Production and Certification of Synthetic Selenium Isotopic Reference Materials

Due to intensive research into selenium isotopes in recent years, the increasing requirement for reliable and comparable measurement results has created a strong demand for selenium isotopic certified reference materials (iCRM) that were previously not available. To address this, eleven selenium iCRMs were developed, including ten synthetic iCRMs (GBW 04447–GBW 04456) and one natural iCRM (GBW 04457). The synthetic iCRMs were prepared with ⁷⁶Se, ⁷⁸Se, ⁸⁰Se and ⁸²Se solutions and a natural selenium solution; the natural iCRM was prepared with highly pure selenium material. The property values of isotope ratios in these iCRMs were certified by calibrated mass spectrometry with a collision cell multi‐collector ICP‐MS. The mass discrimination effect of the instrument was corrected with corresponding ⁷⁸Se/⁷⁶Se isotope mixtures and ⁸²Se/⁷⁶Se isotope mixtures, which were gravimetrically prepared with purified, isotopically enriched selenium materials. Homogeneity and stability tests were performed, and no significant influences were found. The uncertainty of the property values of the iCRMs was evaluated according to the Guide to the Expression of Uncertainty in Measurement (GUM) of ISO/BIPM and ISO Guide 35. The δ^82/76Se value of GBW 04457 relative to NIST SRM 3149 was also calculated. These iCRMs are intended for use in calibration of instruments and evaluation of methods for the determination of selenium isotope ratios.     

Une méthode de quantification de la dégradation d'un escarpement de faille au cours des cycles climatiques du Quaternaire : la faille de Jobourg (Nord Cotentin,France)Quantification of a fault-scarp degradation through Quaternary: the Jobourg fault (North Cotentin,France)

The degradation of the Jobourg fault-scarp occurred by cryoclastic processes in a periglacial environment during a part of Quaternary time. An attempt of quantification indicates a bulk scarp erosion of about 39 m³ m^?2, while the head accumulated at the bottom of the fault scarp only represents 4.6 m³ m^?2. To cite this article: M. Font et al., C. R. Geoscience 334 (2002) 171–178.     

Rhinocerotid tooth enamel 18O/16O variability between 23 and 12 Ma in southwestern France

The relationship between the oxygen isotope ratio of mammal tooth enamel and that of drinking water was used to reconstruct changes in the Miocene oxygen isotope ratio of rainfall (meteoric water ${\delta }^{18}$O_MW). These, in turn, are related to climatic parameters (temperature, precipitation and evaporation rate). ${\delta }^{18}$O values of rhinocerotid teeth from the Aquitaine Basin (southwestern France) suggest a significant climatic change between 17 and 12 Ma, characterized by cooling together with precipitation increase, in agreement with other terrestrial and oceanic records. To cite this article: I. Bentaleb et al., C. R. Geoscience 338 (2006).     

Palaeogeography and clay mineralogy of mid-Cretaceous flysches in the Gibraltar Arc area

A combined sedimentological and mineralogical study of several mid-Cretaceous sequences of the western Betic Cordillera and northern Rif has lead to the distinction of three main palaeogeographic areas. The basins of these areas received influxes of terrigenous sediments from different source areas. The southern Iberian margin was fed from the Iberian palaeocontinent and its clay-mineral association is characterized by a high content of well crystallized illite and kaolinite; the distal part of this margin was locally starved of continental sedimentation, but contains a considerable clayey contribution, probably oceanic in origin, made up mainly of smectites, illite and palygorskite. The sediments in the North African margin and the southern part of the North African Flysch Trough came from the African continent, the typical Aptian-Albian clay-mineral association being well crystallized illite, illite-smectite mixed layers, kaolinite, chlorite and lesser quantities of vermiculite. The terrigenous supply to the Mauritanian Realm of the North African Flysch Trough came from the Meso-Mediterranean terrane, and its usual Aptian-Albian clay association is illite, vermiculite, illite-smectite mixed layers and kaolinite. A significant change in the clay mineralogy occurred during the late Albian-early Cenomanian in the two former areas, consisting of a decrease in the detrital supply and a concomitant increase in smectites and palygorskite.The sedimentological and mineralogical evolution of this area was controlled by a combination of tectonic, eustatic and climatic changes in the westernmost Tethys during the mid-Cretaceous.     

