature conditions and 6 porosity shows a maximum storage capacity of 540 mcf ac ft or 159 scf ton

thermal maturity of the barnett shale determined from well log analysis intensive development with large scale fracturing treatments has made the barnett shale play newark east field in the fort worth basin the largest shale gas field in the world the mississippian barnett shale is an organic rich self sourced reservoir rock thermal maturity thickness and total organic carbon are the most important geological factors for commercial gas production from this shale formation the log derived thermal maturity index mi has been developed in an effort to better understand and predict hydrocarbon phases across the basin maturity index was calculated using three types of open hole logs neutron porosity deep resistivity and density porosity or bulk density the derivation of mi is based on the hypotheses that shale gas is generated and stored locally without apparent migration from outside sources and that the water saturation and the density of generated hydrocarbons decrease with an increase in thermal maturity maturity index correlates well with initial gas oil ratios gor from well production data based on this correlation an empirical relationship has been demonstrated for the fort worth basin this method is useful in understanding the thermal maturity levels of barnett shale source rock in the gas generation window mapping mi gor and gas heating value from hundreds of wells identifies the various maturity stages and areas of barnett shale that generate oil condensate wet gas or dry gas in the fort worth basin

the characteristics and significance of conventional and unconventional sinian silurian gas systems in the sichuan basin central china abstract oil and gas discoveries within proterozoic cambrian strata and the majority of shale gas production occurs in relatively stable tectonic regions and characterised by moderate thermal maturity r o o 2 5 the system comprises two components namely a conventional sinian cambrian dolomite hosted gas resource and an unconventional cambrian silurian shale gas deposit both represent trillion cubic meter accumulations the migration accumulation type sinian cambrian gas system is a result of numerous processes including 1 paleo high trapping within a relatively stable tectonic setting 2 appropriate source materials located in a paleo rift trough 3 large scale dolomite grainstone reservoirs located near the paleo high 4 adequate gas produced from in situ crude oil cracking and 5 gypsum salt and shale cap rock preservation the self contained source reservoir cambrian silurian shale gas system is localized by deepwater organic rich shelf facies characterized by high silicon and calcium contents the recent discovery of these two massive gas fields in old and over matured sedimentary strata has effectively extended the upper maturity limit of r o over 3 0 which may indicate the efficacy of broadening current natural gas exploration areas thus potentially increasing global natural gas resources significantly furthermore the discovery may spark interest in natural gas exploration in widely distributed old strata thus encouraging co development of conventional and unconventional petroleum accumulations

a model for porosity evolution in shale reservoirs an example from the upper devonian duvernay formation western canada sedimentary basin the influence of thermal maturity on porosity in shale samples from the upper devonian duvernay formation is examined the samples span a maturity range from immature to the wet gas window porosity decreases from immature to the oil window primarily because of compaction relatively high porosity of wet gas window samples is ascribed to formation of secondary organic pores feldspar dissolution pores and primary pore preservation by the quartz framework the final decline in the porosity of the dry gas window samples is explained by greater compaction the disappearance of secondary organic pores and feldspar dissolution pores porosity correlates positively to quartz content and negatively to carbonate content no relationship was evident between porosity and clay or total organic carbon content no obvious correlations exist between rock composition and permeability except that sio2 content shows a weakly positive correlation to permeability permeability is highest in immature samples which have the greatest pore and pore throat sizes nitrogen adsorption and mercury injection analysis show that pore and pore throat sizes decrease with increasing maturity visible pores imaged by scanning electron microscopy and helium ion microscopy exist as organic pores including bubblelike pores developed within organic matter om and fissure type pores intraparticle pores mainly developed within carbonate grains and interparticle pores either within a clay rich matrix or between rigid mineral grains in immature samples the primary pores are interparticle pores between clay minerals and other mineral grains the om fissures are ubiquitous in oil window samples and secondary bubblelike om hosted pores are well developed within gas window samples

