TY - CONF A1 - Vogl, Jochen T1 - Certification of an isotope reference material (IRM) for magnesium: Determination of SI traceable isotope ratios T2 - 14th International Symposium on Biological and Environmental Reference Materials (BERM 14) CY - National Harbor, Maryland 20745 USA DA - 2015-10-11 PY - 2015 N1 - Geburtsname von Mieller, Björn: Brandt, B. - Birth name of Mieller, Björn: Brandt, B. AN - OPUS4-34483 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen 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 - JOUR A1 - Yu, Jialu A1 - Oelze, Marcus A1 - Schannor, Mathias A1 - Nordstad, Simon A1 - Vogl, Jochen T1 - New Potential Haematite and Magnetite Reference Materials for Iron Isotope Measurements by Solution Nebulisation MCICPMS and by In Situ nsLAMCICPMS N2 - Iron isotope ratios of haematite (Fe2O3) and magnetite (Fe3O4) provide insights into geochemical, environmental and planetary processes. In most studies, Fe isotope measurements are commonly performed using solution nebulisation multi-collector inductively coupled plasma-mass spectrometry (SN-MC-ICP-MS). Nanosecond laser ablation multi-collector inductively coupled plasma-mass spectrometry (ns-LA-MC-ICP-MS) requires minimal sample preparation, and provides spatially resolved variation of iron isotopes at micro-scale. However, homogeneous and matrix-matched haematite/magnetite reference materials are lacking for precise in situ isotopic measurement. The iron isotope ratios of two potential reference materials resembling natural haematite (HMIE-NP-B01) and natural magnetite (MAKP-NP-B01) were characterised. Size fractions between 5–63 μm of the powdered Fe oxides were milled to nanoparticles, freeze-dried, homogenised, and pressed into pellets. The materials were then evaluated using SN-MC-ICP-MS and LA-MC-ICP-MS. Sample powders of the two materials were measured by SN-MC-ICPMS after sample digestion and column separation and pressed pellets were analysed directly via ns-LA-MC-ICP-MS. In both cases iron isotope delta values are reported relative to the certified reference material IRMM-014, used as the bracketing standard (calibrator). The solution measurements yielded δ56Fe values of -0.25 ± 0.08‰ (N = 13, 2s) for HMIE-NP-B01, and -0.05 ± 0.09‰ (N = 12, 2s) for MAKP-NP-B01, considered as the preferred Fe isotope delta values. In situ isotopic analysis via ns-LA-MC-ICP-MS yielded δ56Fe values of -0.28 ± 0.28‰ (N = 19, 2s) for HMIE-NP-B01 and -0.12 ± 0.24‰ (N = 22, 2s) for MAKP-NP-B01, consistent with the solution Fe isotope data. The homogeneity of Fe isotopes of the pellets was evaluated by ns-LA-MC-ICP-MS analyses of three different positions to further confirm that both materials are isotopically homogeneous. Both materials can be considered as potential quality control and bracketing reference materials for Fe isotopic measurements by in situ ns-LA-MC-ICP-MS analysis. KW - Laser ablation KW - Fe isotope KW - Fe-oxides PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-654755 DO - https://doi.org/10.1111/ggr.70037 SN - 1639-4488 SP - 1 EP - 12 PB - John Wiley & Sons Ltd. AN - OPUS4-65475 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 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 - 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 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 - TY - JOUR A1 - Mieller, Björn A1 - Vogl, Jochen A1 - Noordmann, J. A1 - Kaltenbach, A. A1 - Rienitz, O. T1 - Preparation and characterization of primary magnesium mixtures for the ab initio calibration of absolute magnesium isotope ratio measurements N2 - We report an appropriate preparation of binary isotope calibration mixtures of the three stable isotopes of magnesium to be used in the ab initio calibration of multicollector mass spectrometers (ICPMS and TIMS). For each of the three possible combinations of binary mixtures ("24Mg" + "25Mg", "24Mg" + "26Mg", and "25Mg" + "26Mg"), three individual setups have been prepared under gravimetric control, each of them with an isotope ratio close to unity, and a total magnesium mass fraction close to 20 mg kg-1. The preparation was designed to occur via an intermediate dilution of a parent solution of a highly purified specimen of the isotopically enriched magnesium materials. For the application as calibration mixtures, a complete uncertainty budget was set up, and is presented and discussed in detail, including the aspects that went into the design of the dilution and mixing approach to minimize uncertainty. The principle parameters for the purpose of