TY - CONF A1 - Vogl, Jochen T1 - Isotope ratio measurements and certification of iRMs at BAM N2 - This presentation gives a short overview of isotope ratio measurements being carried out in the past few years at BAM in different fields such as plant metabolism, food web structures and archaeology. The corresponding isotope reference materials which have been certified at BAM in parallel are presented as well. Additionally an outlook is being provided on future iRM projects. T2 - Meeting of the Isotope Ratio Working Groupt of CCQM CY - Ottawa, Canada DA - 04.10.2018 KW - Isotope reference material KW - Delta value KW - Isotope amount ratio KW - Traceability KW - Uncertainty PY - 2018 AN - OPUS4-47159 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Vogl, Jochen T1 - Roadmap for the purity determination of pure metallic elements – Basic rinciples and helpful advice T2 - BIPM Webpage N2 - High purity materials can serve as a realisation of the Système International d’Unitès (SI) unit amount of substance for the specific element. Solutions prepared from such high purity materials using gravimetric preparation and the concept of molar mass are used as calibration solutions in many fields of analytical chemistry. Calibration solutions prepared this way provide the traceability to the SI and are the metrological basis in elemental analysis. The preparation and characterization of such primary pure substances, representing the realisation of the SI unit amount of substance, is undertaken only by a small number of National Metrology Institutes (NMI) and Designated Institutes (DI). Many other NMIs and DIs, however, prepare elemental calibration solutions as calibrants for their measurement services, such as the certification of matrix Reference Materials or the provision of reference values for Proficiency Testing schemes. The elemental calibration solutions used for this purpose are not a direct service to customers, such as preparing secondary calibration solutions, but provide the source of traceability for the other services. Hence, it is necessary for the NMI or DI to obtain data on the purity of the pure metals or other materials used to prepare the solutions with measurement uncertainties meeting the needs of the above described services. This is commonly undertaken as a “fit for purpose” assessment, appropriate for the uncertainty requirement of the service provided to customers. As a consequence, total purity measurements are a long-term strategy of CCQM-IAWG. Several studies were conducted (CCQM-P107, CCQM-K72 and CCQM-P149) on the measurement of the purity of zinc. From these studies, several conclusions can be drawn for the purity assessment of a pure (metallic) element. These conclusions will be put together in this document in order to assist all NMIs/DIs in performing a purity assessment, whenever needed. KW - Purity assessment KW - Metal assay approach KW - Impurity assessment approach KW - Traceability PY - 2018 UR - https://www.bipm.org/wg/CCQM/IAWG/Allowed/April_2017/CCQM-IAWG17-28.pdf.pdf SP - 1 EP - 9 CY - Sevre AN - OPUS4-46834 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Koenig, Maren T1 - Isotope dilution mass spectrometry applied as primary method of measurement with examples from the ENVCRM project N2 - The presentation describes the application of isotope dilution mass spectrometry as a primary method of measurement with all Advantages and disadvantges. This is exempflified for the candidate reference materials within the EnvCRM Project. T2 - Workshop Matrix Reference Materials for Environmental Analysis CY - Gebze, Turkey DA - 16.05.2018 KW - Reference material KW - Soil KW - Heavy metals PY - 2018 AN - OPUS4-45896 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Vocke, B. T1 - Delta values & isotope ratios - potential CCQM comparisons N2 - The talk presents several potential CCQM comparisons for delta values and isotope ratios with a focus on metals and semi-metals. T2 - CCQM IRWG Meeting CY - Paris, France DA - 18.04.2018 KW - Isotope amount ratio KW - Traceability KW - Uncertainty PY - 2018 AN - OPUS4-45895 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Phukphatthanachai, Pranee A1 - Vogl, Jochen A1 - Traub, Heike A1 - Jakubowski, Norbert A1 - Panne, Ulrich T1 - A new approach of using polyethylene frits for the quantification of sulphur in copper metals by isotope dilution LA-ICP-MS and comparison with conventional IDMS techniques JF - Journal of Analytical Atomic Spectrometry N2 - Polyethylene (PE) frits were used to quantify sulphur in copper and its alloys by isotope dilution combined with LA-ICP-MS as an alternative approach to conventional sample preparation: the copper samples were spiked, the spiked samples were dissolved, the resulting solutions were absorbed in the PE frits and finally the PE frits were analysed by LA-ICP-MS. A prerequisite for such a support material is a low sulphur blank and thus PE was selected for this purpose. The absorption efficiency of the PE frits was studied for varying sulphur amounts ranging from 2 mg S to 80 mg S showing that more than 99.5% of the loaded sulphur was absorbed by the frit. The so prepared PE frits were measured by LA-ICP-MS and yielded a good linearity (R2 ¼ 0.999) for the sulphur ion intensities corresponding to sulphur amounts up to 40 mg S; the associated sensitivity is approximately 3.4 x 10⁴ cps μg⁻¹ for ³²S. For the validation of the developed procedure the reference materials BAM-M376a, BAM-228 and BAM-227 were applied such that 2 μg S, 5 μg S and 11 μg S were absorbed in the PE frits, respectively. These samples were pre-quantified for the adsorbed sulphur amount by external calibration LA-ICP-MS yielding sulphur amounts of 0.9 μg, 5.1 μg and 8.5 μg (quantified for ³²S only), respectively. Relative Standard deviations of the isotope ratios were below 5% in average (n ¼ 3 lines) in all cases (except for the pure spike solution). These samples were then analysed by LA-ICP-IDMS and the measurement results were validated by comparing them with the results obtained by conventional ICP-IDMS. The obtained relative expanded measurement uncertainties ranged between 10% and 26%. Pearson's coefficient was used to express the correlation between both techniques; the obtained value was 0.999 demonstrating a strong correlation. Contrary to most published LA-ICP-IDMS procedures, the developed procedure enables SI-traceability for the measurement results. The metrological traceability to the SI for the sulphur mass fractions in copper was established by an unbroken chain of comparisons, each accompanied by an uncertainty budget. Thus, the measurement results are considered reliable, acceptable and comparable within the stated measurement uncertainty. The metrological traceability chain from the kg down to mass fraction in the samples obtained by LA-ICP-IDMS is presented as well. KW - Laser ablation KW - IDMS KW - Traceability KW - Uncertainty KW - Purity PY - 2018 DO - https://doi.org/10.1039/c8ja00116b SN - 0267-9477 SN - 1364-5544 VL - 33 IS - 9 SP - 1506 EP - 1517 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-45899 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Rosner, M. A1 - Curbera, J. A1 - Peltz, U. A1 - Peplinski, Burkhard T1 - Lead isotope analysis in magic artefacts from the Berlin museums JF - Archaeological and Anthropological Sciences N2 - A set of 59 ancient magical artefacts, mainly made of lead, was selected from the collections of the Staatliche Museen zu Berlin in order to unravel their origins. All the selected artefacts have been studied for their Pb isotope compositions, which covered the whole range of the Mediterranean ore deposits. However, the majority (≈86%) were made of lead matching the small compositional range of the Laurion ore deposits. Only eight out of the 59 artefacts were made of recycled lead or lead from other ore deposits. Additionally, all but two were approximately dated based on their inscriptions. The lead isotopic composition together with information obtained from the inscriptions, the resulting dating, the context of the find and the known history of each item allowed us to gain more detailed information about the origins of these magical artefacts. The Attic provenance of 36 curse tablets was confirmed, whereas for 11 curse tablets previously classified as non-Attic, the provenance was either confirmed and specified (six artefacts) or changed to Attic (five artefacts). Surprisingly, the majority (six out of eight) of the analysed curse tablets from the Egyptian collection showed a lead isotopic composition closely matching that of Laurion. A Laurion-like lead isotopic composition was also observed for three of the four analysed oracular tablets from Dodona. Together with the dating information, this points to Laurion as the major and dominant lead source in the Aegean, at least during the fourth–third century B.C. The few curse tablets from earlier than the fourth–third century B.C. point to the use of multiple and thus isotopically more variable lead sources compared with the Roman times. KW - Lead isotopes KW - Pb isotopes KW - Greek curse tablets KW - Antikensammlung Berlin KW - Ägyptisches Museum Berlin PY - 2018 DO - https://doi.org/10.1007/s12520-016-0445-6 SN - 1866-9557 SN - 1866-9565 VL - 10 IS - 5 SP - 1111 EP - 1127 PB - Springer Verlag CY - Berlin AN - OPUS4-45628 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Noordmann, J. A1 - Rosner, M. A1 - Goenaga-Infante, H. A1 - Štrok, M. A1 - Pramann, A. A1 - Vanhaecke, F. A1 - Meisel, T. A1 - Pröfrock, D. A1 - Prohaska, T. A1 - Vocke, R.D. A1 - Richter, S. T1 - Absolute Isotope Ratios N2 - Measurement results and scientific models leading to important decisions in forensics, food fraud or climatology are based on isotope ratio data. Molar masses of multi-isotopic elements are as well based on isotope ratio data. Thus, in the case of Si, isotope ratios directly impact the redefinition of the SI base units kilogram and mole. Therefore, new strategies are required leading to new primary isotope reference materials, whose isotope ratios are traceable to the SI. This in turn will ensure the comparability of isotope ratio data and will render the traceability exception requested by the CCQM superfluous. Such new procedures will be developed for the key elements S, Si, Ca, Sr and Nd at relative uncertainty levels of ≤ 0.01 %. T2 - EURAMET TC-MC Meeting CY - Vienna, Austria DA - 05.02.2018 KW - Metrology in chemistry KW - Isotope amount ratio KW - SI traceability KW - Atomic weight KW - Molar mass KW - Synthetic isotope mixtures PY - 2018 AN - OPUS4-44644 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Kipphardt, Heinrich A1 - Richter, Silke A1 - Bremser, Wolfram A1 - Arvizu Torres, M. A1 - Lara Manzano, J. A1 - Buzoianu, M. A1 - Hill, S. A1 - Petrov, P. A1 - Goenaga-Infante, H. A1 - Sargent, M. A1 - Fisicaro, P. A1 - Labarraque, G. A1 - Zhou, T. A1 - Turk, G. C. A1 - Winchester, M. A1 - Miura, T. A1 - Methven, B. A1 - Sturgeon, R. A1 - Jährling, R. A1 - Rienitz, O. A1 - Mariassy, M. A1 - Hankova, Z. A1 - Sobina, E. A1 - Krylov, A. I. A1 - Kustikov, Y. A. A1 - Smirnov, V. V. T1 - Establishing comparability and compatibility in the purity assessment of high purity zinc as demonstrated by the CCQM-P149 intercomparison JF - Metrologia : international journal of pure and applied metrology N2 - For the first time, an international comparison was conducted on the determination of the purity of a high purity element. Participants were free to choose any analytical approach appropriate for their institute’s applications and services. The material tested was a high purity zinc, which had earlier been assessed for homogeneity and previously used in CCQM-K72 for the determination of six defined metallic impurities. Either a direct metal assay of the Zn mass fraction was undertaken by EDTA titrimetry, or an indirect approach was used wherein all impurities, or at least the major ones, were determined and their sum subtracted from ideal purity of 100 %, or 1 kg/kg. Impurity assessment techniques included glow discharge mass spectrometry, inductively coupled plasma mass spectrometry and carrier gas hot extraction/combustion analysis. Up to 91 elemental impurities covering metals, non-metals and semi-metals/metalloids were quantified. Due to the lack of internal experience or experimental capabilities, some participants contracted external laboratories for specific analytical tasks, mainly for the analysis of non-metals. The reported purity, expressed as zinc mass fraction in the high purity zinc material, showed excellent agreement for all participants, with a relative standard deviation of 0.011 %. The calculated reference value, w(Zn) = 0.999 873 kg/kg, was assigned an asymmetric combined uncertainty of + 0.000025 kg/kg and – 0.000028 kg/kg. Comparability amongst participating metrology institutes is thus demonstrated for the purity determination of high purity metals which have no particular difficulties with their decomposition / dissolution process when solution-based analytical methods are used, or which do not have specific difficulties when direct analysis approaches are used. Nevertheless, further development is required in terms of uncertainty assessment, quantification of non-metals and the determination of purity of less pure elements and/or for those elements suffering difficulties with the decomposition process. KW - Purity assessment KW - Direct metal assay KW - Impurity assessment KW - Non-metal analysis KW - High-purity elements KW - SI-traceability PY - 2018 DO - https://doi.org/10.1088/1681-7575/aaa677 SN - 1681-7575 SN - 0026-1394 VL - 55 IS - 2 SP - 211 EP - 221 PB - Institute of Physics Publishing CY - Bristol AN - OPUS4-44257 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Phukphatthanachai, Pranee A1 - Panne, Ulrich A1 - Jakubowski, Norbert A1 - Vogl, Jochen T1 - SI-traceable quantification of sulphur in copper metal and its alloys by ICP-IDMS JF - Journal of Analytical Atomic Spectrometry N2 - Previously applied methods for the quantification of sulphur in copper and other pure metals revealed a lack of SI-traceability and additionally showed inconsistent results, when different methods were compared. Therefore, a reference procedure is required which allows SI-traceable values accompanied by a Sound uncertainty budget. In this study a procedure was developed for the quantification of total sulphur in copper at low concentration levels using inductively coupled plasma-isotope dilution mass spectrometry (ICP-IDMS). The major part of the copper matrix was separated by adding ammonia which forms a complex with the copper while releasing the sulphur followed by chromatographic separation using a weak cation resin. After that the sulphur fraction was further purified by chromatographic means using first an anion exchange method and second a chelating resin. The developed procedure shows high performance, especially concerning high efficiency in matrix removal (>99.999%) while keeping the recovery of sulphur above 80%. Procedure blanks are in the order of 3–53 ng resulting in LOD and LOQ values of 0.2 mg g1 and 0.54 mg g1, respectively. The procedure is sufficient to facilitate value assignment of the total sulphur mass fraction in reference materials. Additionally, relative measurement uncertainties were calculated to be below 1% and the measurement results were traceable to the SI. The procedure reported in this study is a new reference procedure for sulphur measurement in copper, being fit for two major purposes, certification of reference materials and assignment of reference values for inter-laboratory comparison. KW - Traceability KW - Measuremment uncertainty KW - Isotope dilution mass spectrometry KW - Reference measurements PY - 2018 DO - https://doi.org/10.1039/c7ja00338b SN - 0267-9477 SN - 1364-5544 VL - 33 IS - 1 SP - 90 EP - 101 PB - Royal Society of Chemistry CY - Cambridge, UK AN - OPUS4-43614 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -