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 - Xiao, J. A1 - Vogl, Jochen A1 - Rosner, M. A1 - Deng, L. A1 - Jin, Z. T1 - A validated analytical procedure for boron isotope analysis in plants by MC-ICP-MS JF - Talanta N2 - Boron (B) is an essential micronutrient for plant growth. Lack of valid methods for pretreatment and measurement of δ11B in plant restrict applications of it in the biosphere. Dry ashing, one step cation exchange and micro-sublimation were combined to separate and purify boron (B) in plant tissues. The low procedure blank, high B recovery and the accurate δ11B values of the plant reference materials demonstrate that this method is suitable and valid for B pretreatment and δ11B measurement in plant samples by MC-ICP-MS. Based on this method, the δ11B in different plants (Brassica napus, Chenopodium album L, moss, lichen, and Nostoc commune) was analyzed. For Brassica napus, δ11B increased gradually from root to leaf, and then decreased to rapeseed. For the same parts, the δ11B increased from the lower parts to the higher parts. This variation may be due to the B(OH)3 transporter of NIP6;1 and the incorporation of B into the cell. The reason for lower δ11B values in shell and rapeseed compared to those in leaves presumably is to the preferred Transport of borate in the phloem. The largest δ11B fractionation between leaf and root in Brassica napus and Chenopodium album L was +24.2‰ and +26.6‰, respectively. The large variation and fractionation of δ11B within plants indicates that δ11B is a good tracer to study the B translocation mechanisms and metabolism within plants. The δ11B in Nostoc commune, lichen, and moss showed variations of -4.1‰ to +21.5‰, −9.4‰ to +7.3‰, and −18.3‰ to +11. 9‰, respectively. In the same site, δ11B in different plants ranked Nostoc commune>moss>lichen and δ11B in mosses growing in different environment ranked soil>tree>rock. Rain and soil available B are the main B sources for these plants. The δ11B in Nostoc commune, lichen, and moss may be a useful tracer to study the atmospheric B input. In the future, plants culture experiments under certain environments and studies from molecular level are necessary to decipher the variation of δ11B and fractionation mechanisms within plants. KW - Boron isotope KW - Isotopic fractionation KW - Micro-sublimation KW - Plant tissue KW - MC-ICP-MS PY - 2019 DO - https://doi.org/10.1016/j.talanta.2018.12.087 SN - 0039-9140 SN - 1873-3573 VL - 196 SP - 389 EP - 394 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-47160 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 - CONF A1 - Vogl, Jochen T1 - Absolute isotope ratios - a proposed research topic N2 - An introduction into absolute isotope ratios is given, with application fields ranging from fundamental science to geochronology and forensics. This is followed by a proposal for developing new calibration approaches for obtaining absolute isotope ratios at unrivaled uncertainty levels. This new developments will set the basis for improvements in all scientific fields. T2 - EURAMET TC-MC Workshop on Isotope Ratio Analysis CY - Bern, Switzerland DA - 05.02.2020 KW - Absolute isotope ratio KW - Isotope fractionation KW - Metrology KW - Fundamental science PY - 2020 AN - OPUS4-50346 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dariz, P. A1 - Wortmann, U. G. A1 - Vogl, Jochen A1 - Schmid, Thomas T1 - Beautiful Pietàs in South Tyrol (Northern Italy): local or imported works of art? JF - Heritage Science N2 - The study, dedicated to Beautiful Pietàs conserved in South Tyrol (Northern Italy), aims to establish, for the first time, a connection between Austroalpine raw materials and the high-fired gypsum mortars constituting the Gothic figure groups in question. The origin and chronology of this stylistically and qualitatively differing ensemble have been subject of art historical debate for nearly a century. The discourse is dominated by three main hypotheses: itinerary of an Austrian artist versus itinerary of the work of art created in an artist’s workshop in Austria versus itinerary of the stylistic vocabulary via graphical or three-dimensional models. The comparison of the δ34S values and the 87Sr/86Sr ratios of the gypsum mortars and Austroalpine sulphate deposits (in a compilation of own reference samples and literature data) points to the exploitation of sediments in the Salzkammergut and possibly also in the evaporite district of the Eastern Calcareous Alps, thus evidencing the import of the sculptures and not the activities of local South Tyrolean or itinerant artists. Two geochronological units are distinguishable: The Pietà in the Church St. Martin in Göflan can be assigned to Upper Permian raw material, whereas the metrologically consistent sculptures in the Church of Our Lady of the Benedictine Abbey Marienberg and in the Chapel St. Ann in Mölten correlate with deposits of the Early Triassic (or the Lower-Middle Triassic transition). The medieval gypsum mortars also differ in their mineralogical characteristics, i.e. in their geologically related minor components, as in the first case, characterised by a significant proportion of primary anhydrite, natural carbonate impurities mainly consist of calcite (partly converted to lime-lump-like aggregates), whereas in the second group dolomite (or rather its hydration products after pyrometamorphic decomposition) predominates, accompanied by celestine, quartz and potassium feldspar. The Pietà in the Cathedral Maria Himmelfahrt in Bozen turned out to be made of Breitenbrunn calcareous sandstone (Leitha Mountains, Burgenland, Austria), which is why the sample is not considered in the geochemical analysis. KW - High-fired gypsum mortar KW - Sulphur isotope KW - Strontium isotope KW - Polarised light microscopy KW - Raman microspectroscopy PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545610 DO - https://doi.org/10.1186/s40494-022-00678-6 SN - 2050-7445 VL - 10 IS - 1 SP - 1 EP - 17 PB - Springer Nature AN - OPUS4-54561 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Xiao, J. A1 - Vogl, Jochen A1 - Rosner, M. A1 - Jin, Z. T1 - Boron isotope fractionation in soil-plant systems and its influence on biogeochemical cycling JF - Chemical Geology N2 - Boron (B) is an essential mineral nutrient for higher plants. Although B plant nutrition is well studied, the B isotope fractionation at the soil-plant interface, within plant metabolism, and its influence on biogeochemical cycling is not fully understood. Boron concentrations and isotope variations (δ11B) of the dicotyledonous plants of Chenopodium album and Brassica napus and their growing soils along a climatic gradient were analyzed to decipher these unresolved issues of the B behavior. The boron concentrations and δ11B values show an increasing trend from roots to leaves for both plants, while a decreasing trend from flower to shell and to seed for Brassica napus. A large boron isotope fractionation occurs within the plants with median Δ11Bleaf-root ≈ +20‰, which is related to different boron transporters and transportation ways. Formation of borate dimerized rhamnogalacturonan II in cell and B(OH)3 transportation in xylem lead to heavier δ11B values from root to stem and leaf while B(OH)4􀀀 transportation in phloem lead to lighter δ11B values from flower to shell and seed. Although samples cover a distinct transect with systematically different climatic conditions, Δδ11B within the individual plant compartments and between the bulk plants and the soil available B do not show any systematic variation. This suggests that B uptake from the soil into Chenopodium album and Brassica napus occurs without a distinct isotope fractionation at the soil-plant interface (median Δ11Bbulkplant-soil = 􀀀 0.2‰) and plants are able to regulate boron uptake. Both the observed large B fractionation within plant and low or absent B isotope fractionation at the soil-plant interface may have profound implications for the biological and geological B cycle. If this observed boron behavior also exists in other plants, their litters would be an important source for exporting 11B-rich biological material from continental ecosystems via rivers to the global oceans. This may be helpful for the explanation of ocean B cycle and the increasing δ11B values over the Cenozoic. KW - Boron isotopic composition KW - Boron isotope fractionation KW - Soil available boron KW - Biological boron recycling KW - Chenopodium album KW - Brassica napus PY - 2022 DO - https://doi.org/10.1016/j.chemgeo.2022.120972 SN - 0009-2541 VL - 606 SP - 1 EP - 8 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-55031 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Geilert, Sonja A1 - Vogl, Jochen A1 - Rosner, M. A1 - Eichert, T. T1 - Boron isotope variability related to boron speciation (change during uptake and transport) in bell pepper plants and SI traceable n(11B)/n(10B) ratios for plant reference materials JF - Rapid Communications in Mass Spectrometry N2 - Rationale: Boron (B) is an essential micronutrient in plants and its isotope variations are used to gain insights into plant metabolism, which is important for crop plant cultivation. B isotope variations were used to trace intra‐plant fractionation mechanisms in response to the B concentration in the irrigation water spanning the range from B depletion to toxic levels. Methods: A fully validated analytical procedure based on multi‐collector inductively coupled plasma mass spectrometry (MC‐ICP‐MS), sample decomposition and B Matrix separation was applied to study B isotope fractionation. The Validation was accomplished by establishing a complete uncertainty budget and by applying reference materials, yielding expanded measurement uncertainties of 0.8‰ for pure boric acid solutions and ≤1.5‰ for processed samples. With this validated procedure SI traceable B isotope amount ratios were determined in plant reference materials for the first time. Results: The B isotope compositions of Irrigation water and bell pepper samples suggest passive diffusion of the heavy 11B isotope into the roots during low to high B concentrations while uptake of the light 10B isotope was promoted during B depletion, probably by active processes. A systematic enrichment of the heavy 11B isotope in higher located plant parts was observed (average Δ11Bleaf‐roots = 20.3 ± 2.8‰ (1 SD)), possibly by a facilitated transport of the heavy 11B isotope to growing Meristems by B transporters. Conclusions: The B isotopes can be used to identify plant metabolism in Response to the B concentration in the irrigation water and during intra‐plant B transfer. The large B isotope fractionation within the plants demonstrates the importance of biological B cycling for the global B cycle. KW - isotope fractionation KW - boron KW - delta value KW - metabolism KW - bell pepper KW - SI traceability KW - measurement uncertainty PY - 2019 DO - https://doi.org/10.1002/rcm.8455 SN - 1097-0231 SN - 0951-4198 VL - 33 IS - 13 SP - 1137 EP - 1147 PB - John Wiley & Sons Ltd. AN - OPUS4-48213 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Rienitz, O. A1 - Rosner, M. A1 - Brandt, B. A1 - Kasemann, S. A. A1 - Kraft, R. A1 - Malinovskiy, D. A1 - Meixner, A. A1 - Noordmann, J. A1 - Raab, S. A1 - Schuessler, J. A. A1 - Vocke, R. D. T1 - Calibration of Mg isotope amount ratios and delta values N2 - In the past, δ26/24Mg measurements were referenced to NIST SRM 980, the initial zero of the δ26/24Mg scale. With the development of MC-ICPMS, the detection of small but measurable isotopic differences in different chips of SRM 980 became apparent. To solve this problem a suite of magnesium isotope reference materials, ERM-AE143, -AE144 and -AE145, has been certified in a first study by applying an ab initio calibration for absolute Mg isotope ratios without any a priori assumptions, a procedure which fulfils all requirements of a primary method of measurement. We could achieve for the first time measurement uncertainties for isotope amount ratios close to the typical precision of magnesium delta values, δ26/24Mg, which are at the 0.1 ‰ level (2SD). In addition, it was demonstrated that commonly used fractionation laws are invalid for correcting Mg isotope ratios in multi-collector ICPMS as they result in a bias which is not covered by its associated uncertainty. Depending on their type, fractionation laws create a bias up to several per mil, with the exponential law showing the smallest bias between 0.1 ‰ to 0.7 ‰. With these isotope reference materials, it is possible to establish SI-traceability for magnesium delta measurements. To realize this, we organized a second study within which five expert laboratories participated to cross-calibrate all available magnesium isotope standards, which are NIST SRM 980, IRMM-009, ERM-AE143, ERM-AE144, ERM-AE145 and the standards DSM3 and Cambridge-1. The mean δ26/24Mg values for the individual iRMs, calculated from the laboratory means show 2 SD reproducibilities varying between 0.025 and 0.093 ‰. Propagated measurement uncertainties suggest a standard uncertainty of about 0.1‰ for δ26/24Mg determinations (2SD). Thus, SI traceability for magnesium isotope amount ratios and delta values is demonstrated to be established. T2 - European Winter Conference on Plasma Spectrochemistry CY - Pau, France DA - 03.02.2019 KW - Delta value KW - SI-traceability KW - Absolute isotope ratio PY - 2019 AN - OPUS4-47710 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Rienitz, O. A1 - Rosner, M. A1 - Mieller, Björn A1 - Kasemann, S. A1 - Kraft, R. A1 - Malinovskiy, D. A1 - Meixner, A. A1 - Noordmann, J. A1 - Rabb, S. A1 - Schuessler, J. A. A1 - Vocke, R. D. T1 - Calibration of Mg isotope amount ratios and delta values N2 - In the past, δ26/24Mg measurements were referenced to NIST SRM 980, the initial zero of the δ26/24Mg scale. With the development of MC-ICPMS, the detection of small but measurable isotopic differences in different chips of SRM 980 became apparent. To solve this problem a suite of magnesium isotope reference materials, ERM-AE143, -AE144 and -AE145, has been certified in a first study by applying an ab initio calibration for absolute Mg isotope ratios without any a priori assumptions, a procedure which fulfils all requirements of a primary method of measurement. We could achieve for the first time measurement uncertainties for isotope amount ratios close to the typical precision of magnesium delta values, δ26/24Mg, which are at the 0.1 ‰ level (2SD). In addition, it was demonstrated that commonly used fractionation laws are invalid for correcting Mg isotope ratios in multi-collector ICPMS as they result in a bias which is not covered by its associated uncertainty. Depending on their type, fractionation laws create a bias up to several per mil, with the exponential law showing the smallest bias between 0.1 ‰ to 0.7 ‰. With these isotope reference materials, it is possible to establish SI-traceability for magnesium delta measurements. To realize this, we organized a second study within which five expert laboratories participated to cross-calibrate all available magnesium isotope standards, which are NIST SRM 980, IRMM-009, ERM-AE143, ERM-AE144, ERM-AE145 and the standards DSM3 and Cambridge-1. The mean δ26/24Mg values for the individual iRMs, calculated from the laboratory means show 2 SD reproducibilities varying between 0.025 and 0.093 ‰. Propagated measurement uncertainties suggest a standard uncertainty of about 0.1‰ for δ26/24Mg determinations (2SD). Thus, SI traceability for magnesium isotope amount ratios and delta values is demonstrated to be established. T2 - 53rd annual conference of the DGMS including 27th ICP-MS User's Meeting CY - Münster, Germany DA - 01.03.2020 KW - Isotope ratio KW - Delta value KW - Metrology KW - Magnesium KW - Magnesium isotope ratios PY - 2020 N1 - Geburtsname von Mieller, Björn: Brandt, B. - Birth name of Mieller, Björn: Brandt, B. AN - OPUS4-50549 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - CCQM IRWG draft strategy for all elements except for noble gases and H, C, N, O N2 - The presentation describes the draft strategy for metalloids and semi-metals within the IRWG at CCQM. This includes the definition of the measurements space, a suitable set of key comparisons and pilot studies and a proposal for a harmonized CMC application. T2 - EURAMET TC-MC Workshop on Isotope Ratio Analysis CY - Bern, Switzerland DA - 05.02.2020 KW - CMC KW - Measurement space KW - Metrology KW - Isotope ratio PY - 2020 AN - OPUS4-50345 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rienitz, O. A1 - Jährling, R. A1 - Noordmann, J. A1 - Pape, C. A1 - Röhker, K. A1 - Vogl, Jochen A1 - Manzano, J. V. L. A1 - Kozlowski, W. A1 - Caciano de Siena, R. A1 - Marques Rodrigues, J. A1 - Galli, A. H. A1 - Yim, Y.-H. A1 - Lee, K.-S. A1 - Lee, J. H. A1 - Min, H.