Chemometric analysis of High resolution spectra for precise and accurate isotope amount ratio determination
- Magnesium is a major element in the hydrosphere and biosphere and plays important roles in (bio-) geochemical and physiological cycles. Mg has three stable isotopes, 24Mg, 25Mg and 26Mg. It is due to their relatively large mass difference (~8% between) that isotope fractionation leads to slight variations of isotope amount ratios in biological, environmental and geological samples. Traditionally, isotope amount ratios are measured by mass spectrometric methods. Their drawbacks include the high costs for instruments and their operation, experienced operators and elaborate time-consuming chromatographic sample preparation. Recently, an optical spectrometric method has been proposed as faster and low-cost alternative for the analysis of isotope ratios: high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). For the determination of Mg isotope ratios in selected rock reference materials, the high-resolution molecular absorption spectrum ofMagnesium is a major element in the hydrosphere and biosphere and plays important roles in (bio-) geochemical and physiological cycles. Mg has three stable isotopes, 24Mg, 25Mg and 26Mg. It is due to their relatively large mass difference (~8% between) that isotope fractionation leads to slight variations of isotope amount ratios in biological, environmental and geological samples. Traditionally, isotope amount ratios are measured by mass spectrometric methods. Their drawbacks include the high costs for instruments and their operation, experienced operators and elaborate time-consuming chromatographic sample preparation. Recently, an optical spectrometric method has been proposed as faster and low-cost alternative for the analysis of isotope ratios: high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). For the determination of Mg isotope ratios in selected rock reference materials, the high-resolution molecular absorption spectrum of in-situ generated MgF molecule was studied applying multivariate analysis and the results compared with MC-ICP-MS. Samples were dissolved by acid digestion and Mg isotopes analyzed with and without matrix. The absorption spectra were recorded for MgF for the electronic transition X 2Σ → B 2Σ+. The MgF spectrum is described as the linear combination of their isotopic components or isotopologues: 24MgF, 25MgF, and 26MgF. The isotope analysis was done by deconvolution of the MgF spectrum by partial least square regression (PLS). A PLS model was built and calibrated with enriched isotope spikes and certified reference materials. Spectra data was preprocessed by a derivate of second order and venetian blinds cross-validation was employed for finding the optimum latent variables. Finally, the model was refined by a genetic algorithm which identified the best subset of variables for a precise and accurate regression. Results are compatible with those obtained by MC-ICP-MS with an accuracy of ± 0.3‰ with uncertainties ranging between 0.02 to 0.6‰.…
Autor*innen: | Carlos Enrique Abad AndradeORCiD |
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Koautor*innen: | S. Florek, H. Becker-Ross, S. Muench, M. Okruss, Michael Tatzel, Jochen VoglORCiD, Norbert JakubowskiORCiD, Ulrich PanneORCiD |
Dokumenttyp: | Vortrag |
Veröffentlichungsform: | Präsentation |
Sprache: | Englisch |
Jahr der Erstveröffentlichung: | 2019 |
Organisationseinheit der BAM: | 1 Analytische Chemie; Referenzmaterialien |
1 Analytische Chemie; Referenzmaterialien / 1.1 Anorganische Spurenanalytik | |
1 Analytische Chemie; Referenzmaterialien / 1.6 Anorganische Referenzmaterialien | |
P Präsident | |
P Präsident / P.0 Präsident und andere | |
DDC-Klassifikation: | Naturwissenschaften und Mathematik / Chemie / Analytische Chemie |
Freie Schlagwörter: | Chemometric; HR-CS-MAS; Isotope analysis; Magnesium; Molecular spectrum; Multivariate analysis |
Themenfelder/Aktivitätsfelder der BAM: | Chemie und Prozesstechnik |
Chemie und Prozesstechnik / Chemische Charakterisierung und Spurenanalytik | |
Veranstaltung: | Colloquium Analytische Atomspektroskopie CANAS 2019 |
Veranstaltungsort: | Freiberg, Germany |
Beginndatum der Veranstaltung: | 23.09.2019 |
Enddatum der Veranstaltung: | 26.09.2019 |
Verfügbarkeit des Dokuments: | Datei im Netzwerk der BAM verfügbar ("Closed Access") |
Datum der Freischaltung: | 04.12.2019 |
Referierte Publikation: | Nein |
Eingeladener Vortrag: | Nein |