Differential aerobic and anaerobic oxidation of hydrocarbon gases discharged at mud volcanoes in the Nile deep-sea fan

The present study investigates hydrocarbon oxidation processes at Isis and Amon mud volcanoes (MV’s), in the eastern Nile deep-sea fan. In the water column, molecular and carbon isotopic signatures of light hydrocarbons indicate that gases rapidly dissolve in seawater and are partially oxidized.In the upper sediments, anaerobic oxidation of the light hydrocarbons takes place, as clearly shown by their molecular and isotopic composition. These processes lead to the presence of a distinct Sulfate-Hydrocarbon Interface at 120-145 cm and 20-50 cm below the seafloor, for Isis and Amon MV’s, respectively. In contrast to processes occurring in the water column, a clear preferential oxidation of methane, propane and n-butane over ethane and i-butane is observed in the anoxic sediments. Furthermore, for the first time, fractionation factors have been determined for the anaerobic oxidation of propane and butane, being respectively −4.80‰ and −0.7‰ for δ¹³C, and −43.3‰ for δ²H of propane.     

Ar-Ar and I-Xe ages and thermal histories of three unusual metal-rich meteorites

Portales Valley, Sombrerete, and Northwest Africa (NWA) 176 are three unrelated meteorites, which consist of silicate mixed with substantial amounts of metal and which likely formed at elevated temperatures as a consequence of early impacts on their parent bodies. Measured ³⁹Ar-⁴⁰Ar ages of these meteorites are 4477 ± 11 Ma and 4458 ± 16 Ma (two samples of Portales Valley), 4541 ± 12 Ma, and 4524 ± 13 Ma, respectively (Ma = million years; all one-sigma errors). The Ar-Ar data for Portales Valley show no evidence of later open system behavior suggested by some other chronometers. Measured ¹²⁹I-¹²⁹Xe ages of these three meteorites are 4559.9 ± 0.5 Ma, 4561.9 ± 1.0 Ma, and ∼4544 Ma, respectively (relative to Shallowater = 4562.3 ± 0.4 Ma). From stepwise temperature release data, we determined the diffusion characteristics for Ar and Xe in our samples and calculated approximate closure temperatures for the K-Ar and I-Xe chronometers. Adopting results and interpretations about these meteorites from some previous workers, we evaluated all these data against various thermal cooling models. We conclude that Portales Valley formed 4560 Ma ago, cooled quickly to below the I-Xe closure temperature, then cooled deep within the parent body at a rate of ∼4 °C/Ma through K-Ar closure. We conclude that Sombrerete formed 4562 Ma ago and cooled relatively quickly. NWA 176 likely formed and cooled quickly ∼4544 Ma ago, or later than formation times of most meteorite parent bodies. For all three meteorites, the Ar-Ar ages are in better agreement with I-Xe ages and preferred thermal models if we increase these Ar-Ar ages by ∼20 Ma. Such age corrections would be consistent with probable errors in ⁴⁰K decay parameters in current use, as suggested by others. The role of impact heating and possible disruption and partial reassembly of meteorite parent bodies to form some meteorites likely was an important process in the early solar system.     

Evidence for high-pressure core-mantle differentiation from the metal-silicate partitioning of lithophile and weakly-siderophile elements

Liquid Fe metal-liquid silicate partition coefficients for the lithophile and weakly-siderophile elements Ta, Nb, V, Cr, Si, Mn, Ga, In and Zn have been measured in multianvil experiments performed from 2 to 24 GPa, 2023-2873 K and at oxygen fugacities of −1.3 to −4.2 log units relative to the iron-wüstite buffer. Compositional effects of light elements dissolved in the metal liquid (S, C) have been examined and experiments were performed in both graphite and MgO capsules, specifically to address the effect of C solubility in Fe-metal on siderophile element partitioning. The results were used to examine whether there is categorical evidence that a significant portion of metal-silicate equilibration occurred under very high pressures during core-mantle fractionation on Earth. Although the depletion of V from the mantle due to core formation is significantly greater than that of Nb, our results indicate that both elements have similar siderophile tendencies under reducing conditions at low pressures. With increasing pressure, however, Nb becomes less siderophile than V, implying that average metal-silicate equilibration pressures of at least 10-40 GPa are required to explain the Nb/V ratio of the mantle. Similarly the moderately-siderophile, volatile element ratios Ga/Mn and In/Zn are chondritic in the mantle but both volatility and core-mantle equilibration at low pressure would render these ratios strongly sub-chondritic. Our results indicate that pressures of metal-silicate partitioning exceeding 30-60 GPa would be required to render these element ratios chondritic in the mantle. These observations strongly indicate that metal-silicate equilibration must have occurred at high pressures, and therefore support core-formation models that involve deep magma oceans. Moreover, our results allow us to exclude models that envisage primarily low-pressure (<1 GPa) equilibration in relatively small planetary bodies. We also argue that the core cannot contain significant U as this would require metal-silicate equilibration at oxygen fugacities low enough for significant amounts of Ta to have also been extracted from the mantle. Likewise, as In is more siderophile than Pb but similarly volatile and also quite chalcophile it would have been difficult for Pb to enter the core without reversing the relative depletions of these elements in the mantle unless metal-silicate equilibration occurred at high pressures >20 GPa.     

