Intercomparison of tritium and noble gases analyses, 3H/3He ages and derived parameters excess air and recharge temperature

International audienceGroundwater age dating with the tritium-helium (3H/3He) method has become a powerful tool for hydrogeologists. The uncertainty of the apparent 3H/3He age depends on the analytical precision of the 3H measurement and the uncertainty of the tritiogenic 3He component. The goal of this study, as part of the groundwater age-dating interlaboratory comparison exercise, was to quantify the analytical uncertainty of the 3H and noble gas measurements and to assess whether they meet the requirements for 3H/3He dating and noble gas paleotemperature reconstruction. Samples for the groundwater dating intercomparison exercise were collected on 1 February, 2012, from three previously studied wells in the Paris Basin (France). Fourteen laboratories participated in the intercomparison for tritium analyses and ten laboratories participated in the noble gas intercomparison. Not all laboratories analyzed samples from every borehole. The reproducibility of the tritium measurements was 13.5%. The reproducibility of the 3He/4He ratio and 4He, Ne, Ar, Kr and Xe concentrations was 1.4%, 1.8%, 1.5%, 2.2%, 2.9%, and 2.4% respectively. The uncertainty of the tritium and noble gas measurements results in a typical 3H/3He age precision of better than 2.5 years in this case. However, the measurement uncertainties for the noble gas concentrations are insufficient to distinguish the appropriate excess air model if the measured helium concentration is not included. While the analytical uncertainty introduces an unavoidable source of uncertainty in the 3H/3He apparent age estimate, other sources of uncertainty are often much greater and less well defined than the analytical uncertainty

A classical Over Barrier Model to compute charge exchange between ions and one-optical-electron atoms

In this paper we study theoretically the process of electron capture between one-optical-electron atoms (e.g. hydrogenlike or alkali atoms) and ions at low-to-medium impact velocities (v/v_e <= 1) working on a modification of an already developed classical Over Barrier Model (OBM) [V. Ostrovsky, J. Phys. B: At. Mol. Opt. Phys. {\bf 28} 3901 (1995)], which allows to give a semianalytical formula for the cross sections. The model is discussed and then applied to a number of test cases including experimental data as well as data coming from other sophisticated numerical simulations. It is found that the accuracy of the model, with the suggested corrections and applied to quite different situations, is rather high.Comment: 12 pages REVTEX, 5 EPSF figures, submitted to Phys Rev

From atmospheric water isotopes measurement to firn core interpretation in Adélie Land: a case study for isotope-enabled atmospheric models in Antarctica

In a context of global warming and sea level rise acceleration, it is key to estimate the evolution of the atmospheric hydrological cycle and temperature in polar regions, which directly influence the surface mass balance of the Arctic and Antarctic ice sheets. Direct observations are available from satellite data for the last 40 years and a few weather data since the 1950s in Antarctica. One of the best ways to access longer records is to use climate proxies in firn or ice cores. The water isotopic composition in these cores is widely used to reconstruct past temperature variations. We need to progress in our understanding of the influence of the atmospheric hydrological cycle on the water isotopic composition of ice cores. First, we present a 2-year-long time series of vapor and precipitation isotopic composition measurement at Dumont d’Urville Station, in Adélie Land. We characterize diurnal variations of meteorological parameters (temperature, atmospheric water mixing ratio (hereafter humidity) and δ18O) for the different seasons and determine the evolution of key relationships (δ18O versus temperature or humidity) throughout the year: we find that the temperature vs. δ18O relationship is dependent on synoptic events dynamics in winter contrary to summer. Then, this data set is used to evaluate the atmospheric general circulation model ECHAM6-wiso (model version with embedded water stable isotopes) in a coastal region of Adélie Land where local conditions are controlled by strong katabatic winds which directly impact the isotopic signal. We show that a combination of continental (79 %) and oceanic (21 %) grid cells leads model outputs (temperature, humidity and δ18O) to nicely fit the observations, at different timescales (i.e., seasonal to synoptic). Therefore we demonstrate the added value of long-term water vapor isotopic composition records for model evaluation. Then, as a clear link is found between the isotopic composition of water vapor and precipitation, we assess how isotopic models can help interpret short firn cores. In fact, a virtual firn core built from ECHAM-wiso outputs explains much more of the variability observed in S1C1 isotopic record than a virtual firn core built from temperature only. Yet, deposition and post-deposition effects strongly affect the firn isotopic signal and probably account for most of the remaining misfits between archived firn signal and virtual firn core based on atmospheric modeling.</p

Isotopic signals (18O, 2H, 3H) of six major rivers draining the pan-Arctic watershed

Author Posting. © American Geophysical Union, 2012. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 26 (2012): GB1027, doi:10.1029/2011GB004159.We present the results of a 4-year collaborative sampling effort that measured δ18O, δ2H values and 3H activities in the six largest Arctic rivers (the Ob, Yenisey, Lena, Kolyma, Yukon and Mackenzie). Using consistent sampling and data processing protocols, these isotopic measurements provide the best available δ2H and 3H estimates for freshwater fluxes from the pan-Arctic watershed to the Arctic Ocean and adjacent seas, which complements previous efforts with δ18O and other tracers. Flow-weighted annual δ2H values vary from −113.3‰ to −171.4‰ among rivers. Annual 3H fluxes vary from 0.68 g to 4.12 g among basins. The integration of conventional hydrological and landscape observations with stable water isotope signals, and estimation of areal yield of 3H provide useful insights for understanding water sources, mixing and evaporation losses in these river basins. For example, an inverse correlation between the slope of the δ18O-δ2H relation and wetland extent indicates that wetlands play comparatively important roles affecting evaporation losses in the Yukon and Mackenzie basins. Tritium areal yields (ranging from 0.760 to 1.695 10−6 g/km2 per year) are found to be positively correlated with permafrost coverage within the studied drainage basins. Isotope-discharge relationships demonstrate both linear and nonlinear response patterns, which highlights the complexity of hydrological processes in large Arctic river basins. These isotope observations and their relationship to discharge and landscape features indicate that basin-specific characteristics significantly influence hydrological processes in the pan-Arctic watershed.Funding for this research was provided by the U.S. National Science Foundation (OPP-0229302), the National Science and Engineering Research Council of Canada (Discovery grant to JJG and IRD fellowship to YY), the U.S. Geological Survey and the Water Resources Division in the Department of Indian Affairs and Northern Development, Canada.2012-09-2

About the detection of urea in the interstellar medium: the energetic aspect

Context. The results of an observational search for gas phase urea, (NH2)2CO toward the Sgr B2-LMH region, have been reported recently. In spite of strong presumptions, whether it is urea or another species (for example an isomer) seems to remain a pending question. Aims. In this note, we consider the energetic aspect of this would-be detection by addressing the relative stabilities of the 22 isomers that can possibly be formed with the CH4N2O set of atoms. By extension, we also consider the 22 sulphur analogues of CH4N2S chemical formula. Methods. The question was first addressed by means of quantum density functional theory (DFT) simulations. The hybrid B3LYP functional was used throughout. The geometries of the 44 molecules part of this survey were fully optimized and verified to be real minima by vibrational analysis. The lowest isomers found this way were then reconsidered in higher level post Hartree-Fock MP2 and coupled cluster CCSD and CCSD(T) calculations to derive more accurate energy differences and dipole moments, whose knowledge is crucial for interpreting micro- and millimetre-wave spectra. Results. We found that urea and thio-urea are the most stable compounds in their respective families. The closest isomers on the energy scale are the iminol tautomeric forms, HN=COH-NH2 and HN=CSH-NH2, whose rotational constants and dipole moments have also been determined. Conclusions. That urea is the lowest energy isomer possibly formed is a strong argument making the detection of this species more than probable. After formamide and acetamide, this result confirms the greatest stability of the -[NH-C=O]- linkage, underlining the interest of the minimum energy criterion as a tool for the primary search of target molecules. Additionally, thio-urea should the analogue to search for

Characterisation of interfacial adhesion in hemp composites after H2O2 and non-thermal plasma treatments

International audienceInterface optimisation for continuous hemp reinforcements in epoxy resin is a current challenge for the development of biocomposites. A chemical treatment based on hydrogen peroxide and a physical one using a non-thermal plasma have been tested to optimise interface adhesion, by varying several parameters. FTIR analysis and FE-SEM observations have shown the effects of the treatments on chemical and morphological aspects of the treated yarns. Tensile tests on hemp yarns have allowed the selection of the treatment parameters leading to the best strength. Fragmentation tests results showed that the two treatments lead to a decrease in the fragment lengths and thus, an enhancement of the Interfacial Shear Strength (IFSS) values in comparison with the untreated yarn. This is confirmed by the micro-CT observations of the debonding lengths in the vicinity of each yarn fragment extremity. Finally, the plasma treated samples exhibit a better interface adhesion quality (IFSS=44.7±4MPa) than the chemically treated ones (IFSS=24.2±4MPa), which are better than the non-treated ones (IFSS=13.5±4MPa)

Tritium and radiocarbon levels in the Rhône river delta and along the French Mediterranean coastline

International audienc