Source-area controls on the composition of beach and fluvial sands on the southern side of the Gibraltar Strait and Western Alboran Sea (Flysch Basin, Internal and External, Domains, Northern Rif Chain)

The southern side of Gibraltar and the Western Alboran Sea of the northern Rif coasts and rivers provide a natural field laboratory for sampling modern sand at different scales: small catchment basins (first order) and rivers draining mountain belts (second order). The Rifian chain represents a deformed and uplifted thrust-belt and related forelands composed of Palaeozoic nappes, metamorphic and plutonic basement, and their sedimentary Mesozoic and Cenozoic siliciclastic and carbonate cover, respectively. The present physiography of the Rif Chain is shaped by a rugged mountainous relief drained by different scale catchment basins that supply the nearby coastal and marine deep-sea environments. The analysis of the composition of modern fluvial and beach sands is useful for the interpretation of transported sediments by surface processes from the continent toward coasts and later to deep-water environments.Modern beach and fluvial sands of the southern side of Gibraltar and the Western Alboran Sea display three distinct petrologic littoral provinces, from the east to the west and from the north to the south, respectively, designated as: (i) the Tangier–Bel Younech Littoral Province with 90% of sand derived from erosion of Flysch Nappes (Flysch Basin Domain); (ii) the Bel Younech–Sebta Littoral Province with 64% of sand fed mainly by the metamorphic Units of Upper Sebtides and (iii) the Sebta–Ras Mazari Littoral Province with 74% of sand supplied from the epimetamorphic Palaeozoic Ghomaride Nappes and Alpine cover rather than Mesozoic and Cenozoic sedimentary successions of the “Dorsale Calcaire” Units. Comparison of detrital modes of fluvial and coastal marine environments highlights their dispersal pathways and drainage patterns of actualistic sand petrofacies.     

Définition et datation de la Formation de Venaco (Corse) : dépôt d’origine gravitaire d’âge Priabonien

Priabonian age is highlighted for the first time in Corsica in the Venaco Formation using the presence of specific microfauna (in particular some representatives of Turborotalia cerroazulensis lineage). This silicoclastic formation is mainly represented by coarse facies. It is composed of three members from south to north and from oldest towards youngest: member of Uboli, Cardo and Orsu. The sedimentologic analysis reveals a gravity depositional environment, involving different type of currents. Sedimentologic and chronologic characteristics make the Venaco Formation and the Annot Formation (p.p.) equivalent. Dating the Venaco Fm. brings confirmation that the green schist metamorphism of the Variscan batholith and the related deformation are from the pre-Priabonian period.     

Chemical Analysis of Iron Meteorites Using a Hand‐Held X‐Ray Fluorescence Spectrometer

We evaluate the performance of a hand‐held XRF (HHXRF) spectrometer for the bulk analysis of iron meteorites. Analytical precision and accuracy were tested on metal alloy certified reference materials and iron meteorites of known chemical composition. With minimal sample preparation (i.e., flat or roughly polished surfaces) HHXRF allowed the precise and accurate determination of most elements heavier than Mg, with concentrations > 0.01% m/m in metal alloy CRMs, and of major elements Fe and Ni and minor elements Co, P and S (generally ranging from 0.1 to 1% m/m) in iron meteorites. In addition, multiple HHXRF spot analyses could be used to determine the bulk chemical composition of iron meteorites, which are often characterised by sulfide and phosphide accessory minerals. In particular, it was possible to estimate the P and S bulk contents, which are of critical importance for the petrogenesis and evolution of Fe‐Ni‐rich liquids and iron meteorites. This study thus validates HHXRF as a valuable tool for use in meteoritics, allowing the rapid, non‐destructive (a) identification of the extraterrestrial origin of metallic objects (i.e., archaeological artefacts); (b) preliminary chemical classification of iron meteorites; (c) identification of mislabelled/unlabelled specimens in museums and private collections and (d) bulk analysis of iron meteorites.     

A Review of the IAG GeoPT™ and Certification Programmes,their Protocols,and the Differences between the Original and Potential Modifications to the Certification Protocol

The IAG conducts two programmes, the GeoPT ^? proficiency test and a certification programme that are closely interconnected. Both support the quality control/quality assurance activities of geochemical laboratories. Each derives an estimate of ‘true value’ for a number of samples, but arrives at that estimate, and its uncertainty, differently. This review discusses the history of the two programmes and compares the ‘true values’ and their uncertainties obtained through each. It then considers ‘fitness‐for‐purpose’ issues related to both GeoPT ^? and certification uncertainties. Issues related to potential modification of the IAG protocol for certification are also considered.     

Small-scale ductile shear zones as transposed rheologically weak domains: A numerical modeling investigation and practical application

We test the hypothesis that small ductile shear zones are developed from initial rheologically weak domains. We regard weak domains as ellipsoidal inhomogeneities and apply Eshelby's formalism extended for power-law viscous materials to investigate the kinematics and finite strain evolution of the partitioned flow fields in weak domains. We show that, under an imposed bulk flow field, weak domains, regardless of their initial shapes and orientations, deform into zone-like features at relatively small bulk strains and the deformation paths inside weak domains have all characteristics expected in ductile shear zones. We apply our model to the Cap de Creus area Spain, where abundant small ductile shear zones exist. To relate the fabrics inside these shear zones with the regional deformation, we take a multi-scale approach. We assume that the area contained many weak domains which were randomly shaped and oriented initially and were deformed into shear zones eventually in response to the regional flow. We constrain the regional flow field by the fabric patterns across the area and compute numerically the partitioned flow fields in individual weak domains. The latter are related to fabrics inside shear zones. Our model reproduces first-order features of field-observed fabrics. Although the deformation path of each shear zone was close to simple shearing, the deformation of the whole belt was not. Our approach also resolves the strain compatibility problem for a finite-sized shear zone embedded in a far less deformed country rock.     

In Situ Determination of Au and Cu in Natural Pyrite by Near‐Infrared Femtosecond Laser Ablation‐Inductively Coupled Plasma‐Quadrupole Mass Spectrometry: No Evidence for Matrix Effects

Gold and copper concentrations were determined in natural pyrite by near‐infrared femtosecond LA‐ICP‐QMS, using both sulfide reference materials (pyrrhotite Po‐726 and in‐house natural chalcopyrite Cpy‐RM) and NIST SRM 610 as external calibrators. Firstly, using NIST SRM 610 as the external calibrator, we calculated the Au concentration in Po‐726 and the Cu concentration in Cpy‐RM. The calculated concentration averages for Au and Cu were similar to the values published for Po‐726 and Cpy‐RM, respectively. Secondly, we calculated Au and Cu concentrations taking NIST SRM 610 as an unknown sample and using Po‐726 and Cpy‐RM as external calibrators. Again, the average values obtained closely reflected the preferred concentrations for NIST SRM 610. Finally, we calculated Au and Cu concentrations in natural pyrite using sulfide and silicate reference materials as external calibrators. In both cases, calculated concentrations were very similar, independent of the external calibrator used. The aforementioned data, plus the fact that we obtained very small differences in relative sensitivity values (percentage differences are between 5% and 17% for ⁵⁷Fe, ⁶³Cu and ¹⁹⁷Au) on analyses of silicate and sulfide RMs, indicate that there were no matrix effects related to the differences in material composition. Thus, it is possible to determine Au and Cu in natural sulfides using NIST silicate glasses as an external calibrator.