-S. A1 - Chingbo, C. A1 - Naijie, S. A1 - Qian, W. A1 - Ren, T. A1 - Jun, W. A1 - Tangpaisarnkul, N. A1 - Suzuki, T. A1 - Nonose, N. A1 - Mester, Z. A1 - Yang, L. A1 - Pagliano, E. A1 - Greenberg, P. A1 - Mariassy, M. A1 - Näykki, T. A1 - Cankur, O. A1 - Coskun, F. G. A1 - Ari, B. A1 - Can, S. Z. T1 - CCQM-K122 "Anionic impurities and lead in salt solutions" JF - Metrologia N2 - The determination of the mass fractions of bromide, sulfate, and lead as well as the isotopic composition of the lead (expressed as the molar mass and the amount fractions of all four stable lead isotopes) in an aqueous solution of sodium chloride with a mass fraction of 0.15 g/g was the subject of this comparison. Even though the mass fractions ranged from 3 μg/g (bromide) to 50 ng/g (lead), almost all results reported agreed with the according KCRVs. KW - Absolute isotope ratio KW - Lead isotope ratios KW - Metrology KW - Traceability PY - 2020 DO - https://doi.org/10.1088/0026-1394/57/1A/08012 VL - 57 IS - 1A SP - 8012 PB - IOP Science AN - OPUS4-51156 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Molloy, J. L. A1 - Winchester, M. R. A1 - Butler, T. A. A1 - Possolo, A. M. A1 - Rienitz, O. A1 - Roethke, A. A1 - Goerlitz, V. A1 - Caciano de Sena, R. A1 - Dominguez Almeida, M. A1 - Yang, L. A1 - Methven, B. A1 - Nadeau, K. A1 - Romero Arancibia, P. A1 - Bing, W. A1 - Tao, Z. A1 - Snell, J. A1 - Vogl, Jochen A1 - Koenig, Maren A1 - Kotnala, R. K. A1 - Swarupa Tripathy, S. A1 - Elishian, C. A1 - Ketrin, R. A1 - Suzuki, T. A1 - Oduor Okumu, T. A1 - Yim, Y.-H. A1 - Heo, S. W. A1 - Min, H. S. A1 - Sub Han, M. A1 - Lim, Y. A1 - Velina Lara Manzano, J. A1 - Segoviano Regalado, F. A1 - Arvizu Torres, M. A1 - Valle Moya, E. A1 - Buzoianu, M. A1 - Sobina, A. A1 - Zyskin, V. A1 - Sobina, E. A1 - Migal, P. A1 - Linsky, M. A1 - Can, S. Z. A1 - Ari, B. A1 - Goenaga Infante, H. T1 - CCQM-K143 Comparison of Copper Calibration Solutions Prepared by NMIs/DIs JF - Metrologia N2 - CCQM-K143 is a key comparison that assesses participants’ ability to prepare single element calibration solutions. Preparing calibration solutions properly is the cornerstone of establishing a traceability link to the International System of Units (SI), and therefore should be tested in order to confirm the validity of CCQM comparisons of more complex materials. CCQM-K143 consisted of participants each preparing a single copper calibration solution at 10 g/kg copper mass fraction and shipping 10 bottled aliquots of that solution to the coordinating laboratory, the National Institute of Standards and Technology (NIST). The masses and mass fraction for the prepared solutions were documented with the submitted samples. The solutions prepared by all participants were measured at NIST by high performance inductively coupled plasma optical emission spectroscopy (HP-ICP-OES). The intensity measurements for copper were not mapped onto values of mass fraction via calibration. Instead, ratios were computed between the measurements for copper and simultaneous measurements for manganese, the internal standard, and all subsequent data reductions, including the computation of the KCRV and the degrees of equivalence, were based on these ratios. Other than for two participants whose measurement results appeared to suffer from calculation or preparation errors, all unilateral degrees of equivalence showed that the measured values did not differ significantly from the KCRV. These results were confirmed by a second set of ICP-OES measurements performed by the Physikalisch-Technische Bundesanstalt (PTB). CCQM-K143 showed that participants are capable of preparing calibration solutions starting from high purity, assayed copper metal. Similar steps are involved when preparing solutions for other elements, so it seems safe to infer that similar capabilities should prevail when preparing many different, single-element solutions. KW - Metrology KW - Primary calibration solution KW - Traceability PY - 2020 DO - https://doi.org/10.1088/0026-1394/58/1A/08006 SN - 0026-1394 VL - 58 IS - 1A SP - 08006 PB - IOP Science CY - Cambridge AN - OPUS4-51983 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - CCQM-P213: BAM procedure for obtaining Cu delta values N2 - BAM participated in the CCQM pilot study P213 for obtaining copper isotope delta values. This presentations provides details on the MC-ICP-MS based measruement procedure, which has been applied to obtain such copper delta values. T2 - IRWG Meeting CY - Online meeting DA - 12.05.2022 KW - Isotope delta value KW - Copper KW - Metrology KW - Traceability PY - 2022 AN - OPUS4-55162 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - CCQM-P213: BAM procedure for obtaining Cu delta values N2 - BAM participated in the CCQM pilot study P213 for obtaining copper isotope delta values. This presentations provides details on the MC-ICP-MS based measruement procedure, which has been applied to obtain such copper delta values. T2 - IRWG Meeting 2022 CY - Online meeting DA - 20.09.2022 KW - Isotope ratio KW - Copper KW - Metrology KW - Traceability KW - Uncertainty PY - 2022 AN - OPUS4-55864 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Yim, Y.-H. A1 - Lee, K.-S. A1 - Goenaga-Infante, H A1 - Malinovskiy, D. A1 - Hill, S. A1 - Ren, T. A1 - Wang, J. A1 - Vocke, R. D. A1 - Murphy, K. E. A1 - Nonose, N. A1 - Rienitz, O. A1 - Noordmann, J. T1 - Certification of ERM-EB400, the first matrix reference material for lead isotope amount ratios, and ERM-AE142, a lead solution providing a lead isotopic composition at the edge of natural variation JF - Geostandards and Geoanalytical Research N2 - Lead isotope amount ratios are commonly used in diverse fields such as archaeometry, geochemistry and forensic science. Currently, five reference materials with certified lead isotope amount ratios are available, namely NIST SRM 981, 982 and 983, GBW-04442 and NMIJ 3681-a. Only NIST SRM 981 and NMIJ 3681-a have approximately natural isotopic compositions, and NIST SRM 981 is predominantly used for correcting mass discrimination/mass fractionation in the applied mass spectrometric procedures. Consequently, there is no other certified reference material available to be used for validation and/or quality control of the analytical procedures applied to lead isotope amount ratio measurements. To fill this gap, two new reference materials have been produced and certified for their lead isotope amount ratios. For both certified reference materials, complete uncertainty budgets have been calculated and SI traceability has been established. This provides the users with independent means for validating and verifying their analytical procedures and for conducting quality control measures. ERM-EB400 is a bronze material with a nominal lead mass fraction of 45 mg kg-1 and certified lead isotope amount ratios of n(206Pb)/n(204Pb) = 18.072(17) mol mol-1, n(207Pb)/n(204Pb) = 15.578(18) mol mol-1 and n(208Pb)/n(204Pb) = 38.075(46) mol mol-1 with the associated expanded uncertainties (k = 2) given in brackets. ERM-AE142 is a high-purity solution of lead in 2% nitric acid with a nominal mass fraction of 100 mg kg-1 and certified Pb isotope amount ratios of n(206Pb)/n(204Pb) = 21.114(17) mol mol-1, n(207Pb)/n(204Pb) = 15.944(17) mol mol-1 and n(208Pb)/n(204Pb) = 39.850(44) mol mol-1 with the associated expanded uncertainties (k = 2) given in brackets. Both materials are specifically designed to fall within the natural lead isotopic variation and to assist users with the validation and verification of their analytical procedures. Note that while one of these reference materials requires the chemical separation of Pb from its matrix (ERM-EB400), the other does not (ERM-AE142). As additional information, δ208/206PbNIST SRM981 values are provided for both materials. For ERM-AE142, a delta value of δ208/206PbNIST SRM981 = -28.21(30) ‰ was obtained, and for ERM-EB400, a delta value of δ208/206PbNIST SRM981 = -129.47(38) ‰ was obtained, with the associated expanded uncertainties (k = 2) given in brackets. KW - Lead isotope variations KW - Radiogenic isotopes KW - Isotope reference material KW - Metrology in chemistry KW - Measurement uncertainty PY - 2019 DO - https://doi.org/10.1111/ggr.12253 SN - 1751-908X SN - 1639-4488 VL - 43 IS - 1 SP - 23 EP - 37 PB - John Wiley & Sons AN - OPUS4-47383 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Isleyen, Alper A1 - Can, Suleyman Z. A1 - Cankur, Oktay A1 - Tunc, Murat A1 - Vogl, Jochen A1 - Koenig, Maren A1 - Horvat, Milena A1 - Jacimovic, Radojko A1 - Zuliani, Tea A1 - Fajon, Vesna A1 - Jotanovic, Aida A1 - Gaževic, Luka A1 - Milosevic, Milena A1 - Ochsenkuehn–Petropoulou, Maria A1 - Tsopelas, Fotis A1 - Lymberopoulou, Theopisti A1 - Tsakanika, Lamprini-Areti A1 - Serifi, Olga A1 - Ochsenkuehn, Klaus M. A1 - Bulska, Ewa A1 - Tomiak, Anna A1 - Kurek, Eliza A1 - Cakılbahçe, Zehra A1 - Aktas, Gokhan A1 - Altuntas, Hatice A1 - Basaran, Elif A1 - Kısacık, Barıs A1 - Gumus, Zeynep T1 - Certification of the total element mass fractions in UME EnvCRM 03 soil sample via a joint research project JF - Accreditation and Quality Assurance N2 - Soil certified reference material (CRM), UME EnvCRM 03 was produced by a collaborative approach among national metrology institutes, designated institutes and university research laboratories within the scope of the EMPIR project: Matrix Reference Materials for Environmental Analysis. This paper presents the sampling and processing methodology, homogeneity, stability, characterization campaign, the assignment of property values and their associated uncertainties in compliance with ISO 17034:2016. The material processing methodology involves blending a natural soil sample with a contaminated soil sample obtained by spiking elemental solutions for 8 elements (Cd, Co, Cu, Hg, Ni, Pb, Sb and Zn) to reach the level of warning risk monitoring values specified for metals and metalloids of soils in Europe. Comparative homogeneity and stability test data were obtained by two different institutes, ensuring the reliability and back up of the data. The certified values and associated expanded uncertainties for the total mass fractions of thirteen elements (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, V and Zn) are established. The developed CRM can be used for the development and validation of measurement procedures for the determination of the total mass fractions of elements in soil and also for quality control/assurance purposes. The developed CRM is the first example of a soil material originating from Türkiye. KW - Total element content KW - Soil KW - CRM KW - Certification KW - Environmental pollution monitoring PY - 2024 DO - https://doi.org/10.1007/s00769-024-01597-8 SN - 1432-0517 SP - 1 EP - 9 PB - Springer Science and Business Media LLC AN - OPUS4-59954 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kazlagić, Anera A1 - Rosner, M. A1 - Cipriani, A. A1 - Frick, D. A. A1 - Glodny, J. A1 - Hoffmann, E. J. A1 - Hora, J. M. A1 - Irrgeher, J. A1 - Lugli, F. A1 - Magna, T. A1 - Meisel, T. C. A1 - Meixner, A. A1 - Possolo, A. A1 - Pramann, A. A1 - Pribil, M. J. A1 - Prohaska, T. A1 - Retzmann, Anika A1 - Rienitz, O. A1 - Rutherford, D. A1 - Paula-Santos, G. M. A1 - Tatzel, M. A1 - Widhalm, S. A1 - Willbold, M. A1 - Zuliani, T. A1 - Vogl, Jochen T1 - Characterisation of conventional 87Sr/86Sr isotope ratios in cement, limestone and slate reference materials based on an interlaboratory comparison study JF - Geostandards and Geoanalytical Research N2 - An interlaboratory comparison (ILC)was organised to characterise 87Sr/86Sr isotope ratios in geological and industrial reference materials by applying the so-called conventional method for determining 87Sr/86Sr isotope ratios. Four cements (VDZ 100a,VDZ 200a, VDZ 300a, IAG OPC-1), one limestone (IAG CGL ML-3) and one slate (IAG OU-6) reference materials were selected, covering a wide range of naturally occurring Sr isotopic signatures. Thirteen laboratories received aliquots of these six reference materials together with a detailed technical protocol. The consensus values for the six reference materials and their associated measurement uncertainties were obtained by applying a Gaussian, linear mixed effects model fitted to all the measurement results. By combining the consensus values and their uncertainties with an uncertainty contribution for potential heterogeneity, reference values ranging from 0.708134 mol mol-1 to 0.729778 mol mol-1 were obtained with relative expanded uncertainties of ≤ 0.007 %. This study represents an ILC on conventional 87Sr/86Sr isotope ratios, within which metrological principles were considered and the compatibility of measurement results obtained by MC-ICP-MS and by MC-TIMS is demonstrated. The materials characterised in this study can be used as reference materials for validation and quality control purposes and to estimate measurement uncertainties in conventional 87Sr/86Sr isotope ratio measurement. KW - Sr isotope analysis KW - Isotope ratios KW - Cement KW - Geological material KW - MC-TIMS KW - MC-ICP-MS KW - Interlaboratory comparison KW - Measurement uncertainty KW - Cconventional method PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-579836 DO - https://doi.org/10.1111/ggr.12517 SN - 1639-4488 VL - 47 IS - 4 SP - 821 EP - 840 PB - Wiley online library AN - OPUS4-57983 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Brauckmann, C. A1 - Pramann, A. A1 - Rienitz, O. A1 - Schulze, A. A1 - Phukphatthanachai, P. A1 - Vogl, Jochen T1 - Combining Isotope Dilution and Standard Addition - Elemental Analysis in Complex Samples N2 - A new method combining isotope dilution mass spectrometry (IDMS) and standard addition has been developed to determine the mass fractions w of different elements in complex matrices: (a) silicon in aqueous tetramethylammonium hydroxide (TMAH), (b) sulfur in biodiesel fuel, and (c) iron bound to transferrin in human serum. All measurements were carried out using inductively coupled plasma mass spectrometry (ICP–MS). The method requires the gravimetric preparation of several blends (bi)—each consisting of roughly the same masses (mx,i) of the sample solution (x) and my,i of a spike solution (y) plus different masses (mz,i) of a reference solution (z). Only these masses and the isotope ratios (Rb,i) in the blends and reference and spike solutions have to be measured. The derivation of the underlying equations based on linear regression is presented and compared to a related concept reported by Pagliano and Meija. The uncertainties achievable, e.g., in the case of the Si blank in extremely pure TMAH of urel (w(Si)) = 90% (linear regression method, this work) and urel (w(Si)) = 150% (the method reported by Pagliano and Meija) seem to suggest better applicability of the new method in practical use due to the higher robustness of regression analysis. T2 - CITAC Best Paper Award Ceremony CY - Online meeting DA - 21.06.2022 KW - Isotope dilution mass spectrometry KW - Standard addition KW - ICP-MS KW - Blank characterization KW - Silicon KW - Sulfur KW - Transferrin KW - Tetramethylammonium hydroxide KW - Biodiesel fuel KW - Human serum PY - 2022 AN - OPUS4-55032 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Brauckmann, C. A1 - Pramann, A. A1 - Rienitz, O. A1 - Schulze, A. A1 - Phukphatthanachai, Pranee A1 - Vogl, Jochen T1 - Combining Isotope Dilution and Standard Addition—Elemental Analysis in Complex Samples JF - Molecules N2 - A new method combining isotope dilution mass spectrometry (IDMS) and standard addition has been developed to determine the mass fractions w of different elements in complex matrices: (a) silicon in aqueous tetramethylammonium hydroxide (TMAH), (b) sulfur in biodiesel fuel, and (c) iron bound to transferrin in human serum. All measurements were carried out using inductively coupled plasma mass spectrometry (ICP–MS). The method requires the gravimetric preparation of several blends (bi)—each consisting of roughly the same masses (mx,i) of the sample solution (x) and my,i of a spike solution (y) plus different masses (mz,i) of a reference solution (z). Only these masses and the isotope ratios (Rb,i) in the blends and reference and spike solutions have to be measured. The derivation of the underlying equations based on linear regression is presented and compared to a related concept reported by Pagliano and Meija. The uncertainties achievable, e.g., in the case of the Si blank in extremely pure TMAH of urel (w(Si)) = 90% (linear regression method, this work) and urel (w(Si)) = 150% (the method reported by Pagliano and Meija) seem to suggest better applicability of the new method in practical use due to the higher robustness of regression analysis. KW - Isotope dilution mass spectrometry KW - tandard addition KW - ICP-MS KW - lank characterization KW - Silicon KW - Sulfur KW - Transferrin KW - Tetramethylammonium hydroxide KW - Biodiesel fuel KW - Human serum PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-526376 DO - https://doi.org/10.3390/molecules26092649 VL - 26 IS - 9 SP - 2649 PB - MDPI CY - Basel AN - OPUS4-52637 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yang, L. A1 - Vogl, Jochen A1 - Mann, J. A1 - Kraft, R. A1 - Vocke, R. A1 - Pramann, A. A1 - Eberhardt, J. A1 - Rienitz, O. A1 - Lee, K.