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.     

In situ measurement of Re-Os isotopes in mantle sulfides by laser ablation multicollector-inductively coupled plasma mass spectrometry: analytical methods and preliminary results

A method has been developed for the in situ determination of Re-Os isotopes in single grains of sulfides in mantle-derived peridotites using a laser ablation microprobe attached to a multicollector-induced coupled plasma mass spectrometer (MC-ICPMS). High-precision Os isotope analysis by MC-ICPMS is demonstrated by the measurement of interlaboratory Os standards. Evaluation of mass bias correction procedures shows that the exponential law provides the best fit to the Os isotope data and that the ratio of the mass fractionation coefficients for Re and Os remains constant for the range of typical instrument operating conditions. This relationship enables the accurate and precise correction of the isobaric interference of ¹⁸⁷Re on ¹⁸⁷Os for ¹⁸⁷Re/¹⁸⁸Os values up to 1.6.Results are presented for single sulfide inclusions in olivine macrocryts from kimberlites in the Siberian and Slave Cratons, and sulfides enclosed in silicates and interstitial to silicates in peridotite xenoliths from the Slave Craton and Massif Central, France. Enclosed sulfides larger than 50 μm in diameter and with Os contents ≥40 ppm give ¹⁸⁷Os/¹⁸⁸Os ratios with a precision of 0.1% (2 SE), which is equivalent to N-TIMS whole-rock data. Interstitial sulfides typically have lower Os (10 to 30 ppm) and give analyses with lower precision (∼1 to 2%) but still provide valuable information on the movement of Os within the lithosphere. The sulfide inclusions in silicates preserve significantly less radiogenic Os isotopic compositions than interstitial sulfides and accordingly produce significantly older and more realistic Re-Os age information. Whole-rock Os isotope compositions reflect the proportions of different generations of enclosed and interstitial sulfides; this calls into question the significance of many published “depletion ages.”     

Paléoenvironnements et caractérisation des roches mères pétrolières des séries pré-salifères du bassin intérieur du Gabon

The Interior Basin of Gabon, created during the break-up between South America and Africa, displays thick Neoproterozoic to Aptian p.p. fluvio-lacustrine deposits overlain by Aptian to Albian marine facies. Rock–Eval analyses from outcrop and drillhole samples show high content in organic matter (up to 25%) related to types I and II. These intervals are encountered within Permian, Neocomian–Barremian as well as Aptian siliciclastic succession. They constitute fairly good to excellent potential petroleum source rocks, which are most probably at the origin of oil indices recognized both in drillholes and in surface.     

An Early-Cambrian UPb apatite cooling age for the high-temperature regional metamorphism in the Piancó area,Borborema Province (NE Brazil): initial conclusions

The Borborema Province (BP) of northeastern Brazil is a complex crustal assemblage, which has undergone a polycyclic evolution during the Proterozoic. In the Piancó-Alto Br??gida belt, a metamorphosed leucosome vein inserted in amphibolites has a trace element pattern suggesting a T-MORB protolith. Apatites yield a REE pattern indicating growth in equilibrium with garnet, thus pointing to its metamorphic origin. UPb analyses yield an age of 540±5 Ma interpreted as a cooling age following amphibolite facies regional metamorphism associated with granitic emplacement at ca. 580 Ma. The resulting slow cooling rates (ranging from ca. 2.5 to 5 °C Ma^?1) are consistent with underplating of mafic magmas, or crustal thickening caused by nappe stacking, as possible processes governing the metamorphic evolution of the BP. To cite this article: B. Dhuime et al., C. R. Geoscience 335 (2003).     

Sulfur and selenium systematics of the subcontinental lithospheric mantle: Inferences from the Massif Central xenolith suite (France)

