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

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).     

Direct Determination of Lead Isotope Ratios by Laser Ablation-Inductively Coupled Plasma-Quadrupole Mass Spectrometry in Lake Sediment Samples

A direct method for the determination of lead isotopic ratios by laser ablation-inductively coupled plasma-quadrupole mass spectrometry (LA-ICP-QMS) is presented. Samples of lake sediments were ground and pressed as pellets before being analysed. Mass bias was corrected by analysing an external calibration sample manufactured with pure silica doped with NIST SRM 981 solution. The efficiency of the mass bias correction was checked by comparing the ICP-MS data with lead isotopic ratios determined by thermal ionisation mass spectrometry (TIMS). The average long term reproducibilities were 0.40%, 0.40%, 0.20% and 0.30% (RSD) respectively for the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb ratios. The method was applied to the study of lake sediment samples, in order to determine the amount and origin of historical contamination by lead.     

Iron Isotopic Compositions of Geological Reference Materials and Chondrites

High‐precision iron isotopic compositions for Fe‐bearing geological reference materials and chondrites with a wide range of matrices (e.g., silicates, oxides, organic‐bearing materials) are reported. This comprehensive data set should serve as a reference for iron isotopic studies across a range of geological and biological disciplines for both quality assurance and inter‐laboratory calibration. Where comparison is available, the iron isotopic compositions of most geological reference materials measured in this study were in agreement with previously published data within quoted uncertainties. Recommendations for the reporting of future iron isotopic data and associated uncertainties are also presented. Long‐term repeat analyses of all samples indicate that highly reproducible iron isotopic measurements are now obtainable (± 0.03‰ and ± 0.05‰ for δ⁵⁶Fe and δ⁵⁷Fe, respectively).     

Application des outils chimiques et isotopiques à l'étude de la relation hydrodynamique entre les aquifères profonds de Sfax et de la Djeffara de Gabès Nord (Sud-Est tunisien)

Résumé

L'étude des bassins côtiers de Sfax et de la Djeffara de Gabès Nord, basée sur l'interprétation des données hydrochimiques (éléments majeurs) et isotopiques (¹⁸O, ²H et ¹⁴C), a permis une meilleure compréhension du fonctionnement hydrodynamique de l'aquifère Miocène le long de la frange côtière. En effet, d'après les données géochimiques, apparaît la présence de deux types de faciès chimiques: chloruré sodique dans le bassin de Sfax et mixte à chloruré sodique dans le bassin de Gabès Nord. Cette transition d'un faciès à un autre souligne la variabilité des origines de minéralisation des eaux. L'utilisation des outils isotopiques a permis l'identification d'une eau relativement ancienne à l'exception de quelques poches de recharge récente matérialisées à partir du relief de Zemlet El Beida en amont du bassin de Gabès Nord. Ceci a été vérifié par les fortes activités en¹⁴C des eaux dans cette région. Par conséquent, on peut noter que le passage du Sud au Nord le long de la côte est marqué par une grande variation latérale de lithologie et d'épaisseur de la formation aquifère, soulignant ainsi l'indépendance de chacun des deux réservoirs de Sfax et de la Djeffara de Gabès en absence de toute continuité hydrodynamique entre les deux bassins.

Editeur Z.W. Kundzewicz; Editeur associé S. Faye

Citation Ben Cheikh, N., Zouari, K., et Abidi, B., 2012. Application des outils chimiques et isotopiques à l'étude de la relation hydrodynamique entre les aquifères profonds de Sfax et de la Djeffara de Gabès Nord (Sud-Est tunisien). Hydrological Sciences Journal, 57 (8), 1662–1671.     

Comprehensive Chemical and Isotopic Analyses of Basalt and Sediment Reference Materials

Geochemical studies of geological samples require the precise determination of their major and trace element contents and, when measured, of their isotopic compositions. It is now commonly accepted that the accuracy and precision of geochemical analyses are best estimated by the concomitant analysis of international reference materials run as unknown samples. Although the composition of a wide selection of basalts is relatively well constrained, this is far from being the case for sedimentary materials. We present here a comprehensive set of major and trace element data as well as Nd, Hf, Sr and Pb isotopic compositions for thirteen commonly used international reference materials – eight magmatic rocks (BHVO‐2, BR, BE‐N, BR 24, AGV‐1, BIR‐1, UB‐N, RGM‐1) and five sediments (JLk‐1, JSd‐1, JSd‐2, JSd‐3, LKSD‐1). We determined the concentrations of over forty elements in the magmatic rocks together with Sr, Nd, Hf and Pb isotopic compositions. Our trace element results were both accurate (difference ≤ 3%) and precise (reproducibility at 1s ≤ 3%) and the isotopic results were very similar to other published values. In contrast, we observed a significant chemical and isotopic variability in the sedimentary materials, which we attribute to mineral heterogeneities in the powders. Despite the limitation imposed by this heterogeneity, our work presents a complete set of data determined with a precision not yet achieved in the literature for sedimentary material. We also provide the first Nd, Hf and Pb isotopic measurements for the five sediments, which are commonly used by the geochemical community. Our study of both basalt and sediment reference materials represents a comprehensive and self‐consistent set of geochemical data and can therefore be considered as a reference database for the community.     

Precise Determination of Sm and Nd Concentrations and Nd Isotopic Compositions in Highly Depleted Ultramafic Reference Materials

In this study, a high‐precision method for the determination of Sm and Nd concentrations and Nd isotopic composition in highly depleted ultramafic rocks without a preconcentration step is presented. The samples were first digested using the conventional HF + HNO₃ + HClO₄ method, followed by the complete digestion of chromite in the samples using HClO₄ at 190–200 °C and then complete dissolution of fluoride formed during the HF decomposition step using H₃BO₃. These steps ensured the complete digestion of the ultramafic rocks. The rare earth elements (REEs) were separated from the sample matrix using conventional cation‐exchange chromatography; subsequently, Sm and Nd were separated using the LN columns. Neodymium isotopes were determined as NdO⁺, whereas Sm isotopes were measured as Sm⁺, both with very high sensitivity using single W filaments with TaF₅ as an ion emitter. Several highly depleted ultramafic rock reference materials including USGS DTS‐1, DTS‐2, DTS‐2b, PCC‐1 and GSJ JP‐1, which contain extremely low amounts of Sm and Nd (down to sub ng g^?1 level), were analysed, and high‐precision Sm and Nd concentration and Nd isotope data were obtained. This is the first report of the Sm‐Nd isotopic compositions of these ultramafic rock reference materials except for PCC‐1.     

Proposal for an International Molybdenum Isotope Measurement Standard and Data Representation

Molybdenum isotopes are increasingly widely applied in Earth Sciences. They are primarily used to investigate the oxygenation of Earth's ocean and atmosphere. However, more and more fields of application are being developed, such as magmatic and hydrothermal processes, planetary sciences or the tracking of environmental pollution. Here, we present a proposal for a unifying presentation of Mo isotope ratios in the studies of mass‐dependent isotope fractionation. We suggest that the δ^98/95Mo of the NIST SRM 3134 be defined as +0.25‰. The rationale is that the vast majority of published data are presented relative to reference materials that are similar, but not identical, and that are all slightly lighter than NIST SRM 3134. Our proposed data presentation allows a direct first‐order comparison of almost all old data with future work while referring to an international measurement standard. In particular, canonical δ^98/95Mo values such as +2.3‰ for seawater and ?0.7‰ for marine Fe–Mn precipitates can be kept for discussion. As recent publications show that the ocean molybdenum isotope signature is homogeneous, the IAPSO ocean water standard or any other open ocean water sample is suggested as a secondary measurement standard, with a defined δ^98/95Mo value of +2.34 ± 0.10‰ (2s).     

SLRS‐5 Elemental Concentrations of Thirty‐Three Uncertified Elements Deduced from SLRS‐5/SLRS‐4 Ratios

The fifth version of natural river water certified reference material, SLRS‐5 (National Research Council – Conseil National de Recherches Canada), is commonly used to control the quality of major and trace element measurements. Concentrations of silicon and thirty‐one uncertified trace elements have been reported for the certified reference material SLRS‐4, but they are not yet available for SLRS‐5. Here, SLRS‐5/SLRS‐4 ratios were deduced from SLRS‐5 and SLRS‐4 measurements by inductively coupled plasma‐atomic emission spectrometry and high‐resolution inductively coupled plasma‐mass spectrometry for certified elements and thirty‐five uncertified elements (rare earth elements, B, Bi, Br, Cs, Ga, Ge, Hf, Li, Nb, P, Pd, Rb, Rh, S, Sc, Si, Sn, Th, Ti, Tl, Y). Both reference materials were measured directly one after the other, so that calculated elemental ratios would not be notably influenced either by calibration uncertainties or by eventual long‐term instrumental drift. The computed ratios are in good agreement with those deduced from the certified values. We also report concentrations for thirty‐three uncertified elements in SLRS‐5 by combining the measured SLRS‐5/SLRS‐4 ratios and the published SLRS‐4 values. The resulting new data set provides target SLRS‐5 values, which will be useful in quality control procedures.     

Production and Certification of a Unique Set of Isotope and Delta Reference Materials for Boron Isotope Determination in Geochemical,Environmental and Industrial Materials

Isotopic reference materials are essential to enable reliable and comparable isotope data. In the case of boron only a very limited number of such materials is available, thus preventing adequate quality control of measurement results and validation of analytical procedures. To address this situation a unique set of two boron isotope reference materials (ERM‐AE102a and ‐AE104a) and three offset δ¹¹B reference materials (ERM‐AE120, ‐AE121 and ‐AE122) were produced and certified. The present article describes the production and certification procedure in detail. The isotopic composition of all the materials was adjusted by mixing boron parent solutions enriched in ¹⁰B or ¹¹B with a boron parent solution having a natural isotopic composition under full gravimetric control. All parent solutions were analysed for their boron concentration as well as their boron isotopic composition by thermal ionisation mass spectrometry (TIMS) using isotope dilution as the calibration technique. For all five reference materials the isotopic composition obtained on the basis of the gravimetric data agreed very well with the isotopic composition obtained from different TIMS techniques. Stability and homogeneity studies that were performed showed no significant influence on the isotopic composition or on the related uncertainties. The three reference materials ERM‐AE120, ERM‐AE121 and ERM‐AE122 are the first reference materials with natural δ¹¹B values not equal to 0‰. The certified δ¹¹B values are ?20.2‰ for ERM‐AE120, 19.9‰ for ERM‐AE121 and 39.7‰ for ERM‐AE122, each with an expanded uncertainty (k = 2) of 0.6‰. These materials were produced to cover about three‐quarters of the known natural boron isotope variation. The ¹⁰B enriched isotope reference materials ERM‐AE102a and ERM‐AE104a were produced for industrial applications utilising ¹⁰B for neutron shielding purposes. The certified ¹⁰B isotope abundances are 0.29995 for ERM‐AE102a and 0.31488 for ERM‐AE104a with expanded uncertainties (k = 2) of 0.00027 and 0.00028, respectively. Together with the formerly certified ERM‐AE101 and ERM‐AE103 a unique set of four isotope reference materials and three offset δ¹¹B reference materials for boron isotope determination are now available from European Reference Materials.