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.     

Precise and Accurate In Situ Determination of Lead Isotope Ratios in NIST,USGS, MPI‐DING and CGSG Glass Reference Materials using Femtosecond Laser Ablation MC‐ICP‐MS

Lead isotope ratio data were obtained with good precision and accuracy using a 266 nm femtosecond laser ablation (fLA) system connected to a multi‐collector ICP‐MS (MC‐ICP‐MS) and through careful control of analytical procedures. The mass fractionation coefficient induced by 266 nm femtosecond laser ablation was approximately 28% lower than that by 193 nm excimer laser ablation (eLA) with helium carrier gas. The exponential law correction method for Tl normalisation with optimum adjusted Tl ratio was utilised to obtain Pb isotopic data with good precision and accuracy. The Pb isotopic ratios of the glass reference materials NIST SRM 610, 612, 614; USGS BHVO‐2G, BCR‐2G, GSD‐1G, BIR‐1G; and MPI‐DING GOR132‐G, KL2‐G, T1‐G, StHs60/80‐G, ATHO‐G and ML3B‐G were determined using fLA‐MC‐ICP‐MS. The measured Pb isotopic ratios were in good agreement with the reference or published values within 2s measurement uncertainties. We also present the first high‐precision Pb isotopic data for GSE‐1G, GSC‐1G, GSA‐1G and CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 glass reference materials obtained using the femtosecond laser ablation MC‐ICP‐MS analysis technique.     

Uranium and Thorium Concentration and Isotopic Composition in Five Glass (BHVO‐2G,BCR‐2G,NKT‐1G,T1‐G,ATHO‐G) and Two Powder (BHVO‐2, BCR‐2) Reference Materials

Here we report uranium and thorium isotopic ratios and elemental concentrations measured in solid reference materials from the USGS (BHVO‐2G, BCR‐2G, NKT‐1G), as well as those from the MPI‐DING series (T1‐G, ATHO‐G). Specifically created for microanalysis, these naturally‐sourced glasses were fused from rock powders. They cover a range of compositions, elemental concentrations and expected isotopic ratios. The U‐Th isotopic ratios of two powdered source materials (BCR‐2, BHVO‐2) were also characterised. These new measurements via multi‐collector thermal ionisation mass spectrometry and multi‐collector inductively coupled plasma‐mass spectrometry can now be used to assess the relative performance of techniques and facilitate comparison of U‐Th data amongst laboratories in the geoscience community for in situ and bulk analyses.     

Enhancing the Two-Step Floating Catchment Area Model for Community Food Access Mapping: Case of the Supplemental Nutrition Assistance Program

In this article, a Gaussian-based two-step floating catchment area (2SFCA) model is applied to evaluate the geographical accessibility to Supplemental Nutrition Assistance Program (SNAP)-authorized retailers. First, the proposed method considers the interaction between the food supply (in terms of categorized benefit redemptions) and demand (in terms of benefit-receiving households). Second, the model is used to visualize food access patterns at the level of refined administrative units (i.e., census block groups). The developed food access metric was compared to the U.S. Department of Agriculture (USDA) Food Access Research Atlas, justifying the validity of this new method for small area estimation. The following are important observations: (1) the choice of catchment size had a considerable impact on the accessibility measure in urban areas (or when small statistical units are used); (2) the 2SFCA measurement had a higher level of correspondence with that of the USDA Atlas at a smaller catchment size for identifying low food access units; and (3) there was no significant inequality regarding SNAP accessibility with respect to different socioeconomic deprivation variables. This new method can better assist the SNAP administration with store authorization on a refined geographic scale. Key Words: food access, inequality, scale, Supplemental Nutrition Assistance Program (SNAP), two-step floating catchment area (2SFCA).     

Sulfur Concentration in Geochemical Reference Materials by Solution Inductively Coupled Plasma‐Mass Spectrometry

With implications for the origin of ore deposits, redox state of the atmosphere, and effects of volcanic outgassing, understanding the sulfur cycle is vital to our investigation of Earth processes. However, the paucity of sulfur concentration measurements in silicate rocks and the lack of well‐calibrated reference materials with concentrations relevant to the rocks of interest have hindered such investigations. To aid in this endeavour, this study details a new method to determine sulfur concentration via high mass resolution solution inductively coupled plasma‐mass spectrometry (ICP‐MS). The method is based on an aqua regia leach, involving relatively rapid sample preparation and analysis, and uses small test portion masses (< 50 mg). We utilised two independently prepared standard solutions to calibrate the analyses, resulting in 4% accuracy, and applied the method to eight geochemical reference materials. Measurements were reproducible to within ~ 10%. Sulfur concentrations and isotopes of six reference materials were measured additionally by elemental analyser‐combustion‐isotope ratio mass spectrometry to independently evaluate the accuracy of the ICP‐MS method. Reference materials that yielded reproducible measurements identical to published values from other laboratories (JGb‐1, JGb‐2 and MAG‐1) are considered useful materials for the measurement of sulfur. Reference materials that varied between studies but were reproducible for a given test portion perhaps suffer from sample heterogeneity and are not recommended as sulfur reference materials.     

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.     

Simultaneous Determination of Fluorine,Chlorine, Bromine and Iodine in Six Geochemical Reference Materials Using Pyrohydrolysis,Ion Chromatography and Inductively Coupled Plasma‐Mass Spectrometry

Concentrations of halogens (fluorine, chlorine, bromine and iodine) were determined in six geochemical reference materials (BHVO‐2, GS‐N, JG‐1, JR‐1, JB‐1b, JB‐2). Halogens were first extracted from powdered samples using a pyrohydrolysis technique, then hydrolysis solutions were analysed by ion chromatography for F and Cl and inductively coupled plasma‐mass spectrometry for Br and I. The detection limits in solutions were 100 μg l^?1 for both F and Cl and 10 ng l^?1 for Br and I. Considering the extraction procedure, performed on a maximum of 500 mg of sample and producing 100 ml of pyrohydrolysis solution, detection limits in rock samples were 20 mg kg^?1 for F and Cl and 2 μg kg^?1 for Br and I. The mean analytical errors on the studied composition ranges were estimated at 10 mg kg^?1 for F and Cl, 100 μg kg^?1 for Br and 25 μg kg^?1 for I. The concentration values, based on repeated (generally > 10) sample analysis, were in good agreement generally with published values and narrowed the mean dispersion around mean values. Large dispersions are discussed in terms of samples heterogeneity and contaminations during sample preparation. Basaltic RMs were found to be more suitable for studies of halogen compositions than differentiated rock material, especially granites – the powders of which were heterogeneous in halogens at the 500 mg level.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

An Interpretation of ISO Guidelines for the Certification of Geological Reference Materials

Recommendations for the certification of reference materials, as published by the International Organisation for Standardisation (ISO), are reviewed and proposals made as to how they can be adapted for the certification of new geological reference materials. Whilst acknowledging the important contribution made by the large number of existing matrix-matched geological reference materials, it is recommended that future characterisation programmes should follow the ISO guidelines for certification, not the least so that laboratories can readily use the resultant samples to establish the traceability of geoanalytical results.     

Morphology and kinematics of boudinage vein systems,Great Keppel Island,Queensland

Strongly boudinaged sandstone beds in a Palaeozoic accretionary complex are exposed on Great Keppel Island, off the central Queensland coast. Viewed in profile, the boudins are folded around mesoscopic F₂ hinge zones and overprinted by S₂ foliation indicating formation either during Late Carboniferous subduction accretion (D₁) or during a previously unrecognised discrete early phase of the Permian deformation (D₂). Boudin profiles record an average stretch of 1.51, although the contribution of D₂ and later deformation is not determined. Viewed in the plane of bedding, vein traces are variable and oblique to boudin necks by an average of 12° anticlockwise. The overall en echelon arrangement of veins in boudin necks is a primary feature of the structure and cannot be attributed to later deformation. This pattern of veining indicates oblique extension of the boudin necks by low‐vorticity non‐coaxial flow within the plane of bedding. One possible setting with such kinematics is the limb of a non‐cylindrical fold.