TY - CONF A1 - Vogl, Jochen T1 - The triple isotope calibration approach BT - A new calibration approach for obtaining absolute isotope ratios of multi-isotopic elements N2 - The calibration of isotope ratio measurements is an ongoing challenge since instrumental isotope fractionation (IIF) has been detected in mass spectrometry (MS). There is a variety of approaches which either bypass IIF such as delta measurements or refer to reference materials (RMs) and thus shifting the problem of calibration to somebody else: the RM producer. For certifying isotope RMs with absolute isotope ratios only a few approaches are available, namely the isotope mixture approach, the double spike approach, the mass bias regression model and total evaporation in TIMS. All of them require either enriched isotopes, isotope RMs of another element or an RM for correcting residual error. As the enriched isotopes required for the isotope mixture and the double spike approach need to be fully characterized beforehand, all mentioned calibration approaches require a standard. Here, a new and standard-free calibration approach for obtaining absolute isotope ratios of multi-isotopic elements has been developed. The underlying principle is that each MS suffers from IIF and thus yields a specific isotope fractionation line in a three-isotope diagram. When applying a second MS featuring a different ionization mechanism, we obtain a second isotope fractionation line with a different slope in the same three-isotope diagram. In both cases the absolute isotope ratios range somewhere on the isotope fractionation line. Consequentially, the intersect of both lines yield the absolute isotope ratios of the measured sample. This theory has been tested by measuring Cd and Pb isotope ratios of suitable isotope RMs with a TIMS and an ICP-MS, both equipped with multi-collector array. During the measurements the ionization conditions were changed such that different extent of the isotope fractionation has been achieved. With the resulting data set the theory described above could be verified. The obtained absolute isotope ratios were metrologically compatible with the certified isotope ratios. The remaining average bias of -5 ‰ can be reduced with further improvements. The calibration approach is universal and can be applied to any multi-isotopic element and it is not limited by the type of the mass spectrometer. T2 - Virtual Goldschmidt 2021 CY - Online meeting DA - 04.07.2021 KW - Absolute isotope ratio KW - Traceability KW - Metrology KW - Calibration KW - Uncertainty KW - Triple isotope fractionation PY - 2021 AN - OPUS4-53023 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Kazlagic, Anera A1 - Abad Andrade, Carlos Enrique A1 - Winckelmann, Alexander T1 - New applications and reference materials in isotope analysis N2 - The presentations gives a short introduction into isotope analysis illustrated by examples from archaeology, food provenancing and metrology. In the main part current projects on the provenance determination of cement, the intercalibration of Mg isotope reference materials and the development of a new calibration approach for isotope measurements are presented. T2 - Seminar der Abteilung 1 CY - Online meeting DA - 19.01.2021 KW - Isotope reference material KW - Absolute isotope ratio KW - Metrology KW - Traceability KW - Triple isotope fractionation KW - Archaeometry KW - Cement PY - 2021 AN - OPUS4-52460 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Noireaux, J. A1 - D'Agostino, G. A1 - Hill, S. A1 - Gendre, R. A1 - Cankur, O. A1 - Ghestem, J.-P. A1 - Haraldson, C. A1 - Irrgeher, J. A1 - Jacimovic, R. A1 - Jotanovic, A. A1 - Naykki, T. A1 - Proefrock, D. A1 - Rienitz, O. A1 - Umbricht, G. T1 - Herausforderungen bei der Analytik von Technologie-kritischen Elementen (TCE) in Abfällen N2 - Technologie-kritische Elemente (TCE) sind unentbehrliche Materialien für High-Tech Produkte wie Smartphones, Notebooks und Monitors. Ihr Bedarf wird voraussichtlich aufgrund des gesellschaftlichen Wandels hin zu einer grünen Ökonomie exponentiell ansteigen. Dieser Wandel wird vor allem auch durch erneuerbare Energien und Elektromobilität geprägt (European Green Deal). Diese Entwicklung in Verbindung mit einer nahezu fehlenden TCE Produktion in Europa setzt den Markt unter Druck und führt zu steigenden Preisen. Die Sicherung des TCE Nachschubs wurde in der gegenwärtigen Gesundheitskrise noch dringender und wurde daher auch zu einem der Hauptthemen des COVID-19 Recovery Plan, der eine Stärkung der europäischen Resilienz und Autonomie zum Ziel hat. Ein nachhaltige Lösung ist das Recycling der Abfall- bzw. Wertstoffe und letztendlich eine Circular Economy. Allerdings ist die Analyse von Abfallströmen schwierig und erfordert geeignete analytische Lösungen, die SI-rückführbare und somit vergleichbare Messergebnisse im gesamten Recyclingprozess ermöglichen. Die dafür erforderlichen, für TCE zertifizierte, Referenzmaterialien und nötige standardisierte Verfahren fehlen bisher nahezu vollständig. In diesem Beitrag werden die analytischen Herausforderungen, wie z.B. die extreme Heterogenität der Materialien, Schwierigkeiten beim Probenaufschluss und das Fehlen von Referenzmaterialien diskutiert. Und es wird das EMPIR-Projekt MetroCycleEU vorgestellt, dessen Ziel es ist Referenz- und Routineverfahren für ausgewählte TCE (Co, Ga, Ge, In, Ta, Nd, Pr, Dy, Gd, La, Au, Pt, Pd, Rh) zu entwickeln und Referenzmaterialien für Platinen, LEDs und Li-Batterien bereitzustellen. T2 - Workshop Nachhaltige Prozesse für eine Circular Economy CY - Berlin, Germany DA - 23.09.2021 KW - TCE KW - Circular economy KW - Metrology KW - Traceability KW - Uncertainty PY - 2021 AN - OPUS4-53371 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Phukphatthanachai, P. A1 - Panne, Ulrich A1 - Traub, Heike A1 - Pfeifer, Jens A1 - Vogl, Jochen T1 - Quantification of sulphur in copper and copper alloys by GDMS and LA-ICP-MS, demonstrating metrological traceability to the international system of units N2 - The quantification of the sulphur mass fraction in pure copper and copper alloys by GDMS and LA-ICP-MS revealed a lack of traceability mainly due to a lack of suitable certified reference materials for calibrating the instruments. Within this study GDMS and LA-ICP-MS were applied as routine analytical tools to quantify sulphur in copper samples by applying reference materials as calibrators, which were characterized for their sulphur mass fraction by IDMS beforehand. Different external calibration strategies were applied including a matrix cross type calibration. Both techniques with all calibration strategies were validated by using certified reference materials (others than those used for calibration) and good agreement with the reference values was achieved except for the matrix cross type calibration, for which the agreement was slightly worse. All measurement results were accompanied by an uncertainty statement. For GDMS, the relative expanded (k = 2) measurement uncertainty ranged from 3% to 7%, while for LA-ICP-MS it ranged from 11% to 33% when applying matrix-matched calibration in the sulphur mass fraction range between 25 mg kg-1 and 1300 mg kg-1. For cross-type calibration the relative expanded (k = 2) measurement uncertainty need to be increased to at least 12% for GDMS and to at least 54% for LA-ICP-MS to yield metrological compatibility with the reference values. The so obtained measurement results are traceable to the international system of units (SI) via IDMS reference values, which is clearly illustrated by the unbroken chain of calibrations in the metrological traceability scheme. KW - Sulfur KW - Copper KW - GDMS KW - LA-ICP-MS KW - Uncertainty KW - Traceability KW - SI PY - 2021 U6 - https://doi.org/10.1039/d1ja00137j SN - 0267-9477 VL - 36 IS - 11 SP - 2404 EP - 2414 PB - Royal Society of Chemistry AN - OPUS4-53412 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -