Compositional and Structural Study of Macerals in Coals and Source Rocks Using SIMS

The authors applied the Secondary Ion Mass Spectrometry (SIMS) technique to the analysis of compositions and structures of vitrinites fusinites, fusinites bitumens and graptolites in the hydrocarbon source rocks with different maturities dscribed their SIMS spectral characteristics and found that different macerals have differnt spectra which, reflected the compositional and structural differences of macerals. Moreover, the change bod of parameter CH2+/CH3+ can be used for the evaluation of thermal evolution regularity of macerals in the hydrocarbon source rocks The study results show that the SIMS technique is a powerful means for microara analysis of macerals in coals and source rocks. It is certain that the study level of macerals can be raised by detailed study of SIMS results of SIMS results of macerals.

Depositional Model for Peat Swamp and Coal Facies Evolution Using Sedimentology, Coal Macerals, Geochemistry and Sequence Stratigraphy

As one of the most important source rocks and reservoirs of unconventional natural gas, the sedimentary environment and mode of peat swamp（the predecessor of coal seam） is important to the coal seam＇s spatial distribution, material composition, hydrocarbon generation potential, reservoir physical properties, etc. To reveal the depositional characteristics and history of environmental change in a terrestrial basin during a period of peat accumulation, the Middle Jurassic aged #7 coal from Gaoquan in the Qaidam Basin（NW China） was investigated using sedimentology, maceral composition, geochemistry and sequence stratigraphy. Based on identification of the sedimentary shoreline break belt, wave energy depletion point and position of wave base, the peat swamp system can be subdivided into（1） lakeside plain,（2） low energy lakeshore,（3） high energy lakeshore, and（4） shallow lake subfacies. A new method for determining coal facies is proposed based on the combination of environmental parameters including oxidation-reduction levels, energy conditions and the influence of terrigneous sediments. The evolution of the coal seam shows that peat was deposited mainly in the low energy lakeshore and lakeside plain subfacies. Five types of sequence stratigrpahic surface and two types of parasequence were identified. Forced lake regressions and normal lake regressions are attributed as the causes of sequence boundaries. The sequence stratigraphic framework comprises six sequences and corresponding system tracts, and the curve of base-level for each demonstrates a characteristic initial period of slow rising followed by fast rising and then returning to slow rising. A model indicating the relationship among base-level changes, coal facies evolution, and the environmental features in the swamp is proposed that shows the environmental features of the swamp were controlled by both base-level changes and coal facies. Accompanying depositional environment changes from a lakeside plain to lakeshore and shallow lake caused by increasing rate of base-level rise, water paleosalinity, acidity and the percentage of woody plants decrease, and the bog type alters from the low marsh to raised bog.

Experimental study and evaluation on hydrocarbon generation of macerals

Some typical coal and maceral samples are selected for oil and gas-generatingsystematic thermal simulation experiments, Rock-Eval, GC and GC-MS analyses. Results cause productivity curves of extracts and gaseous, light, liquid as well as total hydrocarbon. Effects of macerals and maturation on hydrocarbon productivities and compositions are synthetically discussed. Evaluation indexes and plan on coal-generated oil and gas in bituminous coal rank are suggested according to the data from experiments and analyses.

THE HYDROCARBON-GENERATING TREND ANALYSIS OF MACERALS IN HYDROCARBON SOURCE ROCKS

The hydrocarbon-generating threshold and pattern of a source rock mainly depend on its constituents of macerals. Different kinds of macerals occurring in a source rock may have variable 'oil window ', especially the 'oil threshold'. In order to recognize the different hydrocarbon generation of macerals, organic petrology may be the only efficient method. In this note, the detailed fluorescence alteration patterns of macerals in the

Laser-induced fluorescence of macerals in relation to its hydrogen richness

On the basis of results from conventional elemental analyses and a unique technique (FAMM? fluorescence alteration of multiple macerals), using a laser fluorescence microprobe, the fluorescence characteristics of various macerals are systematically related to hydrogen content. The amount of fluorescence from inertinite and vitrinite exponentially increases with H/C values. Although liptinite has high fluorescence and high H/C values, the relationship does not follow the same trend as defined for the other maceral groups. Because petroleum yields of a maceral mainly depend upon hydrogen richness, a correlation also exists between fluorescence, and gas to oil ratios from pyrolysis. Because individual organic entities are measured, the laser fluorescence microprobe has the benefit of accommodating heterogeneous organic matter in source rocks and enables determination of oil and gas yields of specific macerals.