Selenium has been analyzed in addition to S in 58 spinel peridotite xenoliths collected in Cenozoic alkali basalts from the Massif Central (France). The S concentration range now available for this suite, calculated from 123 samples, is the largest ever reported for alkali basalt-hosted xenoliths (<3-592 ppm). Likewise, the Se concentrations range between 0.2 and 67 ppb. No partial melting signature can be identified from the S and Se systematic. Half of the analyzed xenoliths have lost S during supergene weathering. By contrast, neither surficial alteration, nor loss of chalcophile elements during eruption can explain the regional-scale variations of S and Se concentrations. A first group of lherzolite xenoliths sampled in Southern Massif Central, from volcanic centers older and spatially unrelated to the Massif Central plume that triggered the Cenozoic volcanism, contains between 20 and 250 ppm S (with occasional S concentrations up to 592 ppm) and 12-67 ppb Se. It is clear that the highest S values, originally interpreted as representing S abundances in the primitive mantle, were in fact enriched by metasomatism. Highly variable S and Se contents (<5-360 ppm; 9-52 ppb) have also been observed in peridotite xenoliths collected in the Northern Massif Central, from volcanic centers mostly older than the plume. Like Group I xenoliths, these Group II xenoliths were strongly metasomatized by volatile-rich carbonated/silicated melts which precipitated Cu-rich sulfides. A third group of xenoliths from Plio-Quaternary basalts spatially related to the Massif Central Plume are uniformly poor in S (10-60 ppm) and Se (9-29 ppb). In this Group III, poikiloblastic textured xenoliths have lost most of their S and Se budget by peridotite-melt interactions at high melt/rock ratios. Taken as a whole, the Massif Central xenolith suite provides further evidence for strong heterogeneities in the S and Se budget of the sub-continental lithospheric mantle. However, the few LREE-depleted fertile lherzolites that escaped strong metasomatic alterations suggest a S- and Se-depleted primitive mantle reservoir compared to currently accepted primitive mantle estimates.     

Using a Convection Model to Predict Altitudes of White Stork Migration Over Central Israel

Soaring migrants such as storks, pelicans and large birds of prey rely on thermal convection during migration. The convection model ALPTHERM was designed to predict the onset, strength, duration and depth of thermal convection for varying topographies for glider pilots, based on atmospheric conditions at midnight. We tested ALPTHERM predictions as configured for two topographies of central Israel, the Coastal Plains and the Judean and Samarian Mountains in order to predict altitudes of migrating white storks (Ciconia ciconia). Migrating flocks of white storks were tracked with a motorized glider, to measure maximum altitudes of migration during spring 2000. A significant positive correlation was found between the maximum daily altitudes of migration measured and the predicted upper boundary of thermal convection for the Coastal Plains and Samarian Mountains. Thirty-minute predictions for the Coastal Plains and Samarian Mountains correlated positively with measured maximum migration altitudes per thermal. ALPTHERM forecasts can be used to alter flight altitudes in both civil and especially military aviation and reduce the hazard of serious aircraft collisions with soaring migrants.     

New palaeogeographic and lake-level reconstructions of Lake Tanganyika: implications for tectonic, climatic and biological evolution in a rift lake

Palaeogeographic and lake-level reconstructions provide powerful tools for evaluating competing scenarios of biotic, climatic and geological evolution within a lake basin. Here we present new reconstructions for the northern Lake Tanganyika subbasins, based on reflection seismic, core and outcrop data. Reflection seismic radiocarbon method (RSRM) age estimates provide a chronological model for these reconstructions, against which yet to be obtained age dates based on core samples can be compared. A complex history of hydrological connections and changes in shoreline configuration in northern Lake Tanganyika has resulted from a combination of volcanic doming, border fault evolution and climatically induced lake-level fluctuations. The stratigraphic expression of lake-level highstands and lowstands in Lake Tanganyika is predictable and cyclic (referred to here as Capart Cycles), but in a pattern that differs profoundly from the classic Van Houten cycles of some Newark Supergroup rift basins. This difference results from the extraordinary topographic relief of the Western Rift lakes, coupled with the rapidity of large-scale lake-level fluctuations. Major unconformity surfaces associated with Lake Tanganyika lowstands may have corresponded with high-latitude glacial maxima throughout much of the mid- to late Pleistocene.
Rocky shorelines along the eastern side of the present-day Ubwari Peninsula (Zaire) appear to have had a much more continuous existence as littoral rock habitats than similar areas along the north-western coastline of the lake (adjacent to the Uvira Border Fault System), which in turn are older than the rocky shorelines of the north-east coast of Burundi. This model of palaeogeographic history will be of great help to biologists trying to clarify the evolution of endemic invertebrates and fish in the northern basin of Lake Tanganyika.