Partial L-moments for the analysis of censored flood samples / Utilisation des L-moments partiels pour l’analyse d’échantillons tronqués de crues

Abstract

Abstract A parameter estimation method is proposed for fitting the generalized extreme value (GEV) distribution to censored flood samples. Partial L-moments (PL-moments), which are variants of L-moments and analogous to ?partial probability weighted moments?, are defined for the analysis of such flood samples. Expressions are derived to calculate PL-moments directly from uncensored annual floods, and to fit the parameters of the GEV distribution using PL-moments. Results of Monte Carlo simulation study show that sampling properties of PL-moments, with censoring flood samples of up to 30% are similar to those of simple L-moments, and also that both PL-moment and LH-moments (higher-order L-moments) have similar sampling properties. Finally, simple L-moments, LH-moments, and PL-moments are used to fit the GEV distribution to 75 annual maximum flow series of Nepalese and Irish catchments, and it is found that, in some situations, both LH- and PL-moments can produce a better fit to the larger flow values than simple L-moments.     

An Exploration of the Interplay between the Measurement Uncertainty and the Number of Samples in Contaminated Land Investigations

In the assessment of potentially contaminated land, the number of samples and the uncertainty of the measurements (including that from sampling) are both important factors in the planning and implementation of an investigation. Both parameters also effect the interpretation of the measurements produced, and the process of making decisions based upon those measurements. However, despite their importance, previously there has been no method for assessing if an investigation is fit‐for‐purpose with respect to both of these parameters. The Whole Site Optimised Contaminated Land Investigation (WSOCLI) method has been developed to address this issue, and to allow the optimisation of an investigation with respect to both the number of samples and the measurement uncertainty, using an economic loss function. This function was developed to calculate an ‘expectation of (financial) loss’, incorporating costs of the investigation itself, subsequent land remediation, and potential consequential costs. To allow the evaluation of the WSOCLI method a computer program ‘OCLISIM’ has been developed to produce sample data from simulated contaminated land investigations. One advantage of such an approach is that as the ‘true’ contaminant concentrations are created by the program, these values are known, which is not the case in a real contaminated land investigation. This enables direct comparisons between functions of the ‘true’ concentrations and functions of the simulated measurements. A second advantage of simulation for this purpose is that the WSOCLI method can be tested on many different patterns and intensities of contamination. The WSOCLI method performed particularly well at high sampling densities producing expectations of financial loss that approximated to the true costs, which were also calculated by the program. WSOCLI was shown to produce notable trends in the relationship between the overall cost (i.e., expectation of loss) and both the number of samples and the measurement uncertainty, which are: (a) low measurement uncertainty was optimal when the decision threshold was between the mean background and the mean hot spot concentrations. (b) When the hot spot mean concentration is equal to or near the decision threshold, then mid‐range measurement uncertainties were optimal. (c) When the decision threshold exceeds the mean of the hot spot, mid‐range measurement uncertainties were optimal. The trends indicate that the uncertainty may continue to rise if the difference between hot spot mean and the decision threshold increases further. (d) In any of the above scenarios, the optimal measurement uncertainty was lower if there is a large geochemical variance (i.e., heterogeneity) within the hot spot. (e) The optimal number of samples for each scenario was indicated by the WSOCLI method, and was between 50 and 100 for the scenarios considered generally; although there was significant noise in the predictions, which needs to be addressed in future work to allow such conclusions to be clearer.     

Reconnaissance par sismique réfraction de la décompression et de l’instabilite des falaises vives du Bessin (Normandie,France)

Résumé

Les falaises normandes du Bessin (France) sont constituées par une succession de formations calcaires et marneuses. De nombreux mouvements de terrain, parfois de grande ampleur, affectent périodiquement ces falaises. La faible résistance mécanique des marnes, mise en évidence lors de l’étude du récent glissement du Bouffay de 1981, a dû être favorisée par un fluage associé à la décompression des calcaires sus-jacents suivant un type de déformation qui peut être observé dans un mouvement quaternaire fossilisé (vallon du Pisseau). Grâce à une reconnaissance systématique de la zone décomprimée par la petite sismique réfraction, des relations simples sont établies, permettant d’évaluer le volume décomprimé â partir des caractéristiques géométriques et lithologiques de la falaise. Ce volume semble définir l’enveloppe à l’intérieur de laquelle les mouvements sont susceptibles d’intervenir.     

Elimination of Interferences in the Determination of Palladium,Platinum and Rhodium Mass Fractions in Moss Samples using ICP‐MS/MS

Moss samples (Pleurozium schreberi) exposed to traffic‐related emission of Pd, Pt and Rh were analysed in this study. Successful elimination of interferences was achieved in the determination of Pd, Pt and Rh mass fractions in these samples using inductively coupled plasma‐tandem mass spectrometry (ICP‐MS/MS). Based on the results, a reliable determination of Pd, Pt and Rh mass fractions in microwave‐digested moss samples was obtained using ammonia (10% NH₃ in He) in the collision/reaction cell when ¹⁰³Rh was measured either on‐mass (103→103) or with mass‐shift (103→171) and mass‐shifts for ¹⁰⁸Pd (108→159) and ¹⁹⁵Pt (195→229) were used. The ICP‐MS/MS procedure was validated using BCR‐723 (road dust) as a reference material. In addition, a good agreement between the ICP‐MS/MS results and the results obtained with cloud point extraction and quadrupole ICP‐MS was observed for the moss samples.     

Strontium,SO42−/Cl− and Mg2+/Ca2+ ratios as tracers for the evolution of seawater into coastal aquifers: the example of Castell de Ferro aquifer (SE Spain)

The strontium content and the SO₄^2?/Cl^? and Mg²⁺/Ca²⁺ ratios were used as natural tracers of the residence time of seawater intrusion into the Castell de Ferro aquifer. Analysis of these parameters indicated the existence of two principal flowpaths in the aquifer. The first flows through the eastern part of the aquifer, through the karstified Castell de Ferro massif; it accommodates a larger and more rapid flow, so that the residence time is shorter, leading to lower SO₄²⁺/Cl^? ratios, lower Sr²⁺ content and higher Mg²⁺/Ca²⁺ ratios. The second flowpath is in the western sector, and flows exclusively through alluvial deposits; the flow here is slower, particularly that flowing towards the sea. Thus the residence time of the water here will be longer and there is scant flushing of the intruded seawater; this is manifested in the high Sr²⁺ content, high SO₄²⁺/Cl^? and low Mg²⁺/Ca²⁺ ratios. To cite this article: P. Pulido-Leboeuf et al., C. R. Geoscience 335 (2003).     

Single Column Sequential Extraction of Ra,Nd, Th,Pa and U from a Natural Sample

A new procedure allowing the sequential extraction of Ra, Nd, Th, Pa and U from the same initial natural sample (sea or river waters, particles, sediments, rocks) is proposed. Extraction recoveries were better than 90%. Procedural blanks ranged from 80 pg (for Nd) to below 1 fg, the detection limit of the MC‐ICP‐MS used (for Pa); all were negligible compared with the amounts of elements currently determined. Based on classical anionic resins attached to a peristaltic pump allowing precise flow rate control, this procedure allowed a consequent reduction of the sample size, which improved the sampling resolution and reduced the sampling cost. It also ensured a better consistency of the samples for the five tracers.     

Abundances of Sulfur,Selenium, Tellurium,Rhenium and Platinum‐Group Elements in Eighteen Reference Materials by Isotope Dilution Sector‐Field ICP‐MS and Negative TIMS

Geological reference materials (RMs) with variable compositions and NIST SRM 612 were analysed by isotope dilution mass spectrometry for bulk rock concentrations of chalcogen elements (sulfur, selenium and tellurium), rhenium and platinum‐group elements (PGEs: Ru, Pd, Os, Ir and Pt), including the isotope amount ratios of ¹⁸⁷Os/¹⁸⁸Os. All concentrations were obtained from the same aliquot after HCl‐HNO₃ digestion in a high pressure asher at 320 °C. Concentrations were determined after chemical separation by negative TIMS, ICP‐MS and hydride generation ICP‐MS (Se, Te). As in previous studies, concentrations of the PGEs in most RMs were found to be highly variable, which may be ascribed to sample heterogeneity at the < 1 g level. In contrast, S, Se and Te displayed good precision (RSD < 5%) in most RMs, suggesting that part of the PGE budget is controlled by different phases, compared with the chalcogen budget. The method may minimise losses of volatile chalcogens during the closed‐system digestion and indicates the different extent of heterogeneity of chalcogens, Re and PGEs in the same sample aliquot. OKUM, SCo‐1, MRG‐1, DR‐N and MAG‐1 are useful RMs for the chalcogens. NIST SRM 612 displays homogenous distribution of S, Se, Te, Pt and Pd in 30 mg aliquots, in contrast with micro‐scale heterogeneity of Se, Pd and Pt.     

Determination of Zr and Hf in a Flux-Free Fusion of Whole Rock Samples using Laser Ablation Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) with Isotope Dilution Calibration

Isotope dilution calibration has been applied to the determination of Zr and Hf in whole rocks by laser ablation (LA)-ICP-MS. Enriched isotopes were added during the preparation of flux-free, synthetic whole rock glasses and homogenised through a combination of grinding and fusion. This method avoids problems, such as solution instability and the chemical resistance of minerals such as zircon, inherent in acid digestion sample preparation. The use of isotope dilution removes the need for external calibration using certified reference material glasses such as NIST SRM 612 for which certified Zr and Hf values are not available. The precision of Zr and Hf determinations were found to be < 1% and 3.5% respectively, limited by Poisson counting statistics which contributed to 50% of the final precision of analysis. Measured values correlate closely with compiled literature values.     

Reassessment of Hydrofluoric Acid Desilicification in the Carius Tube Digestion Technique for Re–Os Isotopic Determination in Geological Samples

In this study, Re and Os isotopes were systematically determined in six geological reference materials (RMs; covering a wide range of lithologies) using the Carius tube (CT) digestion technique with and without hydrofluoric acid desilicification. Our results show that the HF desilicification increased the Re extraction efficiency (by 9–15%) evidenced from basaltic and andesitic rocks (e.g., BHVO‐2, TDB‐1 and AGV‐2). This implies that a small proportion of Re resides in silicate phases. For mafic–ultramafic rocks (e.g., BCR‐2, WGB‐1 and WPR‐1), Re extraction efficiencies obtained by the CT digestion with and without HF desilicification were similar. This may indicate that Re in these rocks may dominantly reside in some phases (e.g., magnetite and sulfides) that could be completely dissolved in aqua regia solutions without the aid of HF desilicification. Our results also show that the HF desilicification increased Os extraction efficiency (by 13–99%) in some RMs (e.g., BHVO‐2, WGB‐1 and AGV‐2). This observation suggests that a portion of Os‐rich trace phases may occur as inclusions in the silicate phases that act as isolators at ~ 200 mesh sizes. This study demonstrates that the HF desilicification step prior to CT digestion is important for complete extraction of Re and Os in geological samples.     

Thermicité et déformation de la marge continentale dans le Sud de la Tasmanie (Australie) : résultats préliminaires d'une analyse par traces de fission et d'une étude microstructuraleFission track reconnaissance of the thermal and tectonic settings of the South Tasman rise

We present and discuss a few fission track data, and microstructural observations, from rock samples dredged along the western and southwestern continental margin of Tasmania. The results allow assessing the thermal and tectonic regimes that were active prior to and during the margin creation. The different ages, as provided by fission tracks, and deformational styles, as evidenced from microstructures, are then tentatively correlated with the two main rifting episodes, in Late Jurassic–Cretaceous times and Eocene–Oligocene respectively, deduced from kinematical reconstructions, that have led to the present- day southern margin of Tasmania. To cite this article: M. Sélo et al., C. R. Geoscience 334 (2002) 59–66