Graphitization of organic matter and fluid‐deposited graphite in Palaeoproterozoic (Birimian) black shales of the Kaya‐Goren greenstone belt (Burkina Faso,West Africa)

Palaeoproterozoic black shales form an essential part of the Birimian volcanosedimentary belt in Burkina Faso, West Africa. The mean R_max values and the atomic H/C values of the bulk carbonaceous matter (BCM), together with rock structures and mineral assemblages, indicate that these carbon‐rich rocks were metamorphosed to sub‐greenschist and low‐grade greenschist facies. X‐ray diffraction reveals that the (002) ‘graphite’ peak width in half maximum (FWHM) ranges from 0.43 to 0.71 °2θ in sub‐greenschist facies and from 0.27 to 0.41 °2θ in greenschist facies rocks, but the d(002) values in both groups of rocks are approximately the same (～3.35 Å). The BCM of individual samples is composed of particles with very variable shape, reflectance and Raman spectra. Type I particles that predominate in sub‐greenschist facies are fine‐grained, irregular or elongate bodies 1 to 3 μm in size. Their maximum reflectance (R_max) ranges between 2.5% and 8.2%, and Raman parameters R1 and R2 range from 0.5 to 1.4 and 0.5 to 0.8, respectively. Type II particles are lath‐shaped, up to 40 μm large bodies, commonly arranged parallel to white mica flakes. The number of these particles increases from sub‐greenschist to greenschist facies. Maximum reflectance varies between 6% and 11.2% and R1 and R2 Raman parameters range from 0.05 to 0.7 and from 0.1 to 0.5, respectively. Type III particles occur in hydrothermally altered and sheared rocks; these are nodular aggregates composed of grains up to 10 μm in size. This type of particles has very high reflectance (R_max = 11–15%) and its Raman spectra indicate a very high degree of structural ordering corresponding to well‐ordered graphite. Type I particles represent original organic matter in the metasediments. Type II particles are believed to have been formed either in situ by solid‐state transformation of Type I particles or by crystallization from metamorphic fluids. Gradual graphitization of the Type I organic particles and the growth of lath‐shaped Type II particles from a fluid phase is assumed to have taken place under the peak metamorphic conditions associated with the burial of Birimian sediments during thrust tectonism, progressive tectonic accretion and crustal thickening during the D1 event of the Eburnean orogeny. The growth of equant, high‐reflectance postkinematic nodular aggregates of Type III particles is ascribed to the reduction of CO₂‐rich fluids during a hydrothermal event associated with Late Eburnean D2 exhumation and strike–slip movements. Type I carbonaceous particles were only slightly affected by high‐temperature, low‐pressure contact metamorphism during intrusion of Late Eburnean magmatic bodies, whereas formation of Type II or III particles was not recorded in contact‐metamorphosed rocks at all.     

一种页岩含气性热演化规律研究的模拟实验方法

目前针对页岩气赋存规律研究的热模拟实验主要是沿袭常规油气热模拟方法,以粉末态样品开展模拟,研究对象为岩石生成并排出的烃类气体,这种模拟方式未明确页岩气的实质为"滞留气",并且模拟后样品无法开展扫描电镜分析,不能确定岩石孔隙结构变化规律。本文通过石英玻璃管封装块状样开展页岩生烃热模拟实验,并结合一套数据处理方法,尝试建立了一种适合页岩气研究的热模拟实验方法,研究泥页岩在不同演化阶段(Ro范围为0.596%~2.143%)不同赋存状态气体的含量以及岩石微观孔隙特征的变化情况。结果表明,泥岩及油页岩样品的排出气及解析气含量在高成熟度阶段(400℃以后)有明显增加的趋势,结合扫描电镜微观结构分析显示这是由于有机质生气量以及无机孔隙均有增加。本方法可以研究页岩热演化过程中不同赋存状态气体含量及微观孔隙结构的变化,为页岩气勘探开发提供了一种可参考的方法。     

Thermal alteration of coal in the Khasyn coalfield, Magadan region, Russia

The Early Cretaceous coal deposits of the Khasyn coalfield are intruded by Palaeogene diabase dikes. The coal has vitrinite reflectance values of 2.0–2.5% R_o, and characteristics of normal anthracite at some distance from the dikes, but at direct contact with the dike two morphological coal varieties occur: coal inclusions in the diabase dike and dispersed carbonaceous matter within the dike rock. Both types of coaly matter have properties typical of anthracites: strong anisotropy, altered internal structure and high vitrinite reflectance values ranging from 3.8 to 5.5% R_o. The X-ray diffraction measurements of the interplanar spacing d(002) and the crystallite sizes Lc and La show rather similar values for coal inclusions in the dike and dispersed carbonaceous matter. The additional reflection at 3.37 Å, corresponding to semi-graphite admixture, occurs in the coal and carbonaceous matter inside the dike and is absent in the natural coal outside the dike.     

Carbonaceous cherts of the Barberton Greenstone Belt, South Africa: Isotopic, chemical and structural characteristics of individual microstructures

Carbonaceous matter occurring in chert deposits of the 3.4-3.2 Ga old Barberton Greenstone Belt (BGB), South Africa, has experienced low grade regional metamorphism and variable degrees of local hydrothermal alteration. Here a detailed study is presented of in situ analysis of carbonaceous particles by LRS (laser Raman spectroscopy) and SIMS (secondary ion mass spectrometry), reporting degree of structural disorder, carbon isotope ratio and nitrogen-to-carbon ratio. This combination of in situ analytical tools is used to interpret the δ¹³C values of only the best preserved carbonaceous remains, enabling the rejection of non-indigenous (unmetamorphosed) material as well as the exclusion of strongly hydrothermally altered carbonaceous particles. Raman spectroscopy confirmed that all carbonaceous cherts studied here have experienced a regional sub- to lower-greenschist facies metamorphic event. Although this identifies these organics as indigenous to the cherts, it is inferred from petrographic observations that hydrothermal alteration has caused small scale migration and re-deposition of organics. This suggest that morphological interpretation of these carbonaceous particles, and in general of putative microfossils or microlaminae in hydrothermally altered early Archean cherts, should be made with caution. A chert in the Hooggenoeg Formation, which is older than and has been hydrothermally altered by a volcanic event 3445 Ma ago, contains strongly altered carbonaceous particles with a uniform N/C-ratio of 0.001 and a range of δ¹³C that is shifted from its original value. Cherts of the Kromberg Formation post-date this volcanic event, and contain carbonaceous particles with a N/C-ratio between 0.002 and 0.006. Both the Buck Reef Chert and the Footbridge Chert of the Kromberg Formation have retained fairly well-preserved δ¹³C values, with ranges from −34‰ to −24‰ and −40‰ to −32 ‰, respectively. Abiologic reactions associated with hydrothermal serpentinization of ultramafic crust (such as Fischer-Tropsch synthesis) were an unlikely source for carbonaceous material in these cherts. The carbonaceous matter in these cherts has all the characteristics of metamorphosed biologic material.     

SPORE-POLLEN COMPLEXES OF UPPER DEVONIAN OF THE RUSSIAN PLATFORM

Carbonaceous units commonly host or are closely related to lode-gold mineralization in the mesothermal Fazenda Maria Preta (FMP) and Fazenda Canto (FC) deposits of the Paleoproterozoic Rio Itapicuru greenstone belt of northeastern Brazil. In these deposits, the carbonaceous matter occurs mainly as: (1) straight to anastomosing seams (Type I) along or transecting the rock fabric, or as stylolitic structures in quartz veins; (2) single grains composed of an agglomerate of highly anisotropic subgrains (Type II); or (3) single grains with a homogeneous internal texture (Type III), which are either enclosed in Type-I carbonaceous seams or disseminated in the rock matrix. Type-I carbonaceous matter commonly hosts or is overgrown by the gold-related sulfide paragenesis, particularly arsenopyrite, whereas both Type I and Type II enclose crystals of arsenopyrite or occur as inclusions and in sharp contact with the sulfide phases.

The three morphological types of carbonaceous matter exhibit similar Raman spectral characteristics, with distinct D and O peaks at wave numbers between 1351 cm^?1 and 1357 cm^?1, and 1585 cm^?1 and 1598 cm^?1, respectively. In contrast to the FMP deposit, the carbonaceous matter of the FC deposit shows D peaks of higher intensities than the O peaks. The O peaks are accompanied by an additional disorder-induced band on the high wave number side (≈ 1622 cm^?1), and the O/D peak intensity ratios are higher and the half-height O-peak widths smaller. These spectral parameters indicate that the carbonaceous matter in both deposits corresponds to some form of microcrystalline disordered graphitic material and defines a graphitization trend from the FMP to the FC deposit.

The carbonaceous matter of the FMP deposit is isotopically lighter (δ¹³C = ?23.3‰ to ?30.8‰; x = ?27.4 ± 1.8‰ relative to PDB) than the carbonaceous material of the FC (δ¹³C = ?18.5‰ to ?21.0‰, x = ?19.7 ± 0.9‰). These δ¹³C values, together with the geologic evidence, point toward a primarily biogenic organic origin for the carbonaceous matter. The marked differences in the Raman spectral parameters and the δ₁₃C values are interpreted as resulting from different degrees of thermal maturation of carbonaceous matter attained during the regional greenschist metamorphism and granite intrusions of the Rio Itapicuru greenstone belt.

The δ¹³C compositions of CO₂ resulting from the oxidation or hydrolysis of the carbonaceous matter, calculated by applying the equilibrium CO₂-graphite fractionation, fall within the range ?9.7‰ to ?18.8‰ at 360 to 420°C (FMP deposit) and ?6.0° to ?10.0° at 390 to 455°C (FC deposit). These calculated δ¹³C values are lower than those obtained from primary fluid-inclusion CO₂ in gold-bearing veins (?6.0° to ?10.2° for the FMP deposit; ?2.8° to ?4.9° for the FC deposit) and imply that the thermal maturation process of the carbonaceous matter contributed little to changes in the chemistry and isotopic composition of the ore fluid. The presence of the carbonaceous matter may have been an important factor in gold deposition during fluid-carbon interaction, acting: (1) as a chemical trap, by reducing the f(O₂) of the ore fluids or enhancing fluid immiscibility by adding small quantities of CH₄ and N₂ to the fluid phase; and/or (2) as a physical barrier, by adsorbing gold on its surface as activated carbon.     

