Montmorillonite, kaolinite, illite, and chlorite were found to adsorb bitumen and its pentane-soluble and pentane-insoluble fractions. The formation of clay-bitumen complexes is influenced by the nature of the exchangeable cation on the clay and by the solvent carrier which stabilizes the bituminous compounds. Ca-clays adsorb organic compounds more strongly than sodium forms except in the presence of nitrobenzene. Solvents of high dielectric constant, such as nitrobenzene, promote ionization so that the ion-exchange mechanism of adsorption is favored, whereas solvents of lower dielectric constant, such as chloroform, tend to solvate rather than to dissociate bitumens. The behavior of the montmorillonite-bi- tumen complex in variable relative humidity indicates that organic molecules adsorb primarily on external surfaces and cause the clay to become less hydrophilic than prior to treatment. Clay-organic complexes are sufficiently stable to resist powerful organic solvents. The clay-organic complex separated from the Athabasca oil sand behaves similarly during chemical treatment to complexes formed between bitumen and the four reference clay minerals.

The Southern Uplands-Down-Longford Terrane (SUDLT) saw exploration for coal in Ordovician-Silurian marine rocks for several centuries, including well after it was understood that land plant coals would not occur in such rocks. Some lithologies were so carbonaceous that a fuel of sorts was mined. The record of this exploration and mining activity is mostly forgotten, but there are diverse sources to show that it was widespread. Exploration was mostly inspired by outcrops of Moffat Shale, in which deformation and hydrocarbon generation left coal-like products. The hydrocarbon origin conferred high calorific value to the fuel, so it did burn and encouraged exploration. The deposits show that an accretionary prism can be a reservoir of locally abundant carbon.

The increasing exploration and exploitation of hydrocarbon resources hosted by oil and gas shales demands the correct measurement of certain properties of sedimentary rocks rich in organic matter (OM). Two essential properties of OM-rich shales, the total specific surface area (TSSA) and cation exchange capacity (CEC), are primarily controlled by the rock’s clay mineral content (i.e. the type and quantity). This paper presents the limitations of two commonly used methods of measuring bulk-rock TSSA and CEC, ethylene glycol monoethyl ether (EGME) retention and visible light spectrometry of Co(III)-hexamine, in OM-rich rocks. The limitations were investigated using a suite of OM-rich shales and mudstones that vary in origin, age, clay mineral content, and thermal maturity.

Ethylene glycol monoethyl ether reacted strongly with and was retained by natural OM, producing excess TSSA if calculated using commonly applied adsorption coefficients. Although the intensity of the reaction seems to depend on thermal maturity, OM in all the samples analyzed reacted with EGME to an extent that made TSSA values unreliable; therefore, EGME is not recommended for TSSA measurements on samples containing >3% OM.

Some evidence indicated that drying at ⩾200°C may influence bulk-rock CEC values by altering OM in early mature rocks. In light of this evidence, drying at 110°C is recommended as a more suitable pretreatment for CEC measurements in OM-rich shales. When using visible light spectrometry for CEC determination, leachable sample components contributed to the absorbance of the measured wavelength (470 nm), decreasing the calculated bulk rock CEC value. A test of sample-derived excess absorbance with zero-absorbance solutions (i.e. NaCl) and the introduction of corrections to the CEC calculation are recommended.

Tracing interactions during burial-induced organic maturation and associated clay-material alteration is of prime importance for understanding both the individual and combined mineral and organic processes. In the present study the light elements B, Li, O, and H of a sample from oil-prone Eocene Kreyenhagen Shale from San Joaquin Basin (California) were examined. The natural burial-induced temperature increase was simulated by pyrolysis experiments at progressively increasing temperatures (270–365°C) and for varied durations (72–216 h) applied to the whole rock and its <2 μm fraction. The illite structure as well as the K-rich interlayers of the illite-smectite mixed layers were not affected by the pyrolysis experiments and the smectite-rich interlayers did not collapse, while the soluble minerals and the organic matter were altered. The distribution pattern of the rare-earth elements (REEs) from untreated whole rock and of its pyrolyzed equivalents are within analytical uncertainty, which confirms that the changes induced by pyrolysis experiments were minimal in the bulk sample. Conversely, the REEs from the <2 μm fractions were modified significantly, suggesting that the whole rocks and the <2 μm fractions may contain different types of organic materials. Also, only the carbonates, oxides, chlorides, and organic matter were affected together with the smectite-rich interlayers of the illite-smectite structure. Bitumen coating of the smectite interlayers probably increased the amount of B of organic origin in their sites. The δ11B and δ7Li of the successively expelled hydrocarbon phases changed with increasing pyrolysis temperatures, together with the B and Li contents of the hydrocarbon-related fluids. On the basis of the δ11B and δ7Li from pyrolyzed clay fractions, the B released successively was not isotopically homogeneous, probably depending on how the type of organic matter decomposed during the successive pyrolysis steps, and on which components were released. The δ11B of organic-B increased progressively from –2‰ at low experimental temperature up to +9‰ at the highest temperature. The calculated δ7Li that was released also increased relative to the value of the outcropping sample used as a reference, but it remained almost constant from –7‰ at 310°C for 72 h to –8‰ at 365°C for 216 h. The δ18O values of the <2 μm size fractions decreased significantly during pyrolysis above 300°C, but the δD changes were rather modest. The total organic carbon (TOC) remained statistically constant after pyrolysis to 300°C, as did the δ7Li values. The pyrolysis experiments in the present study suggest the presence of bitumen-coated smectite interlayers that could have been misidentified as dehydrated smectite in the literature. Together with abnormal illite K-Ar ages, the occurrence of such bitumen-coated illite-smectite interlayers occurring in source and reservoir rocks could indicate the timing of hydrocarbon maturation relative to illitization.

The Llandovery Folly Sandstone near Presteigne, Powys, contains disseminated thorium mineralization. The thorium occurs as inclusions of thorite and thorianite within sub-millimetre-scale bitumen nodules throughout the sandstone. The nodules grew replacively in situ. The two square kilometres outcrop/subcrop of the sandstone may contain over 500 tonnes thorium.

Several of the Proterozoic natural fission reactors at Oklo, Gabon contain abundant organic matter (bitumen), with which much of the reactor uranium is associated. An understanding of the petrography of the bitumen is important in assessing its role in element retention following fissiogenic reactions. The bitumen is replacive and includes vestiges of detrital grains and clays of the host sandstones. It also contains several generations of mineral phases related to the migration of uranium and daughter lead, and other elements mobilized by hydrothermal activity in the reactor zones. The minerals include (primary) uraninite precipitated after reduction of uranium by organic matter, silicates concentrated in radiation halos around the uraninite, and native lead, galena and further uraninite which migrated from the primary uraninite. The silicates are illitic clays in the immediate vicinity of the reactors, and chloritic more distant from the reactors. Authigenic clays in radiation halos are compositionally distinct from earlier host rock clays. Local migration of uranium and lead is evident as dispersion of the elements through the radiation halos; cross-cutting veinlets of uraninite, native lead and galena, including veinlets extending directly from the primary uraninite crystals; and concentrations of the elements at the margins of bitumen masses. The limit of observed uranium dispersion is within clay immediately beyond the bitumen margins.

Bitumen veins were formerly mined as ‘coal’ from Moinian metamorphic basement at Castle Leod, Strathpeffer, Ross-shire. The abundance and spatial concentration of hydrocarbons implies generation of a large volume of oil that exerted a fluid pressure great enough to open veins to 1+ m width. Biomarker characteristics, including β-carotane and a high proportion of C28 steranes, correlate the bitumen to Lower Devonian non-marine shales separated from the Moinian basement by a major fault. Bitumen in the Moinian basement has higher diasterane/sterane ratios than bitumen in the Devonian sequence, indicating greater levels of biodegradation, which may reflect more interaction with water in the basement. Replacive bitumen nodules in the Moinian basement, containing thoriferous/uraniferous mineral phases, are comparable with bitumen nodules in basement terrains elsewhere. Formation of the nodules represents hydrocarbon penetration of low-permeability basement, consistent with high fluid pressure. Bitumen veins are particularly orientated E–W, and may be associated with E–W transfer faults attributed to Permo-Carboniferous basin inversion.

Bitumen samples and soil samples around a bituminous deposit in Ondo State, Nigeria, wereanalysed for 40K, 226Ra and 232Th employing gamma-rayspectrometry. The activity concentrations of 40K, 226Ra and232Th in soil varied from (45.2 ± 5.3) to (484.2 ± 25.9), BDL (belowdetectable limit) to (27.7 ± 2.1) and (22.8 ± 2.7) to (62.4 ± 6.8) Bq.kg-1,respectively. The corresponding mean values were (240.2 ± 133.5), (13.3 ± 8.0) and (40.0 ±10.2) Bq.kg-1, respectively. The mean activity concentrations of theradionuclides in the bitumen were (58.4 ± 36.4), (16.1 ± 13.3) and (32.5 ± 13.1)Bq.kg-1, respectively, for 40K, 226Ra and232Th. The mean absorbed dose and effective dose for the soil samples were(41.5 ± 8.9) nGy.h-1 and (50.7 ± 10.9) μSv.y-1, respectively, whilethose of the bitumen samples were (29.5 ± 15.6) nGy.h-1 and (36.1 ± 19.1)μSv.y-1, respectively. For radiological hazard assessment, the radiumequivalent activity and the external hazard index were determined. The values of theradium equivalent activity and external hazard index obtained for the soil and bitumensamples were lower than the recommended limit.

The authors identify natural bitumen on stone implements dating to 70 000 BP. It is proposed that this represents residue from hafting, taking the practice back a further 30 000 years from the date previously noted and published in Nature. The bitumen was tracked to a source 40km away, using gas chromatography-mass spectrometry and carbon isotopes.