High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.     

Accurate and Precise Elemental Abundance of Zinc in Reference Materials by an Isotope Dilution Mass Spectrometry TIMS Technique

A thermal ionisation mass spectrometric technique enabled the abundance of Zn in geological and biological reference materials and water samples to be measured by double spiking isotope dilution mass spectrometry enriched in the ⁶⁷Zn and ⁷⁰Zn isotopes. In the past, thermal ionisation mass spectrometry proved to be difficult for low-level zinc isotopic measurements. The size of Zn samples used for isotopic determination, in particular the biological RMs, represents an important breakthrough. These results represent the most accurate and precise concentrations measured for Zn in these samples. The maximum fractional uncertainty was that for TILL-3 (2%), while the minimum fractional uncertainty was 0.7% for both BCR-1 and W-2. The inhomogeneity of Zn in HISS-1 was revealed while other reference materials appeared homogeneous at the 95% confidence uncertainty. The certified concentration of Zn in HISS-1 and IMEP-19 by their producers are 28% and 3.8% higher than the values measured in this work. These are the first Zn concentration measurements in these materials by the isotope dilution-TIMS technique, except for BCR-1, NIES N^o 9 and IMEP-19. Reducing the blank enabled accurate measurement in water at the ng g^-1 level demonstrating the applicability of the technique for low-level Zn samples.     

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.     

A Comparison of In Situ Analytical Methods for Trace Element Measurement in Gold Samples from Various South African Gold Deposits

Trace element concentrations in gold grains from various geological units in South Africa were measured in situ by field emission‐electron probe microanalysis (FE‐EPMA), laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and synchrotron micro X‐ray fluorescence spectroscopy (SR‐μ‐XRF). This study assesses the accuracy, precision and detection limits of these mostly non‐destructive analytical methods using certified reference materials and discusses their application in natural sample measurement. FE‐EPMA point analyses yielded reproducible and discernible concentrations for Au and trace concentrations of S, Cu, Ti, Hg, Fe and Ni, with detection limits well below the actual concentrations in the gold. LA‐ICP‐MS analyses required larger gold particles (> 60 μm) to avoid contamination during measurement. Elements that measured above detection limits included Ag, Cu, Ti, Fe, Pt, Pd, Mn, Cr, Ni, Sn, Hg, Pb, As and Te, which can be used for geochemical characterisation and gold fingerprinting. Although LA‐ICP‐MS measurements had lower detection limits, precision was lower than FE‐EPMA and SR‐μ‐XRF. The higher variability in absolute values measured by LA‐ICP‐MS, possibly due to micro‐inclusions, had to be critically assessed. Non‐destructive point analyses of gold alloys by SR‐μ‐XRF revealed Ag, Fe, Cu, Ni, Pb, Ti, Sb, U, Cr, Co, As, Y and Zr in the various gold samples. Detection limits were mostly lower than those for elements measured by FE‐EPMA, but higher than those for elements measured by LA‐ICP‐MS.     

Modelling uncertainties in short-term reservoir operation using fuzzy sets and a genetic algorithm / Modélisation d’incertitudes dans la gestion de barrage à court terme grâce à des ensembles flous et à un algorithme génétique

Abstract

Abstract Various uncertainties are inherent in modelling any reservoir operation problem. Two of these are addressed in this study: uncertainty involved in the expression of reservoir penalty functions, and uncertainty in determining the target release value. Fuzzy set theory was used to model these uncertainties where the preferences of the decision maker for the fuzzified parameters are expressed as membership functions. Nonlinear penalty functions are used to determine the penalties due to deviations from targets. The optimization was performed using a genetic algorithm with the objectives to minimize the total penalty and to maximize the level of satisfaction of the decision maker with fuzzified input parameters. The proposed formulation was applied to the problem of finding the optimal release and storage values, taking Green reservoir in Kentucky, USA as a case study. The approach offers more flexibility to reservoir decision-making by demonstrating an efficient way to represent subjective uncertainties, and to deal with non-commensurate objectives under a fuzzy multi-objective environment.     

Coupling between weather radar rainfall data and a distributed hydrological model for real-time flood forecasting / Couplage de données pluviométriques issues de radars météorologiques et d’un modèle hydrologique distribué pour la prévision de crue en temps réel

Abstract

Abstract After the destructive flood in 1998, the Chinese government planned to build national weather radar networks and to use radar data for real-time flood forecasting. Hence, coupling of weather radar rainfall data and a hydrological (Xinanjiang) model became an important issue. The present study reports on experience in such coupling at the Shiguanhe watershed. After having corrected the radar reflectivity and the attenuation data, the weather radar rainfall was estimated and then corrected in real time using a Kalman filter. In general, the precipitation estimated from weather radar is reasonably accurate in most of the catchment investigated, after corrections as above. Compared to the results simulated by raingauge data, the simulations based on the weather radar data are of similar accuracy. Present research results show that rainfall estimated from the weather radar, the radar data correction method, the method of coupling, and the Xinanjiang model lend themselves well to application in operational real-time flood forecasting.     

2007年城市极端天气事件及其危害分析

通过对2007年国内一些主要城市发生的极端天气事件分析,以及与城市建设历史发展过程中的比较,表明城市气象灾害对城市安全运行的威胁日趋严重.由于极端降水天气事件的日益增多以及城市本身扩大发展、人口密度不断增加、城市的热岛效应更加明显等原因,客观上存在易产生剧烈的天气现象和城市承灾能力越来越脆弱等问题.在深入分析致灾因素、致灾结果中,提出需要解决的城市建设规划、应急管理体制等科学问题,同时给出了城市防灾减灾的决策建议.     

A Proposal for the Publication of Geochemical Data in the Scientific Literature

A proposal is set out for the information and details that should accompany the publication of geochemical data in the research literature. This proposal is based on the principle that sufficient detail must be included both to allow independent replication of the results and for reviewers to confirm that data are fit‐for‐purpose in supporting the way in which they have been interpreted. In particular, it is recommended that all analytical measurements should be accompanied by an estimate of uncertainty that includes both field sampling and laboratory contributions together with a statement that summarises the way published data conform to the principles of traceability.     

Combined Separation of Cu,Fe and Zn from Rock Matrices and Improved Analytical Protocols for Stable Isotope Determination

Isotope ratios of heavy elements vary on the 1/10000 level in high temperature materials, providing a fingerprint of the processes behind their origin. Ensuring that the measured isotope ratio is precise and accurate depends on employing an efficient chemical purification technique and optimised analytical protocols. Exploiting the disparate speciation of Cu, Fe and Zn in HCl and HNO₃, an anion exchange chromatography procedure using AG1‐×8 (200–400 mesh) and 0.4 × 7 cm Teflon columns was developed to separate them from each other and matrix elements in felsic rocks, basalts, peridotites and meteorites. It required only one pass through the resin to produce a quantitative and pure isolate, minimising preparation time, reagent consumption and total analytical blanks. A ThermoFinnigan Neptune Plus MC‐ICP‐MS with calibrator‐sample bracketing and an external element spike was used to correct for mass bias. Nickel was the external element in Cu and Fe measurements, while Cu corrected Zn isotopes. These corrections were made assuming that the mass bias for the spike and analyte element was identical, and it is shown that this did not introduce any artificial bias. Measurement reproducibilities were ± 0.03‰, ± 0.04‰ and ± 0.06‰ (2s) for δ⁵⁷Fe, δ⁶⁵Cu and δ⁶⁶Zn, respectively.     

Comparison of grey and phase-space rainfall forecasting models using a fuzzy decision method / Comparaison grâce à une méthode de décision floue des modèles gris et d’espace des phases pour la prévision de pluie

Abstract

Abstract This work applies a fuzzy decision method to compare the performance of the grey model with that of the phase-space model, in forecasting rainfall one to three hours ahead. Four indices and two statistical tests are used to evaluate objectively the performance of the forecasting models. However, a trade-off must be made in choosing a suitable model because various indices may lead to different judgements. Therefore, a fuzzy decision model was applied to solve this problem and to make the optimum decision. The results of fuzzy decision making demonstrate that the grey model outperforms the phase-space model for forecasting one hour ahead, but the phase-space model performs better for forecasting two or three hours ahead.