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.     

Osmium-strontium-neodymium-lead isotopic covariations in mid-ocean ridge basalt glasses and the heterogeneity of the upper mantle

Osmium, strontium, neodymium, and lead isotopic data have been obtained for 30 hand picked samples of basaltic glass from the Pacific, Atlantic and Indian mid-oceanic ridges. Large variations in Os isotopic ratios exist in the glasses, from abyssal peridotite-like values to radiogenic compositions similar to oceanic island basalts (¹⁸⁷Os/¹⁸⁶Os and ¹⁸⁷Os/¹⁸⁸Os ratios range from 1.06 to 1.36 and from 0.128 to 0.163, respectively). Os isotopic and elemental data suggest the existence of mixing correlations. This relationship might be ascribed to secondary contamination processes; however, such a hypothesis cannot account for the negative correlation observed between Os and Nd isotopes and the existence of complementary covariations between Os and SrPb isotopes. In this case, OsSrNdPb isotopic variations are unrelated to late post-eruption or shallow level contamination. These relationships provide strong evidence that the Os isotopic composition of the samples are derived from the mantle and thus implies a global chemical heterogeneity of the oceanic upper mantle. The results are consistent with the presence of recycled oceanic crust in the mantle sources of mid-ocean ridge basalts, and indicate that the unique composition of the upper mantle below the Indian ocean results from its contamination by a mantle component characterized by radiogenic Os and particularly unradiogenic Nd and Pb isotopic compositions.     

Solar modulation of cosmogenic nuclide production over the last millennium: comparison between C and Be records

For about the last 30 years it has been recognized that the high frequency component of the tree rings ¹⁴C/¹²C record is dominated by the modulation of the cosmic ray flux by the solar wind. In particular, it has been demonstrated that the three most recent periods of low sunspot occurrence were characterized by high values of atmospheric ¹⁴C/¹²C. During the last millennium other periods of high ¹⁴C/¹²C values were observed but their solar origin is still debatable. In the present work we compare these fluctuations with an independent record of cosmogenic ¹⁰Be measured in ice from the South Pole to check the solar origin of the observed ¹⁴C/¹²C variations. In order to compare quantitatively the results obtained on ¹⁰Be and ¹⁴C, it is necessary to take into account the different behaviour of these two cosmogenic isotopes, and especially the damping effect of the carbon cycle in the case of ¹⁴C. As an input to a 12-box numerical model we used the relative fluctuations of the ¹⁰Be concentrations record measured in South Pole ice and converted it into a synthetic ¹⁴C record. We took into account the fact that ¹⁰Be modulation is enhanced in polar regions due to the orientation of the geomagnetic field. As expected, the fluctuations of the modelled ¹⁴C record are much smaller (a factor of 20) than those observed for the raw ¹⁰Be record. In addition, the variations are smoother and shifted in time by a few decades. The ¹⁰Be-based ¹⁴C variations closely resemble the ¹⁴C measurements obtained on tree rings (R = 0.81). In particular, it is easy to identify periods of maximal ¹⁴C/¹²C which correspond to solar activity minima centred at about 1060, 1320 (Wolf), 1500 (Spörer), 1690 (Maunder) and 1820 (Dalton) yr A.D. Cross-correlation calculations suggest that there is no significant lag between the ¹⁰Be-based ¹⁴C and the tree-ring ¹⁴C records. Our study strongly suggests the dominance of the solar modulation on the cosmonuclide production variations during the last millennium.     

Aerosol polarized phase function and single-scattering albedo retrieved from ground-based measurements

Aerosol optical parameters, polarized phase function and single-scattering albdeo, have been retrieved from ground-based sun photometer measurements in Beijing 2003. The measured aerosol optical thickness varies from 0.12 to 0.77 with an average value of 0.39. The measured Ångström coefficient ranges from 0.75 to 1.47 with an average value of 1.21. The retrieved single-scattering albedo at 870 nm is within the 0.76–0.94 range and the average value is 0.85, suggests there are considerable aerosol absorptions in Beijing. The maximum value of retrieved polarized phase function at 870 nm ranges from 0.068 to 0.225 with an average value of 0.16, and it illustrates good correlations with the Ångström coefficient, i.e. the relative size of aerosol particles. Analyses of measurements and theoretical calculations show the polarized phase function is sensitive to aerosol size distribution and complex refractive index, especially the imaginary part of the refractive index which denotes aerosol light absorbing effects. These results suggest that the polarized phase function is an effective and unique aerosol optical parameter and is able to improve the retrieval of aerosol physical properties.     