Evaluating the thermal metamorphism of CM chondrites by using the pyrolytic behavior of carbonaceous macromolecular matter

The degrees of thermal metamorphism of 10 CM chondrites and of the Allende CV3 chondrite were evaluated from the viewpoint of “graphitization” of the carbonaceous macromolecular matter by means of flash pyrolysis-gas chromatography (GC). The unheated chondrites, Yamato- (Y-) 791198, Murray and Cold Bokkeveld, yielded larger amounts and wider varieties of pyrolyzates than the chondrites strongly heated in the parent asteroids, Y-82054, Y-86695, and Belgica- (B-) 7904, and Asuka- (A-) 881334 (more strongly heated than Y-793321, which has been weakly heated, but lesser than the other strongly heated meteorites). The weakly heated chondrites, Y-793321 and A-881458, showed intermediate features. The data indicate that graphitization of the carbonaceous matter is most extreme in the strongly heated chondrites and that during graphitization, the matter has lost its labile portion, which can generate pyrolyzates such as naphthalene. In order to establish a new method for the evaluation of the degree of graphitization of chondritic carbonaceous matter, a diagram was developed to show the relationship between the total amounts of pyrolyzates with retention times later than 5 min (=S_RT>5) and the ratio of the amount of naphthalene, a pyrolysis product, to S_RT>5 (=S_N/S_RT>5). The diagram indicates a possible evolutionary pathway of graphitization of the carbonaceous matter in carbonaceous chondrites.     

Organic geochemistry and petrology of barren and Mo–Ni–PGE mineralized marine black shales of the Lower Cambrian Niutitang Formation (South China)

Marine black shales of the Lower Cambrian Niutitang Formation in southern China host Mo–Ni–platinum group elements (PGE) mineralization confined to a phosphate- and pyrite-rich stratiform body (max. 20-cm thick). The H/C atomic ratio, carbon isotopic composition, FTIR spectra of bulk organic matter, and spectra of extractable part of organic matter indicate similar sources and thermal evolution of organic matter in barren and mineralized black shales.The morphology and relative abundance of organic particles in barren and mineralized shales are different. In barren black shales, organic particles comprise only elongated bodies and laminae 2–10 μm across or elongated larger bodies (> 10 μm) with R_max = 2.96–5.21% (Type I particles). Mineralized black shales contain Type I particles in rock matrix (90–95 vol%), small veinlets or irregular organic accumulations (Type II particles, 1–5 vol%) that display weak to well developed mosaic texture and a variable reflectance (R_max = 3.55–8.65%), and small (< 1 to 5 μm) rounded or irregular Type III organic particles (1–4 vol%) distributed within phosphate nodules and sulphide rip-up clasts. Type III particles show similar reflectance as particles of Type I in rock matrix. Type I particles are interpreted as remnants of in situ bacterially reworked organic matter of cyanobacteria/algal type, Type II as solidified products or oil-derived material (migrabitumen), and Type III particles as remnants of original organic matter in phosphatized or sulphidized algal/microbial oncolite-like bodies. Equivalent vitrinite reflectances of Type I and III particles in barren and mineralized rocks are similar and correspond to semi-anthracite and anthracite. Micro-Raman spectra of organic particles in rocks display a wide belt in the area of 1600 cm^− 1 (G belt) and approximately the same belt in the area of 1350 cm^− 1 (D belt). The ratio of integrated areas of the two belts correlate with R_max values.The Mo–Ni–PGE mineralized body is interpreted as to represent a remnant of phosphate- and sulphide-rich subaquatic hardground supplied with organic material derived from plankton and benthic communities as well as with algal/microbial oncolite-like bodies that originated in wave-agitated, shallow-water, nearshore environment.     

Nitrogen and argon isotopic signatures in graphite from the 3.8-Ga-old Isua Supracrustal Belt, Southern West Greenland

The problems involved with the interpretation of carbon isotopes as indicators for early life in highly metamorphosed early Archean rocks have prompted the search for additional chemical and isotopic biomarkers. Here we report an attempt to identify the origin of carbonaceous matter in the 3.8 Ga old Isua Supracrustal Belt in southern West Greenland by measuring the concentration and isotopic composition of a trapped nitrogen component. Stepped-combustion/pyrolysis-mass spectrometry of carbonaceous matter in several rock samples revealed three different reservoirs of trapped nitrogen: (1) nitrogen associated with a very small amount of reactive carbonaceous material, (2) nitrogen intercalated in graphite, correlated with intercalated radiogenic argon, (3) nitrogen strongly retained at defects or chemically bound in the graphite structure. The δ¹⁵N of nitrogen associated with reactive carbonaceous matter (ca. +6‰) overlaps with that of average Phanerozoic sedimentary organic matter, and is believed to be part of nonindigenous postmetamorphic biologic material. In situ Raman spectroscopy confirmed the high degree of crystallinity of the metamorphosed indigenous carbonaceous material, and this material is further referred to as graphite. Graphite interpreted as epigenetic (associated with Mg,Mn-siderite in metacarbonates) contains a very small strongly retained nitrogen component with a low δ¹⁵N ratio (−3 to −1‰). This range overlaps with values that are typically found in Archean kerogens, but also those of a metamorphically emplaced inorganic basaltic source. Geological constraints suggest that this graphite incorporated nitrogen from surrounding metabasaltic rocks. Graphite interpreted as syngenetic and biogenic found in a turbidite deposit is relatively similar to this Mg,Mn-siderite-derived graphite, based on degree of graphite crystallinity, amount of trapped radiogenic argon, low nitrogen concentration and δ¹⁵N signature. We conclude that nitrogen concentration and its isotope ratio in graphite cannot be used conclusively as a biomarker in these rocks from the highly metamorphosed Isua Supracrustal Belt.     

Graphitization of carbonaceous matter during metamorphism with references to carbonate and pelitic rocks of contact and regional metamorphisms,Japan

This study is an attempt to correlate the graphitization process of carbonaceous matter during metamorphism with metamorphic grade. Graphitization can be parameterized using crystal structure and chemical and isotopic compositions. The extent of graphitization could be characterized mainly by temperature, duration of metamorphism and rock composition. We compared the graphitization trends for two metamorphic terrains, a contact aureole of the Kasuga area and a regional metamorphic terrain of high-temperature/low pressure type of the Ryoke metamorphic terrain in Northern Kiso area, Central Japan, and for two different lithologies (carbonate and pelite), using X-ray diffractogram, DTA-TG analysis, and chemical and stable isotope analyses. During contact metamorphism, graphitization and carbon isotopic exchange reactions proceeded simultaneously in pelitic and carbonate rocks. The decreases in basal spacing d(002) of the carbonaceous matter in carbonate rocks is greatly accelerated at temperatures higher than about 400° C. Furthermore, carbon isotopic ratios of graphite in carbonate rocks also change to ¹³C-enriched values implying exchange with carbonates. The beginning of this enrichment of ¹³C in the carbonaceous matter coincides with an abrupt increase of the graphitization processes. Carbon isotopic shifting up to 5 in pelites could be observed as metamorphic temperature increased probably by about 400° C. Carbonaceous matter in pelitic rocks is sometimes a mixture of poorly crystallized organic matter and well-crystallized graphite detritus. DTA-TG analysis is an effective tool for the distinction of detrital graphitic material. Two sources for the original carbon isotopic composition of carbonaceous matter in pelites in the Kasuga contact aureole can be distinguished, about-28 and-24 regardless of the presence of detrital graphite, and were mainly controlled by depositional environment of the sediments. Graphitization in limestones and pelitic rocks in regional metamorphism proceeds further than in a contact aureole. In the low-temperature range, the differences in extent of graphitization between the two metamorphic regions is large. However, at temperatures higher than 600° C, the extent of graphitization in both regions is indistinguishable. The degree of graphitization is different in limestones and pelitic rocks from the Ryoke metamorphic terrain. We demonstrate that the graphitization involves a progressive re-construction process of the crystal structure. The sequence of the first appearance of crystal inter planar spacing correlates with the metamorphic grade and indicates the crystal growth of three-dimensional structured graphite.     

Thermal maturity and organic composition of Pennsylvanian coals and carbonaceous shales, north-central Texas: Implications for coalbed gas potential

Thermal maturity was determined for about 120 core, cuttings, and outcrop samples to investigate the potential for coalbed gas resources in Pennsylvanian strata of north-central Texas. Shallow (< 600 m; 2000 ft) coal and carbonaceous shale cuttings samples from the Middle-Upper Pennsylvanian Strawn, Canyon, and Cisco Groups in Archer and Young Counties on the Eastern Shelf of the Midland basin (northwest and downdip from the outcrop) yielded mean random vitrinite reflectance (R_o) values between about 0.4 and 0.8%. This range of R_o values indicates rank from subbituminous C to high volatile A bituminous in the shallow subsurface, which may be sufficient for early thermogenic gas generation. Near-surface (< 100 m; 300 ft) core and outcrop samples of coal from areas of historical underground coal mining in the region yielded similar R_o values of 0.5 to 0.8%. Carbonaceous shale core samples of Lower Pennsylvanian strata (lower Atoka Group) from two deeper wells (samples from ~ 1650 m; 5400 ft) in Jack and western Wise Counties in the western part of the Fort Worth basin yielded higher R_o values of about 1.0%. Pyrolysis and petrographic data for the lower Atoka samples indicate mixed Type II/Type III organic matter, suggesting generated hydrocarbons may be both gas- and oil-prone. In all other samples, organic material is dominated by Type III organic matter (vitrinite), indicating that generated hydrocarbons should be gas-prone. Individual coal beds are thin at outcrop (< 1 m; 3.3 ft), laterally discontinuous, and moderately high in ash yield and sulfur content. A possible analog for coalbed gas potential in the Pennsylvanian section of north-central Texas occurs on the northeast Oklahoma shelf and in the Cherokee basin of southeastern Kansas, where contemporaneous gas-producing coal beds are similar in thickness, quality, and rank.     