Oxygen isotopes composition of sapphires from the French Massif Central: implications for the origin of gem corundum in basaltic fields

Alluvial and colluvial gem sapphires are common in the basaltic fields of the French Massif Central (FMC) but sapphire-bearing xenoliths are very rare, found only in the Menet trachytic cone in Cantal. The O-isotope composition of the sapphires ranges between 4.4 and 13.9‰. Two distinct groups have been defined: the first with a restricted isotopic range between 4.4 and 6.8‰ (n = 22; mean δ¹⁸O = 5.6 ± 0.7‰), falls within the worldwide range defined for blue-green-yellow sapphires related to basaltic gem fields (3.0 < δ¹⁸O < 8.2‰, n = 150), and overlaps the ranges defined for magmatic sapphires in syenite (4.4 < δ¹⁸O < 8.3‰, n = 29). A second group, with an isotopic range between 7.6 and 13.9‰ (n = 9), suggests a metamorphic sapphire source such as biotite schist in gneisses or skarns. The δ¹⁸O values of 4.4–4.5‰ for the blue sapphire-bearing anorthoclasite xenolith from Menet is lower than the δ¹⁸O values obtained for anorthoclase (7.7–7.9‰), but suggest that these sapphires were derived from an igneous reservoir in the subcontinental spinel lherzolitic mantle of the FMC. The presence of inclusions of columbite-group minerals, pyrochlore, Nb-bearing rutile, and thorite in these sapphires provides an additional argument for a magmatic origin. In the FMC lithospheric mantle, felsic melts crystallized to form anorthoclasites, the most evolved peraluminous variant of the alkaline basaltic melt. The O-isotopic compositions of the first group suggests that these sapphires crystallized from felsic magmas under upper mantle conditions. The second group of isotopic values, typified for example by the Le Bras sapphire with a δ¹⁸O of 13.9‰, indicates that metamorphic sapphires from granulites were transported to the surface by basaltic magma.     

Large-scale distributed deformation controlled topography along the western Africa–Eurasia limit: Tectonic constraints

In the interior of the Iberian Peninsula, the main geomorphic features, mountain ranges and basins, seems to be arranged in several directions whose origin can be related to the N–S plate convergence which occurred along the Cantabro–Pyrenean border during the Eocene–Lower Miocene time span. The Iberian Variscan basement accommodated part of this plate convergence in three E–W trending crustal folds as well as in the reactivation of two left-lateral NNE–SSW strike-slip belts. The rest of the convergence was assumed through the inversion of the Iberian Mesozoic Rift to form the Iberian Chain. This inversion gave rise to a process of oblique crustal shortening involving the development of two right lateral NW–SE shear zones. Crustal folds, strike-slip corridors and one inverted rift compose a tectonic mechanism of pure shear in which the shortening is solved vertically by the development of mountain ranges and related sedimentary basins. This model can be expanded to NW Africa, up to the Atlasic System, where N–S plate convergence seems also to be accommodated in several basement uplifts, Anti-Atlas and Meseta, and through the inversion of two Mesozoic rifts, High and Middle Atlas. In this tectonic situation, the microcontinent Iberia used to be firmly attached to Africa during most part of the Tertiary, in such a way that N–S compressive stresses could be transmitted from the collision of the Pyrenean boundary. This tectonic scenario implies that most part of the Tertiary Eurasia–Africa convergence was not accommodated along the Iberia–Africa interface, but in the Pyrenean plateboundary. A broad zone of distributed deformation resulted from the transmission of compressive stresses from the collision at the Pyrenean border. This distributed, intraplate deformation, can be easily related to the topographic pattern of the Africa–Eurasia interface at the longitude of the Iberian Peninsula.Shortening in the Rif–Betics external zones – and their related topographic features – must be conversely related to more “local” driven mechanisms, the westward displacement of the “exotic” Alboran domain, other than N–S convergence. The remaining NNW–SSE to NW–SE, latest Miocene up to Present convergence is also being accommodated in this zone straddling Iberia and Morocco, at the same time as a new ill-defined plate boundary that is being developed between Europe and Africa.     

Carbon catalysed hydrogen exchange in petroleum source rocks

Exchange of carbon bound hydrogen has been observed when alkenes, saturated and aromatic hydrocarbons are heated at moderate temperatures on carbonaceous surfaces (activated carbon and coal). Isomerisation of alkenes and the formation of hydrogenated/dehydrogenated products from the saturated and aromatic reactants resulted. A suite of crude oils from the Carnarvon Basin (Western Australia) have been analysed with a view to comparing their relative abundances of structurally similar hydrocarbons. The consistent relationships between hydrocarbons in crude oils that are chemically related via hydrogenation/dehydrogenation reactions suggest that a hydrogen exchange process similar to that demonstrated in laboratory experiments occurs during crude oil formation in sedimentary rocks.     

Physical modelling of sand injectites

Sand injectites are structures that result from intrusion of fluidized sand into fractures. We have studied them in the Tampen Spur area of the North Sea, and have reproduced them experimentally, by driving compressed air through layers of sand, glass microspheres, and silica powder. The silica powder was cohesive and capable of hydraulic fracturing, whereas the sand and glass microspheres were almost non-cohesive and therefore able to fluidize. The models were dynamically similar to their natural counterparts, for as long as equilibrium was static. When the processes became dynamic, so that inertial forces were significant, the scaling was approximate and the corresponding Reynolds numbers differed. The experimental apparatus was a square box, 1 m × 1 m wide, resting on a grid of fluid diffusers. During the experiments, the fluid pressure increased, until it attained and surpassed the weight of overburden. Flat-lying hydraulic fractures, containing air, formed within cohesive and least permeable layers. Heterogeneities in material properties and layer thicknesses were responsible for localizing fracture networks. When any one network broke through to the surface, rapid flow of air through the fractures fluidized the underlying mobile materials and even depleted some of the layers. Some of the fluidized material extruded at the surface through vents, forming volcanoes and sheets. The remainder lodged at depth, forming sand injectites or laccoliths. Conical sand injectites formed preferentially, where layers had high resistance to bending. Laccoliths formed nearer the surface, where overlying layers had low resistance to bending. The experimental sand injectites were broadly similar to those in the Tampen Spur area of the North Sea, as well as other areas.