A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

Variations of U and Sr isotope ratios in Alsace and Luxembourg rain waters: origin and hydrogeochemical implications

Major and trace element concentrations, as well as Sr and U isotope ratios, were measured in rainwater samples collected in three different locations in Alsace (East of France) and Luxembourg: a mid-altitude mountain site (Aubure Environment HydroGeochemical Observatory), an urban site (Strasbourg) and a peri-urban site located in an area of well developed industrial activity (Esch-sur-Alzette in Luxembourg). Results highlight the quite high spatial and temporal variability of the chemical and isotopic characteristics of rainwater at the regional scale. They also suggest a quite systematic contribution of a local component in the chemical composition of rainwater. In urban and peri-urban sites, the local component is certainly linked to human activities, as it is well illustrated in this study with the Esch-sur-Alzette samples. On the other hand, for the Aubure site, i.e. a small forested watershed of mid-altitude mountain, data presented in this study demonstrate the influence of the vegetation on the chemical composition of rainwater for alkali and calc-alkali elements, as well as for the Sr isotope ratios. Such a result questions the reliability of the method classically used to estimate the rainwater contribution on the river chemical budget. In addition, data of the present study confirm the very low content of uranium in rainwater and demonstrate, especially through the U isotope analysis of Aubure rainwater, the negligible effect of rainwater on U budget of river waters. This work thus outlines the property of U to be a geochemical tracer specific of weathering fluxes carried by rivers. To cite this article: F. Chabaux et al., C. R. Geoscience 337 (2005).     

Petrology of the Jurassic Shah-Kuh granite (eastern Iran), with reference to tin mineralization

The Shah-Kuh granitic pluton of eastern Central Iran was emplaced 165 Ma ago, in an active continental margin setting. It is made of two main units: a granodioritic unit (SiO₂=63–71 wt%) to the north–west and a syenogranitic unit (SiO₂=73–77 wt%) to the south–east. The former unit displays seriate medium-grained textures and contains locally abundant mafic enclaves. The latter unit is medium- to coarse-grained and porphyritic, with 0.5–3 cm long K-feldspar megacrysts. Fine-grained granitic bodies are present in both units. The rocks are metaluminous to slightly peraluminous (I-type) and peraluminous (S-type) and belong to the ilmenite-series granites. Fractional crystallization appears to have been a very effective differentiation process in both units, and the fractionated mineral assemblages are determined by mass balance calculations. Isotopic data (Sr_i=0.7065 and εNdt=−2.5) are consistent with a young upper crustal protolith. Tin mineralization in sheeted quartz-tourmaline (-cassiterite) veins is spatially associated with the granodioritic unit. The veins formed by hydraulic fracturing when the granodioritic to monzogranitic magma became water-saturated and exsolved a fluid phase during crystallization. The reduced nature of this magma is responsible for the incompatible behaviour of Sn, likely to favour Sn concentration in the residual melt and then in the exsolved fluid. Another fluid phase was exsolved by the syenogranitic magma and was responsible for local greisenized granites, characterized by high Y and HREE-contents and non-fractionated REE distribution patterns. Field and mineralogical data show that the (B, Sn) vein-forming fluid was different from the (F, Li) greisen-forming fluid.     

Hydrogen isotopic composition of water from fossil micrometeorites in howardites

We have measured the hydrogen isotopic composition (D/H ratios) of the water from 13 carbonaceous chondritic microclasts (CCMs, size <1 mm) trapped in two howardites (Kapoeta and Yamato-793497) early in the evolution of Solar System. The division into tochilinite-rich; magnetite-rich, olivine-poor; magnetite-rich, olivine-rich CCM types is corroborated by the hydrogen isotopic compositions. Both mineralogy and hydrogen isotopic compositions demonstrate that tochilinite-rich CCMs represent CM2 chondritic matter. In contrast, there is no good match between the isotopic and mineralogical properties of the magnetite-rich CCMs and the known groups of carbonaceous chondrites, suggesting that magnetite-rich CCMs represent a new kind of chondritic matter, not yet sampled in meteorite collections. This demonstrates that the view of the asteroid belt revealed by the collection of meteorites is incomplete. The study of (micro)clasts offers a unique opportunity to better decipher the nature and relative abundance of asteroids.The average hydrogen isotopic composition of water belonging to CCMs, D/H = (152.0 ± 4.8) × 10⁻⁶ (1σ_m), is similar to that of Antarctic micrometeorites (AMMs), D/H = (161.2 ± 3.8) × 10⁻⁶ (1σ_m). The similarity, in terms of mineralogy and hydrogen isotopic composition, between CCMs and AMMs demonstrates that the composition of the micrometeorites has not been modified over the whole history of the Solar System. It indicates that the composition of the micrometeorite flux onto Earth has been, and is, dominated by a mixture of CM2-like; magnetite-rich, olivine-poor; magnetite-rich, olivine-rich carbonaceous chondritic matter exemplified by CCMs found in howardites. Because CCMs have not suffered atmospheric entry, they provide an abundant source of pristine micrometeorites.The average D/H ratio of the whole population of CCMs is identical within errors to that of the Earth (149 ± 3 × 10⁻⁶). The match between the CCMs D/H ratio and that of the Earth is especially remarkable because 1) three different populations of CCMs are needed to make the D/H ratio of the Earth; 2) there is no single carbonaceous chondrite group for which a similar match exists. This observation suggests that CCMs population might be representative of the late veneer agent(s) that delivered water to the Earth.     

Three dimensional numerical simulation of residential building on shrink–swell soils in response to climatic conditions

Shrink–swell soils can cause distresses in buildings, and every year, the economic loss associated with this problem is huge. This paper presents a comprehensive system for simulating the soil–foundation–building system and its response to daily weather conditions. Weather data include rainfall, solar radiation, air temperature, relative humidity, and wind speed, all of which are readily available from a local weather station or the Internet. These data are used to determine simulation flux boundary conditions. Different methods are proposed to simulate different boundary conditions: bare soil, trees, and vegetation. A coupled hydro‐mechanical stress analysis is used to simulate the volume change of shrink–swell soils due to both mechanical stress and water content variations. Coupled hydro‐mechanical stress‐jointed elements are used to simulate the interaction between the soil and the slab, and general shell elements are used to simulate structural behavior. All the models are combined into one finite element program to predict the entire system's behavior. This paper first described the theory for the simulations. A site in Arlington, Texas, is then selected to demonstrate the application of the proposed system. Simulation results are shown, and a comparison between measured and predicted movements for four footings in Arlington, Texas, over a 2‐year period is presented. Finally, a three‐dimensional simulation is made for a virtual residential building on shrink–swell soils to identify the influence of various factors. Copyright © 2015 John Wiley & Sons, Ltd.     

A methodology for regionalizing 3‐D effective porosity at watershed scale in crystalline aquifers

An innovative approach for regionalizing the 3‐D effective porosity field is presented and applied to two large, overexploited, and deeply weathered crystalline aquifers located in southern India. The method derives from earlier work on regionalizing a 2‐D effective porosity field in that part of an aquifer where the water table fluctuates, which is now extended over the entire aquifer using a 3‐D approach. A method based on geological and geophysical surveys has also been developed for mapping the weathering profile layers (saprolite and fractured layers). The method for regionalizing 3‐D effective porosity combines water table fluctuation and groundwater budget techniques at various cell sizes with the use of satellite‐based data (for groundwater abstraction), the structure of the weathering profile, and geostatistical techniques. The approach is presented in detail for the Kudaliar watershed (983 km²) and tested on the 730 km² Anantapur watershed. At watershed scale, the effective porosity of the aquifer ranges from 0.5% to 2% in Kudaliar and between 0.3% and 1% in Anantapur, which agrees with earlier works. Results show that (a) depending on the geology and on the structure of the weathering profile, the vertical distribution of effective porosity can be very different and that the fractured layers in crystalline aquifers are not necessarily characterized by a rapid decrease in effective porosity and (b) that the lateral variations in effective porosity can be larger than the vertical ones. These variations suggest that within a same weathering profile, the density of open fractures and/or degree of weathering in the fractured zone may significantly vary from a place to another. The proposed method provides information on the spatial distribution of effective porosity that is of prime interest in terms of flux and contaminant transport in crystalline aquifers. Implications for mapping groundwater storage and scarcity are also discussed, which should help in improving groundwater resource management strategies.     

Modeling the 2D behavior of dry‐stone retaining walls by a fully discrete element method

The dry‐stone retaining walls (DSRW) have been tipped as a promising solution for sustainable development. However, before recently, their behavior is relatively obscure. In this study, discrete element method (DEM) approach was applied to simulate the plane strain failure of these walls. A commercial DEM package (PFC2D™) was used throughout this study. The authors used a fully discrete approach; thus, both the wall and the backfill were modeled as discrete elements. The methodology for obtaining the micromechanical parameters was discussed in detail; this includes the three mechanical sub‐systems of DSRWs: wall, backfill and interface. The models were loaded progressively until failure, and then the results were compared with the full‐scale experimental results where the walls were loaded, respectively, with hydrostatic load and backfill. Despite its complexity and its intensive calculation time, DEM model can then be used to validate a more simplified approach. Copyright © 2015 John Wiley & Sons, Ltd.