Mass Fractions of S,Cu, Se,Mo, Ag,Cd, In,Te, Ba,Sm, W,Tl and Bi in Geological Reference Materials and Selected Carbonaceous Chondrites Determined by Isotope Dilution ICP‐MS

Mass fractions of S, Cu, Se, Mo, Ag, Cd, In, Te, Ba, Sm, W and Tl were determined by isotope dilution sector field ICP‐MS in the same sample aliquot of reference materials using HF‐HNO₃ digestion in PFA beakers in pressure bombs and glassy carbon vessels in a high‐pressure asher (HPA‐S) for comparison. Additionally, Bi was determined by internal standardisation relative to Tl. Because isobaric and oxide interferences pose problems for many of these elements, efficient chromatographic separation methods in combination with an Aridus desolvator were employed to minimise interference effects. Repeated digestion and measurement of geological reference materials (BHVO‐1, BHVO‐2, SCo‐1, MAG‐1, MRG‐1 and UB‐N) gave results with < 5% relative intermediate precision (1s) for most elements, except Bi. Replicates of NIST SRM 612 glass digested on a hot plate were analysed by the same methods, and the results agree with reference values mostly within 2% relative deviation. Data for the carbonaceous chondrites Allende, Murchison, Orgueil and Ivuna are also reported. Digestion in a HPA‐S was as efficient as in pressure bombs, but some elements displayed higher blank levels following HPA‐S treatment. Pressure bomb digestion yielded precise data for volatile S, Se and Te, but may result in high blanks for W.     

Evolution microtectonique et paléo-champs de contraintes du Bassin de Vienne

Résumé

Une étude des structures cassantes permet de préciser l’évolution tectonique du Bassin de Vienne, généralement considéré comme un bassin de type « pull apart » typique. Le champ de contrainte ottnangien-carpathien (18,5-16, 5 Ma) est caractérisé par une compression NNW-SSE. Pendant le Badénien-Sannanticn (16,5-11 Ma) une zone cisaillante sénestre de direction NE-SW a été formée dans un régime en compression N-S et extension E-W. En liaison avec cette zone décrochante trois types d’extension locale conduisent à une forte subsidence dans les dépression : extension NE-SW parallèle aux accidents sénestres, extension E-W entre les décrochements et extension NW-SE au-dessus des zones décrochantes profondes. Le champ de contrainte vers la fin du Sannaticn est marqué par une compression ENE-WSW, tandis que celui du Pannonicn- récent est similaire á celui du Miocène moyen.

Une rotation de la paléocontrainte maximale horizontale, de NNW-SSE a ENE-SSW est mise en évidence pendant la période Ottnangien-Sannantien (18,5-11 Ma). Cette rotation est parallèle A celle des directions de mise en place des nappes carpathicnnes externes. L’origine des rotation est l’échappement continental des Alpes orientales et des Carpathes septentrionales vers le NE et son blocage graduel d’Ouest en Est au front des nappes carpathiennes. Après ce blocage, l’échappement a continué avec une faible intensité du Pannonien à l’Actuel. Alors que l’échappement a été initié par une compression N-S due á la collision Europe-promontoire Adriatique, le champ de contrainte à l’intérieur des blocs échappés reflète l’effet de leur blocage au front des nappes carpalhiques.     

A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

Determination of Molybdenum, Antimony and Tungsten at sub μg g−1 Levels in Geological Materials by ID-FI-ICP-MS

We have developed a rapid and accurate method for the determination of Mo, Sb and W in geological samples using isotope dilution inductively coupled plasma-mass spectrometry with a flow injection system (ID-FI-ICP-MS). The chemical procedure requires HF digestion of the sample with a Mo-Sb-W mixed spike, subsequent evaporation and dissolution of Mo, Sb and W from Mg and Ca fluorides with HF. Recovery yields of Mo, Sb and W in the extraction were > 94% for samples of peridotite, basalt and andesite composition, with the exception of W in samples of peridotite composition for which recovery was 81%. No matrix effects were observed in the determination of the isotope ratios of Mo, Sb and W in solutions prepared from peridotite, basalt and andesite samples down to a dilution factor of 100. Detection limits of Mo, Sb and W in silicate materials were at the several ng g⁻¹ level. Analysis of the silicate reference materials PCC-1, DTS-1, BCR-1, BHVO-1, AGV-1 from the US Geological Survey and JP-1, JB-1, -2, -3, JA-1, -2, and -3 from the Geological Survey of Japan as well as the Smithsonian reference Allende powder yielded reliable Mo, Sb and W concentrations. The repeatability in the analysis of basalts and andesites was < 9%. This technique requires only 0.2 ml sample solution, and is therefore suitable for analyzing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates.     

Molybdenum Mass Fractions and Isotopic Compositions of International Geological Reference Materials

The double‐spike method with multi‐collector inductively coupled plasma‐mass spectrometry was used to measure the Mo mass fractions and isotopic compositions of a set of geological reference materials including the mineral molybdenite, seawater, coral, as well as igneous and sedimentary rocks. The long‐term reproducibility of the Mo isotopic measurements, based on two‐year analyses of NIST SRM 3134 reference solutions and seawater samples, was ≤ 0.07‰ (two standard deviations, 2s, n = 167) for δ^98/95Mo. Accuracy was evaluated by analyses of Atlantic seawater, which yielded a mean δ^98/95Mo of 2.03 ± 0.06‰ (2s, n = 30, relative to NIST SRM 3134 = 0‰) and mass fraction of 0.0104 ± 0.0006 μg g^?1 (2s, n = 30), which is indistinguishable from seawater samples taken world‐wide and measured in other laboratories. The comprehensive data set presented in this study serves as a reference for quality assurance and interlaboratory comparison of high‐precision Mo mass fractions and isotopic compositions.     

Le Viséen supérieur d'Azarhare (Maroc central) : environnements de dépôt,datation et évolution diagénétique

The unexplored area of Azarhare in central Morocco is studied thanks to three sections composed of five lithological facies Main biostratigraphical and sedimentological results concern (1) the identification of Late Visean biozones, with important presence of problematic algae Ungdarella, (2) the regional extension of deposit sequences SD5, SD6 and SD7 previously defined, (3) and an analysis of the diagenetic kaolinite. To cite this article: A. Karim et al., C. R. Geoscience 337 (2005).     

Analysis of flood propagation changes in the Kienstock—Bratislava reach of the Danube River/Analyse des changements de propagation des crues dans le tronçon Kienstock—Bratislava du Fleuve Danube

Abstract

In the first part of this study, a flood wave transformation analysis for the largest historical floods in the Danube River reach Kienstock–Bratislava was carried out. For the simulation of the historical (1899 and 1954) flood propagation, the nonlinear river model NLN-Danube (calibrated on the recent river reach conditions) was used. It was shown that the simulated peak discharges were not changed significantly when compared to their historical counterparts. However, the simulated hydrographs exhibit a significant acceleration of the flood wave movement at discharges of between 5000 and 9000 m³ s^-1. In the second part, the travel time-water level relationships between Kienstock and Bratislava were analysed on a dataset of the flood peak water levels for the period 1991–2002. An empirical regression routing scheme for the Danube short-term water level forecast at Bratislava station was derived. This is based on the measured water level at Kienstock gauging station.     

Influences of coupled wind–water processes on suspended sediment grain size: an example from tributaries of the Yellow River / Influences de processus couplés éoliens-hydriques sur la granulométrie des matières en suspension: exemple d'affluents du Fleuve Jaune

Abstract

Some unique coupled wind–water erosion processes exist in the desert-loess transitional zone in the middle Yellow River basin. Based on data from 40 stations on 29 rivers, a study was made on the influence of such processes on suspended sediment grain-size characteristics of the tributaries of the Yellow River. Results show that the percentage of >0.05-mm grain size decreases with the increased annual mean precipitation, but increases with the increase in the annual mean number of sand-dust storm days. The percentage of <0.01-mm grain size increases with the increase in the annual mean precipitation, but decreases with the increase in the annual number of sand-dust storm days. Based on annual mean data from 40 stations, multiple regression equations were established between the percentages of >0.05-mm grain size (r _>0.05) and <0.01-mm grain size (r _<0.01), annual mean precipitation (P _m) and annual mean number of sand-dust storm days (D _ss). On this basis, the relative contributions of the variations in D _ss and P _m to the variation in r _>0.05 and r _<0.01 were estimated. The results indicate that the variation in sand-dust storm frequency exerts greater influences on the variation in grain-size characteristics of suspended load than does the variation in annual mean precipitation. With the increase in the coupled wind–water processes index, expressed by P _m/D _ss, the percentage of >0.05-mm grain size in suspended sediment decreases and the percentage of <0.01-mm grain size increases. With the variation in P _m/D _ss, different combinations of r _>0.05 with r _<0.01 appear, which have some influence on the formation of hyperconcentrated flows. There exist some optimal ratios of coarse to fine fractions in suspended sediment that make sediment concentrations of hyperconcentrated flows the highest. The optimal r _>0.05/r _<0.01 value is related to some range of the index P _m/D _ss. When the P _m/D _ss index falls in this range, the optimum combination of relative coarse with fine sediments in the suspended load appears, and thus results in the peak values of sediment concentration.     

DÉTERMINATION DU DÉBIT DES PUITS INCOMPLETS DE NAPPES LIBRES FONCÉS EN TERRAIN ISOTROPE ET ANISOTROPE

ABSTRACT

In this paper, the author relies on Darcy's law and on an hypothesis formulated from experimental considerations to establish a semi-empirical formula for the calculation of the discharge of partially penetrating wells of free aquifer sunk in isotropic soils.

This relatively simple relation applied to 27 cases studied under an experimental design or numerical computations, reveals itself to have an unexpected accuracy.

Starting from previous formula, the author establishes another one for partially penetrating wells bored in anisotropic soils.     

Statistics of extremes and estimation of extreme rainfall: II. Empirical investigation of long rainfall records / Statistiques de valeurs extrêmes et estimation de précipitations extrêmes: II. Recherche empirique sur de longues séries de précipitations

Abstract

Abstract In the first part of this study, theoretical analyses showed that the Gumbel distribution is quite unlikely to apply to hydrological extremes and that the extreme value distribution of type II (EV2) is a more consistent choice. Based on these theoretical analyses, an extensive empirical investigation is performed using a collection of 169 of the longest available rainfall records worldwide, each having 100–154 years of data. This verifies the theoretical results. In addition, it shows that the shape parameter of the EV2 distribution is constant for all examined geographical zones (Europe and North America), with value κ = 0.15. This simplifies the fitting and the general mathematical handling of the distribution, which become as simple as those of the Gumbel distribution.