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

Laurent Binet  Didier Gourier  François Robert 《Geochimica et cosmochimica acta》2004,68(4):881-891

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.  相似文献   

Variations of U and Sr isotope ratios in Alsace and Luxembourg rain waters: origin and hydrogeochemical implications     

Franois Chabaux  Jean Riotte  Anne-Dsire Schmitt  Jean Carignan  Pierre Herckes  Marie-Claire Pierret  Henry Wortham 《Comptes Rendus Geoscience》2005,337(16):4612

Major and trace element concentrations, as well as Sr and U isotope ratios, were measured in rainwater samples collected in three different locations in Alsace (East of France) and Luxembourg: a mid-altitude mountain site (Aubure Environment HydroGeochemical Observatory), an urban site (Strasbourg) and a peri-urban site located in an area of well developed industrial activity (Esch-sur-Alzette in Luxembourg). Results highlight the quite high spatial and temporal variability of the chemical and isotopic characteristics of rainwater at the regional scale. They also suggest a quite systematic contribution of a local component in the chemical composition of rainwater. In urban and peri-urban sites, the local component is certainly linked to human activities, as it is well illustrated in this study with the Esch-sur-Alzette samples. On the other hand, for the Aubure site, i.e. a small forested watershed of mid-altitude mountain, data presented in this study demonstrate the influence of the vegetation on the chemical composition of rainwater for alkali and calc-alkali elements, as well as for the Sr isotope ratios. Such a result questions the reliability of the method classically used to estimate the rainwater contribution on the river chemical budget. In addition, data of the present study confirm the very low content of uranium in rainwater and demonstrate, especially through the U isotope analysis of Aubure rainwater, the negligible effect of rainwater on U budget of river waters. This work thus outlines the property of U to be a geochemical tracer specific of weathering fluxes carried by rivers. To cite this article: F. Chabaux et al., C. R. Geoscience 337 (2005).  相似文献   

Modeling of in-situ crystallization processes in the Permian mafic layered intrusion of Mont Collon (Dent Blanche nappe, western Alps)     

Philippe Monjoie  Fran  ois Bussy  Henriette Lapierre  Hans-Rudolf Pfeifer 《Lithos》2005,83(3-4):317-346

The Mont Collon mafic complex is one of the best preserved examples of the Early Permian magmatism in the Central Alps, related to the intra-continental collapse of the Variscan belt. It mostly consists (> 95 vol.%) of ol + hy-normative plagioclase-wehrlites, olivine- and cpx-gabbros with cumulitic structures, crosscut by acid dikes. Pegmatitic gabbros, troctolites and anorthosites outcrop locally. A well-preserved cumulative sequence is exposed in the Dents de Bertol area (center of intrusion). P–T calculations indicate that this layered magma chamber emplaced at mid-crustal levels at about 0.5 GPa and 1100 °C. The Mont Collon cumulitic rocks record little magmatic differentiation, as illustrated by the restricted range of clinopyroxene mg-number (Mg#_cpx = 83–89). Whole-rock incompatible trace-element contents (e.g. Nb, Zr, Ba) vary largely and without correlation with major-element composition. These features are characteristic of an in-situ crystallization process with variable amounts of interstitial liquid L trapped between the cumulus mineral phases. LA-ICPMS measurements show that trace-element distribution in the latter is homogeneous, pointing to subsolidus re-equilibration between crystals and interstitial melts. A quantitative modeling based on Langmuir's in-situ crystallization equation successfully duplicated the REE concentrations in cumulitic minerals of all rock facies of the intrusion. The calculated amounts of interstitial liquid L vary between 0 and 35% for degrees of differentiation F of 0 to 20%, relative to the least evolved facies of the intrusion. L values are well correlated with the modal proportions of interstitial amphibole and whole-rock incompatible trace-element concentrations (e.g. Zr, Nb) of the tested samples. However, the in-situ crystallization model reaches its limitations with rock containing high modal content of REE-bearing minerals (i.e. zircon), such as pegmatitic gabbros. Dikes of anorthositic composition, locally crosscutting the layered lithologies, evidence that the Mont Collon rocks evolved in open system with mixing of intercumulus liquids of different origins and possibly contrasting compositions. The proposed model is not able to resolve these complex open systems, but migrating liquids could be partly responsible for the observed dispersion of points in some correlation diagrams. Absence of significant differentiation with recurrent lithologies in the cumulitic pile of Dents de Bertol points to an efficiently convective magma chamber, with possible periodic replenishment.  相似文献   

Lateglacial palaeoenvironments and palaeoclimates from Conty and Houdancourt, northern France, reconstructed from Beetle remains     

Philippe Ponel  Russell Coope  Pierre Antoine  Nicole Limondin-Lozouet  Chantal Leroyer  Andr-Valentin Munaut  Jean-Franois Pastre  Frdric Guiter 《Quaternary Science Reviews》2005,24(23-24):2449-2465

Two Lateglacial insect sequences are described (a) from Conty, in the Selle valley and (b) from Houdancourt in the Oise valley, both in northern France. These investigations are part of a multidisciplinary investigation involving archaeology, sedimentology, geomorphology, geochronology and palaeontology (pollen, macroscopic plant remains, vertebrates, molluscs and insect fossils). The sequences of insect assemblages date from the latter part of the Bølling to the end of the Allerød periods. Environmental analysis of these faunas shows that rivers with riffles and pools meandered across flood plains. The river was extensively fringed with reedy vegetation. The only trees growing close to the river were of Salix and/or Populus. All the insect assemblages indicate that the thermal climates during the Bølling and Allerød periods were similar to one another and during both periods were very nearly as warm as that of the present day. No insect fossils were recovered from the sediments attributed to the Older Dryas interval though other evidence from these sites suggests that this event was decidedly colder than those immediately preceding and succeeding it. Comparisons are made between Lateglacial climatic patterns in northern France with those elsewhere in Europe.  相似文献   

Potentiometric titrations of Bacillus subtilis cells to low pH and a comparison of modeling approaches     

Jeremy B. Fein  Jean-François Boily  Drew Gorman-Lewis 《Geochimica et cosmochimica acta》2005,69(5):1123-1132

To provide constraints on the speciation of bacterial surface functional groups, we have conducted potentiometric titrations using the gram-positive aerobic species Bacillus subtilis, covering the pH range 2.1 to 9.8. Titration experiments were conducted using an auto-titrator assembly, with the bacteria suspended in fixed ionic strength (0.01 to 0.3 M) NaClO₄ solutions. We observed significant adsorption of protons over the entire pH range of this study, including to the lowest pH values examined, indicating that proton saturation of the cell wall did not occur under any of the conditions of the experiments. Ionic strength, over the range studied here, did not have a significant effect on the observed buffering behavior relative to experimental uncertainty. Electrophoretic mobility measurements indicate that the cell wall is negatively charged, even under the lowest pH conditions studied. These experimental results necessitate a definition of the zero proton condition such that the total proton concentration at the pH of suspension is offset to account for the negative bacterial surface charge that tends towards neutrality at pH <2.The buffering intensity of the bacterial suspensions reveals a wide spread of apparent pKa values. This spread was modeled using three significantly different approaches: a Non-Electrostatic Model, a Constant Capacitance Model, and a Langmuir-Freundlich Model. The approaches differ in the manner in which they treat the surface electric field effects, and in whether they treat the proton-active sites as discrete functional groups or as continuous distributions of related sites. Each type of model tested, however, provides an excellent fit to the experimental data, indicating that titration data alone are insufficient for characterizing the molecular-scale reactions that occur on the bacterial surface. Spectroscopic data on the molecular-scale properties of the bacterial surface are required to differentiate between the underlying mechanisms of proton adsorption inherent in these models. The applicability and underlying conceptual foundation of each model is discussed in the context of our current knowledge of the structure of bacterial cell walls.  相似文献   

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature     

Abby Kavner  François Bonet  Justin Simon 《Geochimica et cosmochimica acta》2005,69(12):2971-2979

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from −0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ⁵⁶Fe values (relative to IRMM-14) ranging from −0.18(±0.02) to −2.290(±0.006) ‰, and corresponding δ⁵⁷Fe values of −0.247(±0.014) and −3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus’s theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.  相似文献   

Using raw regional climate model outputs for quantifying climate change impacts on hydrology          下载免费PDF全文