-S. A1 - Lim, J. S. A1 - Sobina, E. A1 - Song, P. A1 - Wang, J. A1 - Mester, Z. A1 - Meija, J. T1 - Copper isotope delta measurements in high purity materials: CCQM-P213 pilot study JF - Metrologia N2 - Accurate and precise isotope ratio measurements of heavy elements are playing an increasinglyimportant role in modern analytical sciences and have numerous applications. Today, isotope ratio measurements are typically performed with two principal techniques: thermal ionization mass spectrometry (TIMS) and multiple collector-inductively coupled plasma mass spectrometry (MC-ICP-MS). To obtain accurate results by mass spectrometry, isotopic certified reference materials (iCRMs) are needed for mass bias correction and for the validation of the method used for analysis.Thus, it is of paramount importance to achieve measurement comparability of all data reported, and to assess measurement capability of each CRM producer/National Metrology Institute (NMI). Therefore, the international comparison (CCQM-P213) was performed to assess the analytical capabilities of NMIs for the accurate determination of copper isotope ratio delta values in high purity materials. The study was proposed by the coordinating laboratories, National Research Council Canada (NRC), National Institute of Standards and Technology (NIST), Bundesanstalt für Materialforschung und -prüfung (BAM) and Physikalisch-Technische Bundesanstalt (PTB), as an activity of the Isotope Ratio Working Group (IRWG) of the Consultative Committee for Amount of Substance - Metrology in Chemistry and Biology (CCQM). Participants included six NMIs and one designated institute (DI) from the six countries. Although no measurement method was prescribed by the coordinating laboratories, MC-ICP-MS with either standard-sample bracketing (SSB) or combined SSB with internal normalization (C-SSBIN) models for mass bias correction were recommended. Results obtained from the six NMIs and one DI were in good agreement. KW - Comparability KW - Traceability KW - Metrology KW - Isotope delta KW - Copper PY - 2023 DO - https://doi.org/10.1088/0026-1394/60/1A/08019 VL - 60 IS - 1A SP - 1 EP - 23 PB - IOP Science AN - OPUS4-58040 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Cu project on calibration approaches for absolute isotope ratios N2 - This presentations summarizes the difficulties in the purification of enriched copper isotopes by high vacuum subimation. It shows as well thelimitations for a CCQM key comparison on this topic. T2 - CCQM Isotope Ratio Work Group Meeting CY - Bern, Switzerland DA - 09.10.2019 KW - Absolute isotope ratio KW - Isotope purification KW - Metal sublimation KW - Gravimtric isotope mixtures PY - 2019 AN - OPUS4-49518 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Solovyev, N. A1 - El-Khatib, Ahmed A1 - Costas-Rodrigues, M. A1 - Schwab, K. A1 - Griffin, E. A1 - Raab, A. A1 - Platt, B. A1 - Theuring, F. A1 - Vogl, Jochen A1 - Vanhaecke, F. T1 - Cu, Fe and Zn isotope ratios in murine Alzheimer's disease models suggest specific signatures of amyloidogenesis and tauopathy JF - Journal of Biological Chemistry N2 - Alzheimer’s disease (AD) is characterized by accumulation of tau and amyloid-beta in the brain, and recent evidence suggests a correlation between associated protein aggregates and trace elements, such as copper, iron and zinc. In AD, distorted brain redox homeostasis and complexation by amyloid-beta and hyperphosphorylated tau May alter the isotopic composition of essential mineral elements. Therefore, high-precision isotopic analysis may reveal changes in the homeostasis of these elements. We used inductively coupled plasma-mass spectrometry (ICP-MS)-based techniques to determine the total Cu, Fe and Zn contents in the brain, as well as their isotopic compositions in both mouse brain and serum. Results for male transgenic tau (Line 66, L66) and amyloid/presenilin (5xFAD) mice were compared to those for the corresponding age- and gendermatched wild-type control mice (WT). Our data show that L66 brains showed significantly higher Fe levels than the corresponding WT. Significantly less Cu, but more Zn was found in 5xFAD brains. We observed significantly lighter isotopic compositions of Fe (enrichment in the lighter isotopes) in the brain, and in serum of L66 mice compared to WT. For 5xFAD mice, Zn exhibited a trend towards a lighter isotopic composition in brain and a heavier isotopic composition in serum compared to WT. Neither mouse model yielded differences in the isotopic composition of Cu. Our findings indicate significant pathology-specific alterations of Fe and Zn brain homeostasis in mouse models of AD. The associated changes in isotopic composition May serve as a marker for proteinopathies Underlying AD and other types of dementia. KW - Alzheimer’s disease KW - Tau KW - Amyloid-beta KW - Copper KW - Iron KW - Zinc KW - Multi-collector inductively coupled plasma-mass spectrometry (ICP-MS) KW - Brain KW - Serum KW - Isotopic analysis KW - Total element determination PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-520214 DO - https://doi.org/10.1016/j.jbc.2021.100292 VL - 296 SP - 100292 PB - Elsevier Inc. CY - Amsterdam AN - OPUS4-52021 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Kazlagic, Anera A1 - Rosner, M. A1 - Cipriani, A. A1 - Frick, D. A. A1 - Glodny, J. A1 - Hoffmann, E. J. A1 - Hora, J. M. A1 - Irrgeher, J. A1 - Lugli, F. A1 - Magna, T. A1 - Meisel, T. C. A1 - Meixner, A. A1 - Possolo, A. A1 - Pramann, A. A1 - Pribil, M. J. A1 - Prohaska, T. A1 - Retzmann, A. A1 - Rienitz, O. A1 - Rutherford, D. A1 - Paula-Santos, G. M. A1 - Tatzel, M. A1 - Widhalm, S. A1 - Willbold, M. A1 - Zuliani, T. A1 - Vogl, Jochen T1 - Data of the characterisation of conventional 87Sr/86Sr isotope ratios in cement, limestone and slate reference materials based on an interlaboratory comparison study N2 - This dataset represents the electronic supplementary material (ESM) of the publication entitled "Characterisation of conventional 87Sr/86Sr isotope ratios in cement, limestone and slate reference materials based on an interlaboratory comparison study", which is published in Geostandards and Geoanalytical Research under the DOI: 10.1111/GGR.12517. It consists of four files. 'ESM_Data.xlsx' contains all reported data of the participants, a description of the applied analytical procedures, basic calculations, the consensus values, and part of the uncertainty assessment. 'ESM_Figure-S1' displays a schematic on how measurements, sequences and replicates are treated for the uncertainty calculation carried out by PTB. 'ESM_Technical-protocol.pdf' is the technical protocol of the interlaboratory comparison, which has been provided to all participants together with the samples and which contains bedside others the definition of the measurand and guidelines for data assessment and calculations. 'ESM_Reporting-template.xlsx' is the Excel template which has been submitted to all participants for reporting their results within the interlaboratory comparison. Excel files with names of the the structure 'GeoReM_Material_Sr8786_Date.xlsx' represent the Rcon(87Sr/86Sr) data for a specific reference material downloaded from GeoReM at the specified date, e.g. 'GeoReM_IAPSO_Sr8786_20221115.xlsx' contains all Rcon(87Sr/86Sr) data for the IAPSO seawater standard listed in GeoReM until 15 November 2022. KW - Reference data KW - Strontium isotope ratio KW - Interlaboratory comparison KW - Reference material KW - Cement KW - Geological material KW - Value assignment KW - Measurement uncertainty KW - Conventional method PY - 2023 UR - https://doi.org/10.5281/zenodo.7804445 DO - https://doi.org/10.5281/zenodo.7804444 PB - Zenodo CY - Geneva AN - OPUS4-57809 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tukhmetova, Dariya A1 - Lisec, Jan A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Data processing made easy: standalone tool for automated calculation of isotope ratio from transient signals – IsoCor JF - Journal of Analytical Atomic Spectrometry N2 - Despite numerous advantages offered by hyphenation of chromatography and electrokinetic separation methods with multicollector (MC) ICP-MS for isotope analysis, the main limitation of such systems is the decrease in precision and increase in uncertainty due to generation of short transient signals. To minimize this limitation, most authors compare several isotope ratio calculation methods and establish a multi-step data processing routine based on the precision and accuracy of the methods. However, to the best of our knowledge, there is no universal data processing tool available that incorporates all important steps of the treatment of the transient signals. Thus, we introduce a data processing application (App) IsoCor that facilitates automatic calculation of isotope ratios from transient signals and eases selection of the most suitable method. The IsoCor App performs baseline subtraction, peak detection, mass bias correction, isotope ratio calculation and delta calculation. The feasibility and reliability of the App was proven by reproducing the results from isotope analysis of three elements (neodymium, mercury and sulfur) measured on-line via hyphenated systems. The IsoCor App provides trackability of the results to ensure quality control of the analysis. KW - Isotope ratio KW - Transient signal KW - MC-ICP-MS KW - Data processing KW - App PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-559068 DO - https://doi.org/10.1039/D2JA00208F VL - 37 IS - 11 SP - 2401 EP - 2409 PB - Royal Society of Chemistry AN - OPUS4-55906 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 - CONF A1 - Vogl, Jochen T1 - Detector deadtime N2 - Deadtime effects for counting detectors in ICP-MS and deadtime correction are discussed. Approaches for determining the deadtime are presented. T2 - Workshop & Training "Isotope Ratio Analysis" CY - Pathum Thani, Thailand DA - 06.12.2023 KW - Counting detector KW - Detector deadtime KW - Isotope ratio KW - Dual mode detector PY - 2023 AN - OPUS4-59166 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Pramann, A. A1 - Vogl, Jochen A1 - Flierl, L. A1 - Rienitz, O. T1 - Determination of absolute (SI‐traceable) isotope ratios: The use of Gravimetric Isotope Mixtures N2 - The presentation is brief overview on how to use gravimetric isotope mixtures to determine SI traceable isotope ratios. There is no mass spectrometer on earth that directly measures isotope ratios. Mass spectrometers will always measure signal intensity ratios instead. The actual problem is that the measured intensity ratios differ more or less from the isotope ratios. The difference can be up to more than 10 % in case of lithium while it‘s below 1 % in case of the heavier elements like lead or uranium. Consequently, the signal intensity ratios are expressed for example in V/V depending on the type of mass spectrometer you are using, while the isotope ratios are expressed in mol/mol. This phenomenon is called Instrumental Isotopic Fractionation (or short IIF) but the more common name is still mass bias (even though this name is not entirely correct). To convert the measured into the isotope ratio usually a simple multiplication with a so-called correction (or short K) factor is done. Therefore, the problem is to determine the K factor. In absence of isotope reference materials the golden route is via gravimetric isotope mixtures, which will be explained within the presentation. T2 - CCRI-CCQM Workshop on the use of mass spectrometry in radionuclide metrology: Opportunities and challenges - Video Tutorial CY - Online meeting DA - 14.02.2023 KW - Absolute isotope ratio KW - Traceability KW - Uncertainty KW - Isotope mixtures PY - 2023 AN - OPUS4-57172 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - You, Zengchao A1 - Winckelmann, Alexander A1 - Vogl, Jochen A1 - Recknagel, Sebastian A1 - Abad Andrade, Carlos Enrique T1 - Determination of calcium, iron, and selenium in human serum by isotope dilution analysis using nitrogen microwave inductively coupled atmospheric pressure plasma mass spectrometry (MICAP-MS) JF - Analytical and bioanalytical chemistry N2 - In this study, we demonstrate the applicability of nitrogen microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) for Ca, Fe, and Se quantification in human serum using isotope dilution (ID) analysis. The matrix tolerance of MICAP-MS in Na matrix was investigated, uncovering that high Na levels can suppress the signal intensity. This suppression is likely due to the plasma loading and the space charge effect. Moreover, 40Ca and 44Ca isotopic fractionation was noted at elevated Na concentration. Nine certified serum samples were analyzed using both external calibration and ID analysis. Overestimation of Cr, Zn, As, and Se was found in the results of external calibration, which might be resulted from C-induced polyatomic interference and signal enhancement, respectively. Further investigations performed with methanol showed a similar enhancement effect for Zn, As, and Se, potentially supporting this assumption. The mass concentrations determined with ID analysis show metrological compatibility with the reference values, indicating that MICAP-MS combined with ID analysis can be a promising method for precise Ca, Fe, and Se determination. Moreover, this combination reduces the influences of matrix effects, broadening the applicability of MICAP-MS for samples with complex matrix. KW - Selenium KW - Nitrogen microwave inductively coupled atmospheric pressure mass spectrometry KW - Isotope dilution KW - Human serum KW - Calcium KW - Iron PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598664 DO - https://doi.org/10.1007/s00216-024-05274-0 SN - 1618-2642 SP - 1 EP - 9 PB - Springer CY - Berlin AN - OPUS4-59866 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Can, S. Z. A1 - Engin, B. A. A1 - İşleyen, A. A1 - Jotanovic, A. A1 - Acosta, O. A1 - Prina, P. A1 - Schvartz, M. A1 - Savić, M. A1 - Stojanović, M. A1 - Ahumada, D. A. A1 - Abella, J. P. A1 - Näykki, T. A1 - Saro-Aho, T. A1 - Vogl, Jochen A1 - Koenig, Maren A1 - Rienitz, O. A1 - Noordmann, J. A1 - Pape, C. A1 - Towara, J. A1 - Kakoulides, E. A1 - Alexopoulos, C. A1 - Ketrin, R. A1 - Mardika, E. A1 - Komalasari, I. A1 - Elishian, C. A1 - Naujalis, E. A1 - Knašienė, B. A1 - Uribe, C. A1 - Carrasco, E. A1 - Zoń, A. A1 - Warzywoda, B. A1 - Stakheev, A. A1 - Dobrovolskiy, V. A1 - Stolboushkina, T. A1 - Glinkova, A. A1 - Sobina, E. A1 - Tabatchikova, T. A1 - Gažević, L. A1 - Paunovic, M. A1 - Jaćimović, R. A1 - Zuliani, T. A1 - Zambra, R. P. A1 - Napoli, R. T1 - Determination of elements in river water JF - Metrologia N2 - The need for quality assessment of anthropogenic impact on environmental pollution is increasing due to discharge from various industries, the use of chemicals in agriculture and the consumption of fossil fuels. Diminishing resources such as natural waters used for the cultivation of agricultural products, plant and animal habitats are under severe pollution pressure and are at constant risk. Several parameters, such as Pb, Cd, Ni, Hg were listed by Water Framework Directive in Directive(2008/105/EC) in the priority substances. Cadmium and Hg were identified as priority hazardous substances whereas As is an important contaminant for its potential toxicological and carcinogenic effects. An inter-comparison study is organised in EURAMET TC-MC in order to demonstrate the capability participants for measuring five elements in river water. The participants carried out measurements for analytes: Pb, Cd, Ni and As as mandatory elements, and Se as an optional one. Participants were asked to perform the measurements with respect to the protocol provided. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA). KW - Metrology KW - Traceability KW - Toxic elements KW - River water PY - 2023 DO - https://doi.org/10.1088/0026-1394/60/1A/08001 VL - 60 IS - 1a SP - 1 EP - 40 PB - BIPM & IOP Publishing Ltd AN - OPUS4-56786 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Winckelmann, Alexander A1 - Morcillo Garcia-Morato, Dalia A1 - Richter, Silke A1 - Recknagel, Sebastian A1 - Riedel, Jens A1 - Vogl, Jochen A1 - Panne, Ulrich A1 - Abad Andrade, Carlos Enrique T1 - Determination of lithium in human serum by isotope dilution atomic absorption spectrometry JF - Analytical and bioanalytical chemistry N2 - The therapeutic dose of lithium (Li) compounds, which are widely used for the treatment of psychiatric and hematologic disorders, is close to its toxic level; therefore, drug monitoring protocols are mandatory. Herein, we propose a fast, simple, and low-cost analytical procedure for the traceable determination of Li concentration in human serum, based on the monitoring of the Li isotope dilution through the partially resolved isotope shift in its electronic transition around 670.80 nm using a commercially available high-resolution continuum source graphite furnace atomic absorption spectrometer. With this technique, serum samples only require acidic digestion before analysis. The procedure requires three measurements—an enriched 6Li spike, a mixture of a certified standard solution and spike, and a mixture of the sample and spike with a nominal 7Li/6Li ratio of 0.82. Lanthanum has been used as an internal spectral standard for wavelength correction. The spectra are described as the linear superposition of the contributions of the respective isotopes, each consisting of a spin-orbit doublet, which can be expressed as Gaussian components with constant spectral position and width and different relative intensity, reflecting the isotope ratio in the sample. Both the spectral constants and the correlation between isotope ratio and relative band intensity have been experimentally obtained using commercially available materials enriched with Li isotopes. The Li characteristic mass (mc) obtained corresponds to 0.6 pg. The procedure has been validated using five human serum certified reference materials. The results are metrologically comparable and compatible to the certified values. The measurement uncertainties are comparable to those obtained by the more complex and expensive technique, isotope dilution mass spectrometry. KW - Lithium KW - Human serum KW - Isotope dilution KW - Atomic absorption spectrometry KW - High-resolution continuum source graphite furnace atomic absorption spectrometry PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-532446 DO - https://doi.org/10.1007/s00216-021-03636-6 VL - 414 IS - 1 SP - 251 EP - 256 PB - Springer CY - Berlin AN - OPUS4-53244 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kazlagic, Anera A1 - Russo, Francesco A1 - Vogl, Jochen A1 - Sturm, Patrick A1 - Stephan, D. A1 - Gluth, Gregor ED - Resch-Genger, Ute ED - Koch, Matthias ED - Meermann, Björn ED - Weller, Michael G. T1 - Development of a sample preparation procedure for Sr isotope analysis of Portland cements JF - Analytical and bioanalytical chemistry N2 - The 87Sr/86Sr isotope ratio can, in principle, be used for provenancing of cement. However, while commercial cements consist of multiple components, no detailed investigation into their individual 87Sr/86Sr isotope ratios or their influence on the integral 87Sr/86Sr isotope ratio of the resulting cement was conducted previously. Therefore, the present study aimed at determining and comparing the conventional 87Sr/86Sr isotope ratios of a diverse set of Portland cements and their corresponding Portland clinkers, the major component of these cements. Two approaches to remove the additives from the cements, i.e. to measure the conventional 87Sr/86Sr isotopic fingerprint of the clinker only, were tested, namely, treatment with a potassium hydroxide/sucrose solution and sieving on a 11-µm sieve. Dissolution in concentrated hydrochloric acid/nitric acid and in diluted nitric acid was employed to determine the 87Sr/86Sr isotope ratios of the cements and the individual clinkers. The aim was to find the most appropriate sample preparation procedure for cement provenancing, and the selection was realised by comparing the 87Sr/86Sr isotope ratios of differently treated cements with those of the corresponding clinkers. None of the methods to separate the clinkers from the cements proved to be satisfactory. However, it was found that the 87Sr/86Sr isotope ratios of clinker and cement generally corresponded, meaning that the latter can be used as a proxy for the clinker 87Sr/86Sr isotope ratio. Finally, the concentrated hydrochloric acid/nitric acid dissolution method was found to be the most suitable sample preparation method for the cements; it is thus recommended for 87Sr/86Sr isotope analyses for cement provenancing. KW - Cement KW - Provenancing KW - Sr isotopes KW - Portland clinker KW - Dissolution PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-542239 DO - https://doi.org/10.1007/s00216-021-03821-7 SN - 1618-2642 SN - 1618-2650 VL - 414 IS - 15 (Topical collection: Analytical methods and applications in the materials and life sciences) SP - 4379 EP - 4389 PB - Springer CY - Berlin AN - OPUS4-54223 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tukhmetova, Dariya A1 - Lisec, Jan A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Development of an Online Isotope Dilution CE/ICP–MS Method for the Quantification of Sulfur in Biological Compounds JF - Analytical Chemistry N2 - We report an analytical methodology for the quantification of sulfur in biological molecules via a speciesunspecific postcolumn isotope dilution (online ID) approach using capillary electrophoresis (CE) coupled online with inductively coupled plasma−mass spectrometry (online ID CE/ICP−MS). The method was optimized using a mixture of standard compounds including sulfate, methionine, cysteine, cystine, and albumin, yielding compound recoveries between 98 and 105%. The quantity of sulfur is further converted to the quantity of the compounds owing to the prior knowledge of the sulfur content in the molecules. The limit of detection and limit of quantification of sulfur in the compounds were 1.3−2.6 and 4.1−8.4 mg L−1, respectively, with a correlation coefficient of 0.99 within the concentration range of sulfur of 5−100 mg L−1. The capability of the method was extended to quantify albumin in its native matrix (i.e., in serum) using experimentally prepared serum spiked with a pure albumin standard for validation. The relative expanded uncertainty of the method for the quantification of albumin was 6.7% (k = 2). Finally, we tested the applicability of the method on real samples by the analysis of albumin in bovine and human sera. For automated data assessment, a software application (IsoCor) which was developed by us in a previous work was developed further for handling of online ID data. The method has several improvements compared to previously published setups: (i) reduced adsorption of proteins onto the capillary wall owing to a special capillary-coating procedure, (ii) baseline separation of the compounds in less than 30 min via CE, (iii) quantification of several sulfur species within one run by means of the online setup, (iv) SI traceability of the quantification results through online ID, and (v) facilitated data processing of the transient signals using the IsoCor application. Our method can be used as an accurate approach for quantification of proteins and other biological molecules via sulfur analysis in complex matrices for various fields, such as environmental, biological, and pharmaceutical studies as well as clinical diagnosis. Sulfur is an essential element in living organisms, where it plays important roles in various biological processes, such as protein synthesis, enzyme activity, and antioxidant defense. However, the biological effects of different sulfur species can vary widely, and imbalances in sulfur speciation have been observed in a range of diseases, including cancer, Alzheimer’s disease, and diabetes.1−3 The accurate quantification of sulfur and its species in biological samples requires sensitive and selective analytical techniques. In recent years, separation techniques coupled online with inductively coupled plasma−mass spectrometry (ICP−MS) have emerged as powerful online analytical tools complementary to molecular spectrometric methods for speciation analysis of biological compounds. External calibration4−9 and isotope dilution (ID)10−15 are common calibration approaches applied for online quantification of sulfur species in complex samples. The ID analysis is advantageous over. KW - Analytical Chemistry KW - CE/MC-ICP-MS KW - species-specific isotope information PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594736 DO - https://doi.org/10.1021/acs.analchem.3c03553 SN - 0003-2700 SP - 1 EP - 8 PB - American Chemical Society (ACS) AN - OPUS4-59473 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weber, K. A1 - Weber, M. A1 - Menneken, M. A1 - Kral, A. G. A1 - Mertz-Kraus, R. A1 - Geisler, T. A1 - Vogl, Jochen A1 - Tütken, T. T1 - Diagenetic stability of non-traditional stable isotope systems (Ca, Sr, Mg, Zn) in teeth – An in-vitro alteration experiment of biogenic apatite in isotopically enriched tracer solution JF - Chemical Geology N2 - Stable isotope ratios and trace element concentrations of fossil bones and teeth are important geochemical proxies for the reconstruction of diet and past environment in archaeology and palaeontology. However, since diagenesis can significantly alter primary diet-related isotope signatures and elemental compositions, it is important to understand and quantify alteration processes. Here, we present the results of in-vitro Alteration experiments of dental tissues from a modern African elephant molar reacted in aqueous solutions at 30 °C and 90 °C for 4 to 63 days. Dental cubes with ≈ 3 mm edge length, comprising both enamel and dentin, were placed into 2 mL of acidic aqueous solution enriched in different isotopes (25Mg, 44Ca, 67Zn, 86Sr, initial pH 1). Element and isotope distribution profiles across the reacted cubes were measured with LA-(MC-)ICP-MS and EMPA, while potential effects on the bioapatite crystal structure were characterised by Raman spectroscopy. In all experiments isotope ratios measured by LA-(MC-)ICP-MS revealed an alteration of the enamel in the outer ≈ 200–300 μm. In contrast, dentin was fully altered (≈ 1.4 mm) after one week at 90 °C while the alteration did not exceed a depth of 150–200 μm during the 30 °C experiments. Then, the tracer solution started also to penetrate through the enamel-dentin junction into the innermost enamel, however, leaving the central part of the enamel unaltered, even after three months. The Raman spectra suggest an initial demineralisation in the acidic environment while organic matter (i.e. collagen) is still preserved. In the 90 °C experiment, Raman spectra of the v1 PO4) band of the dentin shift over time towards synthetic hydroxylapatite patterns and the Ca (and Sr) concentrations in the respective solutions decrease. This indicates precipitation of newly formed apatite. Isotope and element concentration profiles across the dental tissues reveal different exchange mechanisms for different isotope systems. Magnesium is leached from enamel and dentin, while Zn is incorporated into the apatite crystal structure. However, the distribution of both elements is not affected in the innermost enamel where their concentrations do not change over the whole duration of the experiments. We found no correlation of reaction depth in the cubes and experimental duration, which might be caused by natural variability of the dental material already at the beginning of the experiment. Our alteration experiments in a closed system at high temperatures ≤90 °C and low initial pH demonstrate that at least the central part of mm-thick mammalian enamel apatite seems to be resistant against alteration preserving its pristine bioapatite mineral structure as well as its in-vivo elemental and isotopic composition. The experiments assess diagenetic alteration in a novel multi-proxy approach using in-situ analyses in high spatial resolution. It is demonstrated that the isotopes of Ca, Sr, Zn and Mg in the dentin are prone for diagenetic alteration, while enamel is more resistant against alteration and could be used for dietary and physiological reconstructions in fossil teeth. KW - Bioapatite KW - Isotopes KW - Raman spectroscopy KW - Diagenesis KW - LA-(MC-)ICP-MS KW - EPMA PY - 2021 DO - https://doi.org/10.1016/j.chemgeo.2021.120196 VL - 572 SP - 120196 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-52447 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 - Kazlagić, Anera A1 - Stephan, D. A1 - Ostermann, Markus A1 - Possolo, A. A1 - Vogl, Jochen T1 - Fingerprinting Portland cements by means of 87Sr/86Sr and 143Nd/144Nd isotope ratios and geochemical profiles JF - Advances in Cement Research N2 - This study uses conventional 87Sr/86Sr and 143Nd/144Nd isotope and interelement ratios of Ca, Sr, K, Mn, Mg and Ti as fingerprints for provenancing ordinary Portland cements (OPC). Herein, the first database of Sr and Nd isotope ratios investigated in OPCs, stemming from 29 cement plants located worldwide, was created. The results show that the Sr isotope ratios of OPCs are higher than those of seawater from the observed geological period. The spread of 143Nd/144Nd in OPCs is not as large as the spread for 87Sr/86Sr isotope ratios. However, the combination of both Sr and Nd isotope ratios provides the potential for distinguishing between cements of different production sites. Most of the OPCs investigated have measurable differences in their 87Sr/86Sr and 143Nd/144Nd isotope ratios, which can be employed as a valuable analytical fingerprinting tool. In the case of equivocal results, divisive hierarchical clustering was employed to help overcome this issue. The construction of geochemical profiles allowed the computing of suitably defined distances between cements and clustering them according to their chemical similarity. By applying this methodology, successful fingerprinting was achieved in 27 out of the 29 ordinary Portland cements that were analysed. KW - Elemental fingerprints KW - Geochemistry KW - Portland cement KW - Sr and Nd isotope analysis KW - Statistical analysis PY - 2023 DO - https://doi.org/10.1680/jadcr.23.00018 SN - 0951-7197 SP - 1 EP - 12 PB - Emerald Publishing Limited AN - OPUS4-57979 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 - Winckelmann, Alexander A1 - Nowak, S. A1 - Richter, Silke A1 - Recknagel, Sebastian A1 - Riedel, Jens A1 - Vogl, Jochen A1 - Panne, Ulrich A1 - Abad Andrade, Carlos Enrique T1 - High-Resolution Atomic Absorption Spectrometry Combined With Machine Learning Data Processing for Isotope Amount Ratio Analysis of Lithium JF - Analytical Chemistry N2 - An alternative method for lithium isotope amount ratio analysis based on a combination of high-resolution atomic absorption spectrometry and spectral data analysis by machine learning (ML) is proposed herein. It is based on the well-known isotope shift of approximately 15 pm for the electronic transition 22P←22S at around the wavelength of 670.8 nm, which can be measured by the state-of-the-art high-resolution continuum source graphite furnace atomic absorption spectrometry. For isotope amount ratio analysis, a scalable tree boosting ML algorithm (XGBoost) was employed and calibrated using a set of samples with 6Li isotope amount fractions, ranging from 0.06 to 0.99 mol mol–1, previously determined by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS). The calibration ML model was validated with two certified reference materials (LSVEC and IRMM-016). The procedure was applied toward the isotope amount ratio determination of a set of stock chemicals (Li2CO3, LiNO3, LiCl, and LiOH) and a BAM candidate reference material NMC111 (LiNi1/3Mn1/3Co1/3O2), a Li-battery cathode material. The results of these determinations were compared with those obtained by MC-ICP-MS and found to be metrologically comparable and compatible. The residual bias was −1.8‰, and the precision obtained ranged from 1.9 to 6.2‰. This precision was sufficient to resolve naturally occurring variations, as demonstrated for samples ranging from approximately −3 to +15‰. To assess its suitability to technical applications, the NMC111 cathode candidate reference material was analyzed using high-resolution continuum source atomic absorption spectrometry with and without matrix purification. The results obtained were metrologically compatible with each other. KW - Lithium KW - Isotope KW - Machine learning KW - Algorithms KW - Reference material KW - AAS KW - Atomic Absorption Spectrometry PY - 2021 DO - https://doi.org/10.1021/acs.analchem.1c00206 SN - 1520-6882 VL - 93 IS - 29 SP - 10022 EP - 10030 PB - American Chemical Society CY - Washington, DC, USA AN - OPUS4-53028 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Rosner, M. A1 - Kasemann, S. A. A1 - Kraft, R. A1 - Meixner, A. A1 - Noordmann, J. A1 - Rabb, S. A1 - Rienitz, O. A1 - Schuessler, J. A. A1 - Tatzel, Michael A1 - Vocke, R. D. T1 - Intercalibration of Mg isotope delta scales and realisation of SI traceability for Mg isotope amount ratios and isotope delta values JF - Geostandards and