investigations on the methane sorption capacity of marine shales from sichuan basin china abstract high pressure methane sorption isotherms measured at 30 50 and 80 c and pressure up to 20 mpa were measured on lower silurian marine shales from sichuan basin of china the effect of total organic carbon content temperature thermal maturity mineral composition and pore structure on methane sorption capacity has been investigated a linear combination approach has been developed to predict the langmuir sorption capacity of shales based on the mass fractions of their organic and inorganic components this information can be used to estimate the in situ sorption capacity of shale layers as a function of burial depth formation pressure and temperature and composition methane sorption capacity of the dry shales shows a positive relationship with toc and specific surface area the langmuir pressure decreases with increasing maturity but the toc normalized langmuir sorption capacity of over mature shales also decreases with increasing thermal maturity this may be related to the carbonization of highly over mature organic matter for the samples investigated approximately 16 3 46 7 average 28 6 of the methane sorption can be attributed to clay minerals and 46 5 81 5 to average 67 6 organic matter in these shales respectively using the linear combination approach the calculated langmuir sorption capacity function matches the measured values reasonably methane sorption capacity computed as a function of depth for a mean hydrostatic pressure gradient of 0 01 mpa m and a geothermal gradient of 0 03 c m shows a rapid increase and reaches a maximum between 900 and 1800 m followed by a slow decrease with increasing depth at shallow burial depths 900 1800 m sorption capacity is controlled by the geothermal gradient higher geothermal gradients result in a steeper decline of sorption capacity

the methane sorption capacity of paleozoic shales from the sichuan basin china the methane sorption capacities of paleozoic shales from the sichuan basin were investigated the primary results show they have sorption capacities ranging between 0 94 and 4 29 cm3 grock at stp comparable to the sorption capacity 1 27 2 41 cm3 grock at stp of barnett shale however the sorption isotherms indicate that most of the sichuan basin shales would reach their approximate sorption equilibrium at 3 4 mpa in contrast to the continuously upward trend of north american shales a general positive relationship between toc content and methane sorption capacity indicates that toc content is the major controlling factor for the methane sorption of the sichuan shales a negative relationship between the clay mineral content and the sorption capacity of these shales may suggest that clay minerals play an insignificant role in the methane sorption of these paleozoic shales sorption capacities and variation ranges are generally ordered as to geological age viz cambrian silurian permian

organic nanopore structure and fractal characteristics of wufeng and lower member of longmaxi shales in southeastern sichuan china abstract organic nanopores in shale gas reservoirs are the main storage space for free gas and adsorbed gas and directly affect the occurrence mode and movement of shale gas in this study field emission scanning electron microscopy fe sem low pressure gas n2 and co2 adsorption and mercury injection capillary pressure micp analyses were performed and interpreted with statistical and fractal analyses to investigate the organic pore structure in the upper ordovician wufeng shale o3w and the lower silurian lower member of longmaxi shale s1l it was found that organic pores in 15 samples from 8 layers of the wufeng longmaxi shale section are usually developed in discrete organic matter particles organic matter associated with clay minerals and organic matter associated with pyrite framboids the size shape and quantity of organic pores vary greatly the organic pores in wufeng formation layer 1 are densely developed in organic matter particles with relatively small sizes and irregular shapes the organic pores in the lower part of the lower member of longmaxi formation layers 3 4 and 5 are less developed and have relatively larger pore sizes with an elliptical shape in contrast the organic pores in the upper part of the lower member of longmaxi formation layers 6 7 8 and 9 are the least developed with elliptical shapes and pore sizes in between the two cases above a higher value of fractal dimension refers a more complex form and this value of whole organic pores with full range of sizes dwop is the largest and followed by organic macropores dop 50 organic pores with pore sizes between 4 nm and 50 nm dop4 50 and organic pores with pore sizes less than 4 nm dop

paleo ocean redox environments of the upper ordovician wufeng and the first member in lower silurian longmaxi formations in the jiaoshiba area sichuan basin a study of paleo ocean redox environments is important for understanding the deposition of black shale and has practical implications for shale gas exploration here we selected a total of 52 shal

the organic matter distribution and methane capacity of the lower cretaceous strata of northeastern british columbia canada abstract the methane sorption capacity of a succession of sandstone siltstone shale and coal from the lower cretaceous fort st john group of northeastern british columbia was investigated average organic matter om content for all formations is 2 3 wt with a minimum of 0 6 wt and maximum of 10 1 wt the methane sorption capacity ranges between 0 19 and 2 74 cm3 g at 6 mpa and at 30 c total gas capacity free and sorbed gas ranges between 2 2 and 16 6 cm3 g at 6 mpa micropore volumes range between 0 43 and 1 69 cm3 100 g a positive correlation exists between the om content micropore volume and the methane capacity of shales shales with high methane capacities have either high contents of inertodetrinite or vitrinite moisture content shows a positive relationship with om content micropore volume and methane capacity the negative relationship between moisture and surface area derived from n2 adsorption suggests the moisture is located within the microporosity of the om and also explains the positive relationship between methane capacity and moisture the high inertodetrinite and vitrinite contents correlate with sea level regressions that delivered terrestrial om from coastal plains located south of the study area into the basin