Jie Chen  François P. Brissette  Pan Liu  Jun Xia 《水文研究》2017,31(24):4398-4413

General circulation model outputs are rarely used directly for quantifying climate change impacts on hydrology, due to their coarse resolution and inherent bias. Bias correction methods are usually applied to correct the statistical deviations of climate model outputs from the observed data. However, the use of bias correction methods for impact studies is often disputable, due to the lack of physical basis and the bias nonstationarity of climate model outputs. With the improvement in model resolution and reliability, it is now possible to investigate the direct use of regional climate model (RCM) outputs for impact studies. This study proposes an approach to use RCM simulations directly for quantifying the hydrological impacts of climate change over North America. With this method, a hydrological model (HSAMI) is specifically calibrated using the RCM simulations at the recent past period. The change in hydrological regimes for a future period (2041–2065) over the reference (1971–1995), simulated using bias‐corrected and nonbias‐corrected simulations, is compared using mean flow, spring high flow, and summer–autumn low flow as indicators. Three RCMs driven by three different general circulation models are used to investigate the uncertainty of hydrological simulations associated with the choice of a bias‐corrected or nonbias‐corrected RCM simulation. The results indicate that the uncertainty envelope is generally watershed and indicator dependent. It is difficult to draw a firm conclusion about whether one method is better than the other. In other words, the bias correction method could bring further uncertainty to future hydrological simulations, in addition to uncertainty related to the choice of a bias correction method. This implies that the nonbias‐corrected results should be provided to end users along with the bias‐corrected ones, along with a detailed explanation of the bias correction procedure. This information would be especially helpful to assist end users in making the most informed decisions.  相似文献   

Quantitative morphometric analysis of the Jama River profile in a tectonically active margin (Northwestern Ecuador)     

Pedro S.B.REYES  Mauricio E.VALAREZO  Jenry CóRDOVA  Fran?ois A.MICHAUD  Camilo ZAPATA 《山地科学学报》2018,15(5):966-975

The longitudinal profile of a river channel can be described in function of mathematical expressions. The logarithmic fit is the most used method to describe the relative equilibrium of a channel elevation profile. Rivers showing zones of high channel gradient and convex-upward profiles can be evaluated in function of the offset distance with respect to the logarithmic curve. The Jama River profile has been constructed using differential GPS data for the downstream reach and 4-m-grid DEM data base for the remaining headward profile. The resulting longitudinal profile shows a prominent knickpoint of about 80 m in elevation characterized by sharp local convexity. The offset distance in vertical direction from the logarithmic plot is interpreted as the successive accumulation of multiple uplift episodes associated with the Jama Fault System activity. The horizontal offset is suggested to represent the remaining retreated distance for the upstream propagation of the Jama knickpoint. The highly resistant Cretaceous rocks outcropping along the Jama knickpoint reach acts as an inflection point between two subprofiles that show well-fitted logarithmic curves, thereby representing a temporary partitioned equilibrium along the Jama River profile.  相似文献   

Grand Activity Minima and Maxima via Dual Dynamos     

Ölçek  Deniz  Charbonneau  Paul  Lemerle  Alexandre  Longpré  Gabriel  Boileau  Florence 《Solar physics》2019,294(7):1-9

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Assessing regression‐based statistical approaches for downscaling precipitation over North America          下载免费PDF全文

Jie Chen  François P. Brissette  Robert Leconte 《水文研究》2014,28(9):3482-3504

This paper assesses linear regression‐based methods in downscaling daily precipitation from the general circulation model (GCM) scale to a regional climate model (RCM) scale (45‐ and 15‐km grids) and down to a station scale across North America. Traditional downscaling experiments (linking reanalysis/dynamical model predictors to station precipitation) as well as nontraditional experiments such as predicting dynamic model precipitation from larger‐scale dynamic model predictors or downscaling dynamic model precipitation from predictors at the same scale are conducted. The latter experiments were performed to address predictability limit and scale issues. The results showed that the downscaling of daily precipitation occurrence was rarely successful at all scales, although results did constantly improve with the increased resolution of climate models. The explained variances for downscaled precipitation amounts at the station scales were low, and they became progressively better when using predictors from a higher‐resolution climate model, thus showing a clear advantage in using predictors from RCMs driven by reanalysis at its boundaries, instead of directly using reanalysis data. The low percentage of explained variances resulted in considerable underestimation of daily precipitation mean and standard deviation. Although downscaling GCM precipitation from GCM predictors (or RCM precipitation from RCM predictors) cannot really be considered downscaling, as there is no change in scale, the exercise yields interesting information as to the limit in predictive ability at the station scale. This was especially clear at the GCM scale, where the inability of downscaling GCM precipitation from GCM predictors demonstrates that GCM precipitation‐generating processes are largely at the subgrid scale (especially so for convective events), thus indicating that downscaling precipitation at the station scale from GCM scale is unlikely to be successful. Although results became better at the RCM scale, the results indicate that, overall, regression‐based approaches did not perform well in downscaling precipitation over North America. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献