geoanalytical research N2 - The continuous improvement of analytical procedures using multi-collector technologies in ICP-mass spectrometry has led to an increased demand for isotope standards with improved homogeneity and reduced measurement uncertainty. For magnesium, this has led to a variety of available standards with different quality levels ranging from artefact standards to isotope reference materials certified for absolute isotope ratios. This required an intercalibration of all standards and reference materials, which we present in this interlaboratory comparison study. The materials Cambridge1, DSM3, ERMAE143, ERM-AE144, ERM-AE145, IRMM-009 and NIST SRM 980 were cross-calibrated with expanded measurement uncertainties (95% confidence level) of less than 0.030‰ for the δ25/24Mg values and less than 0.037‰ for the δ26/24Mg values. Thus, comparability of all magnesium isotope delta (δ) measurements based on these standards and reference materials is established. Further, ERM-AE143 anchors all magnesium δ-scales to absolute isotope ratios and therefore establishes SI traceability, here traceability to the SI base unit mole. This applies especially to the DSM3 scale, which is proposed to be maintained. With ERM-AE144 and ERM-AE145, which are product and educt of a sublimation-condensation process, for the first time a set of isotope reference materials is available with a published value for the apparent triple isotope fractionation exponent θapp, the fractionation relationship ln α(25/24Mg)/ln α(26/24Mg). KW - Delta scale KW - Traceability KW - Scale anchor KW - Absolute isotope ratio KW - Comparability KW - Triple isotope fractionation PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-511557 DO - https://doi.org/10.1111/ggr.12327 SN - 1751-908X VL - 44 IS - 3 SP - 439 EP - 457 PB - Wiley-Blackwell CY - Oxford AN - OPUS4-51155 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Kazlagić, Anera A1 - Rosner, M. A1 - Cipriani, A. A1 - Frick, D. A. A1 - Glodny, J. A1 - Hoffmann, J. E. A1 - Hora, J. M. A1 - Irrgeher, J. A1 - Lugli, F. A1 - Magna, T. A1 - Meisel, T. C. A1 - Meixner, A. A1 - Possolo, A. A1 - Pramann, A. A1 - Pribil, M. J. A1 - Prohaska, T. A1 - Retzmann, A. A1 - Rienitz, O. A1 - Rutherford, D. A1 - Paula-Santos, G. M. A1 - Tatzel, M. A1 - Widhalm, S. A1 - Willbold, M. A1 - Zuliani, T. T1 - Interlaboratory comparison on conventional 87Sr/ 86Sr isotope ratio analysis by applying MC-ICP-MS and MC-TIMS N2 - The variation of isotope ratios is increasingly used to unravel natural and technical questions. With new upcoming techniques and research topics in the last two decades, such as material provenance or food authenticity to animal and human migration studies, the number of published isotope data has strongly increased. Here, isotope reference materials are indispensable to enable a reliable method validation or even SI-traceability. The fast development and broad availability of inductively coupled plasma mass spectrometry instrumentation (ICP-MS) also lead to an expansion of the classical research areas and new elements are under investigation. Owing to this large expansion of the field, the production and certification of isotope reference materials for calibration and validation is lagging behind, even for classical applications such as conventional 87Sr/86Sr isotope ratio analysis. To improve this situation, BAM organized an interlaboratory comparison (ILC) comprising of thirteen international laboratories for the characterisation of 87Sr/86Sr isotope ratios in geochemical and industrial reference materials. Six reference materials (four cements and two rocks) were provided as powder requiring extensive sample preparation prior to isotopic measurement. Additional requirements included the use of the conventional method for obtaining 87Sr/86Sr isotope ratios, also known as radiogenic 87Sr/86Sr isotope ratios, and the assessment of the measurement uncertainty. The primary goal was to evaluate potential differences in the application of multicollector thermal ionization mass spectrometry (MC-TIMS) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) for conventional 87Sr/86Sr isotope ratio determination, with a secondary goal to provide reference values for the 87Sr/86Sr isotope ratios in these potential new reference materials. All reported results are accompanied by an uncertainty statement and are traceable to the conventional method, which will be described in detail within this presentation. Current state-of-the-art statistical models were used to ensure the proper evaluation of the reported results and their associated measurement uncertainties within the frame of this ILC. Combined with results from appropriate homogeneity assessment, reference values for 87Sr/86Sr isotope ratios will be assigned. T2 - European Winter Conference on Plasma Spectrochemistry CY - Ljubljana, Slovenia DA - 29.01.2023 KW - Conventional isotope ratio KW - Reference material KW - Uncertainty KW - Comparability PY - 2023 AN - OPUS4-58011 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kazlagic, Anera A1 - Rosner, M. A1 - Vogl, Jochen A1 - Cipriani, A. A1 - Frick, D. A. A1 - Glodny, J. A1 - Hoffmann, J. E. A1 - Hora, J. M. A1 - Irrgeher, J. A1 - Lugli, F. A1 - Magna, T. A1 - Meisel, T. C. A1 - Meixner, A. A1 - Possolo, A. A1 - Pramann, A. A1 - Pribil, M. A1 - Prohaska, T. A1 - Retzmann, A. A1 - Rienitz, O. A1 - Rutherford, D. A1 - Paula-Santos, G. A1 - Tatzel, M. A1 - Widhalm, S. A1 - Willbold, M. A1 - Zuliani, T. T1 - Investigating the differences between MC-ICP-MS and MC-TIMS using conventional 87Sr/86Sr isotope ratios in limestone and slate reference materials N2 - The Federal Institute for Materials Research and Testing (BAM) organised an interlaboratory comparison (ILC) for the characterisation of 87Sr/86Sr isotope ratios in limestone (IAG/CGL ML-3) and Penrhyn slate (IAG OU-6) reference materials by applying the conventional method for 87Sr/86Sr isotope ratios. Samples were sent to thirteen analytical laboratories . Since both samples are powdered, rock materials, dissolution of the sample and Sr isolation via ion exchange chromatography were mandatory. This was done using acid, microwave/acid, bomb/acid digestion or borate fusion and subsequent isolation of Sr by means of commercially available ion exchange resins. In this study, we present and discuss the potential effects that differences between laboratories, and between two instrumental measurement techniques (i.e., MC-ICP-MS and MC-TIMS), may have upon the dispersion of measurement results of the 87Sr/86Sr isotope ratio in the two aforementioned reference materials. We used a statistical mixed effects model to assess the potential effects of both the laboratory and the measurement technique. Consensus values for both materials and associated standard uncertainties {(IAG/CGL ML-3 (0.708245±0.000004) mol/mol; IAG OU-6 (0.729769±0.000008) mol/mol} were estimated by fitting a linear, Gaussian mixed effects model (Pinheiro and Bates 2000) using the R function “lmer” defined in package “lme4”. The statistical results showed that there is no significant effect attributable to differences between instrumental techniques when both materials are considered together, or separately. The p-value of the test of significance of the measurement technique effect is greater than 0.54. For both materials there were statistically significant effects attributable to differences between laboratories when the measurement results for both materials were considered together and separately. This effect is less than 0.00004 in absolute value. However, for neither material did consideration or disregard for such differences induce significant changes in the estimate of the consensus value for the 87Sr/86Sr isotope ratio. Therefore, the effects attributable to differences between instrumental techniques or between laboratories can safely be disregarded when computing the best estimate for the true value of 87Sr/86Sr isotope ratio in these materials, by the community of expert laboratories represented in this study. T2 - GeoAnalysis 2022 CY - Freiberg, Germany DA - 06.08.2022 KW - Isotope ratio KW - Conventional isotope ratio KW - ILC KW - Traceability KW - Uncertainty KW - Isotope reference materials PY - 2022 AN - OPUS4-56848 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kazlagic, Anera A1 - Vogl, Jochen A1 - Rosner, M. A1 - Cipriani, A. A1 - Frick, D. A. A1 - Glodny, J. A1 - Hoffmann, J. E. A1 - Hora, J. M. A1 - Irrgeher, J. A1 - Lugli, F. A1 - Magna, T. A1 - Meisel, T. C. A1 - Meixner, A. A1 - Possolo, A. A1 - Pramann, A. A1 - Pribil, M. A1 - Prohaska, T. A1 - Retzmann, A. A1 - Rienitz, O. A1 - Rutherford, D. A1 - Paula-Santos, G. A1 - Tatzel, M. A1 - Widhalm, S. A1 - Willbold, M. A1 - Zuliani, T. T1 - Investigating the differences in 87Sr/ 86Sr isotope ratio measurements between MC-ICP-MS and MC-TIMS in cement RMs N2 - Thirteen laboratories participated in an international interlaboratory comparison for the determination of 87Sr/86Sr isotope ratios in four cement reference materials (RM) using the conventional method for 87Sr/86Sr isotope ratios analyses. Sample dissolution and Sr isolation via ion exchange chromatography were required since the cement samples were distributed as powders. Analytical preparation included the use of various digestion methods including mixed mineral acids, microwave/acid, bomb/acid digestion or borate fusion, followed by Sr separation using ion exchange chromatography. In this study, we evaluated whether any statistically significant differences were attributable to instrumental differences (i.e., MC-ICP-MS and MC-TIMS), or to laboratory-specific techniques (different sample preparation techniques, Sr isolation and the procedures for correcting the data outputs). To evaluate these effects, consensus values for cement RMs and associated standard uncertainties were estimated by fitting a linear, Gaussian mixed effects model using the R function “lmer” defined in package “lme4”. No statistically significant effects (SSE) attributable to instrumental differences regardless of whether the materials are considered together or separately were evident. There were SSE attributable to differences between laboratories for three cement RMs when the individual cements were considered separately. Since consideration or disregard for such differences does not induce significant changes in the estimate of the consensus values for the 87Sr/86Sr isotope ratios in cement RMs, these effects can safely be neglected when calculating the best estimates for the true values of 87Sr/86Sr isotope ratios in these RMs. T2 - ICP-MS Anwender*innentreffen 2022 CY - Leoben, Austria DA - 05.09.2022 KW - Conventional isotope ratio KW - Reference material KW - Metrology KW - Traceability KW - Uncertainty PY - 2022 AN - OPUS4-55682 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - IRWG strategy update N2 - An update of the IRWG strategy for the period 2023-2030 is given. The status and the futuere work of the task group on quantities, symbols and units is discussed. The present status of IRWG comparisons is shown and the need for specific key comparisons is discussed. T2 - CCQM IRWG Meeting CY - Sevres, France DA - 24.04.2023 KW - Isotope ratio KW - Traceability KW - Metrology PY - 2023 AN - OPUS4-57400 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - IRWG strategy update N2 - This talk presents a strategy update of the Isotope Ratio Working Group of CCQM. The focus is on future comparisons and the promotion of international comparability. T2 - IRWG Meeting CY - Online meeting DA - 12.05.2022 KW - Isotope ratio KW - Traceability KW - Metrology PY - 2022 AN - OPUS4-55160 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 T1 - Isotope Ratio Analysis N2 - Basic information on isotope ratio analysis is provided. Isotope fractionation is discussed and the measurement process is described. Additionally, practical examples are provided. T2 - Workshop & Training "Isotope Ratio Analysis" CY - Pathum Thani, Thailand DA - 06.12.2023 KW - Isotope fractionation KW - Mass spectrometry KW - Terminology PY - 2023 AN - OPUS4-59164 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Isotope Ratio Measurement - Quantities and calibration N2 - The quantities and the terminoly in isotope ratio measurements is presented, followed by explaining calibration approaches for isotope ratio measurements. Sources of error and bias are presented and special focus is given on single detector mass spectrometry. T2 - Workshop & Training "Isotope Ratio Analysis" CY - Pathum Thani, Thailand DA - 06.12.2023 KW - Isotope fractionation KW - Matrix separation KW - Interferences KW - Noise KW - Optimization PY - 2023 AN - OPUS4-59165 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Isotope Ratio Measurements and Certification of iCRMs at BAM N2 - A short overview on isotope ratio measurements at BAM and related CRM activities is given. The current isotope CRM range offered by BAM and future iCRM projects are presented. T2 - CCQM IRWG Meeting CY - Sevres, France DA - 24.04.2023 KW - Absolute isotope ratio KW - Reference material KW - Metrology KW - Traceability PY - 2023 AN - OPUS4-57399 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - 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 - CONF A1 - Vogl, Jochen T1 - Isotope ratio working group at CCQM N2 - The presentation gives the reasons for initiation of an isotope ratio working group at CCQM level, describes the process and provides the auduince with the initial working plan. T2 - EURAMET TC-MC Workshop on Isotope Ratio Analysis CY - Bern, Switzerland DA - 05.02.2020 KW - Metrology KW - Absolute isotope ratio KW - Isotope ratio KW - Delta value PY - 2020 AN - OPUS4-50344 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Rienitz, O. A1 - Rosner, M. A1 - Tatzel, M. A1 - Brandt, B. A1 - Henehan, M. J. A1 - Kasemann, S. A. A1 - Kraft, R. A1 - Malinovskiy, D. A1 - Meixner, A. A1 - Noordmann, J. A1 - Rabb, S. A1 - Schüssler, J. A. A1 - Tütken, M. A1 - Vocke, R. D. T1 - Isotope ratios and delta values with minimal measurement uncertainties -measuring magnesium using MC-ICP-MS N2 - Multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) has evolved significantly since its introduction in 1992. The second and third generation instruments now allow isotope ratio measurements at unprecedented precisions, 0.001 % or better. However, precision alone is not enough for producing accurate and reliable isotope ratio measurements. Metrological considerations such as the selection of suitable calibration strategies, proper assessment of instrumental biases, and the estimation of overall measurement uncertainty remain critical to the measurement process. Properly assessed, measurement uncertainty then provides the interval within which a result can be considered both accurate and precise. All mass spectrometric measurements are affected by instrumental mass discrimination and produce isotope ratios that are biased relative to their “true” ratio. To produce accurate and traceable isotope ratio measurements, it is imperative that certified isotope reference materials (iCRMs) be used for calibration and validation purposes. iCRMs reporting absolute isotope ratios are an analyst’s first choice, particularly when its uncertainty is sufficient for the intended use. However, when smaller uncertainties are required to resolve subtle differences between samples, delta-scale measurements become important. Here, the difference between an isotope ratio measured in a sample and in an internationally accepted isotope reference material (iRM) is determined. This deviation can be positive or negative relative to the iRM, is called a delta value, and is often expressed in per mil units. This presentation will highlight the potential for MC-ICP-MS to produce isotope ratio measurements with minimal uncertainties by examining three applications involving Mg isotopes: 1) the certification of a set of iCRMs for their absolute isotope ratio using a gravimetric isotope mixture approach; 2) the comparison of these iCRMs with currently accepted Mg delta-scale reference materials through intercalibration, and 3) the determination of isotope fractionation exponents for geochemical applications. T2 - 4th International Conference on Frontiers in Mass Spectrometry CY - Kottayam, Kerala, India DA - 04.12.2019 KW - Triple isotope fractionation KW - Absolute isotope ratio KW - Delta value KW - Mangesium PY - 2019 AN - OPUS4-50004 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Oelze, Marcus A1 - Rosner, M. A1 - Rienitz, O. T1 - Isotope reference materials N2 - The variation of isotope ratios is increasingly used to unravel natural and technical questions. In the past, the investigation and interpretation of such variations was the field of a limited number of experts. With new upcoming techniques and research topics in the last decades, such as provenance or food authenticity studies, the number of published isotope data strongly increased. Instrumental developments such as the enhancement of inductively coupled plasma mass spectrometers (ICP-MS) from an instrument for simple quantitative analysis to highly sophisticated isotope ratio machines influenced this process significantly. While in former times only experts in mass spectrometry were able to produce reliable isotope data, nowadays many laboratories, never been in touch with mass spectrometry before, produce isotope data with an ICP-MS. Isotope reference materials (iCRM) are indispensable to enable a reliable method validation or in rare cases even SI-traceability. The fast development and the broad availability of ICP-MS also lead to an expansion of the classical research areas and new elements are under investigation. Irrespective of the investigated element or the knowledge of the user all isotope ratio applications require reference materials either for correction of instrumental isotope fractionation, for method validation or to provide a common accepted basis as needed for delta measurements. This presentation will outline the basic principles and illustrate the urgent need for new iCRMs. Consequently, the production and certification of iCRMs will be discussed and illustrated by examples of already completed certification projects. Finally, plans for future iCRMs to be produced at BAM will be presented. T2 - ICP-MS Anwender*innentreffen 2022 CY - Leoben, Austria DA - 05.09.2022 KW - Absolute isotope ratio KW - Traceability KW - Metrology KW - Comparability KW - Uncertainty KW - Isotope reference materials KW - Delta scale PY - 2022 AN - OPUS4-55681 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Raab, A. A1 - Vogl, Jochen A1 - Solovyev, N. A1 - El-Khatib, Platt A1 - Costas-Rodriguez, M. A1 - Schwab, K. A1 - Griffin, E. A1 - Platt, B. A1 - Theuring, F. A1 - Vanhaecke, F. T1 - Isotope signature of iron, copper and zinc in mouse models (L66 and 5XFAD) and their controls used for dementia research N2 - Introduction: The influence of copper, iron and zinc concentrations on the formation of ß-amyloid plaques and neurofibrillary tangles in Alzheimer’s disease (AD) is widely discussed in the community. The results from human and animal studies so far are mixed with some studies showing a correlation and others not. From a number of studies, it is known that disease state and isotopic composition of essential elements can be coupled. Aim: The aim of the study was to identify changes in element content and isotopic composition in two transgenic mouse models used in AD research compared to their genetic WT relatives and to establish whether element content and isotopic signature between different laboratories is comparable. Methods: ß-amyloid (5xFAD) and tau overexpressing (L66) mice together with their matching wild-types were bred at dedicated facilities in accordance with the European Communities Council Directive (63/2010/EU). Serum and brain were sampled after sacrifice and the samples distributed among the participants of the study. The tissues were acid digested for total element determination and high-precision isotope ratio determination. Element content was determined by either sector-field or quadrupole-based inductively coupled plasma mass spectrometry (ICPMS). For the determination of isotope ratios multi-collector ICPMS was used. Results: Total copper content was significantly higher for L66 and their matched WT compared to 5xFAD and WT. Brains of L66 mice contained more Fe in brain than their WT, Zn and Cu were not significantly different between L66 and WT. Whereas 5xFAD mice had a slightly lower Cu and slightly higher Zn concentration in brain compared to WT. The isotopic signature in brain of L66 mice for Fe was different from their controls, whereas Zn isotope ratios were influenced in 5xFAD mice compared to their WT. The Cu isotopic ratio did not seem to be influenced in either strain. In serum, the shifts were less pronounced. Conclusion: Even though neither Tau-protein nor amyloid precursor protein are known to be metal-dependent / -containing proteins, the overexpression of both influences the Fe, Cu and Zn metabolism in brain and to some extent also in serum as can be seen not only using total element determination but probably more clearly studying the isotopic signature of Fe, Cu and Zn. T2 - The International Conference of Trace Elements and Minerals (ICTEM) 2022 CY - Aachen, Germany DA - 05.06.2022 KW - Isotope ratio KW - Isotope delta value KW - Metrology KW - Alzheimer disease KW - Measurement uncertainty PY - 2022 AN - OPUS4-55204 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Raab, A. A1 - Solovyev, N. A1 - El-Kathib, Ahmed A1 - Vogl, Jochen A1 - Costas-Rodriguez, M. A1 - Vanhaecke, F. A1 - Schwab, K. A1 - Griffin, E. A1 - Platt, B. A1 - Theuring, F. T1 - Isotope signature of iron, copper and zinc in mouse models (L66 and 5XFAD) and their controls used for dementia research N2 - Introduction: The influence of copper, iron and zinc concentrations on the formation of ß-amyloid plaques and neurofibrillary tangles in Alzheimer’s disease (AD) is widely discussed in the community. The results from human and animal studies so far are mixed with some studies showing a correlation and others not. From a number of studies, it is known that disease state and isotopic composition of essential elements can be coupled. Aim: The aim of the study was to identify changes in element content and isotopic composition in two transgenic mouse models used in AD research compared to their genetic WT relatives and to establish whether element content and isotopic signature between different laboratories is comparable. Methods: ß-amyloid (5xFAD) and tau overexpressing (L66) mice together with their matching wild-types were bred at dedicated facilities in accordance with the European Communities Council Directive (63/2010/EU). Serum and brain were sampled after sacrifice and the samples distributed among the participants of the study. The tissues were acid digested for total element determination and high-precision isotope ratio determination. Element content was determined by either sector-field or quadrupole-based inductively coupled plasma mass spectrometry (ICPMS). For the determination of isotope ratios multi-collector ICPMS was used. Results: Total copper content was significantly higher for L66 and their matched WT compared to 5xFAD and WT. Brains of L66 mice contained more Fe in brain than their WT, Zn and Cu were not significantly different between L66 and WT. Whereas 5xFAD mice had a slightly lower Cu and slightly higher Zn concentration in brain compared to WT. The isotopic signature in brain of L66 mice for Fe was different from their controls, whereas Zn isotope ratios were influenced in 5xFAD mice compared to their WT . The Cu isotopic ratio did not seem to be influenced in either strain. In serum, the shifts were less pronounced. Conclusion: Even though neither Tau-protein nor amyloid precursor protein are known to be metal-dependent / -containing proteins, the overexpression of both influences the Fe, Cu and Zn metabolism in brain and to some extent also in serum as can be seen not only using total element determination but probably more clearly studying the isotopic signature of Fe, Cu and Zn. T2 - International Conference of Trace Elements and Minerals CY - Aachen, Germany DA - 05.06.2022 KW - Isotope delta value KW - Copper KW - Zinc KW - Iron KW - Dementia PY - 2022 AN - OPUS4-58230 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Irrgeher, J. T1 - IUPAC Commission on Isotopic Abundances and Atomic Weights its history, role, and work N2 - This presentation provides a short introduction to the Commission on Isotopic Abundances and Atomic Weights (CIAAW). It describes the role of the Commission and provides an insight into its work and the corresponding principal tasks. Finally, it provides the reader with the latest achievements and with the most recent publications. T2 - IUPAC Virtual General Assembly CY - Online meeting DA - 25.07.2023 KW - Absolute isotope ratio KW - Atomic weights KW - Metrology KW - Traceability KW - Isotope reference material PY - 2023 AN - OPUS4-58013 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 - Chronakis, Michail Ioannis A1 - von der Au, Marcus A1 - Faßbender, Sebastian A1 - Vogl, Jochen A1 - Meermann, Björn T1 - MDG-ICP-ToF-MS: A Versatile Tool for Quantification in the field of Single Particle ICP-MS Using Isotope Dilution N2 - In the interest of exploring their potential in the field of single particle analysis, a Microdroplet Generator (MDG) was coupled to an ICP-ToF-MS. Isotopic Dilution Analysis was also incorporated for the size determination of three different Platinum nanoparticles samples (50, 63 and 70 nm). The performance of the technique was validated by comparison to traditional size characterization techniques (sp-ICP-ToF-MS, TEM), while the robustness of the technique was proven by incorporating NaCl in the samples’ matrix, up to 100 mg/L. T2 - European Winter Conference on Plasma Spectrochemistry CY - Ljubljana, Slovenia DA - 29.01.2023 KW - MDG KW - Single Particle KW - Isotope Dilution PY - 2023 AN - OPUS4-57643 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Measurement Uncertainty in Isotope Ratio Measurements N2 - The importance for measurement uncertainty in isotope ratio measurements is expalined and different approaches for calculating measurement uncertainty for absolute isotope ratios, isotope deltas and conventional isotope ratios are presented. T2 - Workshop & Training "Isotope Ratio Analysis" CY - Pathum Thani, Thailand DA - 06.12.2023 KW - Isotope delta KW - Absolute isotope ratio KW - Conventional isotope ratio PY - 2023 AN - OPUS4-59169 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Metrology in Chemistry - Basics and international structure N2 - Basics in Metrology in Chemistry are explained and the international structure of the metrology network is presented. T2 - Workshop & Training "Isotope Ratio Analysis" CY - Pathum Thani, Thailand DA - 06.12.2023 KW - Metrology in Chemistry KW - Traceability KW - Uncertainty PY - 2023 AN - OPUS4-59163 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 - JOUR A1 - Vogl, Jochen A1 - Paz, B. A1 - Völling, E. T1 - On the ore provenance of the Trojan silver artefacts JF - Archaeological and Anthropological Sciences N2 - Lead isotopes are a well-established tool to trace the geographic origin of samples and artefacts in archaeology and geochemistry. In archaeology, lead isotopes are often applied to gain information on the provenance of the used ores especially in lead and silver artefacts. The assignment of a specific and unambiguous provenance in most cases is not possible or at least hindered due to several limitations such as ore deposits overlapping in their lead isotopic composition, a large spread within one ore deposit or a missing overlap with known mining sites. Such difficult cases can only be solved by using information from sources being independent of the isotope data. This information can be of chemical nature such as concentrations of key elements or they can be of archaeological nature such as cultural or trade route information.Within this study, we combined lead isotope data of ores and artefacts with silver mass fractions in the ore deposits, Au/Ag-ratios in ores and artefacts and finally archaeological Information on the cultural context in the Mediterranean and Anatolian Region. This approach enabled us to significantly reduce the potential number of mining regions. Finally, the potential sources could be narrowed down to the three remaining locations the Central Taurus, Arap Dağ and the Eastern Troad. Beneath these three locations, the Central Taurus shows the highest probability for the geographic origin of the galena which has been used to create the Trojan silver artefacts. KW - Trojan silver artefacts KW - Priam's treasure KW - Lead isotope composition KW - Central Taurus KW - Ore provenance KW - Elemental composition PY - 2019 DO - https://doi.org/10.1007/s12520-018-0756-x SN - 1866-9557 SN - 1866-9565 VL - 11 IS - 7 SP - 3267 EP - 3277 PB - Springer Verlag AN - OPUS4-48272 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Matschat, Ralf A1 - Richter, Silke A1 - Vogl, Jochen A1 - Kipphardt, Heinrich T1 - On the way to SI traceable primary transfer standards for amount of substance measurements in inorganic chemical analysis JF - Analytical and bioanalytical chemistry N2 - During its 25 years of existence, the Inorganic Analysis Working Group of the Consultative Committee for Amount of Substance: Metrology in Chemistry and Biology (CCQM IAWG) has achieved much in establishing comparability of measurement results. Impressive work has been done on comparison exercises related to real-world problems in fields such as ecology, food, or health. In more recent attempts, measurements and comparisons were focused on calibration solutions which are the basis of most inorganic chemical measurements. This contribution deals with the question of how to achieve full and transparent SI traceability for the values carried by such solutions. Within this framework, the use of classical primary methods (CPMs) is compared to the use of a primary difference method (PDM). PDM is a method with a dual character, namely a metrological method with a primary character, based on the bundling of many measurement methods for individual impurities, which lead to materials with certified content of the main component. As in classical methods, where small corrections for interferences are accepted, in PDM, many small corrections are bundled. In contrast to classical methods, the PDM is universally applicable to all elements in principle. Both approaches can be used to certify the purity (expressed as mass fraction of the main element) of a high-purity material. This is where the metrological need of National Metrology Institutes (NMIs) for analytical methods meet the challenges of analytical methods. In terms of methods, glow discharge mass spectrometry (GMDS) with sufficient uncertainties for sufficiently small impurity contents is particularly noteworthy for the certification of primary transfer standards (PTS), and isotope dilution mass spectrometry (IDMS), which particularly benefits from PTS (back-spikes) with small uncertainties, is particularly noteworthy for the application. The corresponding relative uncertainty which can be achieved using the PDM is very low (< 10−4). Acting as PTS, they represent the link between the material aspect of the primary calibration solutions and the immaterial world of the International System of Units (SI). The underlying concepts are discussed, the current status of implementation is summarised, and a roadmap of the necessary future activities in inorganic analytical chemistry is sketched. It has to be noted that smaller measurement uncertainties of the purity of high-purity materials not only have a positive effect on chemical measurements, but also trigger new developments and findings in other disciplines such as thermometry or materials science. KW - Inorganic chemical analysis KW - Primary transfer standards (PTSs) KW - Traceability KW - Classical primary measurement method (CPM) KW - Primary difference measurement method (PDM) KW - Metrology in chemistry PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-572743 DO - https://doi.org/10.1007/s00216-023-04660-4 SN - 1618-2642 SN - 1618-2650 VL - 415 SP - 3057 EP - 3071 PB - Springer CY - Berlin AN - OPUS4-57274 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmidt, C. A1 - Hensen, C. A1 - Wallmann, K. A1 - Liebetrau, V. A1 - Tatzel, Michael A1 - Schurr, S. L. A1 - Kutterolf, S. A1 - Haffert, L. A1 - Geilert, Sonja A1 - Hübscher, C. A1 - Lebas, E. A1 - Heuser, A. A1 - Schmidt, M. A1 - Strauss, H. A1 - Vogl, Jochen A1 - Hansteen, T. T1 - Origin of High Mg and SO4 Fluids in Sediments of the Terceira Rift, Azores‐Indications for Caminite Dissolution in a Waning Hydrothermal System JF - Geochemistry, Geophysics, Geosystems N2 - During R/V Meteor cruise 141/1, pore fluids of near surface sediments were investigated to find indications for hydrothermal activity in the Terceira Rift (TR), a hyperslow spreading center in the Central North Atlantic Ocean. To date, submarine hydrothermal fluid venting in the TR has only been reported for the D. João de Castro seamount, which presently seems to be inactive. Pore fluids sampled close to a volcanic cone at 2,800‐m water depth show an anomalous composition with Mg, SO4, and total alkalinity concentrations significantly higher than seawater and a nearby reference core. The most straightforward way of interpreting these deviations is the dissolution of the hydrothermally formed mineral caminite (MgSO4 0.25 Mg (OH)2 0.2H2O). This interpretation is corroborated by a thorough investigation of fluid isotope systems (δ26Mg, δ30Si, δ34S, δ44/42Ca, and 87Sr/86Sr). Caminite is known from mineral assemblages with anhydrite and forms in hydrothermal recharge zones only under specific conditions such as high fluid temperatures and in altered oceanic crust, which are conditions generally met at the TR. We hypothesize that caminite was formed during hydrothermal activity and is now dissolving during the waning state of the hydrothermal system, so that caminite mineralization is shifted out of its stability zone. Ongoing fluid circulation through the basement is transporting the geochemical signal via slow advection toward the seafloor. KW - Isotope ratio KW - Delta value KW - Pore fluids KW - Magnesium KW - Hydrothermal fluid PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-503430 DO - https://doi.org/10.1029/2019GC008525 VL - 20 IS - 12 SP - 6078 EP - 6094 PB - Wiley AN - OPUS4-50343 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Pb isotope ratio analysis N2 - The determination of Pb isotope ratios by TIMS and ICP-MS is discussed and applications from archaeology are provided. T2 - Workshop & Training "Isotope Ratio Analysis" CY - Pathum Thani, Thailand DA - 06.12.2023 KW - Isotope reference material KW - Provenance KW - Silver artefacts KW - Curse tablets PY - 2023 AN - OPUS4-59167 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Retzmann, Anika A1 - Faßbender, Sebastian A1 - Rosner, M. A1 - von der Au, Marcus A1 - Vogl, Jochen T1 - Performance of second generation ICP-TOFMS for (multi-)isotope ratio analysis: a case study on B, Sr and Pb and their isotope fractionation behavior during the measurements JF - Journal of Analytical Atomic Spectrometry N2 - The performance of second generation ICP-TOFMS, equipped with a micro-channel plate (MCP) enabling multi-isotope detection, in terms of isotope ratio precision and instrumental isotopic fractionation (IIF) for (multi-)isotope ratio analysis was thoroughly assessed for B, Sr and Pb. Experimental isotope ratio precision of 0.14 % for 11B/10B intensity ratio, 0.15 % for 87Sr/86Sr intensity ratio and 0.07% for 208Pb/206Pb intensity ratio were obtained at high signal levels ($500 mg L−1) which is comparable to first generation ICP-TOFMS. The long-term stability of isotope ratios, measured over several hours and expressed as repeatability, is between 0.05 % and 1.8 % for B, Sr and Pb. The observed IIF per mass unit is negative for B (i.e., −11 % for 11B/10B) which is in accordance with measurements using sector field (MC) ICP-MS. But the observed IIF per mass unit is positive for Sr (i.e., 2 % for 87Sr/86Sr) and Pb (i.e., 4.5 % for 208Pb/206Pb) which is not in accordance with measurements using sector field (MC) ICP-MS. Furthermore, different IIFs per mass unit were observed for different isotope pairs of the same isotopic system (i.e., Sr, Pb) and adjacent isotopic systems (i.e., Pb vs. Tl). This and the observations from three-isotope plots for Sr and Pb show that ion formation, ion extraction, ion transmission, ion separation and ion detection in second generation ICP-TOFMS is subject to IIF that does not follow the known mass dependent fractionation laws and is possibly caused by mass independent fractionation and/or multiple (contradictory) fractionation processes with varying contributions. The non-mass dependent IIF behavior observed for second generation ICP TOFMS has profound consequences for the IIF correction of isotope raw data, including application of multi-isotope dilution mass spectrometry (IDMS) using ICP-TOFMS. Hence, only IIF correction models that correct also for mass independent fractionation are applicable to calculate reliable isotope ratios using second generation ICP-TOFMS. In the present study, reliable d11B values, and absolute B, Sr and Pb isotope ratios could be determined using the SSB approach in single-element solutions as well as in a mixture of B, Sr and Pb, where the isotopes were measured simultaneously. KW - ICP-TOFMS KW - Isotope delta value KW - Isotope amount ratio KW - Conventional isotope ratio KW - Instrumental isotope fractionation PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-582239 DO - https://doi.org/10.1039/d3ja00084b SN - 0267-9477 VL - 38 IS - 10 SP - 2144 EP - 2158 PB - Royal Society of Chemistry AN - OPUS4-58223 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Rienitz, O. T1 - Plan for comparison on absolute Cu isotope ratios by applying the isotope mixture approach N2 - The reference method for obtaining absolute isotope ratios still is the isotope mixture approach. Due the huge efforts required the full isotope mixture approach is applied only by a few institutes worldwide. To enable an IRWG key comparison with a sufficiently large number of participants a proposal for absolute cu isotope ratios is presented where participants will be provided with the enriched isotopes, the isotope mixtures and the samples. In parallel a pilot study will be organized where alternative approaches for obtaining absolute Cu isotope ratios can be applied. T2 - CCQM IRWG Meeting CY - Sevres, France DA - 24.04.2023 KW - Absolute isotope ratio KW - Traceability KW - Metrology PY - 2023 AN - OPUS4-57401 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Plan for comparison on absolute Cu isotope ratios by applying the isotope mixture approach N2 - Based on a previously circulated questionnaire, the plan for a key comparison is presented which focuses on the determination of absolute copper isotope ratios by the means of synthetic isotope mixtures. T2 - IRWG Meeting CY - Online meeting DA - 12.05.2022 KW - Absolute isotope ratio KW - Traceability KW - CCQM PY - 2022 AN - OPUS4-55161 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kazlagic, Anera A1 - Vogl, Jochen A1 - Gluth, Gregor A1 - Stephan, D. T1 - Provenancing of cement using elemental analyses and isotope techniques – The state-of-the-art and future perspectives JF - Journal of analytical atomic spectrometry N2 - With the aim of identifying the origin and the manufacturer of a cement, a reliable procedure that provides unambiguous results is needed. Such procedure could resolve practical issues in damage research, liability issues and forensic investigations. A substantial number of attempts for fingerprinting of building materials, including cement, has already been carried out during the last decades. Most of them were based on concentration analysis of the main elements/components. This review provides an overview of provenance studies of cement and the main approaches commonly used. Provenance studies of cement via isotope techniques are also presented and discussed as representatives of the state-of-the-art in the field. Due to the characteristic properties and the occurrence of carefully selected isotope ratios, unique fingerprints of different kinds of materials can be provided by these methods. This property has largely been explored in various scientific fields such as geo- and cosmochemistry, food forensics, archaeology, geochronology, biomedical studies, and climate change processes. However, the potential of isotope techniques in cement and concrete research for provenance studies has barely been investigated. Therefore, the review outlines a suitable approach using isotope ratios, which could lead to reliable provenancing of cementitious materials in the future. KW - Cement KW - Sr isotopes KW - Provenance PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-533762 DO - https://doi.org/10.1039/d1ja00144b VL - 36 IS - 10 SP - 2030 EP - 2042 PB - The Royal Society of Chemistry CY - Cambridge, UK AN - OPUS4-53376 LA - eng 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 JF - Journal of Analytical Atomic Spectrometry 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 DO - 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 - TY - CONF A1 - Vogl, Jochen A1 - Rienitz, O. A1 - Rosner, M. A1 - Brandt, B. A1 - Kasemann, S. A. A1 - Kraft, R. A1 - Malinovskiy, D. A1 - Meixner, A. A1 - Noordmann, J. A1 - Rabb, S. A1 - Schuessler, J. A. A1 - Vocke, R. D. T1 - Realization of SI traceability for Mg isotope amount ratios & delta values N2 - In isotope ratio applications metrological principles such as measurement uncertainty and SI traceability often are not considered or realized. This is also well-documented by the traceability exception related to delta scale isotope ratio measurements CCQM requested from the CIPM. Generally, delta scale isotope ratio measurements can be performed on a precision level that is significantly lower than the uncertainty level of isotope amount ratio measurements. In the case of magnesium, we demonstrated for the first time that isotope amount ratios can be measured with uncertainties close to the typical precision of magnesium delta values, δ26/24Mg, which are at the 0.1 ‰ level. In the past, δ26/24Mg measurements were referenced to NIST SRM 980, the initial zero of the δ26/24Mg scale. With the development of MC-ICPMS, the detection of small but measurable isotopic differences in different chips of NIST SRM 980 became apparent and NIST SRM 980 was replaced by an intermediate artefact, DSM3. To solve this problem a suite of magnesium isotope reference materials, ERM-AE143, -AE144, and -AE145, has been certified in a first study by applying an ab initio calibration for absolute Mg isotope ratios without any a priori assumptions, a procedure which fulfils all requirements of a primary method of measurement. Thus, these materials qualified to establish SI-traceability for magnesium delta measurements. In a second study five expert laboratories participated to cross-calibrate all available magnesium isotope standards, which are NIST SRM 980, IRMM-009, ERM-AE143, ERM-AE144, ERM-AE145 and the standards DSM3 and Cambridge-1. The mean δ26/24Mg values for the individual iRMs, calculated from the laboratory means show 2 SD reproducibilities varying between 0.025 and 0.093 ‰. Propagated measurement uncertainties suggest a standard uncertainty of about 0.1 ‰ for δ26/24Mg determinations. Thus, SI traceability for magnesium isotope amount ratios and delta values is demonstrated to be established. T2 - CCQM Workshop on "Advances in Metrology in Chemistry and Biology" CY - Sèvres, France DA - 09.04.2019 KW - Delta values KW - SI traceability KW - Isotope amount ratio KW - Magnesium PY - 2019 AN - OPUS4-47930 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 - JOUR A1 - Vogl, Jochen A1 - Rienitz, O. A1 - Pramann, A. A1 - Flierl, L. T1 - Scale Conversion and Uncertainty Calculations in Isotope Delta Measurements JF - Geostandards and Geoanalytical Research N2 - Isotope ratio applications are on the increase and a major part of which are delta measurements, because they are easier to perform than the determination of absolute isotope ratios while offering lower measurement uncertainties. Delta measurements use artefact-based scales and therefore scale conversions are required due to the lack of the scale defining standards. Such scale conversions often form the basis for comparing data being generated in numerous projects andtherefore need to be as accurate as possible. In practice, users are tempted to apply linear approximations, which are not sufficiently exact, because delta values are defined by nonlinear relationships. The bias of such approximations often is beyond typical measurement uncertainties and its extent can hardly be predicted. Therefore, exact calculations are advised. Here, the exact equations and the bias of the approximations are presented, and calculations are illustrated by real-world examples. Measurement uncertainty is indispensable in this context and therefore, its calculation is described as well for determining delta values but also for scale conversions. Approaches for obtaining a single delta measurement and for repeated measurements are presented. For the latter case, a new approach for calculating the measurement uncertainty is presented, which considers covariances between the isotope ratios. KW - Delta isotope standard KW - Delta scale KW - In-house calibration solution KW - Isotope ratios KW - Isotope reference material KW - Measurement uncertainty KW - Scale conversion PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-557254 DO - https://doi.org/10.1111/ggr.12450 SN - 1639-4488 VL - 46 IS - 4 SP - 773 EP - 787 PB - Wiley AN - OPUS4-55725 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 - TY - JOUR A1 - von der Au, Marcus A1 - Faßbender, Sebastian A1 - Chronakis, Michail A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Size determination of nanoparticles by ICP-ToF-MS using isotope dilution in microdroplets JF - Journal of Analytical Atomic Spectrometry N2 - Within this work, the combination of a microdroplet generator and an ICP-ToF-MS for nanoparticle analysis is presented. For the size determination of platinum nanoparticles an on-line isotope dilution analysis approach was developed. The 194Pt/195Pt isotopic ratio was used for the characterization of the particles, while the 182W/183W isotopic ratio was monitored simultaneously for mass bias correction. The on-line ID-MDG-sp-ICP-ToF-MS approach was deployed for the size determination of three platinum nanoparticle samples (50 nm, 63 nm, 70 nm); for validation, complementary size characterization techniques (sp-ICP-ToF-MS and TEM) were used. The robustness of this technique was evidenced, by using sodium chloride concentrations up to 100 mg L−1 as a matrix component. Our new on-line ID MDG-sp-ICP-ToF-MS approach is a promising tool for the fast and reliable determination of nanoparticles' size in severe matrix concentrations, e.g., environmental samples. KW - ICP-ToF-MS KW - Nanoparticles KW - Isotope Dilution PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-552727 DO - https://doi.org/10.1039/D2JA00072E SN - 0267-9477 VL - 37 IS - 6 SP - 1203 EP - 1207 PB - Royal Society of Chemistry AN - OPUS4-55272 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Faßbender, Sebastian A1 - von der Au, Marcus A1 - Koenig, Maren A1 - Pelzer, J. A1 - Piechotta, Christian A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Species-specific isotope dilution analysis of monomethylmercury in sediment using GC/ICP-ToF-MS and comparison with ICP-Q-MS and ICP-SF-MS JF - Analytical and bioanalytical chemistry N2 - A recently introduced inductively coupled plasma-time-of-flight-mass spectrometer (ICP-ToF-MS) shows enhanced sensitivity compared to previous developments and superior isotope ratio precision compared to other ToF and commonly used single-collector ICP-MS instruments. Following this fact, an improvement for isotope dilution ICP-MS using the new instrumentation has been reported. This study aimed at investigating whether this improvement also meets the requirements of species-specific isotope dilution using GC/ICP-MS, where short transient signals are recorded. The results of the analysis of monomethylmercury (MMHg) of a sediment reference material show that isotope ratio precision of ICP-MS instruments equipped with quadrupole, sector-field, and time-of-flight mass analyzers is similar within a broad range of peak signal-to-noise ratio when analyzing one isotopic system. The procedural limit of quantification (LOQ) for MMHg, expressed as mass fraction of Hg being present as MMHg, w(Hg)MMHg, was similar as well for all investigated instruments and ranged between 0.003 and 0.016 μg/kg. Due to the simultaneous detection capability, the ICP-ToF-MS might, however, be more favorable when several isotopic systems are analyzed within one measurement. In a case study, the GC/ICP-ToF-MS coupling was applied for analysis of MMHg in sediments of Finow Canal, a historic German canal heavily polluted with mercury. Mass fractions between 0.180 and 41 μg/kg (w(Hg)MMHg) for MMHg, and 0.056 and 126 mg/kg (w(Hg)total) for total mercury were found in sediment samples taken from the canal upstream and downstream of a former chemical plant. KW - Methylmercury KW - Legacy pollution KW - Finow Canal KW - Isotope dilution KW - Mercury speciation PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-529967 DO - https://doi.org/10.1007/s00216-021-03497-z SN - 1618-2642 VL - 413 IS - 21 SP - 5279 EP - 5289 PB - Springer CY - Berlin AN - OPUS4-52996 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Sr isotope ratio analysis N2 - The measurment of Sr isotope ratios is described and examples from food authenticity, provenancing of cement and pietas are provided. T2 - Workshop & Training "Isotope Ratio Analysis" CY - Pathum Thani, Thailand DA - 06.12.2023 KW - Conventional isotope ratios KW - Gypsum KW - Cement KW - Cheese PY - 2023 AN - OPUS4-59168 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Prohaska, T. A1 - Irrgeher, J. A1 - Benefield, J. A1 - Böhlke, J. K. A1 - Chesson, L. A. A1 - Coplen, T. B. A1 - Ding, T. A1 - Dunn, P. J. H. A1 - Gröning, M. A1 - Holden, N. E. A1 - Meijer, H. A. J. A1 - Moossen, H. A1 - Possolo, A. A1 - Takahashi, Y. A1 - Vogl, Jochen A1 - Walczyk, T. A1 - Wang, J. A1 - Wieser, M. E. A1 - Yoneda, S. A1 - Zhu, X.