the later calibration of the mass spectrometers are the absolute masses of isotopically enriched magnesium materials in the primary calibration mixtures. For the first time relative expanded uncertainties U (k = 2) for these masses of ≤0.005% could be achieved for all mixtures. KW - Atomic weight KW - Magnesium KW - Isotope mixture KW - Purity PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-352564 DO - https://doi.org/10.1039/c5ja00284b SN - 0267-9477 SN - 1364-5544 N1 - Geburtsname von Mieller, Björn: Brandt, B. - Birth name of Mieller, Björn: Brandt, B. N1 - Corrigendum: Journal of analytical atomic spectrometry 34 (2019) 2340 VL - 31 IS - 1 SP - 179 EP - 196 PB - Royal Society of Chemistry CY - London AN - OPUS4-35256 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Mieller, Björn A1 - Noordmann, J. A1 - Rienitz, O. A1 - Malinovskiy, D. T1 - Characterization of a series of absolute isotope reference materials for magnesium: ab initio calibration of the mass spectrometers, and determination of isotopic compositions and relative atomic weights N2 - For the first time, an ab initio calibration for absolute Mg isotope ratios was carried out, without making any a priori assumptions. All quantities influencing the calibration such as the purity of the enriched isotopes or liquid and solid densities were carefully analysed and their associated uncertainties were considered. A second unique aspect was the preparation of three sets of calibration solutions, which were applied to calibrate three multicollector ICPMS instruments by quantifying the correction factors for instrumental mass discrimination. Those fully calibrated mass spectrometers were then used to determine the absolute Mg isotope ratios in three candidate European Reference Materials (ERM)-AE143, -AE144 and -AE145, with ERM-AE143 becoming the new primary isotopic reference material for absolute isotope ratio and delta measurements. The isotope amount ratios of ERM-AE143 are n(25Mg)/n(24Mg) = 0.126590(20) mol/mol and n(26Mg)/n(24Mg) = 0.139362(43) mol/mol, with the resulting isotope amount fractions of x(24Mg) = 0.789920(46) mol/mol, x(25Mg) = 0.099996(14) mol/ mol and x(26Mg) = 0.110085(28) mol/mol and an atomic weight of Ar(Mg) = 24.305017(73); all uncertainties were stated for k = 2. This isotopic composition is identical within uncertainties to those stated on the NIST SRM 980 certificate. The candidate materials ERM-AE144 and -AE145 are isotopically lighter than ERM-AE143 by 1.6 ‰ and 1.3 ‰, respectively, concerning their n(26Mg)/n(24Mg) ratio. The relative combined standard uncertainties are ≤0.1 ‰ for the isotope ratio n(25Mg)/n(24Mg) and ≤0.15 ‰ for the isotope ratio n(26Mg)/ n(24Mg). In addition to characterizing the new isotopic reference materials, it was demonstrated that commonly used fractionation laws are invalid for correcting Mg isotope ratios in multicollector 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 ‰ and 0.7 ‰. KW - isotope reference material KW - absolute measurements KW - mass spectrometry KW - atomic weight KW - magnesium PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-370931 DO - https://doi.org/10.1039/C6JA00013D SN - 0267-9477 N1 - Geburtsname von Mieller, Björn: Brandt, B. - Birth name of Mieller, Björn: Brandt, B. VL - 31 IS - 7 SP - 1440 EP - 1458 PB - Royal Society of Chemistry CY - Cambridge, UK AN - OPUS4-37093 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 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 - 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 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 - 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 - 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 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 T1 - What isotopes can do... N2 - The talk gives Brief overview on the effects causing isotope variations in nature and some typical applications. It also Points to a potential application in corrosin sciences. T2 - Final Colloquium: Microbiologically influenced corrosion CY - Berlin, Germany DA - 21.05.2019 KW - Iron isotope fractionation KW - Microbially induced corrosion PY - 2019 AN - OPUS4-48273 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - New Hematite and Magnetite Reference Material for In Situ 56Fe Measurements N2 - Characterisation of two potential reference materials. Hematite (HMIE-NP-B01) and magnetite (MARK-NP-B01) for Fe isotope ratios in situ analysis via LA-MC-ICP-MS. T2 - EWCPS 2025 CY - Berlin, Germany DA - 03.03.2025 KW - Fe isotope KW - Fe-dominated