geochemical evolution of organic rich shales with increasing maturity a stxm and tem study of the posidonia shale lower toarcian northern germany hydrocarbon generation and retention processes occurring within gas shales as a response to increases in thermal maturation are still poorly constrained while efforts have been directed at unravelling the resource potential composition and textures of these economically important unconventional systems their spatial variability in chemistry and structure is still poorly documented at the sub micrometer scale here we have characterized samples of the lower toarcian posidonia shale samples from northern germany at varying stages of thermal maturation using a combination of compositional organic geochemistry and spectromicroscopy techniques including synchrotron based scanning transmission x ray microscopy stxm we document geochemical and mineralogical heterogeneities down to the nanometer scale within the investigated samples as a function of their level of thermal maturity in particular authigenic albite crystals containing nanometric halite inclusions have been documented within the investigated mature and overmature samples the presence of such tracers of palaeobrine carbonate interactions supports a maturation scenario for the lower toarcian posidonia shale intimately related to ascending brine fluids rather than a maturation scenario solely resulting from high heat flows in addition various types of asphaltene and nso rich bitumen have been detected within the same samples very likely genetically derived from thermally degraded organic precursors furthermore the formation of nanoporous pyrobitumen has been inferred for samples of gas window maturity likely resulting from the formation of gaseous hydrocarbons by providing in situ insights into the fate of bitumen and pyrobitumen as a response to the thermal evolution of the macromolecular structure of kerogen the results reported here constitute an important step towards better constraining hydrocarbon generation processes during natural shale gas maturation

gas saturation and co2 enhancement potential of coalbed methane reservoirs as a function of depth the influence of moisture temperature coal rank and differential enthalpy on the methane ch4 and carbon dioxide co2 sorption capacity of coals of different rank has been investigated by using high pressure sorption isotherms at 303 318 and 333 k ch4 and 318 333 and 348 k co2 respectively the variation of sorption capacity was studied as a function of burial depth of coal seams using the corresponding langmuir parameters in combination with a geothermal gradient of 0 03 k m and a normal hydrostatic pressure gradient taking the gas content corresponding to 100 gas saturation at maximum burial depth as a reference value the theoretical ch4 saturation after the uplift of the coal seam was computed as a function of depth according to these calculations the change in sorption capacity caused by changing pressure temperature conditions during uplift will lead consistently to high saturation values therefore the commonly observed undersaturation of coal seams is most likely related to dismigration losses into adjacent formations and atmosphere finally we attempt to identify sweet spots for co2 enhanced coalbed methane co2 ecbm production the co2 ecbm is expected to become less effective with increasing depth because the co2 to ch4 sorption capacity ratio decreases with increasing temperature and pressure furthermore co2 ecbm efficiency will decrease with increasing maturity because of the highest sorption capacity ratio and affinity difference between co2 and ch4 for low mature coals

mississippian barnett shale fort worth basin north central texas gas shale play with multi trillion cubic foot potential the mississippian barnett shale serves as source seal and reservoir to a world class unconventional natural gas accumulation in the fort worth basin of north central texas the formation is a lithologically complex interval of low permeability that requires artificial stimulation to produce at present production is mainly confined to a limited portion of the northern basin where the barnett shale is relatively thick 300 ft 92 m organic rich presentday total organic carbon 3 0 thermally mature vitrinite reflectance 1 1 and enclosed by dense limestone units able to contain induced fractures the most actively drilled area is newark east field currently the largest gas field in texas newark east is 400 mi 2 1036 km 2 in extent with more than 2340 producing wells and about 2 7 tcf of booked gas reserves cumulative gas production from barnett shale wells through 2003 was about 0 8 tcf wells in newark east field typically produce from depths of 7500 ft 2285 m at rates ranging from 0 5 to more than 4 mmcf day estimated ultimate recoveries per well range from 0 75 to as high as 7 0 bcf efforts to extend the current barnett play beyond the field limits have encountered several challenges including westward and northward increases in oil saturation and the absence of lithologic barriers to induced fracture growth patterns of oil and gas occurrence in the barnett in conjunction with maturation and burial history data indicate a complex multiphased thermal evolution with episodic expulsion of hydrocarbons and secondary cracking of primary oils to gas

porosity of devonian and mississippian new albany shale across a maturation gradient insights from organic petrology gas adsorption and mercury intrusion the evolution of porosity in shales with increasing maturity was examined in a suite of five new albany shale samples spanning a maturity range from immature vitrinite reflectance ro 0 35 to postmature ro 1 41 devonian to lower mississippian new albany shale samples from the illinois basin used in this study contain marine type ii kerogen having total organic carbon contents from 1 2 to 13 0 wt organic petrology co2 and n2 low pressure adsorption and mercury intrusion capillary pressure techniques were used to quantify pore volumes pore sizes and pore size distributions increasing maturity of the new albany shale is paralleled by many changes in the characteristics of porosity the total porosity of 9 1 vol in immature new albany shale decreases to 1 5 vol in the late mature sample whereas total pore volumes decrease from 0 0365 to 0 0059 cm3 g in the same sequence reversing the trend at even higher maturity the postmature new albany shale exhibits higher porosity and larger total pore volumes compared to the late mature sample with increasing maturity changes in total porosity and total pore volumes are accompanied by changes in pore size distributions and relative proportions of micropores mesopores and macropores porosity related variances are directly related to differences in the amount and character of the organic matter and mineralogical composition but maturity exerts the dominant control upon these characteristics we conclude that organic matter transformation due to hydrocarbon generation and migration is a pivotal cause of the observed porosity differences

geological controls on the accumulation of shale gas a case study of the early cambrian shale in the upper yangtze area abstract the results of sedimentological mineralogical geochemical and petrophysical studies on the early cambrian shale in the upper yangtze area are summarized to provide insights on the paleoenvironmental conditions diagenetic evolution and preservation conditions that give rise to shale gas accumulation the lower cambrian organic rich qiongzhusi shale is mainly developed in the outer shelf facies of an intracratonic sag average total organic carbon toc 1 3 2 5 and in the southeast margin average toc 3 5 5 5 of the upper yangtze area the thermal maturity values reqv of the qiongzhusi shale range from 2 19 to 4 23 while first increasing and then decreasing from the center of the sichuan basin outward the average porosities of the qiongzhusi shale from the outer shelf facies association fa5 in the intracratonic rift range from 1 5 to 3 41 and those from the outer shelf facies association fa4 in the southeast sichuan and guizhou areas range from 1 32 to 2 56 the organic matter om content and the development degree of om pores are the main factors that control the porosity and pore structure of the qiongzhusi shale for the outer shelf deposits in the intracratonic rift a quartz detrital origin content ranging between 25 and 35 is most favorable for providing an effective support framework for om pore development due to the mixture of brittle and clay minerals for the outer shelf deposits in the southeastern margin of the upper yangtze area the high om content and poor compaction resistance cause a poor development of om pores with a smaller average pore diameter than that in the outer shelf shale of the intracratonic rift in addition the carbonization of om in the overmature qiongzhusi shale change the microstructure and decrease the om pore volume due to poor preservation conditions the gas content is generally low in the organic rich shale in the eastern and southeastern parts of the upper yangtze region the qiongzhusi shale in the interior of the sichuan basin with good preservation conditions high pressure coefficients and high gas contents is a favorable area for shale gas accumulation and potential exploitation

mechanisms of shale gas storage implications for shale gas exploration in china this article reviews the mechanisms of shale gas storage and discusses the major risks or uncertainties for shale gas exploration in china at a given temperature and pressure the gas sorption capacities of organic rich shales are primarily controlled by the organic matter richness but may be significantly influenced by the type and maturity of the organic matter mineral composition especially clay content moisture content pore volume and structure resulting in different ratios of gas sorption capacity gsc to total organic carbon content for different shales in laboratory experiments the gsc of organic rich shales increases with increasing pressure and decreases with increasing temperature under geologic conditions assuming hydrostatic pressure gradient and constant thermal gradient the gsc increases initially with depth due to the predominating effect of pressure passes through a maximum and then decreases because of the influence of increasing temperature at greater depth this pattern of variation is quite similar to that observed for coals and is of great significance for understanding the changes in gsc of organic rich shales over geologic time as a function of burial history at an elevated temperature and pressure and with the presence of moisture the gas sorption capacities of organic rich shales are quite low as a result adsorption alone cannot protect sufficient gas for high maturity organic rich shales to be commercial gas reservoirs two models are proposed to predict the variation of gsc and total gas content over geologic time as a function of burial history high contents of free gas in organic rich shales can be preserved in relatively closed systems loss of free gas during postgeneration uplift and erosion may result in undersaturation the total gas contents lower than the sorption capacity and is the major risk for gas exploration in marine organic rich shales in china

