Petrologic and geochemical characteristics of “barkinite” from the Dahe mine, Guizhou Province, China

Although “barkinite” has long been studied by many geologists, its geochemical characteristics and environment of deposition are still not known in detail. In order to study the petrography and geochemical characteristics of “barkinite”, coal samples from two Permian coal seams were taken from the Dahe mine, Guizhou Province. The samples were separated into maceral fractions, and then analyzed by microscopical, isotopic, Rock-Eval, and geochemical methods. The microscopical results indicate that “barkinite” occurs as four main types. According to their relationship to other maceral groups, “barkinite” is ostensibly formed under variably dry–wet or oxidizing–reducing conditions. The extract yield, isotope data and Rock-Eval values of “barkinite” are different from other macerals. Microscopical and geochemical results indicate that “barkinite” forms part of the liptinite group.     

A study of the kinetic parameters of individual macerals from Upper Permian coals in South China via open-system pyrolysis

A unique Upper Permian coal, Leping coal, is widely distributed in South China. The coal samples studied in the paper were collected from two mines in the Shuicheng coalfield of Guizhou Province, southwest China. The geochemical works including coal petrography, maceral content, Rock–Eval pyrolysis, and kinetic modelling of hydrocarbon-generating have been carried out on whole coal and individual macerals. The higher contents of volatile matter, elemental hydrogen, and tar yield, and the high hydrocarbon generation potential of the Leping coals are attributed to their high content of “barkinite”, a special liptinite maceral.The hydrocarbon generation potential of “barkinite” (S₂=287 mg/g, hydrogen index (HI)=491 mg/g TOC) is greater than that of vitrinite (S₂=180 mg/g, HI=249 mg/g TOC), and much higher than that of fusinite (S₂=24 mg/g, HI=35 mg/g TOC). At the same experimental conditions, “barkinite” has a higher threshold and a narrower “oil window” than those of vitrinite and fusinite, and consequently, can generate more hydrocarbons in higher coalification temperature and shorter geological duration. Data from the activation energy distributions indicate that “barkinite” has a more homogenous chemical structure than that of vitrinite and fusinite. The above-mentioned characteristics are extremely important for exploring hydrocarbon derived from the Leping coals in South China.     

Geological and laboratory evidence for early generation of large amounts of liquid hydrocarbons from suberinite and subereous components

Suberinite, and subereous components of amorphous nature, comprise largely unrecognized, proficient sources of liquid hydrocarbons. Due to difficulties in recognizing the presence of subereous components and suberinite in organic sediments, the contributions of these liptinitic components to the organic input of source rocks are easily underestimated. Severe chemical alterations of suberinite in the vitrinite reflectance range of R_o = 0.35–0.60% are demonstrated. Organic geochemical data, obtained from samples subjected to natural maturation, reveal that subereous components/suberinite undergoes early thermal degradation to generate large amounts of hydrocarbons below R_o = 0.60%. Data obtained from laboratory maturation of immature, suberinite-rich coals indicate that about 50% of the potential of suberinite for generating C₁₂₊ hydrocarbons has already been exhausted during natural maturation of the samples, prior to the onset of the traditionally defined “oil window”. The present data (a) contradict the assumption that suberinite is mainly sourced by selective preservation/enrichment of a stable, highly aliphatic biopolymer, i.e. “suberan” and (b) suggest that suberinite contains appreciable amounts of aliphatic and aromatic moieties which are released at low thermal stress.     

Striking liptinitic bark remains peculiar to some Late Permian Chinese coals

An unusual liptinite coal component has been reported in the Chinese literature over the past sixty years. It has been described as a maceral in the Chinese National Standard (1991), but it has not been named internationally. In Chinese literature it is called “barkinite”, on the basis of its morphological features and because it is believed to have originated as bark tissue.“Barkinite” occurs in Late Permian, marine-influenced coals and is best represented in the Changguang, Leping and Shuicheng Basins of southern China.The material originates from plant periderm or the bark of higher plants. However, “bark” contains a variety of substances, including resin and suberin, which are recognised as the precursors of the resinite and suberinite macerals. “Barkinite” is distinguished by (i) its thickness; individual pieces can be more than ten cells thick and several centimetres long and (ii) it fluoresces strongly at 0.6% vitrinite reflectance and loses its fluorescence at about 1.1% vitrinite reflectance.The reporting of “barkinite” from only Chinese coals may be due to its origin from Lepidodendron and Psaronius flora, which was common in the Northern Hemisphere during the Carboniferous, but which was isolated to China by the Late Permian. It is proposed that the remnant flora evolved into unique forms in China by the Late Permian. Lepidodendron and Psaronius remains, coupled with a strongly marine-influenced, peat-forming environment have given rise to “barkinite” and to its restricted distribution.     