minerals KW - Laser ablation KW - LA-MC-ICP-MS PY - 2015 AN - OPUS4-62827 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen 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 N1 - Geburtsname von Mieller, Björn: Brandt, B. - Birth name of Mieller, Björn: Brandt, B. AN - OPUS4-47930 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 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 - 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 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 T1 - Preparation of an absolute isotope reference material for magnesium T2 - CCQM, IAWG Meeting CY - Tsukuba, Japan DA - 2014-10-14 PY - 2014 N1 - Geburtsname von Mieller, Björn: Brandt, B. - Birth name of Mieller, Björn: Brandt, B. AN - OPUS4-31559 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen 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 N1 - Geburtsname von Mieller, Björn: Brandt, B. - Birth name of Mieller, Björn: Brandt, B. AN - OPUS4-50004 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen 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 N1 - Geburtsname von Mieller, Björn: Brandt, B. - Birth name of Mieller, Björn: Brandt, B. AN - OPUS4-47710 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Merchel, Silke A1 - Berger, Achim A1 - Görner, Wolf A1 - Radtke, Martin A1 - Reinholz, Uwe A1 - Riesemeier, Heinrich A1 - Vogl, Jochen A1 - Frisch, A. A1 - Reiche, I. T1 - Kunst- und Kulturgüter unter "Beschuss" T2 - GDCh-Jahrestagung Chemie 2003 ; Jahrestagung der Fachgruppe Nuklearchemie ; 19. Seminar Aktivierungsanalyse CY - München, Deutschland DA - 2003-10-06 PY - 2003 SN - 3-936028-14-1 N1 - Serientitel: Kurzreferate / GDCh-Jahrestagung Chemie 2003 – Series title: Kurzreferate / GDCh-Jahrestagung Chemie 2003 IS - 5 SP - 68 PB - Gesellschaft Deutscher Chemiker CY - Frankfurt am Main AN - OPUS4-2686 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Frisch, A. A1 - Merchel, Silke A1 - Radtke, Martin A1 - Reinholz, Uwe A1 - Riesemeier, Heinrich A1 - Vogl, Jochen ED - Röhrs, S. T1 - Synchrotron-XRF und PIXE Untersuchungen an bronzezeitlichen Fussringen T2 - Jahrestagung 2003 im Ethnologischen Museum Berlin-Dahlem CY - Berlin, Deutschland DA - 2003-03-12 PY - 2003 SN - 3-00-014223-1 SN - 0949-4057 SP - 101 EP - 103 CY - [Frankfurt am Main] AN - OPUS4-2355 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Morcillo, Dalia A1 - Winckelmann, Alexander A1 - Oelze, Marcus A1 - Leonhardt, Robert A1 - Schmidt, Anita A1 - Richter, Silke A1 - Recknagel, Sebastian A1 - Vogl, Jochen A1 - Panne, Ulrich A1 - Abad Andrade, Carlos Enrique T1 - Exploring Age-Induced Lithium Isotope Fractionation in Lithium-Ion Batteries using Microwave-Induced Cold Nitrogen Plasma Mass Spectrometry N2 - This study explores Microwave-Inductively Coupled Atmospheric-pressure Plasma Mass Spectrometry (MICAP-MS) as a cost-effective alternative to Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) for analyzing lithium isotopic composition in lithium-ion batteries (LIBs). We investigate the performance of MICAP-MS in measuring Li isotope ratios in new and aged commercial lithium cobalt oxide (LCO) batteries. Our results show that MICAP-MS, operating under cold plasma conditions at 800 W with an 8 mm torch position, achieves results metrologically compatible with MC-ICP-MS, with a precision ranging from 0.6‰ to 3.4‰ for δ7Li values. MICAP-MS benefits from a dielectric resonator for uniform plasma, better ion velocity control, and higher energy efficiency. Optimal settings were identified with dwell times of 10 ms for 6Li and 1 ms for 7Li. The study of LIBs revealed that 6Li migrates towards the anode over multiple charge–discharge cycles, causing 7Li to accumulate in the cathode, a fractionation effect that becomes more pronounced with prolonged cycling. MICAP-MS provides a cost-effective, precise alternative to MC-ICP-MS, with lower operational costs and enhanced portability, advancing the study of isotopic fractionation and aging in lithium-ion batteries. KW - MICAP-MS KW - Lithium KW - Battery aging KW - Lithium isotopes KW - Nitrogen plasma KW - Isotope fractionation KW - lithium cobalt oxide KW - LCO PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-643777 DO - https://doi.org/10.1039/d4ja00324a SN - 0267-9477 SP - 1 EP - 11 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64377 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kuroiwa, T. A1 - Zhu, Y. A1 - Inagaki, K. A1 - Long, S. A1 - Christopher, S. A1 - Puelles, M. A1 - Porinsky, M. A1 - Hatamleh, N. A1 - Murby, J. A1 - Merrick, J. A1 - White, I. A1 - Saxby, D. A1 - Caciano de Sena, R. A1 - Dominguez de Almeida, M. A1 - Vogl, Jochen A1 - Phukphatthanachai, Pranee A1 - Fung, W.-H. A1 - Yau, H.-P. A1 - Okumu, T. O. A1 - Kang'iri, J. N. A1 - Tellez, J. A. S. A1 - Campos, E. Z. A1 - Galvan, E. C. A1 - Kaewkhomdee, N. A1 - Taebunpakul, S. A1 - Thiengmanee, U. A1 - Yafa, C. A1 - Tokman, N. A1 - Tunc, M. A1 - Can, S. Z. T1 - Report of the CCQM-K123: trace elements in biodiesel fuel N2 - The CCQM-K123 key comparison was organized by the Inorganic Analysis Working Group (IAWG) of CCQM to assess and document the capabilities of the national metrology institutes (NMIs) or the designated institutes (DIs) to measure the mass fractions of sodium, calcium, potassium, magnesium phosphorous and sulfur in biodiesel fuel (BDF). The National Metrology Institute of Japan (NMIJ) and National Institute of Standards and Technology (NIST) acted as the coordinating laboratories. Results were submitted by 11 NMIs and DIs. The participants used different measurement methods, though most of them used inductively coupled plasma-mass spectrometry (ICP-MS), isotope dilution technique with ICP-MS and inductively coupled plasma-optical emission spectrometry (ICP-OES) with microwave acid digestion. The material was quite challenging and a number of questions were raised at the IAWG meeting. Concerning S, the variation in S results between participants, particularly those using IDMS methods was discussed at the IAWG meeting. BAM, NIST and NMIJ reviewed their experimental conditions, results and/or uncertainty calculations for IDMS. According to the additional evaluation and investigation, the variances between the revised results became smaller than the original one, the revised results were overlapping between IDMS measurements of S content at the k=2 level. It is not possible to calculate a KCRV with values being modified after submission. It was concluded that this KC does not support S measurements. Accounting for relative expanded uncertainty, comparability of measurement results for each of Na, Ca, K, Mg and P was successfully demonstrated by the participating NMIs or DIs. It is expected that sodium, calcium, potassium, magnesium and phosphorus at mass fractions greater than approximately 0.1 mg/kg, 0.1 mg/kg, 0.05 mg/kg, 0.05 mg/kg and 0.1 mg/kg respectively in biodiesel fuel and similar matrices (fuels and oils etc.) can be determined by each participant using the same technique(s) employed for this key comparison to achieve similar uncertainties mentioned in the present report. Furthermore, the results of this key comparison can be utilized along with the IAWG core capability approach. KW - Biodiesel KW - Fuel KW - Sulphur KW - Reference measurement PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-393941 UR - http://iopscience.iop.org/article/10.1088/0026-1394/54/1A/08008/meta DO - https://doi.org/10.1088/0026-1394/54/1A/08008 SN - 0026-1394 SN - 1681-7575 VL - 54 SP - Tech. Suppl. 2017, 08008, 1 EP - 47 PB - IOP Publishing CY - Bristol, UK AN - OPUS4-39394 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Ecker, K. H. A1 - Wätjen, U. A1 - Berger, Achim A1 - Grötzschel, R. A1 - Persson, L. A1 - Pritzkow, W. A1 - Radtke, Martin A1 - Riebe, Gundel A1 - Riesemeier, Heinrich A1 - Vogl, Jochen T1 - Certification of antimony implanted in silicon wafer with a silicon dioxide diffusion barrier - IRMM-302 and BAM-L001 N2 - This Report describes the certification of the reference material antimony implanted in Si/SiO2 intended to be used for calibration of surface and near surface analytical methods. It describes the preparation, homogeneity measurements and the analytical work performed for the certification of both Areal density of antimony Atoms (retained dose) and the isotope amount Ratio as well as giving considerations on the stability of the material. KW - Isotope ratio KW - Areal density KW - Surface analysis PY - 2002 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-355752 SP - 1 EP - 40 PB - Institute for Reference Materials and Measurements CY - Geel, Belgium AN - OPUS4-35575 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kazlagić, 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 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 - Kazlagić, 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 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 - Lemke, Nora A1 - El-Khatib, Ahmed H. A1 - Tchipilov, Teodor A1 - Jakubowski, N. A1 - Weller, Michael G. A1 - Vogl, Jochen T1 - Procedure providing SI‑traceable results for the calibration of protein standards by sulfur determination and its application on tau N2 - Quantitative proteomics is a growing research area and one of the most important tools in the life sciences. Well-characterized and quantified protein standards are needed to achieve accurate and reliable results. However, only a limited number of sufficiently characterized protein standards are currently available. To fill this gap, a method for traceable protein quantification using sulfur isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) was developed in this study. Gel filtration and membrane filtration were tested for the separation of non-protein-bound sulfur in the protein solution. Membrane filtration demonstrated a better performance due to the lower workload and the very low sulfur blanks of 11 ng, making it well suited for high-purity proteins such as NIST SRM 927, a bovine serum albumin (BSA). The method development was accomplished with NIST SRM 927e and a commercial avidin. The quantified mass fraction of NIST SRM 927e agreed very well with the certified value and showed similar uncertainties (3.6%) as established methods while requiring less sample preparation and no species-specific standards. Finally, the developed procedure was applied to the tau protein, which is a biomarker for a group of neurodegenerative diseases denoted “tauopathies” including, e.g., Alzheimer’s disease and frontotemporal dementia. For the absolute quantification of tau in the brain of transgenic mice overexpressing human tau, a well-defined calibration standard was needed. Therefore, a pure tau solution was quantified, yielding a protein mass fraction of (0.328 ± 0.036) g/kg, which was confirmed by amino acid analysis. KW - Iinductively coupled plasma mass spectrometry KW - Isotope dilution KW - Quantitative protein analysis KW - Sulfur KW - SI traceability PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545200 DO - https://doi.org/10.1007/s00216-022-03974-z VL - 414 SP - 4441 EP - 4455 PB - Springer Verlag AN - OPUS4-54520 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Vogl, Jochen A1 - Pritzkow, Wolfgang ED - Vanhaecke, F. ED - Degryse, P. T1 - Reference materials in isotopic analysis N2 - The production of isotopic reference materials (IRMs), which started in the 1960s, has stagnated during the last 15 years. On the other hand, the need for IRMs increased strongly with upcoming ICP-MS techniques, especially with MC instruments, in the beginning of the millennium. In parallel, the precision of the isotope amount ratio determinations reached a level which is beyond that of IRMs certified relying on synthetic isotope mixtures. Additionally, the number of elements for which IRMs are required has increased. This difference between the users’ needs and the limitations of current IRMs can only be solved by providing IRMs defining a δ-scale for each element of interest. Such δ-RMs should be produced as solutions to avoid any complications with homogeneity issues. Whenever possible, isotope amount fractions should be provided additionally, even if the uncertainties are not sufficient for cutting-edge research on isotopic variations. Research should also focus on ways to provide isotope amount fractions with lower uncertainties. For the coming years, around 27 elements have been selected by user communities as "of interest” in this context. These elements are of interest to geo- and cosmochemists, and also to scientists working in the fields of human nutrition, human medicine, veterinary medicine, and food traceability. For 18 elements, such as Pb and U, IRMs or δ-RMs are available, provided as a solution or a solid material with sufficient homogeneity. Nevertheless, in some cases further materials are necessary, because the number of units is too small or the materials are too expensive to be widely accepted by users. At BAM, IRMs and δ-RMs will be produced according to the requirements mentioned above. NIST has also started a program to produce new RMs for δ-values. As discussed at the latest meeting of the IUPAC Commission on Isotopic Abundances and Atomic Weights (CIAAW) in July 2009 in Vienna, these activities will be supported by IUPAC. KW - ICPMS KW - IRM KW - Reference materials KW - Delta reference materials PY - 2012 SN - 978-3-527-32896-3 SN - 978-3-527-65048-4 DO - https://doi.org/10.1002/9783527650484.ch6 SP - 139 EP - 163 PB - Wiley-VCH CY - Weinheim AN - OPUS4-26102 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -