Zr and U determination at trace level in simulated deep groundwater by Q ICP-MS using extraction chromatography

In the framework of trace element analysis by Q ICP-MS in a simulated deep Callovo-Oxfordian groundwater, separation procedures based on extraction chromatography were developed to eliminate the high salt contents and to concentrate Zr and U simultaneously. Theoretical and experimental speciation studies showed the importance of adjusting the medium to HNO₃/HF (0.5 M/0.005 M) to guarantee the stability over time of the analytes before removal of the matrix. Two preconcentration methods based on TRU and TODGA resins were optimized for the simultaneous isolation of Zr and U prior to Q ICP-MS measurements. Using TRU resin, alkali and alkali earth metals contained in the deep groundwater were removed with 2 M HNO₃ whereas Zr and U were recovered with a HNO₃/NH₄HC₂O₄ (0.02 M/0.05 M) medium. For the separation protocol based on TODGA resin, alkali and alkali earth metals were eliminated with 3 M and 11 M HNO₃ while Zr and U were simultaneously stripped with a HNO₃/HF (0.5 M/0.2 M) medium. The procedure optimized on TODGA resin was validated with the French AFNOR NF T90-210 standard by studying linearity, limits of quantification (LOQ) and separation yields. The LOQ was determined at 0.008 μg L(-1) for Zr and U after the separation. Both analytes were recovered quantitatively. Compared to a sample dilution implemented to reduce the matrix effects, the developed preconcentration method allowed improving the sensitivity up to a 20 fold factor for Zr and U measurements at trace level by Q ICP-MS.