Occurence of abundant diradicaloid moieties in the insoluble organic matter from the Orgueil and Murchison meteorites: a fingerprint of its extraterrestrial origin?

The highly aromatic structure of the macromolecular organic matter (OM) of the Murchison and Orgueil meteorites was recently shown to contain free organic radicals which are concentrated in micro-regions in contrast with terrestrial samples which always show an homogeneous distribution of radicals. An additional signature is revealed, in the present study, by the evolution of the radical concentration with temperature. Whereas in terrestrial samples, this concentration is independent of temperature (Curie magnetism), a significant increase is observed above 150 K in the two meteorites. Based on the electronic structure of organic radicals, calculated by Extended Hückel and Density Functional methods, this behavior was assigned to the occurrence of diradicaloid moieties hosted by aromatic structures of 10 to 15 rings and having a quinoidal structure. They represent 40 and 25% of the total radicals in Orgueil and Murchison, respectively. The search for the cosmochemical interpretation of this unique observation should open a new field of experimental investigations.     

Formation of U-depleted rhyolite from a basanite at El Hierro, Canary Islands

Phonolite and trachyte are the felsic magmas of the alkaline magma suites, which characterize the Canary Islands. The October 2011 submarine eruption off El Hierro, the westernmost island, nevertheless, produced a small volume of rhyolitic magma. The rhyolite occurred as highly vesicular, white coloured pumices enveloped in and mingled with darker coloured basanitic pumice. The basanitic pumice is relatively crystal poor with a few euhedral olivines (mostly Fo_77–79), clinopyroxenes and Fe-rich spinels, whereas very rare olivine of same composition is found together with equally rare Fe-sulphide and FeTi-rich oxides in the rhyolite. The Fe–Mg exchange equilibrium in the oxides permits to calculate an equilibrium temperature of 970–890 °C for the rhyolite, in agreement with quartz-melt equilibrium at ca. 930 °C. A striking mineralogical feature of the rhyolite is the presence of rounded to contorted grains of milky quartz, which are xenocrysts incorporated and partly dissolved into the magma. Analyses of residual volatile concentrations in the glasses show that the rhyolite melt was highly degassed, whereas the basanitic glass still has important halogen concentrations. Trace element patterns of the mafic glasses and their elevated incompatible element concentrations are typical of the western Canary Island basanites. In contrast, the trace element composition of the rhyolite shows surprisingly low concentrations for all elements except the most incompatible ones (e.g. Rb, Ba, K and Th). All other measured LILE, HFSE and REE have significantly lower concentration than the basanitic counterpart that can be explained by fractionation of accessory phases (1 % apatite, 1 % sphene and 0.1 % zircon). Surprisingly, low U concentration is presumably related to elevated oxygen fugacity in the rhyolite, causing U to be in a hexavalent state, and fluxing of F-rich gas leading to volatilization of UF₆, known to emanate at low temperature. The results suggest that a gas-rich basanitic melt remobilized a small volume of stagnant rhyolitic melt formed by incorporation of approximately 10 % quartz-rich sediment into a late differentiate of trachytic composition. Sediments at the interface of an old oceanic crust adjacent to a continental shield and younger volcanic island are likely to act as magma traps were sediment assimilation may alter the mantle-derived magma composition. Quartz assimilation thus explains the production of rhyolite magma in a volcanic island characterized by an alkaline magma series from primitive basanites to trachytes.     

Low melting temperature for calcite at 1000 bars on the join CaCO3‐H2O – some geological implications

Melting experiments of calcite were performed on the join CaCO₃‐H₂O at a pressure of 1000 bars. The system evolves to the ternary CaO‐H₂O‐CO₂ system during melting experiments. Our experiments show that partial melting of calcite begins at a low temperature, below 650 °C. Such a low partial melting temperature for carbonates revives the debate about the presence of carbonate melts in the upper crust. More specifically, the conditions for carbonate partial melting are present in carbonate host rocks undergoing contact metamorphism at high temperatures in the presence of water‐rich fluid. The presence of carbonate melts influences physical parameters such as viscosity and permeability in contact aureoles, and, furthermore, decarbonation reactions release massive amounts of CO₂.     

Fingerprinting the 8.2 ka event climate response in a coupled climate model

Using results from coupled climate model simulations of the 8.2 ka climate event that produced a cold period over Greenland in agreement with the reconstructed cooling from ice cores, we investigate the typical pattern of climate anomalies (fingerprint) to provide a framework for the interpretation of global proxy data for the 8.2 ka climate event. For this purpose we developed an analysis method that isolates the forced temperature response and provides information on spatial variations in magnitude, timing and duration that characterise the detectable climate event in proxy archives. Our analysis shows that delays in the temperature response to the freshwater forcing are present, mostly in the order of decades (30 a over central Greenland). The North Atlantic Ocean initially cools in response to the freshwater perturbation, followed in certain parts by a warm response. This delay, occurring more than 200 a after the freshwater pulse, hints at an overshoot in the recovery from the freshwater perturbation. The South Atlantic and the Southern Ocean show a warm response reflecting the bipolar seesaw effect. The duration of the simulated event varies for different areas, and the highest probability of recording the event in proxy archives is in the North Atlantic Ocean area north of 40° N. Our results may facilitate the interpretation of proxy archives recording the 8.2 ka event, as they show that timing and duration cannot be assumed to correspond with the timing and duration of the event as recorded in Greenland ice cores. Copyright © 2011 John Wiley & Sons, Ltd.     

8000 years of vegetation history in the northern Iberian Peninsula inferred from the palaeoenvironmental study of the Zalama ombrotrophic bog (Basque‐Cantabrian Mountains,Spain)

This paper focuses on pollen, spores, non‐pollen palynomorphs (NPPs) and certain geochemical elements from the ombrotrophic blanket bog of Zalama (Basque‐Cantabrian Mountains, northern Iberian Peninsula), with the support of a robust chronology based on 17 AMS ¹⁴C dates. The main results related to the last 8000 years show that, during the early middle Holocene, pines and deciduous forests were the most extensive tree formations. At the beginning of the succession, pines reach 44%, showing regional presence, whereas after 7600 cal. a BP, deciduous forests were particularly abundant. From c. 6500 cal. a BP the pollen diagram constructed from our samples shows the first anthropogenic evidence, linked with the new economic practices related to the Neolithic of the Basque‐Cantabrian Mountains. From 3300 cal. a BP the expansion of Fagus sylvatica is particularly clear, and has since then become one of the dominant forest species in this region. We also discuss the Holocene evolution of other noteworthy plant communities in southwestern Europe, such as Taxus baccata, Juglans and shrublands.     

Stratigraphic modelling of platform architecture and carbonate production: a Messinian case study (Sorbas Basin,SE Spain)

The late Messinian mixed carbonate‐siliciclastic platforms of the Sorbas Basin, known as the Terminal Carbonate Complex, record significant changes in carbonate production and geometry. Their facies and stratigraphic architecture result from complex interactions between base‐level fluctuations, evaporite deformation/dissolution and detrital inputs. A 3D quantitative approach (with DIONISOS software) is used to explore the basin‐scale platform architecture and to quantify the carbonate production of the Terminal Carbonate Complex. The modelling strategy consists in integrating detailed 2D field‐based transects and modern carbonate system parameters (e.g. carbonate production rates, bathymetric and hydrodynamic ranges of production). This approach limits user impact and so provides more objective output results. Tests are carried out on carbonate production rates, subsidence and evaporite deformation/dissolution. Numerical modelling provides accurate predictions of geometries, facies distributions and depositional sequence thicknesses, validated by field data. Comparative statistical testing of the field transects and of the various model outputs are used to discern the relative contribution of the parameters tested to the evolution of basin filling. The 3D visualization and quantification of the main carbonate producers (ooids and microbialites) are discussed in terms of changes in base‐level and detrital supply. This study demonstrates that base‐level fluctuations have the greatest impact on the carbonate budget. Evaporite deformation/dissolution affects the type and amount of carbonate production, inducing a transition from an ooid‐ to microbialite‐dominated system and also has a major effect on stratigraphic architecture by inducing the migration of depocentres. The numerical modelling results obtained using modern carbonate system parameters could also be applied to subsurface ooid‐microbialite reservoirs, and the Terminal Carbonate Complex is a good analogue for such systems.     

Can sediment supply variations create sequences? Insights from stratigraphic forward modelling

Classic sequence stratigraphy suggests depositional sequences can form due to changes in accommodation and due to changes in sediment supply. Accommodation‐dominated sequences are problematic to define rigorously, but are commonly interpreted from outcrop and subsurface data. In contrast, supply‐dominated sequences are much less commonly identified. We employ numerical stratigraphic forward modelling to compare stratal geometries forced by cyclic changes in relative sea level with stratal geometries forced by sediment discharge and water discharge changes. Our quantitative results suggest that both relative sea‐level oscillations and variations in sediment/water discharge ratio are able to form sequence‐bounding unconformities independently, confirming previous qualitative sequences definitions. In some of the experiments, the two types of sequence share several characteristics, such as an absence of coastal‐plain topset deposits and stratal offlap, something typically interpreted as the result of falling relative sea level. However, the stratal geometries differ when variations in amplitude and frequency of relative sea‐level change, sediment/water discharge ratio, transport diffusion coefficient and initial bathymetry are applied. We propose that the supply‐dominated sequences could be recognised in outcrop or in the subsurface if the observations of stratal offlap and the absence of coastal‐plain topset can be made without any strong evidence of relative sea‐level fall (e.g. descending shoreline trajectory). These quantitative results suggest that both supply‐dominated and accommodation‐dominated sequences are likely to occur in the ancient record, as a consequence of multiple, possibly complex, controls.     

Geological and geophysical studies of the Agoudal impact structure (Central High Atlas,Morocco): New evidence for crater size and age

Since the discovery of shatter cones (SCs) near the village of Agoudal (Morocco, Central High Atlas Mountains) in 2013, the absence of one or several associated circular structures led to speculation about the age of the impact event, the number, and the size of the impact crater or craters. Additional constraints on the crater size, age, and erosion rates are obtained here from geological, structural, and geophysical mapping and from cosmogenic nuclide data. Our geological maps of the Agoudal impact site at the scales of 1:30,000 (6 km²) and 1:15,000 (2.25 km²) include all known occurrences of SCs in target rocks, breccias, and vertical to overturned strata. Considering that strata surrounding the impact site are subhorizontal, we argue that disturbed strata are related to the impact event. Three types of breccias have been observed. Two of them (br1‐2 and br2) could be produced by erosion–sedimentation–consolidation processes, with no evidence for impact breccias, while breccia (br1) might be impact related. The most probable center of the structure is estimated at 31°59′13.73?N, 5°30′55.14?W using the concentric deviation method applied to the orientation of strata over the disturbed area. Despite the absence of a morphological expression, the ground magnetic and electromagnetic surveys reveal anomalies spatially associated with disturbed strata and SC occurrences. The geophysical data, the structural observations, and the area of occurrence of SCs in target rocks are all consistent with an original size of 1.4–4.2 km in diameter. Cosmogenic nuclide data (³⁶Cl) constrain the local erosion rates between 220 ± 22 m Ma^?1 and 430 ± 43 m Ma^?1. These erosion rates may remove the topographic expression of such a crater and its ejecta in a time period of about 0.3–1.9 Ma. This age is older than the Agoudal iron meteorite age (105 ± 40 kyr). This new age constraint excludes the possibility of a genetic relationship between the Agoudal iron meteorite fall and the formation of the Agoudal impact site. A chronolgy chart including the Atlas orogeny, the alternation of sedimentation and erosion periods, and the meteoritic impacts is presented based on all obtained and combined data.