Solid bitumen reflectance and Rock-Eval Tmax as maturation indices: an example from the “Nordegg Member”, Western Canada Sedimentary Basin

Marine, organic-rich rock units commonly contain little for vitrinite reflectance (VR₀) measurement, the most commoly used method of assessing thermal maturity. This is true of the Lower Jurassic “Nordegg Member”, a type I/II, sulphur-rich source rock from the Western Canada Sedimentary Basin. This study examines the advantages and pitfalls associated with the use of Rock-Eval T_max and solid bitumen reflectance (BR₀) to determined maturity in the “Nordegg”. Vitrinite reflectance data from Cretaceous coals and known coalification gradients in the study area are used to extrapolate VR₀ values for the “Nordegg”.T_max increases non-linearly with respect to both BR₀ and extrapolated VR₀ values. A sharp increase in the reflectaance of both solid bitumen and vitrinite occurs between T_max 440–450°C, and is coincident with a pronounced decrease in Hydrogen Index values and the loss of solid bitumen and telalginite fluorescence over the same narrow T_max interval. This T_max range is interpreted as the main zone of hydrocarbon generation in the “Nordegg”, and corresponds to extrapolated VR₀ values of 0.55–0.85%. The moderate to high sulphur contents in the kerogen played a significant role in determining the boundaries of the “Nordegg” oil window.A linear relationship between BR₀ and extrapolated VR₀, as proposed elsewhere, is not true for the “Nordegg”. BR₀ increases with respect to extrapolated VR₀ according to Jacob's (1985) formula (VR₀=0.618×(BR₀)+0.40) up to VR₀≈0.72% (BR₀≈0.52%). Beyond this point, BR₀ increases sharply relative to extrapolated VR₀, according to the relatioship VR₀ = 0.277 × (BR₀) + 0.57 (R² = 0.91). The break in the BR₀−VR₀ curve at 0.72%VR₀ is thought to signifiy the peak of hydrocarbon generation and represents a previously unrecognized coalification jump in the solid bitumen analogous to the first coalification jump of liptinites.     

Evidence for cyclic reactions between andalusite, “sericite” and sillimanite, mount franks area, willyama complex N.S.W

In the Mt. Franks area of the Willyama Complex, microfabric evidence suggests that the alteration of andalusite to sillimanite has taken place by a process similar to that suggested by Carmichael (1969). Andalusite is pre- to syn-S₂ in age. Alteration to “sericite” has resulted in the formation of “sericite” laths, some of which are crenulated about S₂, and some which are syn- and post-S₂. “Fibrolite” occurs in these andalusite—“sericite” aggregates within the sillimanite zone and is wholly embedded in “sericite”. “Fibrolite” is pre- to syn-S₂ in age. This evidence is interpreted as suggesting that the formation of sillimanite from andalusite took place via a “sericite” phase.Further microfabric observations are interpreted to imply constant volume for the reaction aluminosilicate → “sericite”. This suggests a situation in which Al³⁺ is relatively mobile but Al⁴⁺ is relatively immobile. This suggestion differs from Carmichael's (1969) idea of Al³⁺ immobility.     

Analysis of unresolved complex mixtures of hydrocarbons extracted from Late Archean sediments by comprehensive two-dimensional gas chromatography (GC×GC)

Hydrocarbon mixtures too complex to resolve by traditional capillary gas chromatography display gas chromatograms with dramatically rising baselines or “humps” of coeluting compounds that are termed unresolved complex mixtures (UCMs). Because the constituents of UCMs are not ordinarily identified, a large amount of geochemical information is never explored. Gas chromatograms of saturated/unsaturated hydrocarbons extracted from Late Archean argillites and greywackes of the southern Abitibi Province of Ontario, Canada contain UCMs with different appearances or “topologies” relating to the intensity and retention time of the compounds comprising the UCMs. These topologies appear to have some level of stratigraphic organization, such that samples collected at any stratigraphic formation collectively are dominated by UCMs that either elute early- (within a window of C₁₅–C₂₀ n-alkanes), early- to mid- (C₁₅–C₃₀ n-alkanes), or have a broad UCM that extends through the entire retention time of the sample (from C₁₅–C₄₂ n-alkanes). Comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC–MS) was used to resolve the constituents forming these various UCMs. Early- to mid-eluting UCMs are dominated by configurational isomers of alkyl-substituted and non-substituted polycyclic compounds that contain up to six rings. Late eluting UCMs are composed of C₃₆–C₄₀ mono-, bi-, and tricyclic archaeal isoprenoid diastereomers. Broad UCMs spanning the retention time of compound elution contain nearly the same compounds observed in the early-, mid-, and late-retention time UCMs. Although the origin of the polycyclic compounds is unclear, the variations in the UCM topology appear to depend on the concentration of initial compound classes that have the potential to become isomerized. Isomerization of these constituents may have resulted from hydrothermal alteration of organic matter.     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