porosity characteristics of the devonian horn river shale canada insights from lithofacies classification and shale composition abstract this study evaluates pore systems of the horn river shale in western canada sedimentary basin from lithofacies classification of core samples to micro scale pore structure investigation samples from the middle and upper devonian horn river shale sequence were examined by core description porosity measurement sem and tem imaging of ion milled samples and nitrogen adsorption analysis in order to develop a better understanding of the controls of organic and inorganic rock constituents on porosity development and pore microstructure five primary shale lithofacies were identified by hand core and thin section analyses massive mudstones massive mudstones with pyrite streaks laminated mudstones bioturbated mudstones and carbonates porosity ranges from 0 62 to 12 04 and shows wide variation between different lithofacies massive mudstones and pyritic mudstones with high total organic carbon toc content have the highest porosity whereas bioturbated mudstones and carbonates with low toc content have the lowest porosity sem and tem images suggest that several kinds of sites for porosity development are present including organic matter pyrite framboids clay platelets quartz rims carbonate grains and microfractures a general positive relationship between toc and porosity indicates that a large proportion of pores are developed in organic matter results from the nitrogen adsorption analysis suggest that samples with more organic matter tend to develop smaller pores thus while porosity development is a combined function of organic matter mineral components fabric and fractures it is most affected by organic matter concentration the muskwa formation and the evie member have more gas storage capacity as they primarily consist of massive mudstones and pyrite rich mudstones showing the best porosity the otter park member has lower porosity which may relate to the fact that its lithofacies mainly consists of laminated mudstones and bioturbated mudstones

processes involved in the origin and accumulation of hydrocarbon gases in the yuanba gas field sichuan basin southwest china abstract natural gases in the superimposed sichuan basin commonly experienced a history of remigration in marine carbonate reservoirs since the late cretaceous the reservoir in the changxing formation p 2 c in the yuanba gas field in the sichuan basin is characterized by a great burial depth of 6200 7000 m and a high temperature about 165 c the gas dryness is 99 73 99 99 and 13 c values of methane and ethane are 31 0 to 28 9 and 29 9 to 25 6 respectively the chemical and isotopic compositions of natural gases abundant reservoir solid bitumen and high reservoir temperature maximum to 240 c indicate that the p 2 c gases are of sapropelic origin and are derived from oil cracking the paleo oil layers recognized by solid bitumen distribution were mainly developed in high position traps when the paleo oil accumulated during the early jurassic reconstructed structural evolution shows the northwest was uplifted sharply and southern part dipped gently to the north in the gas field after oil cracking fluid potential analyses based on changes in the structural configuration imply that gas should re migrate mainly to the northwest the observations that paleo oil water contacts are mainly above the present day gas water contacts in the northwest traps and are below present day gas water contacts in the middle and eastern traps also confirm the gas remigration trend currently high gas production wells are mainly located in northwest traps and in high positions in the middle and eastern traps systematic analyses on early paleo oil accumulation and late gas remigration processes can reduce the economic risks associated with natural gas exploration in the northeastern sichuan basin

characterization of gas shale pore systems by porosimetry pycnometry surface area and field emission scanning electron microscopy transmission electron microscopy image analyses examples from the barnett woodford haynesville marcellus and doig units the nanometer scaled pore systems of gas shale reservoirs were investigated from the barnett marcellus woodford and haynesville gas shales in the united states and the doig formation of northeastern british columbia canada the purpose of this article is to provide awareness of the nature and variability in pore structures within gas shales and not to provide a representative evaluation on the previously mentioned north american reservoirs to understand the pore system of these rocks the total porosity pore size distribution surface area organic geochemistry mineralogy and image analyses by electron microscopy were performed total porosity from helium pycnometry ranges between 2 5 and 6 6 total organic carbon content ranges between 0 7 and 6 8 wt and vitrinite reflectance measured between 1 45 and 2 37 the gas shales in the united states are clay and quartz rich with the doig formation samples being quartz and carbonate rich and clay poor higher porosity samples have higher values because of a greater abundance of mesopores compared with lower porosity samples with decreasing total porosity micropore volumes relatively increase whereas the sum of mesopores and macropore volumes decrease focused ion beam milling field emission scanning electron microscopy and transmission electron microscopy provide high resolution 5 nm images of pore distribution and geometries image analysis provides a visual appreciation of pore systems in gas shale reservoirs but is not a statistically valid method to evaluate gas shale reservoirs macropores and mesopores are observed as either intergranular porosity or are confined to kerogen rich aggregates and show no preferred orientation or align parallel with the laminae of the shale networks of mesopores are observed to connect with the larger macropores within the kerogen rich aggregates

