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.     

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.