Contrasting degrees of recrystallization of carbonaceous material in the Nelson aureole,British Columbia and Ballachulish aureole,Scotland, with implications for thermometry based on Raman spectroscopy of carbonaceous material

The degree of recrystallization of carbonaceous material (CM), as monitored by Raman microspectroscopy, was examined as a function of metamorphic grade in two well‐studied contact aureoles containing carbonaceous pelites: the Nelson aureole, British Columbia and the Ballachulish aureole, Scotland. Here, we use (a) the R2 ratio extracted from the Raman spectrum of CM as a proxy for the degree of graphitization (0.0 in perfect graphite then increasing with structural defects) and (b) the second‐order S1 band (~2,700 cm^?1) as a marker for the tridimensional ordering of CM. The Nelson aureole (garnet–staurolite–andalusite–sillimanite–K‐feldspar sequence, ~550–650°C, 3.5–4.0 kbar) was developed in rocks that were unmetamorphosed prior to contact metamorphism, whereas the Ballachulish aureole (cordierite–andalusite–K‐feldspar–sillimanite sequence, ~550–700°C, ~3.0 kbar) was developed in rocks that had been metamorphosed to garnet grade conditions (~7 kbar, ~500°C) c. 45 Ma before contact metamorphism. Thirty‐one samples were examined from Nelson and 29 samples from Ballachulish. At Nelson, the R2 ratio steadily decreases from ~0.25 to 0.0 as the igneous contact is approached, whereas at Ballachulish, the R2 ratio remains largely unchanged from regional values (~0.20–0.25) until less than 100 m from the igneous contact. The second‐order S1 band reveals that carbonaceous material (CM) was transformed to highly “ordered” locally tridimensional graphitic carbon at Ballachulish by regional metamorphism prior to contact metamorphism, whereas CM was still a disordered turbostratic (bidimensional) material before contact metamorphism in the case of Nelson. Pretexturation of CM likely induced sluggish recrystallization of CM and delayed graphitization in the Ballachulish aureole. Temperatures of recrystallization of the CM in the two aureoles were estimated using different published calibrations of the thermometry based on Raman Spectroscopy of Carbonaceous Material (RSCM), with differences among the calibrations being minor. In the Nelson aureole, temperatures are in reasonable agreement with those indicated by the metapelitic phase equilibria (all within 50°C, most within 25°C). In the Ballachulish aureole, the retarded crystallization noted above results in increasing underestimates of temperatures compared to the metapelitic phase equilibria (up to ~75°C too low within 200 m of the igneous contact). Our study calls for careful attention when using RSCM thermometry in complexly polymetamorphosed rocks to assess properly the meaning of the calculated temperature.     

Depositional environment,hydrocarbon generation and expulsion potential of the middle Permian Pingdiquan source rocks based on geochemical analyses in the eastern Junggar Basin,NW China

As the most important source rocks in the eastern Junggar Basin, the middle Permian Pingdiquan (P₂p) source rocks have attracted increasing attention after the discovery of tight oil in the Shazhang uplift. The P₂p source rocks are widely distributed (up to 7546 km²) and have an elevated thickness in the eastern Junggar Basin. To explore the P₂p tight oil resource in the eastern Junggar Basin, 113 core samples from 34 exploration wells were analysed geochemically and re-examined for their organic matter abundance, type and thermal maturity, hydrocarbon potential and sedimentary environment. Geochemical analysis results indicate that the P₂p source rocks are fair to good source rocks dominated by Type II kerogen, presently in a low mature–mature stage, and biomarkers and trace elements indicate deposition in a terrestrial to coastal environment under oxic to dysoxic, and fresh to brackish conditions, with possible intermittent seawater influence, implying proximity to the open sea. Based on hydrocarbon expulsion modelling, hydrocarbon expulsion began at 0.87% R_o, and the peak expulsion occurred at 1.1% R_o. Hydrocarbon generation intensities in the Shazhang uplift and the Wucaiwan sag are relatively large, with values centred at 4–6.5 million t/km² and 4–6 million t/km², respectively, with total hydrocarbon generation and expulsion from the P₂p source rocks approximately 4.56 × 10⁹ t and 1.44 × 10⁹ t, respectively, indicating significant tight oil exploration potential in the eastern Junggar Basin. The Shazhang uplift and the Wucaiwan sag are two hydrocarbon expulsion centres in the study area with the largest hydrocarbon expulsion intensity centred around the Shazhang uplift, exceeding 3 × 10⁶ t/km². We suggest that the area with high hydrocarbon expulsion intensities is a favourable target for tight oil accumulation and exploration.     

