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.     

HP–UHP metamorphism as an indicator of slab dip variations in the Alpine arc

HP/UHP and LT metamorphic units that commonly occur in the inner parts of mountain belts result from the subduction of continental and oceanic material, most often exhumed prior to continental collision. The prograde pressure–temperature history of HP–UHP rocks strongly depends on the convergence rate and on the subduction zone geometry. The maximum pressure recorded provides a proxy for the depth of shearing off and stacking of HP metamorphic nappes. A 2-D thermal model of continental subduction at lithospheric scale is used to compute the length and pressure peak of detached HP metamorphic units as a function of the slab dip angle and the convergence rate. Model results are applied to the metamorphic nappe pile of the inner Alps. A mean convergence rate of 1 cm/year during the subduction of the Briançonnais terrane is indicated by the paleogeographic reconstructions between 46 and 38 Ma. On this basis, the available petrological data and lengths of metamorphic units are used to compute the variations of the slab dip angle. The slab dip angle is shown to increase, from the northeast to the southwest, along the Alpine arc with estimated values of 20° for Suretta, 30–45° for Monte Rosa and Gran Paradiso, and 60° for Dora Maira. From Eocene to Oligocene times, the increase in slab dip angle is controlled by changes of buoyancy, due to the spatial configuration of the Valaisan trough and the incoming of crustal material within the subduction zone.     

Anisotropic Closure in Squeezing Rocks: The Example of Saint-Martin-la-Porte Access Gallery

In this paper, we analyse the convergence measurements recorded in a gallery excavated in severely squeezing ground. The procedure consists in a preliminary geometrical treatment of the raw data to evaluate the principal axes of deformation by assuming an elliptic deformation of the walls of the gallery. Then the convergence law proposed by Sulem et al. (Int J Rock Mech Min Sci Geomech Abstr 24(3):145–154, 1987a), which is extended to account for anisotropic closure, is fitted on the displacements along the two axes of the obtained ellipse. This procedure is more robust and relevant than fitting the convergence recorded on the most deforming segment or fitting the average value of the convergence along the various segments. An attempt is made to correlate the amount and the direction of anisotropic deformation with the lithology and some geological features described by the dominant discontinuity families.     

A comparative analysis of interface erosion tests

Interface erosion is one of the main phenomena in dams, dikes and their foundations which may increase their failure risk. In laboratories, the jet erosion test (JET) and the hole erosion test (HET) are commonly used for the evaluation of the sensibility of interface erosion of fine soils. The results are interpreted by two distinct methods that are valid for one test only. A new energy analysis of the tests is developed, relating the total eroded mass to the dissipated fluid energy, and a new erosion resistance index is proposed. Seven naturally occurring fine-grained soils, covering a large range of erodibility, are compacted with the Proctor protocol, and they are tested with the two devices. It was shown that by using the commonly used methods, the values of the erosion coefficient are systematically higher with the JET than with the HET and the HET critical shear stress is about fifty times higher than the JET critical shear stress. Thus, the relative soil classifications yielded by the two erodimeters are not exactly the same. Based on energy analysis, values of erosion resistance index are roughly the same for each tested soil with the two apparatuses and a single classification of soil erodibility is obtained.     

Molecular evidence for life in the 3.5 billion year old Warrawoona chert

The biological origin of organic matter in the oldest siliceous sediments (cherts) is still debated. To address this issue, the insoluble organic matter (kerogen) was isolated from a chert of the Warrawoona group. The chemical structure of the kerogen was investigated through a combination of analytical techniques including solid-state ¹³C nuclear magnetic resonance and pyrolysis. Although dominated by aromatic hydrocarbons, the pyrolysate comprises a homologous series of long chain aliphatic hydrocarbons characterized by odd-over-even carbon number predominance. This distribution is only consistent with a biological origin. As kerogen must be contemporaneous of the solidification of the chert, this observation should be regarded as an evidence for the presence of life on Earth, 3.5 By ago.     

Simple formulas for the dynamic stiffness of pile groups

Simple formulas are derived for the dynamic stiffness of pile group foundations subjected to horizontal and rocking dynamic loads. The formulations are based on the construction of a general model of impedance matrices as the condensation of matrices of mass, damping, and stiffness, and on the identification of the values of these matrices on an extensive database of numerical experiments computed using coupled finite element–boundary element models. The formulations obtained can be readily used for the design of both floating piles on homogeneous half‐space and end‐bearing piles and are applicable for a wide range of mechanical and geometrical parameters of the soil and piles, in particular for large pile groups. For the seismic design of a building, the use of the simple formulas rather than a full computational model is shown to induce little error on the evaluation of the response spectra and time histories. Copyright © 2009 John Wiley & Sons, Ltd.     

Probabilistic impedance of foundation: Impact of the seismic design on uncertain soils

In the linear seismic design of buildings, the (deterministic) substructure method is a customary and efficient approach. However, the existence of spatial variability in the parameters of the mechanical model of the soil, as well as parametric errors, calls for the use of probabilistic approaches in order to provide a reliable design of the structure. The construction of probabilistic models of the soil impedance matrix provides a natural path to such approaches within the context of the substructure method. Two main techniques are described in this paper: a parametric one, typically using the stochastic finite element method, and a nonparametric one, which was introduced more recently. The latter is explored more specifically, and the possibilities it offers in terms of seismic design are presented. In particular, it is shown that it allows for the estimation of quantiles of the quantities of interest, rather than confidence intervals, which lead to highly conservative design. Copyright © 2008 John Wiley & Sons, Ltd.     

Dating carbonate rocks with in-situ produced cosmogenic Be: Why it often fails

Surface exposure dating of carbonate rocks using cosmogenic ¹⁰Be is problematic. We have performed step-wise leaching of calcite-rich samples in order to investigate the reasons for this. Results on different grain size fractions clearly indicate the source of atmospheric ¹⁰Be is clay. We demonstrate that partial-leaching procedures, which result in moderate pH levels will not release ¹⁰Be (in-situ produced or atmospheric) due to the instant re-absorption on grain surfaces. By contrast, under strongly acidic conditions, all absorbed ¹⁰Be is leached from aluminosilicates giving abnormally high ¹⁰Be concentrations and consequently exposure ages that are too old. Dating is only possible if samples do not contain any clay minerals or if they can be removed prior to carbonate dissolution.     

Proximal and distal styles of pegmatite-related metasomatic emerald mineralization at Ianapera,southern Madagascar

The Ianapera emerald deposit is located in the Neoproterozoic Vohibory Block of southern Madagascar. The local geology consists of intercalated migmatitic gneissic units and calcareous metasedimentary rocks, containing boudinaged metamorphosed mafic/ultramafic lenses, all intruded by pegmatite veins. These units occur near the hinge of the tightly folded Ianapera antiform, within a few kilometers of the Ampanihy shear zone. Emerald mineralization is hosted by metasomatic phlogopite veins, and bodies developed within the mafic/ultramafic rocks. Based on field and textural relationships, we distinguish proximal and distal styles of mineralization. Proximal mineralization occurs at the contact of pegmatite veins with mafic/ultramafic units; in the distal style, pegmatites are not observed. Three types of emeralds could be distinguished, mainly on the basis of color and mineral zoning. Some of these emeralds have the most Al-depleted and Cr-rich composition ever recorded. Another characteristic feature to the Ianapera deposit and, to our knowledge, yet unreported, is the association of some emeralds with scapolite in metasomatised mafic rocks. Mineral inclusions are common in most emeralds and include phlogopite, carbonates, barite, K-feldspar, quartz, pyrite, zircon, monazite, bastnaesite, phenakite, plus Fe and Cr oxides. However, feldspar and rare earth element-bearing minerals occur predominantly in proximal emeralds, which also have a more incompatible trace-element signature than distal emeralds. We propose a model related to syn- to post-tectonic magmatic-hydrothermal activity. Pegmatitic bodies intruded units of the Ianapera antiform probably during tectonic relaxation. Exsolution of fluids rich in halogens and incompatible elements from the cooling pegmatites caused hydrothermal metasomatism of Cr-bearing mafic/ultramafic rocks in direct contact with the pegmatites. Local fracturing favored fluid infiltration, permitting the formation of distal mineralization. Emerald composition was controlled by the chemistry of the host rock. The presence of carbonate mineral inclusions in the emeralds and the high F-activity indicated by elevated F-contents in newly formed minerals suggest transport of Be as a fluoride-carbonate complex. It seems likely that beryl formation was triggered by precipitation of F-rich phlogopite, which removed the complexing ligand from the fluid.     

Occurence of abundant diradicaloid moieties in the insoluble organic matter from the Orgueil and Murchison meteorites: a fingerprint of its extraterrestrial origin?

The highly aromatic structure of the macromolecular organic matter (OM) of the Murchison and Orgueil meteorites was recently shown to contain free organic radicals which are concentrated in micro-regions in contrast with terrestrial samples which always show an homogeneous distribution of radicals. An additional signature is revealed, in the present study, by the evolution of the radical concentration with temperature. Whereas in terrestrial samples, this concentration is independent of temperature (Curie magnetism), a significant increase is observed above 150 K in the two meteorites. Based on the electronic structure of organic radicals, calculated by Extended Hückel and Density Functional methods, this behavior was assigned to the occurrence of diradicaloid moieties hosted by aromatic structures of 10 to 15 rings and having a quinoidal structure. They represent 40 and 25% of the total radicals in Orgueil and Murchison, respectively. The search for the cosmochemical interpretation of this unique observation should open a new field of experimental investigations.