Measuring Hg Isotopes in Bio-Geo-Environmental Reference Materials

With the emergence of new analytical techniques and the expansion of scientific fields explored by using mercury isotopes, the community needs reference materials (RM) to validate and assure the accuracy of the results. The present work investigates (1) the characterisation of secondary RM in order to validate analytical systems, (2) the effects of two complex matrices on isotopic determination using stannous chloride cold vapour generation coupled to MC-ICP-MS (CV-MC-ICP-MS), (3) the effects of multiple digestion techniques for total Hg extraction and (4) the characterisation of nine geo-bio-environmental RM. Two secondary mono-elemental RMs analysed using two different analytical setups yielded isotopic compositions on δ²⁰²Hg of −3.54 ± 0.27‰ (CRPG-F65A, 2SD, n = 38) and +2.59 ± 0.19‰ (CRPG-RL24H, 2SD, n = 30) relative to the CRM NIST SRM 3133. These two RMs cover the whole range of Hg isotopic fractionation in natural samples and are made available to the scientific community. Complex fly ash and hydroxysulfate green rust matrices were synthesised, spiked with NIST SRM 3133, then digested and finally analysed versus the mono-elemental NIST SRM 3133 to show potential effect of these complex matrices during CV-MC-ICP-MS. Three digestions techniques, including traditional acid digestion, microwave digestion and high pressure-high temperature digestion, were applied to the lichen RM BCR-482 in order to compare advantages and drawbacks of these methods. Finally, the isotopic compositions of nine RMs including soils (NIST SRM 2711; GXR-2; GSS-4), sediment (GSD-10), jasperoid (GXR-1), ore deposit (GXR-3), fly ashes (BCR-176; BCR-176R) and lichen (BCR-482) are reported. These selected materials have δ²⁰²Hg values ranging from −1.75‰ to +0.11‰. Some RMs also presented mass-independent fractionation with Δ¹⁹⁹Hg and Δ²⁰¹Hg of up to −0.6‰.     

Iron Isotope Variations in Coastal Seawater Determined by Multicollector ICP-MS

In this paper, we applied a reliable technique for measuring Fe isotope variations in coastal seawater at nanomolar levels. Iron was directly pre-concentrated from acidified seawater samples onto a nitrilotriacetic acid chelating resin and further purified using anion-exchange resin. Sample recovery, determined using a standard addition method, was essentially quantitative. Iron was then determined using a high-resolution multicollector ICP-MS (Neptune) coupled to an ApexQ desolvation introduction system. The external precision for δ⁵⁶Fe values was 0.11‰ (2s) when using total a Fe quantity between 25 and 100 ng. We initially applied this technique to measure the Fe isotope composition of dissolved Fe from several coastal environments in the north-eastern United States and we observed a range of δ⁵⁶Fe values between -0.9‰ and 0.1‰ relative to the IRMM-14 reference material. Iron isotope compositions of several reference water materials for inter-laboratory comparisons were also reported. Our results suggest that iron in coastal seawater, derived from benthic diagenesis and/or groundwater has negative Fe isotopic signatures that are distinct from other iron sources such as atmospheric deposition and rivers.     

Natural variations of Se isotopic composition determined by hydride generation multiple collector inductively coupled plasma mass spectrometry

Multiple-collector inductively coupled plasma mass spectrometry has been used for the precise measurement of the isotopic composition of Se in geological samples. Se is chemically purified before analysis by using cotton impregnated with thioglycollic acid. This preconcentration step is required for the removal of matrix-interfering elements for hydride generation, such as transitional metals, and also for the quantitative separation of other hydride-forming elements, such as Ge, Sb, and As. The analyte is introduced in the plasma torch with a continuous-flow hydride generation system. Instrumental mass fractionation is corrected with a “standard-sample bracketing” approach. By use of this new technique, the minimum Se required per analysis is lowered to 10 ng, which is one order of magnitude less than the amount needed for the N-TIMS technique. The estimated external precision calculated for the ⁸²Se/⁷⁶Se isotope ratio is 0.25‰ (2σ), and the data are reported as delta notation (‰) relative to our internal standard (MERCK elemental standard solution). Measurements of Se isotopes are presented for samples of standard solutions and geological reference materials, such as silicate rocks, soils, and sediments. The Se isotopic composition of selected terrestrial and extraterrestrial materials are also presented. An overall Se isotope variation of 8‰ has been observed, suggesting that Se isotopes fractionate readily and are extremely useful tracers of natural processes.     

Pyrite tracks assimilation of crustal sulfur in Pyrenean peridotites

Cobalt-bearing pyrite (0.5?C2.0?wt.% Co) is abnormally abundant (up to 35?vol.% of the total volume of the sulfide phase) in some eastern Pyrenean peridotite massifs, compared to pieces of subcontinental mantle studied so far for sulfides. Pyrite occurs as vermicular intergrowths inside pentlandite and/or chalcopyrite or as coarser, blocky grains in the intergranular pores of host peridotites. Those different pyrites are characterized by different platinum-group element systematics (measured by laser ablation microprobe and ICP-MS). Vermicular pyrite intergrown with pentlandite displays Os-, Ir-, Ru- and Rh-enriched chondrite normalized PGE patterns of Monosulfide solid solution (Mss). In contrast, coarse-grained intergranular (??blocky??) pyrites, are PGE-poor. Chalcophile trace elements (i.e. Zn, Pb, Ag, Au) that are not usually concentrated in mantle-derived sulfides were commonly detected. By contrast, selenium contents are generally low, yielding thus pyrite with high S/Se ratio (>10⁵), consistent with a sedimentary sulfur source. Pyrite microtextures and chalcophile trace element contents support a process of assimilation of crustal sulfur from the metamorphosed sedimentary country rocks. These latter generated highly reactive CO₂-S fluids, which were injected into structural discontinuities of the lherzolitic bodies. Sulfur has reacted at T?=?300?C550°C with pre-existing, mantle-derived, metal-rich sulfide assemblages (pentlandite-chalcopyrite). Addition of crustal sulfur did produce Mss which, on cooling, exsolved the Os-rich pyrite in addition to pentlandite. The coarse-grained pyrite types have crystallized directly from S-rich fluids.     

Impact of the LMDZ atmospheric grid configuration on the climate and sensitivity of the IPSL-CM5A coupled model

The IPSL-CM5A climate model was used to perform a large number of control, historical and climate change simulations in the frame of CMIP5. The refined horizontal and vertical grid of the atmospheric component, LMDZ, constitutes a major difference compared to the previous IPSL-CM4 version used for CMIP3. From imposed-SST (Sea Surface Temperature) and coupled numerical experiments, we systematically analyze the impact of the horizontal and vertical grid resolution on the simulated climate. The refinement of the horizontal grid results in a systematic reduction of major biases in the mean tropospheric structures and SST. The mid-latitude jets, located too close to the equator with the coarsest grids, move poleward. This robust feature, is accompanied by a drying at mid-latitudes and a reduction of cold biases in mid-latitudes relative to the equator. The model was also extended to the stratosphere by increasing the number of layers on the vertical from 19 to 39 (15 in the stratosphere) and adding relevant parameterizations. The 39-layer version captures the dominant modes of the stratospheric variability and exhibits stratospheric sudden warmings. Changing either the vertical or horizontal resolution modifies the global energy balance in imposed-SST simulations by typically several W/m² which translates in the coupled atmosphere-ocean simulations into a different global-mean SST. The sensitivity is of about 1.2 K per 1 W/m² when varying the horizontal grid. A re-tuning of model parameters was thus required to restore this energy balance in the imposed-SST simulations and reduce the biases in the simulated mean surface temperature and, to some extent, latitudinal SST variations in the coupled experiments for the modern climate. The tuning hardly compensates, however, for robust biases of the coupled model. Despite the wide range of grid configurations explored and their significant impact on the present-day climate, the climate sensitivity remains essentially unchanged.     

Determination of cirrus radiative parameters from combination between active and passive remote sensing measurements during FRENCH/DIRAC 2001

In the context of the next AQUA Train satellite experiment, airborne measurements were carried out to simulate satellite measurements. They were conducted between September 25 and October 12, 2001, off the coast of southern France over the Atlantic Ocean and over the Mediterranean Sea, respectively. During the intensive Field Radiation Experiment on Natural Cirrus and High-level clouds (FRENCH/DIRAC 2001), natural ice clouds were sampled from in situ and remote sensing measurements. On October 5 and 7, 2001, cirrus cloud decks were described by a complete data set acquired by: (i) in situ microphysical instruments onboard the TBM-700 aircraft: PMS probe, and Polar Nephelometer (ii) and downward-looking radiative instruments onboard the Mystère 20 aircraft: an infrared radiometer, a lidar, a visible imager with polarisation capabilities, and a middle infrared radiometer. Moreover, classical thermodynamical measurements were carried out onboard the Mystère 20. Mean microphysical characteristics of cirrus deck are derived from interpretation of remote sensing measurements. These properties are compared with those derived from in situ microphysical measurements in order to evaluate the radiative impact of natural cirrus clouds.     

Estimating water fluxes in the critical zone using water stable isotope approaches in the Groundnut and Ferlo basins of Senegal

Sustainable water management in semi-arid agriculture practices requires quantitative knowledge of water fluxes within the soil-vegetation-atmosphere system. Therefore, we used stable-isotope approaches to evaluate evaporation (E_a), transpiration (T_a), and groundwater recharge (R) at sites in Senegal's Groundnut basin and Ferlo Valley pasture region during the pre-monsoon, monsoon, and post-monsoon seasons of 2021. The approaches were based upon (i) the isothermal evaporation model (for quantifying E_a); (ii) water and isotope mass balances (to partition E_a and T_a for groundnut and pasture); and (iii) the piston displacement method (for estimating R). E_a losses derived from the isothermal evaporation model corresponded primarily to Stage II evaporation, and ranged from 0.02 to 0.09 mm d⁻¹ in the Groundnut basin, versus 0.02–0.11 mm d⁻¹ in Ferlo. At the groundnut site, E_a rates ranged from 0.01 to 0.69 mm d⁻¹; T_a was in the range 0.55–2.29 mm d⁻¹; and the T_a/ET_a ratio was 74%–90%. At the pasture site, the ranges were 0.02–0.39 mm d⁻¹ for E_a; 0.9–1.69 mm d⁻¹ for T_a; and 62–90% for T_a/ET_a. The ET_a value derived for the groundnut site via the isotope approach was similar to those from eddy covariance measurements, and also to the results from the previous validated HYDRUS-1D model. However, the HYDRUS-1D model gave a lower T_a/ET_a ratio (23.2%). The computed groundwater recharge for the groundnut site amounted to less than 2% of the local annual precipitation. Recommendations are made regarding protocols for preventing changes to isotopic compositions of water in samples that are collected in remote arid regions, but must be analysed days later. The article ends with suggestions for studies to follow up on evidence that local aquifers are being recharged via preferential pathways.