wettability of mississippian barnett shale samples at different depths investigations from directional spontaneous imbibition because of its significant impact on relative permeability capillary pressure stimulation methods and ultimate recovery the wettability of reservoir rocks is a critical factor of the petroleum recovery process however characterizing the wettability of shale with extremely low matrix permeabilities is a challenging task because of the dominant presence of nanopores in shale and high heterogeneity of shale compositions at multiple scales from spontaneous imbibition behavior that uses two types of imbibing fluid water and n decane the present study examines the wettability characteristics of gas window barnett shale samples taken from four different depths of texas united 1 blakely core in wise county in texas imbibition experiments were conducted in two directions parallel and transverse to the lamination of the samples a scaling method was used to analyze imbibition data and observed imbibition behaviors were interpreted to infer the different wettability conditions of four samples with different mineralogy total organic carbon content and pore throat size distribution our results show that wettability significantly affects fluid imbibition behavior and that four tested samples can be divided into three wettability categories more water wet mixed wet and more oil wet overall the variable wettability of barnett samples will affect hydrocarbon storage distribution and production

fractured shale gas systems the first commercial united states natural gas production 1821 came from an organic rich devonian shale in the appalachian basin understanding the geological and geochemical nature of organic shale formations and improving their gas producibility have subsequently been the challenge of millions of dollars worth of research since the 1970s shale gas systems essentially are continuous type biogenic predominant thermogenic or combined biogenic thermogenic gas accumulations characterized by widespread gas saturation subtle trapping mechanisms seals of variable lithology and relatively short hydrocarbon migration distances shale gas may be stored as free gas in natural fractures and intergranular porosity as gas sorbed onto kerogen and clay particle surfaces or as gas dissolved in kerogen and bitumen five united states shale formations that presently produce gas commercially exhibit an unexpectedly wide variation in the values of five key parameters thermal maturity expressed as vitrinite reflectance sorbed gas fraction reservoir thickness total organic carbon content and volume of gas in place the degree of natural fracture development in an otherwise low matrix permeability shale reservoir is a controlling factor in gas producibility to date unstimulated commercial production has been achievable in only a small proportion of shale wells those that intercept natural fracture networks in most other cases a successful shale gas well requires hydraulic stimulation together the devonian antrim shale of the michigan basin and devonian ohio shale of the appalachian basin accounted for about 84 of the total 380 bcf of shale gas produced in 1999 however annual gas production is steadily increasing from three other major organic shale formations that subsequently have been explored and developed the devonian new albany shale in the illinois basin the mississippian barnett shale in the fort worth basin and the cretaceous lewis shale in the san juan basin in the basins for which estimates have been made shale gas resources are substantial with in place volumes of 497 783 tcf the estimated technically recoverable resource exclusive of the lewis shale ranges from 31 to 76 tcf in both cases the ohio shale accounts for the largest share

modeling of gas generation from the barnett shale fort worth basin texas the generative gas potential of the mississippian barnett shale in the fort worth basin texas was quantitatively evaluated by sealed gold tube pyrolysis kinetic parameters for gas generation and vitrinite reflectance ro changes were calculated from pyrolysis data and the results used to estimate the amount of gas generated from the barnett shale at geologic heating rates using derived kinetics for ro evolution and gas generation quantities of hydrocarbon gas generated at ro 1 1 are about 230 l t 7 4 scf t and increase to more that 5800 l t 186 scf t at ro 2 0 for a sample with an initial total organic carbon content of 5 5 and ro 0 44 the volume of shale gas generated will depend on the organic richness thickness and thermal maturity of the shale and also the amount of petroleum that is retained in the shale during migration gas that is reservoired in shales appears to be generated from the cracking of kerogen and petroleum that is retained in shales and that cracking of the retained petroleum starts by ro 1 1 this result suggests that the cracking of petroleum retained in source rocks occurs at rates that are faster than what is predicted for conventional siliciclastic and carbonate reservoirs and that contact of retained petroleum with kerogen and shale mineralogy may be a critical factor in shale gas generation shale gas systems together with overburden can be considered complete petroleum systems although the processes of petroleum migration accumulation and trap formation are different from what is defined for conventional petroleum systems