The petrology and origin of coals from the lower Carboniferous Mattson formation, southwestern district of Mackenzie, Canada

Petrographic analyses were carried out on thin coals and coaly sediments from the Lower Carboniferous Mattson Formation at Clausen Creek and Jackfish Gap-Yohin Ridge in the northern part of the Liard Basin, northern Canada. The composition and optical characteristics indicate that the coals are high-volatile bituminous B, predominantly sapropelic (canneloid) and accumulated subaquatically.The coals are dominantly composed of inertinite-rich and exinite-rich durities with subsidiary inertites and clarodurites; vitrite is minor and liptite is rare. The inertinite-rich microlithotypes are dominated by semifusinite, but micrinite, semimacrinite and ?resino-inertinites are abundant. Sporinite, comprising megaspores, crassispores, tenuispores and miospores, is the dominant liptinite maceral with subsidiary cutinite and minor alginite. Except for pyrite, mineral matter is minimal.Three populations of telocollinite are observed: a low-reflectance variety (I), commonly associated with micrinite (as vitrinertite), displays weak brown fluorescence and a reflectance some 0.4-0.5% lower than type II; type II is non-fluorescing telocollinite, with intermediate reflectance (0.67-0.74% R_om), it occurs as vitrite and is also associated with micrinite; and a higher-reflectance telocollinite (III), having no fluorescence or association with micrinite, has variable reflectance (0.74-0.8% R_om) implying higher oxidation or gelification levels.The abundance of semimacrinite, macrinite and ?resino-inertinites in inertites and durites (I) suggests that much of the peat accumulated subaquatically. Furthermore, fluorescing vitrinite and an abundance of micrinite (derived by oxidation or coalification of bituminite), suggest that the coal accumulated under anaerobic conditions. The predominance of semifusinite in humic laminae and micrinite in sapropelic layers suggests extensive surface or near-surface oxidation of the peat. Oxidised sporinites suggest that they were wind-borne.Depositional environment is interpreted as marginal marine, perhaps in shallow lakes in the middle to upper delta plain. Peat accumulations probably began subaquatically at the oxygen-hydrogen sulphide interface, but periodic subaerial exposure and natural oxidation gave rise to the high inertinite coals. Upper Mattson coals are interbedded with algal laminites and probably accumulated in a lagoonal setting.     

Natural gas potential of Neoproterozoic and lower Palaeozoic marine shales in the Upper Yangtze Platform,South China: geological and organic geochemical characterization

In this article, we describe the geological features of the Ediacaran (upper Sinian), lower Cambrian and lower Silurian shale intervals in the Upper Yangtze Platform, South China, and report on the gas potential of 53 samples from these major marine shale formations. Reflected light microscopy, total organic carbon (TOC) measurement, Rock-Eval, carbon isotope ratio analysis, thermovaporization gas chromatography (Tvap-GC), and open pyrolysis gas chromatography (open py-GC) were used to characterize the organic matter. Measured TOC in this research is normally >2% and averages 5%. TOC contents are roughly positively correlated with increasing geological age, i.e. lower Silurian shales exhibit generally lower TOC contents than lower Cambrian shales, which in turn commonly have lower TOC contents than Ediacaran shales. Kerogen has evolved to the metagenesis stage, which was demonstrated by the abundant pyrobitumen on microphotographs, the high calculated vitrinite reflectance (R_o = 3%) via bitumen reflectance (R_b), as well as δ¹³ C of gas (methane) inclusions. Pyrolysates from Tvap-GC and open py-GC are quantitatively low and only light hydrocarbons were detected. The lower Silurian shale generally exhibits higher generation of hydrocarbon than the lower Cambrian and Ediacaran shale. Cooles’ method and Claypool’s equations were used to reconstruct the original TOC and Rock-Eval parameters of these overmature samples. Excellent original hydrocarbon generation was revealed in that the original TOC (TOC_o) is between 5% and 23%, and original S1+S2 (S1_o+S2_o) is ranging from 29 to 215 mg HC/g rock.     

Correlation between optical, chemical and micro-structural parameters of high-rank coals and graphite

In order to identify the parameters that best characterize the chemical and structural evolution of organic matter during coalification, the relationships between optical, chemical and micro-structural parameters in high-rank coals and natural graphite were studied. The samples include anthracites from Peñarroya–Belmez–Espiel Basin (Spain), Douro Basin (Portugal), and Alto Chicama Basin (Peru); and natural graphite from Canada, Mozambique, and Austria.Correlations between the following optical parameters were assessed: vitrinite random reflectance (R_r), Reflectance Indicating Surfaces (RIS) axis (R_MAX, R_INT and R_MIN), and RIS parameters (R_am, R_ev and R_st), as well as B_w and AI anisotropy parameters. Furthermore, the chemical parameters used were chosen according to their significant variation in coals, namely volatile matter, carbon, and hydrogen contents calculated in dry ash free basis (VM_daf, C_daf, H_daf), as well as the H/C atomic ratio. Structural organization was characterized by micro-Raman spectroscopy and XRD. Raman parameters used were the full width at half maximum (FWHM) and position of G and D1 bands on the first-order Raman spectrum, and the ID1/IG intensity area ratio. The selected XRD parameters were interlayer spacing d₀₀₂, and crystallite sizes L_a and L_c.Results show that: (i) R_MAX RIS axis seems to correlate best with chemical and micro-structural parameters; (ii) for the majority of studied samples, H_daf and H/C atomic ratio are the only chemical parameters with significant correlations with R_MAX; (iii) the FWHM of the G band of Raman spectrum shows good linear correlation with the XRD parameter d₀₀₂; and, (iv) structural organization of carbon materials, as measured by trends in their optical and crystalline parameters, is influenced by their hydrogen content (daf basis) and therefore by the H/C atomic ratio.     

Physical and chemical environments of abnormal vitrinite reflectance evolution in the sedimentary basins

Based on the tested data of pressure and vitrinite reflectance of some wells in sedimentary basins, abnormal high pressure is regarded as not the only factor to retard the increase of vitrinite reflectance (R _o). Apart from the types of the organic matter, the physical environment (temperature and pressure) and chemical environment (fluid composition and inorganic elements) will result in the abnormal vitrinite reflectance values in the sedimentary basins. This paper tested trace elements and vitrinite reflectance data from the the abnormal high pressure and normal pressure strata profiles, respectively, and found that the acidic and lower salinity starta are favorable for the increase of R _o. By discussing the corresponding relationship between the contents of some trace elements in the mudstone and the vitrinite reflectance values, the typical trace elements were found to suppress and/or catalyze the vitrinite reflectance of organic matter, while the elements of Ca, Mn, Sr, B, Ba and P may result in the retardation of R _o. However, elements of Fe, Co, Zn, Ni and Rb may catalyze the organic matter maturation. This study is conductive to the organic maturation correction, oil and gas assessment and thermal history reconstruction by the paleothermometry. Translated from Acta Geologica Sinica, 2006, 80(11): 1760–1769 [译自: 地质学报]     

Optical parameters of maturity of organic matter dispersed in sediments: first results from the Central Apennines (Italy)

Levels of organic maturity of Mesozoic and Tertiary sequences outcropping in the Central Apennines have been established, using vitrinite reflectance techniques, the Thermal Alteration Index and fluorescence colours of organic matter dispersed in sediments. These results provide new constraints throughout the Meso-Cenozoic evolution of this crustal sector. In exploration geology, vitrinite reflectance provides data on hydrocarbon maturation by constraining organic matter maturity. In sedimentary basin modelling, it is adopted to define the palaeothermal regime. Vitrinite reflectance (R_o) also provides information on the burial history of sedimentary basins and may be employed to estimate tectonic uplift and erosion rates. Thermal Alteration Index (TAI) and fluorescence colour values can be correlated with R_o and may be used to estimate the degree of maturation when vitrinite is absent. Samples derived from the Sabini and Tiburtini Mts, in slope facies between the Latium–Abruzzi carbonate Platform and the Umbria–Marche pelagic Basin; from the Simbruini and Ernici Mts, in carbonate Platform facies, and from upper Miocene turbiditic deposits outcropping between the Olevano–Antrodoco Une, towards the West, and the Marsica slope facies, towards the East. Both the pre-terrigenous Meso-Cenozoic sequences show a low grade of organic maturity: the Sabini and Tiburtini Mts show R_o values that are less than 0.4%, and the Simbruini–Ernici Range show R_o values that range between 0.5% and 0.65%. Field analysis indicates that the cause of these low maturity levels is that thick sequences of turbidites were never deposited during the Neogene evolution of the Apennine thrust belt. Moreover, Upper Miocene turbiditic deposits also show low maturity levels, with R_o values that are less than 0.5%, indicating that these deposits were never overthrusted by huge volumes of rocks, during the chain building. The slight increase in the maturity level recorded in the Marsica area may be related to local heating along shear zones in areas of strike-slip tectonics.     

Maturity studies and source-rock potential in the southern Sverdrup Basin, Arctic Canada

The purpose of the study is to better understand the relationship between organic matter optical properties and the presence of potentially large oil and gas accumulations in Arctic Canada. The type and thermal maturity of the dispersed organic matter of the Mesozoic formations in the southern Sverdrup Basin, Melville Island, have been studied using organic petrology and Rock-Eval pyrolysis.All types of organic matter are present in the strata of Mesozoic age. Hydrogen-rich liptinite is dominated by alginite (Botryococcus and Tasmanites), dinoflagellate cysts and amorphous fluorescing matrix. Sporinite, cutinite, resinite and liptodetrinite made up the lesser hydrogen-rich exinite. Vitrinite reflectance in Cretaceous sediments ranges from 0.36 to 0.65% R_o; in Jurassic sediments it ranges from 0.40 to 1.0% R_o and in the Triassic from 0.45 to 1.30% R_o, showing an overall increase with depth of burial.Cretaceous sediments of the Deer Bay Formation are thermally immature and contain organic matter of terrestrial origin. The Upper Jurassic shales of the Ringnes Formation contain predominantly organic matter of liptinitic and exinitic origin with a considerable vitrinitic input. At optimum maturation levels, potential source beds of this formation would have a good hydrocarbon-generating potential. The hydrocarbon potential, however, would be limited to the generation of gases due to the leanness of the source rocks. Parts of the Lower Jurassic Jameson Bay Formation are organic-rich and contain a mixed exinitic/vitrinitic organic matter, Botryococcus colonial algae but visible organic matter is dominated by high plant remains (mainly spores). The Schei Point Group shales and siltstones contain organic matter of almost purely marine origin, whereas the predominantly higher plant-derived organic matter found in the Deer Bay, Jameson Bay and partly in the Ringnes formations have higher TOC. Among the Schei Point Group samples, the Cape Richards and Eden Bay members of the Hoyle Bay Formation are richer in TOC (>2.0%) than the Murray Harbour Formation (Cape Caledonia Member). This may reflect differences in the level of maturity or in the depositional environment (more anoxic conditions for the former).Regional variations in the level of thermal maturity of Mesozoic sediments in Sverdrup Basin appear to be a function of burial depth. The Mesozoic formations thicken towards the basin centre (NNE direction), reflecting the general pattern of increasing thermal maturity north of Sabine Peninsula. However, the regional thermal-maturation pattern of the Mesozoic is not solely a reflection of the present-day geothermal gradient, which indicates that anomalous zones of high geothermal gradient may have existed in the past, at least since when the Mesozoic sediments attained maximum burial depth. The contour pattern of the regional variation of maturity at the base of numerous Triassic formations is similar to that of the structural contours of the Sverdrup Basin, indicating that present-day maturation levels are largely controlled by basin subsidence.     

Organic matter heterogeneities in 2.72 Ga stromatolites: Alteration versus preservation by sulfur incorporation

The stromatolites of the weakly metamorphosed 2.72 Ga Tumbiana Formation present abundant organic globules that resemble in size, shape and distribution the microorganisms observed in modern stromatolites. In order to evaluate the significance of these cell-like organic materials, we characterized organic matter in-situ down to the nanoscale using a combination of Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), Raman microspectroscopy, scanning transmission X-ray microscopy (STXM) and transmission electron microscopy (TEM).These analyses revealed the occurrence of two distinct types of organic matter forming μm-scale textural and chemical heterogeneities distributed in distinct mineralogical laminae of the stromatolites. Type A organic matter, which is by far the most abundant, consists of sulfur-poor organic matter that is located in mud-type laminae at grain boundaries, mostly in association with silicate minerals. In contrast, Type B organic matter is rare and preserved as inclusions in the core of calcite grains forming laminates. It occurs as micrometer-sized cell-like globules containing variable amounts of organic sulfur likely in the form of thiophenes.Different scenarios may account for these compositional heterogeneities in the kerogen. Based on textural and compositional analogies with modern stromatolites, it is argued that Type B sulfur-rich globules may represent microbial cells protected by mineral encapsulation and selectively preserved through polymerization by early diagenetic sulfurization. In modern sediments, this reaction is fuelled by bacterial sulfate reduction (BSR). This metabolism has been widely considered as a major driver in modern stromatolites calcification and could thus have played an important role in the formation of the Tumbiana Formation stromatolites. In contrast, Type A sulfur-poor organic matter corresponds to either fossil extracellular polymer substances (EPS) or recondensed kerogen. This pool was likely not sulfurized due to either local and/or timely variations in the concentrations of H₂S or adverse pyritization driven by the availability of iron. Our observations thus show the need to use spatially-resolved techniques to complement organic geochemistry analyses and provide a detailed analysis of the organic carbon pools composing Archean stromatolites.     

Petalit,LiAlSi4O10: Verfeinerung der Kristallstruktur,Diskussion der Raumgruppe und Infrarot-Messung

Zusammenfassung Die Kristallstruktur von Petalit, LiAlSi₄O₁₀ (a _o =11,7540(11) Å,b _o =5,1395(5) Å,c _o =7,6296(7) Å, =113,04(1)°;Z=2; RaumgruppeC _2h ⁴ -P2/a wurde an natürlichem Material für 1926 Reflexe aufR=0,031 verfeinert. Li hat tetraedrische Koordination. [Si₄ ^[4]O₁₀]-Schichten sind über [Al^[4]O₄]-Tetraeder zu einem dreidimensionalen Gerüst verknüpft. Signifikante Anhaltspunkte für eine Symmetrieerniedrigung nachC _s ² -Pa wurden nicht gefunden. Messungen des Infrarot-Pleochroismus an orientiert geschliffenen Platten von Petalit zeigen das Vorhandensein von wenigen Zehntel Gewichtsprozent OH und deren Orientierung.

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Petalite, LiAlSi₄O₁₀: Refinement of the crystal structure and discussion of the space group and infrared measurements

Summary The crystal structure of natural petalite, LiAlSi₄O₁₀ (a _o =11.7540(11) Å,b _o =5.1395(5) Å,c _o =7.6296(7) Å, =113.04(1)°;Z=2; space groupC _2h ⁴ -P2/a), was refined using 1926 reflexions toR=0.031. Li has tetrahedral coordination. [Si₄ ^[4]O₁₀] sheets are connected by [Al^[4]O₄] tetrahedra to form a three-dimensional network. Significant evidence for the lower symmetryC _s ² -Pa was not found. The measurements of the infrared pleochroism in oriented petalite crystal plates show evidence of OH groups, in the range of a few tenths of weight percent, as well as their orientation.

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