Up to what temperature is petroleum stable? New insights from a 5200 free radical reactions model

The discovery of crude oils and condensates at ever higher temperatures casts doubt on the validity of the usual geochemical modelling approach, that uses empirical reactions and rate constants. The solution used to account for such a high thermal stability is presently to adjust the rate parameters, but the physical meaning and scientific value of such a strategy can be questioned. We have developed a mechanistic model consisting of 5200 lumped free radical reactions to describe the thermal evolution of a mixture of 52 organic species meant to represent light petroleum. Rate constants used are those available in the literature or estimated using well established thermochemistry-reactivity correlations. Chemical structures included in the model are linear, branched and cyclic hydrocarbons, hydro- and alkyl-aromatics, PAHs, and three heteroatomic compounds. Reactions include cracking and alkylation chains and inhibiting and accelerating reactions from the various reactants. This model has been applied to several mixtures with various proportions of reaction inhibitors and accelerators, and to a composition representing a light mature oil. From the results obtained, we conclude that mature oils will be stable up to 240–260 °C, depending on their composition, and that the thermal cracking of oil to gas is not possible under reasonable basin conditions. The kinetics of petroleum cracking are thus much slower than generally recognized.     

Using DC resistivity tomography to detect and characterize mountain permafrost

Direct-current (DC) resistivity tomography has been applied to different mountain permafrost regions. Despite problems with the very high resistivities of the frozen material, plausible results were obtained. Inversions with synthetic data revealed that an appropriate choice of regularization constraints was important, and that a joint analysis of several tomograms computed with different constraints was required to judge the reliability of individual features. The theoretical results were verified with three field experiments conducted in the Swiss and the Italian Alps. At the first site, near Zermatt, Switzerland, the location and the approximate lateral and vertical extent of an ice core within a moraine could be delineated. On the Murtel rock glacier, eastern Swiss Alps, a steeply dipping boundary at its frontal part was observed, and extremely high resistivities of several MΩ indicated a high ice content. The base of the rock glacier remained unresolved by the DC resistivity measurements, but it could be constrained with transient EM soundings. On another rock glacier near the Stelvio Pass, eastern Italian Alps, DC resistivity tomography allowed delineation of the rock glacier base, and the only moderately high resistivities within the rock glacier body indicated that the ice content must be lower compared with the Murtel rock glacier.     

Comparative study of the inelastic response of base isolated buildings

This article presents a numeric comparative study of the inelastic structural response of base isolated buildings. The comparative study includes the following isolation systems: laminated rubber bearings, New Zealand one, pure friction and the frictional pendulum ones. The study is based on obtaining non‐linear response spectra for various design parameters using six earthquake records. Usually the base isolation of a new building seeks to maintain the structure in the linear elastic range. The response of old weak buildings or the response of new ones subjected to extreme earthquakes may not be, necessarily, in the aforementioned ideal elastic range. Consequently, it is important to characterize the response of isolated buildings responding inelastically. A conclusion from this research is that the isolators affect significantly the structural response of weak systems. Rubber isolators seem slightly less sensitive to plastification that may occur in the structure compared to friction isolators. Ductility demands in the structure are affected significantly by friction and neoprene protected systems, in particular sliding ones where larger demands are obtained. Copyright © 2002 John Wiley & Sons, Ltd.     

Comparative studies of the kinetic parameters of various algaenans and kerogens via open-system pyrolyses

Kinetic parameters were determined for the first time, via open-system pyrolyses, on algaenans (highly resistant biomacromolecules that are selectively preserved during kerogen formation) isolated from extant microalgae. Parallel studies were also carried out on 10 kerogens exhibiting, with one exception, a low level of maturity. These kerogens included samples chiefly derived from the selective preservation of the above algaenans and samples mainly, or almost exclusively, derived from the “natural vulcanization” pathway. Important differences in activation energy (E_a) distributions were observed between the four algaenans investigated and correlated with their chemical structures. The kerogens predominantly derived from algaenan-selective preservation (Pula alginite, NE 70 and BJ 248 Torbanites, Rundle Oil Shale) also exhibited pronounced differences in E_a distributions. These distributions provided: (i) information on the diversity of the source materials; and (ii) reflected the occurrence of important differences in chemical structures and thermal behaviour between three of the tested kerogens, even though they are all classified as low maturity type I. The Kimmeridge Clay samples and the Lorca Oil Shale showed broad E_a distributions shifted to low energies when compared with the above algaenans and kerogens. Such shifts reflect an important (or even almost exclusive for some of these kerogens) contribution of materials originating from sulphur incorporation into various lipids during early diagenesis. Finally, the kinetic data derived for the nine low maturity fossil samples were extrapolated to a very low, geological heating rate of 3°C Ma⁻¹ and the generation rate curves and cumulative yield curves thus obtained were compared.     

Harmonic Analysis of Sedimentary Cyclic Sequences in Kansas, Midcontinent, USA

Several stratigraphic sequences in the Upper Carboniferous (Pennsylvanian) in Kansas (Midcontinent, USA) were analyzed quantitatively for periodic repetitions. The sequences were coded by lithologic type into strings of datasets. The strings then were analyzed by an adaptation of a one-dimensional Fourier transform analysis and examined for evidence of periodicity. The method was tested using different states in coding to determine the robustness of the method and data. The most persistent response is in multiples of 8–10 ft (2.5–3.0 m) and probably is dependent on the depositional thickness of the original lithologic units. Other cyclicities occurred in multiples of the basic frequency of 8–10 with persistent ones at 22 and 30 feet (6.5–9.0 m) and large ones at 80 and 160 feet (25–50 m). These levels of thickness relate well to the basic cyclothem and megacyclothem as measured on outcrop. We propose that this approach is a suitable one for analyzing cyclic events in the stratigraphic record.     

A vibrational spectroscopic study of the oxidation of pyrite by molecular oxygen

In situ flow-through attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy has been used to investigate the formation, and step-wise oxidation, of sulfoxyanions at the pyrite surface during oxidation by molecular oxygen. The surface was studied under two different pH regimes (pH 2.5 and pH 5.6) and under two light conditions (dark and ultraviolet light). It was experimentally observed that multiple sulfoxyanions were present at the pyrite surface during oxidation by molecular oxygen, spectroscopically illustrating the concept of sulfur step-wise oxidation. The results from photochemical experiments were complex and suggest a dependence on both pH and surface speciation.     

Le Viséen supérieur d'Azarhare (Maroc central) : environnements de dépôt,datation et évolution diagénétique

The unexplored area of Azarhare in central Morocco is studied thanks to three sections composed of five lithological facies Main biostratigraphical and sedimentological results concern (1) the identification of Late Visean biozones, with important presence of problematic algae Ungdarella, (2) the regional extension of deposit sequences SD5, SD6 and SD7 previously defined, (3) and an analysis of the diagenetic kaolinite. To cite this article: A. Karim et al., C. R. Geoscience 337 (2005).