morphology genesis and distribution of nanometer scale pores in siliceous mudstones of the mississippian barnett shale research on mudrock attributes has increased dramatically since shale gas systems have become commercial hydrocarbon production targets one of the most significant research questions now being asked focuses on the nature of the pore system in these mudrocks our work on siliceous mudstones from the mississippian barnett shale of the fort worth basin texas shows that the pores in these rocks are dominantly nanometer in scale nanopores we used scanning electron microscopy to characterize barnett pores from a number of cores and have imaged pores as small as 5 nm key to our success in imaging these nanopores is the use of ar ion beam milling this methodology provides flat surfaces that lack topography related to differential hardness and are fundamental for high magnification imaging nanopores are observed in three main modes of occurrence most pores are found in grains of organic matter as intraparticle pores many of these grains contain hundreds of pores intraparticle organic nanopores most commonly have irregular bubblelike elliptical cross sections and range between 5 and 750 nm with the median nanopore size for all grains being approximately 100 nm internal porosities of up to 20 2 have been measured for whole grains of organic matter based on point count data from scanning electron microscopy analysis these nanopores in the organic matter are the predominant pore type in the barnett mudstones and they are related to thermal maturation nanopores are also found in bedding parallel wispy organic rich laminae as intraparticle pores in organic grains and as interparticle pores between organic matter but this mode is not common although less abundant nanopores are also locally present in fine grained matrix areas unassociated with organic matter and as nano to microintercrystalline pores in pyrite framboids intraparticle organic nanopores and pyrite framboid intercrystalline pores contribute to gas storage in barnett mudstones we postulate that permeability pathways within the barnett mudstones are along bedding parallel layers of organic matter or a mesh network of organic matter flakes because this material contains the most pores

pore characterization and methane sorption capacity of over mature organic rich wufeng and longmaxi shales in the southeast sichuan basin china abstract currently the upper ordovician wufeng o3w and lower silurian longmaxi s1l formations in southeast sichuan basin have been regarded as one of the most important target plays of shale gas in china in this work using a combination of low pressure gas adsorption n2 and co2 mercury injection porosimetry mip and high pressure ch4 adsorption we investigate the pore characteristics and methane sorption capacity of the over mature shales and discuss the main controlling factors for methane sorption capacity and distribution of methane gas in pore spaces low pressure co2 gas adsorption shows that micropore volumes are characterized by three volumetric maxima at about 0 35 0 5 and 0 85 nm the reversed s shaped n2 adsorption isotherms are type with hysteresis being noticeable in all the samples the shapes of hysteresis loop are similar to the h3 type indicating the pores are slit or plate like mesopore size distributions are unimodal and pores with diameters of 2 16 nm account for the majority of mesopore volume which is generally consistent with mip results the methane sorption capacities of o3w s1l shales are in a range of 1 63 3 66 m3 t at 30 c and 10 mpa methane sorption capacity increase with the toc content surface area and micropore volume suggesting organic matter might provide abundant adsorption site and enhance the strong methane sorption capacity samples with higher quartz content and lower clay content have larger sorption capacity our data confirmed that the effects of temperature and pressure on methane sorption capacity of shale formation are opposite to some extent suggesting that during the burial or uplift stage the gas sorption capacity of hydrocarbon reservoirs can be expressed as a function of burial depth based on the adsorption energy theory when the pore diameter is larger than 2 nm much methane molecular will be adsorbed in pores space with distance to pore wall less than 2 nm while free gas is mainly stored in the pore space with distance to pore wall larger than 2 nm distributions of adsorption space decrease with the increasing pore size while free gas volume increase gradually assuming the pore are cylindrical or sphere particularly when the pore size is larger than 30 nm the content of adsorbed gas space volume is very low and its contribution to the all gas content is negligible

bib sem study of the pore space morphology in early mature posidonia shale from the hils area germany abstract this contribution reports on the study of the pore space morphology in two early mature vr r 0 59 and 0 61 samples of posidonia shale from the hils syncline in germany using broad ion beam bib polishing and high resolution scanning electron microscopy sem this allows imaging pores with resolution down to 10 nm in equivalent diameter d eq and quantitative estimation of porosity using a combination of bse and se detectors and semi automatic segmentation of the gigapixel images the representative elementary area of the samples on the scale of a few mm is inferred to be about 140 140 m 2 pore morphologies and pore sizes are clearly related to the mineral fabric with large differences very large typically several microns pores with internal faceted crystal morphology in recrystallized calcite clasts and smaller pores d eq cf schizosphaerella nanofossils typically 200 nm pores are less common in organic material and in pyrite aggregates pore characteristics are very similar for both samples and porosity resolvable by bib sem is 2 75 and 2 74 pore size distribution can be described by a power law with an exponent about 2 0 and 2 2 respectively for the pore population excluding the fossils pores in the carbonate fossils show dual power law distribution with power law exponents of about 1 and 3 by extrapolating the power law distribution for each sample total porosity is estimated to be 4 8 0 9 1 7 and 6 5 2 7 7 2 respectively this estimate can be compared with 3 4 3 7 and 3 3 3 6 as measured by mercury injection porosimetry we interpret this difference to reflect the unconnected for mercury part of the porosity comparison of imaged pores and mercury injection porosimetry suggest a very high pore body to pore throat ratio this results in a pore model where large pores represented mainly by pores in fossils and calcite grains are connected via a low porous and low permeable clay rich matrix with pore throats below 10 nm in both samples

nano scale pore structure and fractal dimension of organic rich wufeng longmaxi shale from jiaoshiba area sichuan basin investigations using fe sem gas adsorption and helium pycnometry abstract much attention have been recently paid to the upper ordovician wufeng shale o3w and lower silurian longmaxi shale s1l in the jiaoshiba area of sichuan basin which is now the largest producing shale gas field in china field emission scanning electron microscopy fe sem low pressure gas n2 and co2 adsorption helium pycnometry x ray diffraction and geochemical analyses were performed to investigate the pore structure and fractal dimension of the pores in o3w s1l shale formation in the jiaoshiba area fe sem images show that organic matter om pores are dominant in the organic rich samples and these pores are often irregular bubble like elliptical and faveolate in shape while in organic poor samples limited and isolated interparticle interp intraparticle intrap and om pores are observed reversed s shaped isotherms obtained from nitrogen adsorption are type and hysteresis loops indicate that the shape of micropore in the samples is slit or plate like bet surface areas and total pore volume vary from 12 2 to 27 1 m2 g and from 1 8 10 2 to 2 9 10 2 cm3 g with an average of 19 5 m2 g and 2 3 10 2 cm3 g respectively adsorption volume from both n2 and co2 adsorption increases with respect to toc contents porosities obtained from helium porosimetry are comparable with these from gas co2 and n2 adsorption in o3w s1l shale however porosity determined by quantitative fe sem analysis is much smaller which is mainly related to limited resolution and the small areas of investigation based on the frenkel halsey hill fhh model of low pressure n2 adsorption fractal dimensions of the pores varied from 2 737 to 2 823 relationships between pore structure parameters and toc content mineral composition and fractal dimension reveal that the fractal dimension is mainly associated with micropores samples with higher toc content higher quartz content and lower clay content tend to contain more heterogeneous micropores resulting in higher fractal dimensions and more complicated pore structure in shales therefore fractal dimension is an effective parameter to reflect the complexity of pore structure and the degree of micropore development in o3w s1l shale

petrogenesis of the 1 43 ga sherman batholith se wyoming usa a reduced rapakivi type anorogenic granite the 1 43 ga sherman batholith southeastern wyoming usa origin that are found throughout the proterozoic anorogenic granite provinces of the southwestern usa adirshows extreme a type petrochemical characteristics compared with other mid proterozoic granite batholiths of north america it ondacks eastern canada southern greenland and the fennoscandian shield anderson 1983 phanerozoic consists of 1 the sherman granite a coarse grained biotite hornblende granite that locally contains fayalite and pyroxenes 2 examples include paleozoic granites of southeastern australia collins et al 1982 and of corsica poitrasson et the lincoln granite a medium grained biotite granite 3 a porphyritic biotite hornblende granite that probably formed by interaction al 1995 and the mesozoic nigerian younger granites jacobsen et al 1958 and the white mountain magma of granitic and mafic magmas and 4 iron enriched mafic dikes and pods the ilmenite series metaluminous sherman granite series foland allen 1991 anorogenic granite refers to plutons that are not associated with compressional exhibits extreme values of feo feo mgo and is rich in structures and that were emplaced long after any known k ree nb and y it crystallized at temperatures exceeding orogenic event anorogenic or a type granites loiselle 900 c and a pressure of 2 5 kbar with water activity of 0 7 wones 1979 are characterized by low h2o and o2 and dlog fo2 of 0 1 to 0 5 the lincoln granite which is fugacities along with high feo feo mgo k2o peraluminous and has less extreme a type geochemical characteristics na2o and k2o contents a type granites typically are rich crystallized at temperatures as low as 750 c and dlog fo2 of in incompatible elements including rare earth elements around 0 5 units above fmq fayalite magnetite quartz the ree zr nb and ta but poor in co sc cr ni ba rocks of the sherman batholith are chemically equivalent to lavas sr and eu minimum magma liquidus temperatures are from the yellowstone hotspot like the yellowstone magmas the 900 1000 c clemens et al 1986 creaser white sherman batholith probably originated by partial melting of under1991 some workers suggest these rocks are derived plated mantle derived mafic rocks from melting of tonalitic or more felsic crust anderson cullers 1978 collins et al 1982 clemens et al 1986 creaser et al 1991 whereas others relate the granites