Tectonic evolution of the Lachlan Fold Belt, southeastern Australia: constraints from coupled numerical models of crustal deformation and surface erosion driven by subduction of the underlying mantle

We have used a coupled thermo-mechanical finite-element (FE) model of crustal deformation driven by mantle/oceanic subduction to demonstrate that the tectonic evolution of the Lachlan Fold Belt (LFB) during the Mid-Palaeozoic (Late Ordovician to Early Carboniferous) can be linked to continuous subduction along a single subduction zone. This contrasts with most models proposed to date which assume that separate subduction zones were active beneath the western, central and eastern sections of the Lachlan Orogen. We demonstrate how the existing data on the structural, volcanic and erosional evolution of the Lachlan Fold Belt can be accounted for by our model. We focus particularly on the timing of fault movement in the various sectors of the orogen. We demonstrate that the presence of the weak basal decollement on which most of the Lachlan Fold Belt is constructed effectively decouples crustal structures from those in the underlying mantle. The patterns of faulting in the upper crust appears therefore to be controlled by lateral strength contrasts inherited from previous orogenic events rather than the location of one or several subduction zones. The model also predicts that the uplift and deep exhumation of the Wagga-Omeo Metamorphic Belt (WOMB) is associated with the advection of this terrane above the subduction point and is the only tectonic event that gives us direct constraints on the location of the subduction zone. We also discuss the implications of our model for the nature of the basement underlying the present-day orogen.     

A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

Nouvelle interprétation structurale de la « faille Nord- Pyrénéenne » en vallée d'Aspe (Pyrénées-Atlantiques). Remise en question d'un plutonisme ophitique danien dans le secteur de Bedous

In the Aspe Valley (western Pyrenees), the Europe/Iberia boundary corresponds to a complex fracturing zone, called the ‘Bielle–Accous Wrench-Faulting Corridor’, which represents the classical ‘North-Pyrenean Fault’. Located between the High Primary Range and the North-Pyrenean Zone, the BAWC shows different south-verging sheets mainly composed of Triassic materials. The Bedous ophite, associated with Muschelkalk and Keuper sediments, is also Triassic in age and involved in the same Pyrenean thrusting structures. So, contrary to a recent interpretation, this magmatic rock cannot be related to a supposed Danian plutonism inducing metamorphic processes in the surrounding Mesozoic formations. To cite this article: J. Canérot et al., C. R. Geoscience 336 (2004).     

L'archivage des activités humaines par les neiges et glaces polaires : le cas du plomb

The investigation of the occurrence of lead in dated snow and ice from Greenland and Antarctica has played a major role in our understanding of the history of the pollution of the atmosphere of our planet by this metal. Such studies have however proved to be very demanding, mainly because of the extreme purity of polar snow and ice. Reliable measurements can be obtained only if ultra-clean and highly sensitive procedures are used, as pioneered by Clair Patterson. The Greenland data show evidence of large-scale pollution of the atmosphere of the Northern Hemisphere for lead as early as two millennia ago during Greco–Roman times, especially because of mining and smelting activities in southern Spain. It peaked at the end of the 1960s, with lead concentrations in snow about 200 times higher than natural values, before declining during recent times because of the fall in the use of leaded gasoline. Lead pollution in Antarctica was already significant at the end of the 19th century as a consequence of whaling activities, the traffic of coal-powered ships crossing the Cape Horn, and mining activities in South America, South Africa and Australia. After declining because of the opening of the Panama Canal, the great economic depression and World War II, it reached a maximum during the 1980s, with lead concentrations 20 times higher than natural values. Other studies focus on past natural variations of lead in ancient ice dated from the last climatic cycles. To cite this article: C. Boutron et al., C. R. Geoscience 336 (2004).