-K. A1 - Meija, J. T1 - Standard atomic weights of the elements 2021 (IUPAC Technical Report) JF - Pure and Applied Chemistry N2 - Following the reviews of atomic-weight determinations and other cognate data in 2015, 2017, 2019 and 2021, the IUPAC (International Union of Pure and Applied Chemistry) Commission on Isotopic Abundances and Atomic Weights (CIAAW) reports changes of standard atomic weights. The symbol Ar(E) was selected for standard atomic weight of an element to distinguish it from the atomic weight of an element E in a specific substance P, designated Ar(E, P). The CIAAW has changed the values of the standard atomic weights of five elements based on recent determinations of terrestrial isotopic abundances: Ar (argon): from 39.948 ± 0.001 to [39.792, 39.963] Hf (hafnium): from 178.49 ± 0.02 to 178.486 ± 0.006 Ir (iridium): from 192.217 ± 0.003 to 192.217 ± 0.002 Pb (lead): from 207.2 ± 0.1 to [206.14, 207.94] Yb (ytterbium): from 173.054 ± 0.005 to 173.045 ± 0.010 The standard atomic weight of argon and lead have changed to an interval to reflect that the natural variation in isotopic composition exceeds the measurement uncertainty of Ar(Ar) and Ar(Pb) in a specific substance. The standard atomic weights and/or the uncertainties of fourteen elements have been changed based on the Atomic Mass Evaluations 2016 and 2020 accomplished under the auspices of the International Union of Pure and Applied Physics (IUPAP). Ar of Ho, Tb, Tm and Y were changed in 2017 and again updated in 2021: Al (aluminium), 2017: from 26.981 5385 ± 0.000 0007 to 26.981 5384 ± 0.000 0003 Au (gold), 2017: from 196.966 569 ± 0.000 005 to 196.966 570 ± 0.000 004 Co (cobalt), 2017: from 58.933 194 ± 0.000 004 to 58.933 194 ± 0.000 003 F (fluorine), 2021: from 18.998 403 163 ± 0.000 000 006 to 18.998 403 162 ± 0.000 000 005 (Ho (holmium), 2017: from 164.930 33 ± 0.000 02 to 164.930 328 ± 0.000 007) Ho (holmium), 2021: from 164.930 328 ± 0.000 007 to 164.930 329 ± 0.000 005 Mn (manganese), 2017: from 54.938 044 ± 0.000 003 to 54.938 043 ± 0.000 002 Nb (niobium), 2017: from 92.906 37 ± 0.000 02 to 92.906 37 ± 0.000 01 Pa (protactinium), 2017: from 231.035 88 ± 0.000 02 to 231.035 88 ± 0.000 01 Pr (praseodymium), 2017: from 140.907 66 ± 0.000 02 to 140.907 66 ± 0.000 01 Rh (rhodium), 2017: from 102.905 50 ± 0.000 02 to 102.905 49 ± 0.000 02 Sc (scandium), 2021: from 44.955 908 ± 0.000 005 to 44.955 907 ± 0.000 004 (Tb (terbium), 2017: from 158.925 35 ± 0.000 02 to 158.925 354 ± 0.000 008) Tb (terbium), 2021: from 158.925 354 ± 0.000 008 to 158.925 354 ± 0.000 007 (Tm (thulium), 2017: from 168.934 22 ± 0.000 02 to 168.934 218 ± 0.000 006) Tm (thulium), 2021: from 168.934 218 ± 0.000 006 to 168.934 219 ± 0.000 005 (Y (yttrium), 2017: from 88.905 84 ± 0.000 02 to 88.905 84 ± 0.000 01) Y (yttrium), 2021: from 88.905 84 ± 0.000 01 to 88.905 838 ± 0.000 002 KW - Argon KW - Ciaaw.org KW - Hafnium KW - Iridium KW - Lead KW - LSVEC KW - Ytterbium PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-548443 DO - https://doi.org/10.1515/pac-2019-0603 SN - 0033-4545 VL - 94 IS - 5 SP - 573 EP - 600 PB - De Gruyter Verlag CY - Berlin AN - OPUS4-54844 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rienitz, O. A1 - Pramann, A. A1 - Vogl, Jochen A1 - Lee, K.-S. A1 - Yim, Y.-H. A1 - Malinovskiy, D. A1 - Hill, S. A1 - Dunn, P. A1 - Goenaga-Infante, H. A1 - Ren, T. A1 - Wang, J. A1 - Vocke jr., R. D. A1 - Rabb, S: A. A1 - Narukawa, T. A1 - Yang, L. A1 - Mester, Z. A1 - Meija, J. A1 - Aref'ev, D. G. A1 - Marchin, V. A1 - Sharin, A. G. A1 - Bulanov, A. D. A1 - Potapov, A. M. A1 - Otopkova, P. A. A1 - Kessel, R. T1 - The comparability of the determination of the molar mass of silicon highly enriched in 28Si: results of the CCQM-P160 interlaboratory comparison and additional external measurements JF - Metrologia N2 - An international comparison study on the accurate determination of the molar mass M(Si) of silicon artificially enriched in 28Si (x(28Si) > 0.9999 mol mol−1) has been completed. The measurements were part of the high level CCQM-P160 pilot study assessing the ability of National Metrology Institutes (NMIs) and Designated Institutes (DIs) to make such measurements at the lowest possible levels of measurement uncertainty and to identify possible difficulties when measuring this kind of sample. This study supports the molar mass measurements critical to disseminating the silicon route to realizing the new definitions for the kilogram and the mole. Measurements were also made by one external research institute and an external company. The different institutes were free to choose their experimental (mass spectrometric) set-ups and equipment, thereby enabling also the comparison of different techniques. The investigated material was a chemically pure, polycrystalline silicon material. The subsequent modified single crystalline secondary product of this material was intended for the production of silicon which was used for two additional spheres in the context of the redetermination of the Avogadro constant NA, required for the revision of the International System of Units (SI) via fundamental constants which came into force from May 2019. The CCQM pilot study was organized by Physikalisch-Technische Bundesanstalt (PTB). Aqueous silicon solutions were shipped to all participating institutions. The data analysis as well as the uncertainty modelling and calculation of the results was predefined. The participants were provided with an uncertainty budget as a GUM Workbench® file as well as a free software license for the duration of the comparison. The agreement of the values of the molar mass (M(Si) = 27.976 942 577 g mol−1) was excellent with ten out of 11 results reported within the range of relative uncertainty of 1 × 10−8 required for the revision of the SI. KW - Absolute isotope ratio KW - Molar mass KW - Avogadro constant KW - Revision of the SI PY - 2020 DO - https://doi.org/10.1088/1681-7575/abbdbf VL - 57 IS - 6 SP - 065028 PB - IOP Science CY - Cambridge AN - OPUS4-51500 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sargent, M A1 - Goenaga-Infante, H A1 - Inagaki, K A1 - Ma, L A1 - Meija, J A1 - Pramann, A A1 - Rienitz, O A1 - Sturgeon, R A1 - Vogl, Jochen A1 - Wang, J A1 - Yang, L T1 - The role of ICP-MS in inorganic chemical metrology JF - Metrologia N2 - ICP-MS has played a key role in inorganic chemical metrology for 25 years, from the 1993 CIPM feasibility study which led to establishment of the CCQM. Since that time, the Inorganic Analysis Working Group of the CCQM has organised 56 international comparisons involving measurements by ICP-MS and, in a recent comparison, 16 different national institutes submitted their results using the technique. Metrological applications of ICP-MS currently address an enormous range of measurements using a wide variety of instrumentation, calibration strategies and methodologies. This review provides an overview of the ICP-MS field with an emphasis on developments which are of particular relevance to chemical metrology. Examples from CCQM comparisons and the services available from the participants are used to illustrate how the capability and scope of ICP-MS methods have expanded far beyond the expectations of 1993. This is due in part to the research and development Programmes of the national institutes which participate in the CCQM. They have played a key role in advancing new instrumentation and applications for elemental analysis, isotope dilution mass spectrometry, determination of isotopic ratio or composition, and speciation of organometallic compounds. These developments are continuing today, as demonstrated by work in new fields such as heteroatom quantitation of proteins, characterisation and counting of nanoparticles using spICP-MS, and LA-ICP-MS analysis of solid materials. KW - CCQM KW - Metrology KW - Interlaboratory comparison KW - ICP-MS KW - Mass spectrometry KW - Hyphenated KW - Isotope ratio PY - 2019 DO - https://doi.org/10.1088/1681-7575/ab0eac VL - 56 IS - 3 SP - 034005 PB - IOP Publishing AN - OPUS4-47929 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Coplen, T. B. A1 - Holden, N. E. A1 - Ding, T. A1 - Meijer, H. A. J. A1 - Vogl, Jochen A1 - Zhu, X. T1 - The Table of Standard Atomic Weights—An exercise in consensus JF - Rapid Communications in Mass Spectrometry N2 - The present Table of Standard Atomic Weights (TSAW) of the elements is perhaps one of the most familiar data sets in science. Unlike most parameters in physical science whose values and uncertainties are evaluated using the “Guide to the Expression of Uncertainty in Measurement” (GUM), the majority of standard atomic weight values and their uncertainties are consensus values, not GUM-evaluated values. The Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) regularly evaluates the literature for new isotopic-abundance measurements that can lead to revised standard atomic-weight values, Ar(E) for element E. The Commission strives to provide utmost clarity in products it disseminates, namely the TSAW and the Table of Isotopic Compositions of the Elements (TICE). In 2016, the Commission recognized that a guideline recommending the expression of uncertainty listed in parentheses following the standard atomic-weight value, for example, Ar(Se) = 78.971(8), did not agree with the GUM, which suggests that this parenthetic notation be reserved to express standard uncertainty, not the expanded uncertainty used in the TSAW and TICE. In 2017, to eliminate this noncompliance with the GUM, a new format was adopted in which the uncertainty value is specified by the “±” symbol, for example, Ar(Se) = 78.971 ± 0.008. To clarify the definition of uncertainty, a new footnote has been added to the TSAW. This footnote emphasizes that an atomic-weight uncertainty is a consensus (decisional) uncertainty. Not only has the Commission shielded users of the TSAW and TICE from unreliable measurements that appear in the literature as a result of unduly small uncertainties, but the aim of IUPAC has been fulfilled by which any scientist, taking any natural sample from commerce or research, can expect the sample atomic weight to lie within Ar(E) ± its uncertainty almost all of the time. KW - Atomic weight KW - Standard atomic weight KW - Uncertainty PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-551299 DO - https://doi.org/10.1002/rcm.8864 SN - 1097-0231 VL - 36 IS - 15 SP - 1 EP - 15 PB - Wiley AN - OPUS4-55129 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - 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 - JOUR A1 - Vogl, Jochen T1 - The triple-isotope calibration approach: a universal and standard-free calibration approach for obtaining absolute isotope ratios of multi-isotopic elements JF - Analytical and Bioanalytical Chemistry N2 - The theory of a new calibration approach for obtaining absolute isotope ratios of multi-isotopic elements without the use of any standard has been developed. The calibration approach basically uses the difference in the instrumental isotope fractionation of two different types of mass spectrometers, leading to two different fractionation lines in a three-isotope diagram. When measuring the same sample with both mass spectrometers, the different fractionation lines have one point in common: this is the ‘true’ logarithmized isotope ratio pair of the sample. Thus, the intersection of both fractionation lines provides us with the absolute isotope ratios of the sample. This theory has been tested in practice by measuring Cd and of Pb isotope ratios in the certified reference materials BAM-I012 and NIST SRM981 by thermal ionization mass spectrometry and by inductively coupled plasma mass spectrometry while varying the ionization conditions for both mass spectrometers. With this experiment, the theory could be verified, and absolute isotope ratios were obtained, which were metrologically compatible with the certified isotope ratios. The so-obtained absolute isotope ratios are biased by − 0.5% in average, which should be improved with further developments of the method. This calibration approach is universal, as it can be applied to all elements with three or more isotopes and it is not limited to the type of mass spectrometers applied; it can be applied as well to secondary ion mass spectrometry or others. Additionally, this approach provides information on the fractionation process itself via the triple-isotope fractionation exponent θ. KW - Triple isotope fractionation KW - Absolute isotope ratio KW - Mass spectrometry KW - Calibration KW - Uncertainty PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-516364 DO - https://doi.org/10.1007/s00216-020-03050-4 VL - 413 IS - 3 SP - 821 EP - 826 PB - Springer Verlag AN - OPUS4-51636 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pramann, A. A1 - Vogl, Jochen A1 - Rienitz, O. T1 - The Uncertainty Paradox: Molar Mass of Enriched Versus Natural Silicon Used in the XRCD Method JF - MAPAN - Journal of Metrology Society of India N2 - The X-ray crystal density method uses silicon spheres highly enriched in 28Si as a primary method for the dissemination of the SI base unit kilogram yielding smallest possible uncertainties associated with the mass m within a few parts in 10-8. This study compares different available and newly developed analytical methods and their results for the determination of the molar mass M of silicon highly enriched in 28Si (Me) and of silicon (Mx) with an almost natural isotopic distribution. While for Me relative uncertainties urel(Me) in the lower 10-9 range are obtained routinely, it was not possible to fall below a value of urel(Mx) < 4 x 10-6 in the case of natural silicon, which is approximately three orders of magnitude larger. The application of the state-of the-art isotope ratio mass spectrometry accompanied with sophisticated thoroughly investigated methods suggests an intrinsic cause for the large uncertainty associated with the molar mass of natural silicon compared to the enriched material. KW - silicon KW - Molar mass KW - Isotope ratios KW - SI KW - Kilogram KW - Mole KW - XRCD method PY - 2020 DO - https://doi.org/10.1007/s12647-020-00408-y VL - 35 SP - 499 EP - 510 PB - Springer Verlag AN - OPUS4-51637 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tatzel, Michael A1 - Vogl, Jochen A1 - Rosner, M. A1 - Henehan, M. J. A1 - Tütken, T. T1 - Triple Isotope Fractionation Exponents of Elements Measured by MC-ICP-MS - An Example of Mg JF - Analytical Chemistry N2 - In most chemical reactions, stable isotopes are fractionated in a mass-dependent manner, yielding correlated isotope ratios in elements with three or more stable isotopes. The proportionality between isotope ratios is set by the triple isotope fractionation exponent θ that can be determined precisely for, e.g., sulfur and oxygen by IRMS, but not for metal(loid) elements due to the lower precision of MC-ICP-MS analysis and smaller isotopic variations. Here, using Mg as a test case, we compute a complete metrologically robust uncertainty budget for apparent θ values and, with reference to this, present a new measurement Approach that reduces uncertainty on θ values by 30%. This approach, namely, direct educt-product bracketing (sample−sample bracketing), allows apparent θ values of metal(loid) isotopes to be determined precisely enough to distinguish slopes in three-isotope space. For the example of Mg, we assess appropriate quality Control standards for interference-to-signal ratios and Report apparent θ values of carbonate−seawater pairs. We determined apparent θ values for marine biogenic carbonates, where the foraminifera Globorotalia menardii yields 0.514 ± 0.005 (2 SD), the coral Porites, 0.515 ± 0.006 (2 SD), and two specimens of the giant clam Tridacna gigas, 0.508 ± 0.007 (2 SD) and 0.509 ± 0.006 (2 SD), documenting differences in the uptake pathway of Mg among marine calcifiers. The capability to measure apparent θ values more precisely adds a new dimension to metal(loid) δ values, with the potential to allow us to resolve different modes of fractionation in industrial and natural processes. KW - Isotope fractionation KW - Delta value KW - Biogenic carbonates KW - Calcification KW - Magnesium isotope ratios KW - Measurement uncertainty KW - Sample-sample bracketing PY - 2019 DO - https://doi.org/10.1021/acs.analchem.9b02699 VL - 91 IS - 22 SP - 14314 EP - 14322 PB - ACS Publications AN - OPUS4-49818 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -