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.     

Overview of the subsurface structural pattern of the Paris Basin (France): Insights from the reprocessing and interpretation of regional seismic lines

The study presents the methodology used by the French Geological Survey (BRGM) for the building, reprocessing and interpretation of selected regional seismic lines in the Paris intracratonic basin (France): the 14 constructed E-W and N-S regional transects represent a total of 2,516 km length, and are based on the merge of 240 seismic single profiles recorded by petroleum operators between 1971 and 1995. The regional lines have been selected to cross the main oil fields of the Paris Basin, as well as high potential areas for oil exploration. A first difficulty was to recover the raw data necessary to build-up the regional transects. The signal reprocessing, harmonization and merge of the single seismic lines, constituent of the regional transects, are then described; these operations represent the cornerstone of the study. We put the emphasis on the primary static corrections, as the targeted structures are commonly spatially associated with large seismic velocity variations in the upper Cretaceous chalk and Tertiary sedimentary cover.The interpreted regional transects definitely give complementary information to the existing studies, which generally lack seismic (and therefore structural) data: we give an overview of the main structural and geometrical features of the Paris Basin: inversion structures, major unconformities, as well as Permo-Carboniferous basins. We also describe the structural pattern, and show the close relationships between the faults geometry, the faults density, and the geological evolution of the Paris Basin: we distinguish (1) few large-scale polyphase faults, with a Variscan origin, representing the first order structural frame of the Paris Basin; (2) monophase normal faults, with strike-slip features, representing the subsurface prolongation of Cenozoic grabens cropping out in the neighbourhood; (3) deep normal faults, sealed by the base Calcareous Dogger sequence, related to the Permo-Liassic extensional tectonic regime. This large-scale view of the Paris Basin has highlighted several potential exploration targets.     

Decoupling between the middle and upper crust during transpression-related lateral flow: Variscan evolution of the Aston gneiss dome (Pyrenees, France)

We present a structural, AMS, microstructural and kinematic study of the Aston gneiss dome (French Pyrenees), which consists of a core made up of orthogneiss and paragneiss intruded by numerous sills of Carboniferous peraluminous granite. The orthogneiss corresponds to a former Ordovician granitic laccolith. Four Variscan events have been evidenced in this gneiss dome: (i) D1 deformation observed only as relics in the orthogneisses and their country-rocks located above the sillimanite isograd, and characterized by a NS to NE–SW non coaxial stretch associated to top to the south motions (NS convergence); (ii) D2-a deformation observed in the orthogneisses and their country-rocks, mainly migmatitic paragneisses, located below the sillimanite isograd and in the peraluminous granites whatever their structural level, and characterized by an EW to N120°E stretch associated to a top to the east flat shearing (lateral flow in the hot middle crust in a transpressive regime); (iii) D2-b deformation characterized by EW-trending megafolds corresponding to the domes in the middle crust and by EW-trending tight folds with subvertical axial planes in the metasedimentary upper crust; (iv) subvertical medium-temperature mylonitic bands developed by the end of the transpression.The Aston massif is a good example of decoupling between a cold upper crust and a hotter middle crust overheated by a thermal event originated in the upper mantle. This decoupling allowed the lateral flow of the migmatitic middle crust along a direction at high angle with respect to the more or less NS-trending direction of convergence. We suggest that the HT-LP metamorphism developed before the formation of the domes during D2-a, coevally with the emplacement of numerous sills of peraluminous granite, whereas the emplacement of the large calc-alkaline plutons in the upper crust occurred by the end of D2-b. Our data invalidate the previous geodynamical models based on either early or late extensional regime to explain the development of the HT-LP metamorphism. This new interpretation of the dynamics of the Variscan crust of the Pyrenees is consistent with recent studies conducted in Archaean and Palaeoproterozoic hot continental crusts having undergone oblique convergence, and characterized by a competition between vertical thickening and lateral flow induced by the important rheological contrast between two thermally different levels.     

Water release patterns of heated speleothem calcite and hydrogen isotope composition of fluid inclusions

Speleothem fluid inclusions are a potential paleo-precipitation proxy to reconstruct past rainwater isotopic composition (δ¹⁸O, δD). To get a better insight in the extraction of inclusion water from heated speleothem calcite, we monitored the water released from crushed and uncrushed speleothem calcite, heated to 900 °C at a rate of 300 °C/h, with a quadrupole mass spectrometer. Crushed calcite released water in three not well individualised peaks between 25 and 360 °C, 360 and 650 °C and between 650 and 800 °C while uncrushed calcite released water in two distinct temperature intervals: between 25 and 550 °C and between 550 and 900 °C.Water from two speleothems from the Han-sur-Lesse cave was recovered using three different techniques: i) the crushing and heating to 360 °C technique, ii) the decrepitation by heating to 550 °C and iii) the decomposition by heating to 900 °C technique. Measurements of the δD of water recovered by the decomposition of Han-sur-Lesse calcite heated to 900 °C did not show a 20 to 30‰ offset as found by previous authors. However a difference of 7‰ was observed between water released before and after decomposition of the calcite. Water recovery from the Han-sur-Lesse samples suggests that a simple heating technique (up to 550 °C) without crushing could both (a) recover water with δD representative of that of the drip water and (b) double the water yield as compared to the crushing and heating method.Our study warns for possible contamination of the recovered inclusion water with hydration water of lime, responsible for the recovery of water with very negative δD values.     

High‐resolution quantification of earthworm calcite granules from western European loess sequences reveals stadial–interstadial climatic variability during the Last Glacial

High concentrations of calcite fossil granules produced by earthworms (ECG) have been identified in most of the stratigraphical units along the loess‐palaeosol reference sequence of Nussloch (Germany). They are particularly abundant in interstadial brown soils and in tundra gley horizons, the latter reflecting short‐term phases of aggradation then degradation of permafrost. These granules are characterized by a radial crystalline structure produced in the earthworms by specific bio‐mineralization processes. In our study, we used this biological indicator combined with ¹⁴C and OSL dating, and sedimentological parameters to characterize millennial‐time scale climatic variations recorded in loess sequences. The approach is based on high‐resolution counts of ECG throughout a 17‐m‐thick loess sequence (332 samples). Strong increases in granule and mollusc concentrations suggest warmer climate conditions during palaeosol formation phases, associated with increasing biodiversity, biological activity and vegetation cover. Decreased granule concentrations occur within primary loess deposits, indicating a strong correlation with palaeoenvironmental conditions and demonstrating the reliability of ECG concentration variations as a new palaeoenvironmental proxy. Finally, this pattern is also recorded in loess sequences located about 600 km westward in northern France demonstrating the large‐scale validity of this new palaeoclimatic proxy.     

Taxonomic revision of Cylindroporella ? lusitanica Ramalho, 1970: In search for the origins of the Family Dasycladaceae

A study of new material of Cylindroporella ? lusitanica Ramalho, 1970, from the Upper Jurassic (Oxfordian) strata of Portugal identified features not observed previously. This includes the pattern of its laterals, including the gametophores. The algal body plan is unique and justifies the taxonomic reassessment of this species and the introduction of Barattoloporellopsis n. gen. Furthermore this species is most likely a primitive Dasycladaceae, a “missing link” between the modern ones (starting from the Cretaceous times) and their Jurassic ancestors.     

Sediment fingerprinting in fluvial systems： review of tracers,sediment sources and mixing models

Suspended sediments in fluvial systems originate from a myriad of diffuse and point sources, with the relative contribution from each source varying over time and space. The process of sediment fingerprinting focuses on developing methods that enable discrete sediment sources to be identified from a composite sample of suspended material. This review identifies existing methodological steps for sediment fingerprinting including fluvial and source sampling, and critically compares biogeochemical and physical tracers used in fingerprinting studies. Implications of applying different mixing models to the same source data are explored using data from 41 catchments across Europe, Africa, Australia, Asia, and North and South America. The application of seven commonly used mixing models to two case studies from the US （North Fork Broad River watershed） and France （Bldone watershed） with local and global （genetic algorithm） optimization methods identified all outputs remained in the acceptable range of error defined by the original authors. We propose future sediment fingerprinting studies use models that combine the best explanatory parameters provided by the modified Collins （using correction factors） and Hughes （relying on iterations involving all data, and not only their mean values） models with optimization using genetic algorithms to best predict the relative contribution of sediment sources to fluvial systems.     

A helping hand: artificial nest site provisioning increases breeding success of a tropical seabird

Common white terns Gygis alba lay a single egg balanced on rocks or branches and consequently are at risk of low nesting success. A novel technique of hollowing out coconut husks and providing artificial nest sites was developed on Cousine Island, Seychelles. Our study aimed to critically assess whether common white tern nesting success differed between artificial and natural nest sites. For natural nest sites, nesting success and the stage of nest failure were also compared between seasons, nest heights, and tree species. Finally, we compared results from our study to those of a study conducted 10 years ago on the same island. Nesting success differed significantly between artificial nests and natural nests, with the success of artificial nests nearly double that of natural nests. Hatching success was similar for artificial and natural nests (65% and 52% respectively), suggesting coconut husks do not reduce egg losses, but rather provide secure perches for young chicks. Most natural nest failures occurred during the egg phase (70%), followed by the youngest chick phase (21%). Of the eggs that hatched in natural nests, 61% fledged successfully. Tree species and season significantly influenced nesting success for natural nests and nest height varied significantly between tree species. Higher nesting success was observed during the mixed seasonal period (50%) followed by the cooler, windier and drier South-East Monsoon season (33%). The hotter and more humid North-West Monsoon period had the lowest nesting success (20%). Comparisons of nesting success at natural and artificial nest sites with the earlier study did not differ significantly, despite a smaller population of common white terns being present on the island at that stage. Our results support the use of artificial nest sites to improve nesting success for this species and serve as a model for similar species currently under threat.     

Sumixam maximus gen. and sp. nov., a New Pennsylvanian Species of Archaeorthoptera (Neoptera; Indiana, USA)

A new Mazon-Creek-type fossil specimen is described as Sumixam maximus gen. and sp. nov., assigned to the taxon Archaeorthoptera Béthoux and Nel, 2002 (composed of Orthoptera and some fossil relatives): it exhibits one of the diagnostic character states of this taxon, which is the fusion of CuA (emerging from M + CuA) with CuP, or a branch of it. A more precise taxonomic assignment is out of reach. The new taxon exhibits a fusion of the anterior branch of MA with RP, and a point of divergence of MA and MP located near the point of divergence of CuA (from M + CuA), but lack a branching of CuPa. This unique combination of character states is probably derived with respect to a number of contemporaneous species. Sumixam maximus gen. and sp. nov. is most likely the closest known relative of the panorthopterans, which include all the recent Archaeorthoptera.