Organic matter pores in the chang 7 lacustrine shales from the Ordos Basin and its effect on reflectance measurement

To quantify the pore characteristics of various macerals in Chang 7 lacustrine shales,macerals were effectively identified according to their optical and morphological characteristics,and the nanoscale pore structure of macerals was observed by scanning electron microscope.Meanwhile,the reflectances of different positions in the same pieces of vitrinite or solid bitumen with heterogeneous pores development were measured.The results showed that the average contents of sapropelinite,liptinite,vitrinite,inertinite and solid bitumen are 42.7%,8.7%,13.6%,13.8% and 21.2%,respectively,which suggests that the source of the organic matter of the Chang 7 shales is a mixed source input.The organic pores of Chang 7 shales are enriched,and the pore shapes are mostly round or elliptical.The pore size of organic pores has a wide distribution,mainly concentrate in the range of 100-400 nm,and the average plane porosity of organic pores is 10.13%.The size order of the organic pores in various macerals is:solid bitumen<bituminite<alginite<vitrinite<fusinite<liptinite.The abundance order of organic matter pores of each maceral is as follows:alginite>fusinite>bituminite>solid bitumen>vitrinite>liptinite.OM pores are mainly contributed by bituminite,solid bitumen and fusinite.The plane porosity of bituminite increases with maturity.In the process of thermal evolution,the plane porosity of fusinite is distributed in the two ranges of 20%-28% and 1%-7%.The former is mainly the primary pores of the fusinite itself,and the latter is the secondary pores formed in the thermal evolution.As for the organic pores of other macerals,no obvious thermal evolution law was found.Meanwhile,the surface imperfections of vitrinite or solid bitumen is enhanced by the enrichment of organic pores(an increase in pore size or pore number),which may result in the underestimation of their reflectances.

Maceral evolution of lacustrine shale and its effects on the development of organic pores during low mature to high mature stage:A case study from the Qingshankou Formation in northern Songliao Basin,northeast China

Organic matter(OM)hosted pores are crucial for the storage and migration of petroleum in shale reservoirs.Thermal maturity and macerals type are important factors controlling the development of pores therein.In this study,six lacustrine shale samples with different thermal maturities from the first member of the Qingshankou Formation in the Songliao Basin,of which vitrinite reflectance(R_(o))ranging from 0.58% to 1.43%,were selected for a comparative analysis.Scanning electron microscopy(SEM)and reflected light microscopy were combined to investigate the development of organic pores in different macerals during thermal maturation.The results show that alginite and liptodetrinite are the dominant primary macerals,followed by bituminite.Only a few primary organic pores developed in the alginite at the lowest maturity(R_(o)=0.58%).As a result of petroleum generation,oil-prone macerals began to transform to initial-oil solid bitumen at the early oil window(R_(o)=0.73%)and shrinkage cracks were observed.Initial-oil solid bitumen cracked to oil,gas and post-oil bitumen by primary cracking(R_(o)=0.98%).Moreover,solid bitumen(SB)was found to be the dominant OM when R_(o)>0.98%,which indicates that SB is the product of oil-prone macerals transformation.Many secondary bubble pores were observed on SB,which formed by gas release,while devolatilization cracks developed on migrated SB.Additionally,at the late oil window(Ro?1.16%),migrated SB filled the interparticle pore spaces.With further increase in temperature,the liquid oil underwent secondary cracking into pyrobitumen and gas,and spongy pores developed on the pyrobitumen at higher levels of maturity(Ro=1.43%),which formed when pyrobitumen cracked into gas.Vitrinite and inertinite are stable without any visible pores over the range of maturities,verifying their low petroleum generation potential.In addition,it was concluded that clay minerals could have a catalytic effect on the petroleum generation,which may explain why organicclay mixtures had more abundant pores than single OM particles.However,after R_(o)>0.98%,authigenic minerals occupied the organic pore spaces on the organic-clay mixtures,resulting in fewer pores compared to those observed in samples at the early to peak oil window.

Improved maceration techniques to study the fruit vascular anatomy of grape

The visualization and evaluation of fruit vascular bundles in grape are indispensable for understanding the development and growth of the fruit. The vascular bundles in grape are as thin as human hair, and strongly adhere to flesh cells, making it difficult to isolate individual intact vessel elements. Currently there is little information about methods to characterize grape vascular tissue. In this study, we describe an easy and effective technique to visualize the xylem cell structure of the ‘Red Globe' grape(Vitis L.). The intact vascular bundles of the grape were isolated through enzymatic degradation of flesh cells by hydrolases which were effective in removing flesh cells from vascular bundles. This enabled the illustration of the fine surface structure of vessel elements and their arrangement in the vascular bundles of the grape. This modified method to separate the vascular bundles into individual vessel elements was more effective than former methods of manually shaking to isolate individual vessels. Clear images of xylem vessel arrangement and structural characteristics of individual vessel element were acquired by light microscopy(BX51, Olympus, Tokyo, Japan), transmission electron microscopy(Tecnai 12, Philips, Netherlands) and scanning electron microscopy(GeminiSEM 300, Carl Zeiss, Germany). In addition, the 3D structure of vessel elements was observed using confocal laser scanning microscopy(Zeiss: model: LSM-880, Oberkochen, Germany). The imaging techniques for visualizing and analyzing the structure of xylem vessels in grape described in this study are an improvement of past methods. An effective method to isolate grape vascular bundles from flesh cells was also developed, which enables the imaging of the fine surface structure of vessel elements and their arrangement in grape vascular bundles. By adjusting the process of maceration of vascular bundles, an easy and effective method was developed to gently disrupt the plant tissue and isolate individual vessel elements. These improved techniques are suitable to observe the intact morphology of vascular bundles in the grape, improve experimental efficiency and accelerate new discoveries on the anatomical structure of the grape.

Differences in geochemistry and hydrocarbon generation of sourcerock samples dominated by telalginite and lamalginite: A case study on the Permian saline lacustrine source rocks in the Jimusaer Sag, NW China

The Middle Permian Lucaogou Formation in Northwestern China mainly contains typical saline lacustrine oil shale.To study the differences in geochemistry and hydrocarbon generation of source-rock samples in Lucaogou Formation in Jimusaer Sag,57 core samples from two boreholes were analyzed herein by performing total organic carbon(TOC)analysis,RockeEval pyrolysis,and gas chromatographicemass spectrometry experiments on saturated hydrocarbons.The kinetics of oil generation were studied using two samples comprising typical maceral components.The results showed that the hydrocarbons produced by telalginite are relatively rich in pristane(Pr),phytane(Ph),b-carotane,high-carbon normal alkanes,and C29 regular steranes.Hydrocarbons produced by lamalginite contain a significantly higher content of C20 tricyclic terpanes(TT),C21TT,C24 tetracyclic terpanes(TeT),C29 norhopane,and C28 regular sterane.Based on the pyrolysis and biomarker compound parameters,telalginite has a higher conversion rate for hydrocarbons than lamalginite in the low-mature to mature stage,which is consistent with their kinetic analysis.Lamalginite source rock displays a much narrower distribution of activation energies than telalginite source rocks.Such narrower activation energy distribution effectively narrows the main stage of hydrocarbon generation.In addition,the activation energy distribution of lamalginite concentrated in the high-value interval,indicating the characteristics of the relatively lagging hydrocarbon generation of lamalginite.

Identification, evolution and geological indications of solid bitumen in shales: A case study of the first member of Cretaceous Qingshankou Formation in Songliao Basin, NE China

On the basis of sorting out current understanding of solid bitumen (SB) in shales and taking organic-rich shales in the first member of the Cretaceous Qingshankou Formation in the Songliao Basin as an example, the definition, classification, occurrence and evolution path of SB are systemtically studied, and the indicative significance of SB reflectance (Rob) on maturity and its influence on the development of reservoir space are discussed and summarized. The results show that the difference of primary maceral types is primarily responsible for the different evolution paths of SB. Most of the pre-oil bitumen is in-situ SB with only a small amount being of migrated SB, while most of the post-oil bitumen and pyrobitumen are migrated SB. From the immature to early oil maturity stage, bituminite, vitrinite, and inertinite can be distinguished from SB based on their optical characteristics under reflected light, and alginite can be differentiated from SB by their fluorescence characteristics. Under scanning electron microscope, in-situ SB and migrated SB can be effectively identified. Rob increases linearly with increasing vitrinite reflectance (Ro), as a result of a decrease of aliphatic structure and the enhancement of aromatization of SB. Within the oil window three types of secondary pores may develop in SB, including modified mineral pores, devolatilization cracks and bubble holes. At a high maturity stage spongy pores may develop in pyrobitumen. Scanning electron microscopy combined with in-situ SEM-Raman spectroscopy can further reveal the structral information of different types of SB, thus providing crucial data for understanding for understanding OM migration paths, dynamics, and distances at micro-scale.

Spontaneous combustion liability of coal and coal-shale: a review of prediction methods

This study presents a review of the various methods to predict the spontaneous combustion liability of coal and coal-shale. The relative propensity of coal to undergo self-heating can be established by different methods. These methods are well established in their usage, but the fact that no particular test method has become a standard to predict the spontaneous combustion liability indicates that doubt still exists as to the validity of all of them. The underlying principle of all the tests is that the more readily the coal undergoes exothermic oxidation, the more liable it is to self-heat. Comprehensive studies that centres on the international position on research being conducted by academics, different research institutes and industries on spontaneous combustion of coal and coal mine fires were evaluated. Relationships between the geochemical analysis (proximate and ultimate analysis, forms of sulphur, petrographic properties, X-ray diffraction and X-ray fluorescence) and spontaneous combustion testing methods (numerical and experimental approaches) used to predict the spontaneous combustion liability of coal were reviewed. The combination of these tests provides a better understanding of the mechanism that controls the spontaneous combustion phenomena. However, irrespective of the extensive studies that have been conducted over time, spontaneous combustion is still a major problem in the coal value chain.

Coal petrology characteristics of middlings from Qianjiaying fat coal mine

The objective of this paper is to evaluate the coal petrology characteristics of slack middlings(13–0.5 mm)of dense media separation and flotation middlings from Qianjiaying fat coal preparation plant.Phase composition,macerals distribution,microlithotype and mineral occurrence of the two middlings were studied by XRD analysis and polarized light microscopy observation.Macerals distribution and wettability of the float-and-sink products separated from the middlings after grinding was investigated to determine the liberation degree.Studies show that there are more vitrinite and mineral,but less inertinite in slack middlings than in flotation middlings.Macerals associated with mineral in slack middlings is 69.85%,by volume,which is 17.86%higher than that in flotation middlings.Minerals in slack middlings are dominated by pyrite and clay,which are disseminated with the diameter less than2 lm.The main mineral in flotation middlings is clay with size range of 2–20 lm.Single macerals in the slack middlings are diffcult to liberate due to the fne-grained minerals.After grinding,macerals associated with minerals in the slack middlings decrease to 46.73%,by volume,which is higher than in flotation middlings by 25.89%,by volume.For slack middlings with poor liberation degree,density fractions below1.8 g/cm3is hydrophobic with contact angle above 71.5°.For the well liberated flotation middlings,there is signifcant wettability difference among the float-and-sink products.This research is the theoretical basis to realize re-separation of middlings.

Petrology and organic geochemistry of the Baishaping and Damaidi Devonian cutinitic liptobioliths,west of the Kangdian Uplift,China

Devonian cutinitic liptobiolith is a special type of coal formed during the early evolutionary stage of land plants.The Baishaping and Damaidi Devonian coals are notable for their distinct papery,sheet-like texture,and unusually high cutinite content(>50%),belonging to typical cutinitic liptobiolith.They are bituminous coals and have a suppressed vitrinite reflectance.Compared with typical typeⅢkerogen,these liptobioliths are characterized by extremely high yields of volatile matter and high hydrogen contents owing to their enhanced cutinite contents.As indicated by pyrolysis and elemental analysis results,the Devonian cutinitic liptobioliths are dominated by typeⅠ-Ⅱkerogens and have an excellent potential to generate liquid hydrocarbons.The Baishaping cutinitic liptobioliths are mainly composed of ribbon-like thick-walled cutinites,with small amounts of thin-walled type.Vitrinite is only present in trace amounts and is dominated by telinite.Meanwhile,the Damaidi Devonian coals are primarily composed of ribbon-like thin-walled cutinites,followed by collotelinites which are usually sandwiched by cutinites.The different petrological characteristics of the Baishaping and Damaidi liptobioliths might indicate a structural variation in the coal-forming plant cuticles and two distinct coal-forming conditions.The molecular bio markers in the Devonian coals are mainly composed of C_(18)-C_(20)tetracyclic diterpenoids,which are assumed to be the dominant soluble constituent of the Devonian land-plant cuticles and might have played an important role in early land plant radiation.Other molecules include aromatic tetracyclic diterpenoids,3-5 ring polycyclic aromatic hydrocarbons and their methylated counterparts,and C_(16)-and C_(18)-monocarboxylic acids.n-Alkanes are present only in small amounts.The molecular composition of the cutinite-rich coals is unexpected,because cuticular waxes are one of the most important sources of n-alkanes.In general,the petrology and geochemistry of the Devonian cutinitic liptobiolith indicate a distinct structure and composition for the early land-plant cuticles,which is significantly different from that of the plant cuticles since Carboniferous.Devonian cutinitic liptobioliths are of great interest because of their unique petrography,geochemistry,coal-forming plants,and oil-prone potential.Studies on this unique coal type provide a better understanding of coal-forming plants,paleoenvironment,paleoclimate,and early land-plant evolution in the Devonian.

Investigation on the Microstructure Features of Bump-Prone Coal

A series of experiments,using X-ray diffraction, electronic microscope investigation and SEM observation,are carried out to investigate the microstructure characteristics of bump-prone coal. The samples are from four coal seams in two different coal mines,which compose of No.7,No.9 and No.12 coal seams in Zhaogezhuang mine and No.11 seam in Xinzhouyao mine.The microstructure parameters of coal are adopted to calculate the bump liability of

Current Situation and Application in Coal-Generated Hydrocarbons

The characteristics and research methods of terrigenous organic hydrocarbon-generated source rock in coal measures are studied in this thesis. After abundance of organic matters, pyrolysis parameter of rocks and hydrocarbon generated capacity of macerals are basically discussed in coal measures of the Cretaceous Muleng-Chengzihe formation in Suibin depression in Sanjang basin, the hydrocarbon generated grade in coal-genera^ted source rock is ascertained in this depression. At last, we think that it is a main attack prospect in coal-genera^ted hydrocarbons study in the future to research the macerals of coal measures organic source rock and to build a criterion to classify the coal-generated hydrocarbons in Northeast region.

Geochemistry and Organic Petrography of Jordanian Sultani Oil Shale

The Sultani oil shale (OS) deposit is considered as a major fossil fuel source in Jordan. Applying various petrographic and geochemical techniques, this paper aims to study the Sultani OS geochemical and organic petrographic features. Results show that Sultani OS is a bituminous limestone consisting of very fine-grained matrix with rippled micro-laminated texture and muddy material of cryptocrystalline micrite. The rock is rich in Cretaceous microfossil shells filled in organic matter (OM). The fillingOMis bitumen of the migrabitumen type. TheOMcontent reaches up to 17 wt.% with high oil-yielding capacity (up to 12 wt.%). High TOC values suggest that the Sultani OS has a very good source rock potential. Organic petrography shows lowOMmaturity level and reveals two varieties of vitrinite, namely primary and oxidized vitrinite. The latter is derived from terrestrial plant tissues. Additionally, liptinite macerals including alginite and to a lesser extent cutinite, also participate. Various diagenetic features such as pyrite replacement and bitumen thermal alteration have been recorded. Results suggest that Sultani OS is a marinite formed under marine conditions with limited contribution of terrestrialOMinput.

Research on the maceral characteristics of Shenhua coal and efficient and directional direct coal liquefaction technology

In this research,molecular structure models were developed respectively for Shenhua coal vitrinite concentrates(SDV)and inertinite concentrates(SDI),on the basis of information on constitutional unit of Shenhau coal and elemental analysis results obtained from^(13)C-NMR analysis characterization,FTIR analysis characterization,X-ray diffraction XRD and XPS analysis characterization.It can be observed from characterization data and molecular structure models that the structure of SDV and SDI is dominated by aromatic hydrocarbon,with aromaticity of SDI higher than that of SDV;SDV mainly consists of small molecule basic structure unit,while SDI is largely made from macromolecular structure unit.Based on bond-level parameters of the molecular model,the research found through the autoclave experiment that vitrinite liquefaction process goes under thermodynamics control and inertinite liquefaction process under dynamics control.The research developed an efficient directional direct coal liquefaction technology based on the maceral characteristics of Shenhua coal,which can effectively improve oil yield and lower gas yield.

Petrographic characteristics and depositional environment of No.6 coal from Xiaoyugou Mine,Jungar Coalfield,China

This paper discussed the petrographic characteristics of No.6 coal from the Xiaoyugou mine,Jungar Coalfield,Ordos Basin,China.10 samples(7 coal,1 parting mudstone and 2 floor mudstone)were analysed by microscopical and geochemical methods.Four maceral compositions and several associated elements parameters were selected as indicators and corresponding diagrams were drawn to explicate the sedimentary environment.The results indicate that the maceral is dominated by vitrinite and minerals are mainly kaolinite in the No.6 coal.The sedimentary facies vary from barrier island system to tidal-flat which is a deposition process of water body shallowing and the coal-forming plants are herbs and woody plants formed in swamps.

Paleo-fires and Atmospheric Oxygen Levels in the Latest Permian:Evidence from Maceral Compositions of Coals in Eastern Yunnan,Southern China

Inertinite maceral compositions of the Late Permian coals from three sections in the terrestrial and paralic settings of eastern Yunnan are analyzed in order to reveal the paleo-fire events and the atmospheric oxygen levels in the latest Permian. Although the macerals in the studied sections are generally dominated by vitrinite, the inertinite group makes up a considerable proportion. Its content increases upward from the beginning of the Late Permian to the coal seam near the Permian- Triassic boundary. Based on the microscopic features and the prevailing theory that inertinite is largely a by-product of paleo-fires, we suggest that the increasing upward trend of the inertinite abundance in the latest Permian could imply that the Late Permian peatland had suffered from frequent wildfires. Since ignition and burning depend on sufficient oxygen, a model-based calculation suggests that the 02 levels near the Wuchiapingian/Changhsingian boundary and the Permian-Triassic boundary are 27% and 28% respectively. This output adds supports to other discoveries made in the temporal marine and terrestrial sediments, and challenges the theories advocating hypoxia as a mechanism for the PermianTriassic boundary crisis.