The role of “excess” CO2 in the formation of trona deposits

The prevailing theory for the formation of trona [Na₃(CO₃)(HCO₃) · 2(H₂O)] relies on evaporative concentration of water produced by silicate hydrolysis of volcanic rock or volcaniclastic sediments. Given the abundance of closed drainage basins dominated by volcanics, it is puzzling that there are so few trona deposits and present-day lakes that would yield dominantly Na–CO₃ minerals upon evaporation. Groundwater in the San Bernardino Basin (southeastern Arizona, USA and northeastern Sonora, Mexico) would yield mainly Na–CO₃ minerals upon evaporation, but waters in the surrounding basins would not. Analysis of the chemical evolution of this groundwater shows that the critical difference from the surrounding basins is not lithology, but the injection of magmatic CO₂. Many major deposits of trona and Na–CO₃-type lakes appear to have had “excess” CO₂ input, either from magmatic sources or from the decay of organic matter. It is proposed that, along with the presence of volcanics, addition of “excess” CO₂ is an important pre-condition for the formation of trona deposits.     

Geochemistry of hydroxy acids in sediments—I. Some freshwater and brackish water lakes in Japan

Series of α, β, ω and (ω-1) hydroxy fatty acids (FAOHs) were determined in several freshwater and brackish water lacustrine sediments in Japan. Analytical procedure used was digestion of the solvent-extracted sediment with HF/HCl followed by solvent and saponification extraction of the residue. Abundances of α/β and ω-FAOH determined by this procedure were 2–3 times higher than those obtained by single alkaline saponification and of the same order with those provided by HCl hydrolysis. Major portion of α/β-FAOH was obtained by solvent extraction of the acid-treated sediments, while subsequent alkaline saponification was needed for the majority of ω-FAOH to be recovered. Thus determined FAOHs comprised 33–61% (Av. = 42%) of the “bound” acid constituents in the lacustrine surface sediments. The α/β and ω-FAOH composition was principally the same among the samples examined, except for relative proportions of the iso to anteiso C₁₅ and C₁₇ ß(α)-FAOH, which showed significant variations in the ranges of 0.30–1.1 and 0.46–1.5, respectively. In the holomictic lakes, the ratios together with the same ratios of the “bound” branched monocarboxylic acids tended to decrease with increasing water depth of the lakes, suggesting that the ratios may indicate an extent of the early diagenetic alteration of the bacteria-derived lipids either in water column or in surface sediment.     

Predicted CO2 emissions from maceral concentrates of high volatile bituminous Kentucky and Illinois coals

A large collection of well-characterized coals, documented in the Center for Applied Energy Research's (CAER) database, was used to estimate the CO₂ content of maceral concentrates from Kentucky and Illinois high volatile bituminous coals. The data showed no correlation between CO₂ versus coal ranks and between CO₂ versus maceral content. Subsequently, eight sets of low-ash density-gradient centrifugation (DGC) maceral concentrates from five coal beds were examined, spanning in the high volatile rank range. Heating value was not determined on the concentrates, but instead was calculated using the Mott–Spooner formula. There was a good correlation between predicted CO₂ and maceral content for the individual iso-rank (based on vitrinite reflectance, analyzed on whole (parent) coal) sets. In general, the predicted CO₂ increases from liptinite-rich through vitrinite-rich to inertinite-rich concentrates (note: no “concentrates” are absolutely monomaceral).     

The average molecular weight and shape of the “polymeric acids” found in Black Trona Water from the Green River Basin

Macromolecular organic material, called “polymeric acids”, has been isolated from Black Trona Water by exhaustive dialysis and characterized as the sodium salt in 0.10 M sodium carbonate, pH 10, by several physico-chemical methods. Analysis by gel filtration chromatography on Sepharose-CL 6B indicates that the “polymeric acids” are polydisperse and composed of species of relatively high molecular weight ( 4 × 10⁵, using proteins as standards). With this method, the range of molecular weights appears to be rather narrow. If “polymeric acids” are transferred from sodium carbonate, pH 10, into distilled water, selfassociation occurs and all species elute in the void volume. The weight-average molecular weight determined in 0.10 M sodium carbonate, pH 10, by the light scattering method is 1.7 × 10⁵. Sedimentation velocity analysis at 20°C with the analytical ultracentrifuge gives a value for S_20,w of 5.4 and the shape of the Schlieren patterns suggest a polydisperse sample with a relatively narrow range of sizes. Analysis of the molecular weight distribution by a sedimentation equilibrium method indicates that the range of molecular weights is 8 × 10⁴ to 2.1 × 10⁵. The partial specific volume ( ) of “polymeric acids” is 0.874 ml/g. Viscosity measurements yield a value for [η] of 2.5 ml/g, which indicates that the “polymeric acids” are compact (spherical or ellipsoidal) in shape.     

Algal bloom episodes and the formation of bituminite and micrinite in hydrocarbon source rocks: evidence from the Devonian and Mississippian, northern Williston Basin, Canada

Organic petrology (incident light microscopy) of Middle Devonian inter-reef laminates and Devonian-Mississippian epicontinental black shales, Williston Basin, Canada, indicates that algal bloom episodes and consequential bacterial activity played a significant role in the accumulation of amorphous, bituminite III-rich organic microfacies. Corpohuminite-like algal akinete cells produced by filamentous algae during algal bloom periods are persistent maceral inclusions within the potential hydrocarbon source rock intervals. These cells (%R_{o mean} range 0.24-0.90) are regarded as positive indicators of stressful palaeoenvironmental conditions. Unicellular Tasmanites and Leiosphaeridia marine alginite and variably degraded alginite remnants (“ghosts”) within the amorphous kerogen may be products of cell lysis, photo-oxidation and microbial alteration; these processes are characteristic of algal bloom periods. Minute (ca. 1 μm) spheroidal and coccoidal bacteria-like macerals are dispersed throughout the bituminite III network, attesting to the importance of microbial activity within the water column and sediment during and after organic matter accumulation. Dispersed granules, laminations and replacement textures of micrinite-like macerals within bituminite III are interpreted as remnants of microbial alteration rather than a residual product of thermal maturation and hydrocarbon generation.     

Continental rifting as a function of lithosphere mantle strength

The role of the uppermost mantle strength in the pattern of lithosphere rifting is investigated using a thermo-mechanical finite-element code. In the lithosphere, the mantle/crust strength ratio (S_M/S_C) that decreases with increasing Moho temperature T_M allows two strength regimes to be defined: mantle dominated (S_M > S_C) and crust dominated (S_M < S_C). The transition between the two regimes corresponds to the disappearance of a high strength uppermost mantle for T_M > 700 °C. 2D numerical simulations for different values of S_M/S_C show how the uppermost mantle strength controls the style of continental rifting. A high strength mantle leads to strain localisation at lithosphere scale, with two main patterns of narrow rifting: “coupled crust–mantle” at the lowest T_M values and “deep crustal décollement” for increasing T_M values, typical of some continental rifts and non-volcanic passive margins. The absence of a high strength mantle leads to distributed deformations and wide rifting in the upper crust. These numerical results are compared and discussed in relation with series of classical rift examples.     

Characterization of nC7-soluble fractions of the products from mild oxidation of asphaltenes

A significant quantity of hydrocarbons (including alkanes) is occluded in the skeleton of the asphaltene molecule. The hydrocarbons are probably remnants of the “original oil” which had been retained within the asphaltene matrix and protected from the secondary alteration processes that occurred subsequently in the oil reservoirs. In this work we report that oxidation of asphaltenes by stirring with 30%H₂O₂–HAc or NaIO₄–NaH₂PO₄ can release nC₇-soluble oxidized products, including the occluded hydrocarbons. Characterization of the nC₇-soluble fractions of oxidized products can be applied to highlight some geochemical problems, such as in studies of oil–oil correlation, oil–source correlation and secondary alterations of oil reservoirs. It will be especially useful to recover the original geochemical information of some oil reservoirs heavily degraded by post-depositional processes.     

Recognising biodegradation in gas/oil accumulations through the δC compositions of gas components

A large suite of natural gases (93) from the North West Shelf and Gippsland and Otway Basins in Australia have been characterised chemically and isotopically resulting in the elucidation of two types of gases. About 26% of these gases have anomalous stable carbon isotope compositions in the C₁–C₄ hydrocarbons and CO₂ components, and are interpreted to have a secondary biogenic history. The characteristics include unusually large isotopic separations between successive n-alkane homologues (up to +29‰ PDB) and isotopically heavy CO₂ (up to +19.5‰ PDB). Irrespective of geographic location, these anomalous gases are from the shallower accumulations (600–1700 m) where temperatures are lower than 75°C. The secondary biogenic gases are readily distinguishable from thermogenic gases (74% of this sample suite), which should assist in the appraisal of hydrocarbons during exploration where hydrocarbon accumulations are under 2000 m. While dissolution effects may have contributed to the high ¹³C enrichment of the CO₂ component in the secondary biogenic gases, the primary signature of this CO₂ is attributed to biochemical fractionation associated with anaerobic degradation and methanogenesis. Correlation between biodegraded oils and biodegraded “dry” gas supports the concept that gas is formed from the bacterial destruction of oil, resulting in “secondary biogenic gas”. Furthermore, the prominence of methanogenic CO₂ in these types of accumulations along with some isotopically-depleted methane provides evidence that the processes of methanogenesis and oil biodegradation are linked. It is further proposed that biodegradation of oil proceeds via a complex anaerobic coupling that is integral to and supports methanogenesis.     

A risky business: Mining, rent and the neoliberalization of “risk”

Natural resource investment in the mining sector is often mediated through conflicts over rent distribution between corporate capital and landowner states. Recent rounds of neoliberal policy promoted by the World Bank have highlighted the need for landowner states to offer incentives in order to attract “high risk” capital investment. In Sub-Saharan Africa, in particular, countries have been pushed to offer attractive fiscal terms to capital, thereby lowering the proportion traditionally called rent. This paper examines how the concept of “risk” has been mobilized to legitimate such skewed distributional arrangements. While certain conceptions of social and ecological “risk” have been prevalent in political and social theoretic discourse on mining, such focus elides the overwhelming contemporary power of our notion of “neoliberal risk” – or the financial/market risks – in actually setting the distributional terms of mineral investment. We illustrate our argument by examining the nexus of World Bank mining policy promotion and Tanzanian policy in the late 1990s meant to attract foreign direct investment in gold production. In closing, we suggest that just as “risk” is used to legitimate attractive fiscal terms for investment, recent events highlight how skewed distribution of benefits may set into motion risks that corporate capital had not bargained for.     

Environmental control of carbon isotope variations in Pennsylvania black-shale sequences, Midcontinent, U.S.A.

A reversal of the conventional carbon isotope relationship, “terrestrial-lighter-than-marine” organic matter, has been documented for two Pennsylvanian (Desmoinesian) cyclothemic sequence cores from the Midcontinent craton of the central United States. “Deep” water organic-rich phosphatic black shales contain a significant proportion of algal-derived marine organic matter (as indicated by organic petrography, Rock-Eval hydrogen index and ratios) and display the lightest δ¹³C-values (max −27.80‰ for kerogen) while shallower water, more oxic facies (e.g. fossiliferous shales and limestones) contain dominantly terrestrial organic matter and have heavier δ¹³C_kerogen-values (to −22.87‰ for a stratigraphically adjacent coal). δ¹³C-values for extract fractions were relatively homogeneous for the organic-rich black shales with the lightest fraction (often the aromatics) being only 1‰, or less, more negative than the kerogen. Differences between extract fractions and kerogens were much greater for oxic facies and coals (e.g. saturates nearly 5‰ lighter than the kerogen).A proposed depositional model for the black shales calls upon a large influx of nutrients and humic detritus to the marine environment from the laterally adjacent, extremely widespread Pennsylvanian (peat) swamps which were rapidly submerged by transgression of the epicontinental seas. In this setting marine organisms drew upon a CO₂-reservoir which was in a state of disequilibrium with the atmosphere, being affected by isotopically light “recycled-CO₂” derived from the decomposition of peaty material in the water column and possibly from the anoxic diagenesis of organic matter in the sediments.     

Geomagnetic induction anomalies along the hyderabad—kalingapatnam profile

Observations of H- and Z-variations made at ten temporary field stations along the Hyderabad—Bhadrachalam—Kalingapatnam (east coast) profile during February–March, 1973, are analyzed and discussed. The results are also compared with those of the Alibag (west coast)—Hyderabad profile, completed in May–July, 1970.It is found that the Z-ranges of quiet daily variations are enhanced one and a half times the Hyderabad value, and the H-ranges only very slightly reduced at the coastal station of Kalingapatnam. This coastal effect of 6γ in Z_r at Kalingapatnam gradually decreases inland and probably exists upto Salur (70 km inland from the coast). At Bhadrachalam, both H- and Z-ranges of quiet daily variations are found to be enhanced, possibly due to induction effects from deep-seated conductors in the Godavari rift valley. The enhancement of both H and Z daily ranges at Jeypore in the eastern “ghats” (hills) is attributed to induced electric currents in conductors arising from the orogeny well below the “ghats”.It is difficult to separate the coastal effect from the orogenic effect, both of which seem to taper off and merge at Salur.