title: Silicon isotope ratio measurements by inductively coupled plasma tandem mass spectrometry for alteration studies of nuclear waste glasses.
abstract: High-level, long-lived nuclear waste arising from spent fuel reprocessing is vitrified in silicate glasses for final disposal in deep geologic formations. In order to better understand the mechanisms driving glass dissolution, glass alteration studies, based on silicon isotope ratio monitoring of29Si-doped aqueous solutions, were carried out in laboratories. This work explores the capabilities of the new type of quadrupole-based ICP-MS, the Agilent 8800 tandem quadrupole ICP-MS/MS, for accurate silicon isotope ratio determination for alteration studies of nuclear waste glasses. In order to avoid silicon polyatomic interferences, a new analytical method was developed using O2as the reaction gas in the Octopole Reaction System (ORS), and silicon isotopes were measured in mass-shift mode. A careful analysis of the potential polyatomic interferences on SiO+and SiO2+ion species was performed, and we found that SiO+ion species suffer from important polyatomic interferences coming from the matrix of sample and standard solutions (0.5M HNO3). For SiO2+, no interferences were detected, and thus, these ion species were chosen for silicon isotope ratio determination. A number of key settings for accurate isotope ratio analysis like, detector dead time, integration time, number of sweeps, wait time offset, memory blank and instrumental mass fractionation, were considered and optimized. Particular attention was paid to the optimization of abundance sensitivity of the quadrupole mass filter before the ORS. We showed that poor abundance sensitivity leads to a significant shift of the data away from the Exponential Mass Fractionation Law (EMFL) due to the spectral overlaps of silicon isotopes combined with different oxygen isotopes (i.e.28Si16O18O+,30Si16O16O+). The developed method was validated by measuring a series of reference solutions with different29Si enrichment. Isotope ratio trueness, uncertainty and repeatability were found to be <0.2%, <0.5% and <0.6%, respectively. These performances meet the requirements of the studies of nuclear glasses alteration and open up possibilities to use this method for precise determination of silicon content in natural samples by Isotope Dilution.
authors.affiliation: Institut de Radioprotection et de Sûreté Nucléaire (IRSN), PRP-DGE/SRTG/LT2S, Fontenay-aux-Roses, France. Electronic address: alkiviadis.gourgiotis@irsn.fr.
authors.forename: Alkiviadis
authors.initials: A
authors.lastname: Gourgiotis
authors.affiliation: CEA, DEN, DTCD, SECM, F-30207 Bagnols-sur-Cèze, France.
authors.forename: Thomas
authors.initials: T
authors.lastname: Ducasse
authors.affiliation: Institut de Radioprotection et de Sûreté Nucléaire (IRSN), PRP-DGE/SRTG/LT2S, Fontenay-aux-Roses, France.
authors.forename: Evelyne
authors.initials: E
authors.lastname: Barker
authors.affiliation: CEA, DEN, DTCD, SECM, F-30207 Bagnols-sur-Cèze, France.
authors.forename: Patrick
authors.initials: P
authors.lastname: Jollivet
authors.affiliation: CEA, DEN, DTCD, SECM, F-30207 Bagnols-sur-Cèze, France.
authors.forename: Stéphane
authors.initials: S
authors.lastname: Gin
authors.affiliation: Institut de Radioprotection et de Sûreté Nucléaire (IRSN), PRP-DGE/SRTG/LT2S, Fontenay-aux-Roses, France.
authors.forename: Sylvain
authors.initials: S
authors.lastname: Bassot
authors.affiliation: Institut de Radioprotection et de Sûreté Nucléaire (IRSN), PRP-DGE/SRTG/LT2S, Fontenay-aux-Roses, France.
authors.forename: Charlotte
authors.initials: C
authors.lastname: Cazala
keywords: ICP-MS/MS; ICP-QQQ; Nuclear glasses; Silicon isotope ratios; Tandem mass spectrometry; Triple quadrupole