title: Quantitative chemical imaging of element diffusion into heterogeneous media using laser ablation inductively coupled plasma mass spectrometry, synchrotron micro-X-ray fluorescence, and extended X-ray absorption fine structure spectroscopy.
abstract: Quantitative chemical imaging of trace elements in heterogeneous media is important for the fundamental understanding of a broad range of chemical and physical processes. The primary aim of this study was to develop an analytical methodology for quantitative high spatial resolution chemical imaging based on the complementary use of independent microanalytical techniques. The selected scientific case study is focused on high spatially resolved quantitative imaging of major elements, minor elements, and a trace element (Cs) in Opalinus clay, which has been proposed as the host rock for high-level radioactive waste repositories. Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), providing quantitative chemical information, and synchrotron radiation based micro-X-ray fluorescence (SR-microXRF), providing high spatial resolution images, were applied to study Cs migration into Opalinus clay rock. The results indicate that combining the outputs achievable by the two independent techniques enhances the imaging capabilities significantly. The qualitative high resolution image of SR-microXRF is in good agreement with the quantitative image recorded with lower spatial resolution by LA-ICPMS. Combining both techniques, it was possible to determine that the Opalinus clay sample contains two distinct domains: (i) a clay mineral rich domain and (ii) a calcium carbonate dominated domain. The two domains are separated by sharp boundaries. The spatial Cs distribution is highly correlated to the distribution of the clay. Furthermore, extended X-ray absorption fine structure analysis indicates that the trace element Cs preferentially migrates into clay interlayers rather than into the calcite domain, which complements the results acquired by LA-ICPMS and SR-microXRF. By using complementary techniques, the quantification robustness was improved to quantitative micrometer spatial resolution. Such quantitative, microscale chemical images allow a more detailed understanding of the chemical reactive transport process into and within heterogeneous media to be gained.
authors.affiliation: microXAS Beamline Project, Swiss Light Source, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland.
authors.forename: H A O
authors.initials: HA
authors.lastname: Wang
authors.forename: D
authors.initials: D
authors.lastname: Grolimund
authors.forename: L R
authors.initials: LR
authors.lastname: Van Loon
authors.forename: K
authors.initials: K
authors.lastname: Barmettler
authors.forename: C N
authors.initials: CN
authors.lastname: Borca
authors.forename: B
authors.initials: B
authors.lastname: Aeschlimann
authors.forename: D
authors.initials: D
authors.lastname: Günther