TY - JOUR A1 - Abad Andrade, Carlos Enrique A1 - Florek, S. A1 - Becker-Ross, H. A1 - Huang, M.-D. A1 - Heinrich, Hans-Joachim A1 - Recknagel, Sebastian A1 - Vogl, Jochen A1 - Jakubowski, Norbert A1 - Panne, Ulrich T1 - Determination of boron isotope ratios by high-resolution continuum source molecular absorption spectrometry using graphite furnace vaporizers N2 - Boron isotope amount ratios n(10B)/n(11B) have been determined by monitoring the absorption spectrum of boron monohydride (BH) in a graphite furnace using high-resolution continuum source molecular absorption spectrometry (HR-CS-MAS). Bands (0→0) and (1→1) for the electronic transition X1Σ+ → A1Π were evaluated around wavelengths 433.1 nm and 437.1 nm respectively. Clean and free of memory effect molecular spectra of BH were recorded. In order to eliminate the memory effect of boron, a combination of 2% (v/v) hydrogen gas in argon and 1% trifluoromethane in argon, an acid solution of calcium chloride and mannitol as chemical modifiers was used. Partial least square regression (PLS) for analysis of samples and reference materials were applied. For this, a spectral library with different isotopes ratios for PLS regression was built. Results obtained around the 433.1 nm and 437.1 nm spectral regions are metrologically compatible with those reported by mass spectrometric methods. Moreover, for the evaluated region of 437 nm, an accuracy of 0.15‰ is obtained as the average deviation from the isotope reference materials. Expanded uncertainties with a coverage factor of k = 2 range between 0.15 and 0.44‰. This accuracy and precision are compatible with those obtained by mass spectrometry for boron isotope ratio measurements. KW - Boron isotopes KW - Isotope ratios KW - Boron monohydride KW - Molecular absorption KW - High-resolution continuum source absorption spectrometry KW - Graphite furnace KW - Memory effect KW - HR-CS-MAS PY - 2017 UR - http://www.sciencedirect.com/science/article/pii/S0584854717302537 DO - https://doi.org/10.1016/j.sab.2017.08.012 SN - 0584-8547 VL - 136 SP - 116 EP - 122 PB - Elsevier CY - Amsterdam, The Netherlands AN - OPUS4-42071 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 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 - Scharek, Vera M. A1 - Pfeifer, Jens A1 - Vogl, Jochen A1 - Traub, Heike A1 - Meermann, Björn T1 - Tin fractionation analysis in sediment samples via on-line ID ETV/ICP-MS N2 - We report a quantification approach for directly determining total tin and tin-based pollutants/species in sediments via electrothermal vaporization/inductively coupled plasma-mass spectrometry (ETV/ICP-MS) utilizing an on-line isotope dilution mass spectrometry (IDMS) approach. The method was developed and validated using an estuarine sediment reference material (BCR-277R), yielding a recovery of 106%. A relative standard deviation (RSD) of 14%, comparable to published data using a similar method, was obtained. A limit of quantification (LOQ) was estimated at 0.008 mg Sn kg−1 and sufficient for quantifying the total tin mass fraction of surface sediments along the tidal River Elbe course. Hereby, a decrease towards the river mouth, presumably due to dilution effects by less polluted marine sediment, was observed. Besides total tin, monitoring of organotin compounds (OTCs)/species is of interest in sediments due to their toxic effects on aquatic life. The method’s capability was extended by separating an OTC fraction in a sediment certified reference material (CRM) through the ETV temperature program. While spiking experiments with OTC standards confirmed the assignment, only a small fraction of the total certified OTC amount (3%), likely due to matrix effects, was recovered. However, applying the method to real-world samples, OTCs were detectable along the River Elbe course. By this, we demonstrated the potential of our method as a complementary fast-screening approach to species-specific analysis procedures. KW - ETV KW - Sn-Speciation KW - Sediment PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-640137 DO - https://doi.org/10.1007/s00216-025-06064-y SN - 1618-2642 SP - 1 EP - 10 PB - Springer Science and Business Media LLC AN - OPUS4-64013 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schannor, Mathias A1 - Oelze, Marcus A1 - Traub, Heike A1 - He, Yubei A1 - Schmidt, Robin A1 - Heidemann, Luisa A1 - Savic, Lynn Jeanette A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Advancing Biomarker Research: In Situ Cu Isotope Analysis in Liver Tumors by LA-MC-ICP-MS N2 - Stable metal isotopes have received increasing attention as medical biomarkers due to their potential to detect changes in metal metabolism related to diseases. In particular, copper stable isotopes are a powerful tool to identify isotopic variation between tumors and healthy tissue, suggesting application in cancer diagnosis. However, potential mechanisms causing isotope fractionation, such as redox- or bond-forming reactions and interactions of metals during transmembrane import and export, are less well understood. Here, we established an in situ method using laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) to advance our understanding of the underlying processes responsible for isotope fractionation between normal and diseased tissues. Gelatin-based bracketing standards and quality control reference materials, crucial for laser ablation analysis, were developed to allow correction for instrumentally induced isotope fractionation during LA-MC-ICP-MS analysis. Using such matrix-matched standards, the method achieved intermediate precisions for delta values of better than 0.15 ‰ (2 s) for inorganic reference materials and of better than 0.17 ‰ (2 s) for biological reference materials. The developed routine was tested on rabbit VX2 liver tumor samples, a model system resembling human hepatocellular carcinoma (HCC) used to study liver cancer. In situ Cu isotope compositions between healthy (𝛿65/63NIST976(Cu) = −1.5 ‰ to 0.2 ‰) and tumorous (𝛿65/63NIST976(Cu) = 0.0 ‰ to 1.3 ‰) liver tissue show distinct differences in their isotope ratios. The observed isotopic dichotomy is consistent with previous solution-based MC-ICP-MS work, showing enrichment of heavy 65Cu in cancer biopsies relative to healthy tissue. KW - Biomarker KW - Laser Ablation KW - Reference Material PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626865 DO - https://doi.org/10.1021/acs.analchem.4c05626 SN - 1520-6882 VL - 97 IS - 8 SP - 4425 EP - 4432 PB - American Chemical Society (ACS) AN - OPUS4-62686 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Phukphatthanachai, Pranee A1 - Vogl, Jochen A1 - Traub, Heike A1 - Jakubowski, Norbert A1 - Panne, Ulrich T1 - A new approach of using polyethylene frits for the quantification of sulphur in copper metals by isotope dilution LA-ICP-MS and comparison with conventional IDMS techniques 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 - 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 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 VL - 36 IS - 6 SP - 260 EP - 271 PB - Emerald Publishing Limited AN - OPUS4-57979 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 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 - 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 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 - 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 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 - 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 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 - 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 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 - CONF A1 - Vogl, Jochen T1 - Determination of total sulfur in a metal matrix by ICP-IDMS: Example Cu matrix T2 - 14th International Symposium on Biological and Environmental Reference Materials (BERM 14) CY - National Harbor, Maryland 20745 USA DA - 2015-10-11 PY - 2015 AN - OPUS4-34482 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Herwig, Nadine A1 - Stephan, Kristin A1 - Panne, Ulrich A1 - Pritzkow, Wolfgang A1 - Vogl, Jochen T1 - Multi-element screening in milk and feed by SF-ICP-MS N2 - In this study, an analytical procedure for multi-element screening of 40 elements in milk and feed samples was developed. Three different digestion and two different calibration methods were tested for the best suitability. The analytical procedure for the quantification of minor and trace elements is based on sector field ICP-MS (SF-ICP-MS). The method validation revealed good agreement between the determined elemental mass fractions and the certified values of two milk and three feed reference materials. Milk samples of dairy cows at different feeding regimes were collected from two different farms. The results of our study showed significant differences of nine elemental mass fractions (Li, P, Mn, Co, Cu, Rb, Sr, Br, I) between milk from the two locations. Further, a correlation between the elemental mass fractions of milk and the ingested feed and water was observed. KW - Multi-element screening KW - SF-ICP-MS KW - Dairy cows KW - Milk KW - Feed KW - Water PY - 2011 DO - https://doi.org/10.1016/j.foodchem.2010.07.050 SN - 0308-8146 VL - 124 IS - 3 SP - 1223 EP - 1230 PB - Elsevier Ltd. CY - Amsterdam [u.a.] ; Jena AN - OPUS4-22042 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 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 - 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 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 - Morcillo, Dalia A1 - Winckelmann, Alexander A1 - Frick, Daniel A. A1 - Jacobsen, Lars A1 - Seger, Tino A1 - Florek, Stefan A1 - Richter, Silke A1 - Vogl, Jochen A1 - Recknagel, Sebastian A1 - Panne, Ulrich A1 - Abad Andrade, Carlos Enrique T1 - Lithium isotope ratio analysis of geological samples using atomic absorption spectrometry with improved spectral resolution N2 - This study introduces an improved spectrometric method with enhanced precision to determine isotope ratios in geological samples without chromatographic separation. Firstly, the improvement is achieved by increasing the spectral resolution of the spectrometer applied in well-known high-resolution continuum source atomic absorption spectrometry (HR-CS-AAS). The resulting resolving power and linear dispersion of the upgraded setup, which is denoted in the following as HR+CS-AAS, is well adapted to the line widths of the Li isotope components we investigated. Secondly, our proposed method combines optical absorption spectrometry with machine learning data analysis using an extreme gradient boosting algorithm (XGBoost). This method was applied to analyze certified geological reference materials with δLSVEC(7Li/6Li) (hereafter δ7Li) values ranging from −0.5 ‰ to 4.5 ‰. With a pixel related optical resolving power of λ/∆λ ≈ 780 000, we obtain precisions in δ7Li measurements from 1.0 ‰ to 2.5 ‰. The method is validated by comparing the results with multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), confirming its metrological compatibility. This work presents a fast, robust, and reliable method for δ7Li measurement in geological samples. KW - Isotope KW - High-resolution continuum source atomic absorption spectroscopy KW - Lithium KW - Machine learning KW - Echelle spectrometer PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-611807 DO - https://doi.org/10.1016/j.sab.2024.107013 VL - 220 SP - 1 EP - 5 PB - Elsevier BV AN - OPUS4-61180 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rosner, Martin A1 - Vogl, Jochen T1 - Bor: Isotopenverhältnisse und die Herkunft einer Probe N2 - Die Industrie nutzt die Borisotopenanalytik in nukleartechnischen Anwendungen. Umwelt- und Geowissenschaften identifizieren anhand der Borisotopenverhältnisse Kontaminationsquellen und charakterisieren Mischungs- und Fraktionsprozesse. In der Lebensmittelanalytik dient der Parameter dazu, Herkunft und Anbauweise von Obst und Gemüse herauszufinden. Seit kurzem gibt es dafür ein validiertes Verfahren und erste Referenzdaten. KW - Isotopenverhältnisse KW - Herkunft KW - TIMS PY - 2012 SN - 1439-9598 SN - 1521-3854 VL - 60 IS - 2 SP - 147 EP - 149 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-25575 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - New Potential Hematite and Magnetite Reference Materials for Iron Isotope Analysis by Solution- and LA-MC-ICP-MS N2 - Two potential reference materials HMIE-NP-B01 and MARK-NP-B01 for Iron isotope analysis. These two RMs will used later as calibrant the corroded material generated from MIC. T2 - ANAKON 2025 CY - Leipzip, Germany DA - 10.03.2025 KW - Fe isotope KW - Fe-dominated minerals KW - Laser ablation KW - LA-MC-ICP-MS PY - 2025 AN - OPUS4-62829 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - CCQM-P149 Purity determination of zinc to be used as primary standard for zinc determination T2 - CCQM IAWG Meeting CY - Pretoria, South Africa DA - 2013-11-05 PY - 2013 AN - OPUS4-29297 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - CCQM-K72 & P107.1 - Purity of zinc with respect to six metallic analytes T2 - CCQM IAWG Meeting CY - Pretoria, South Africa DA - 2013-11-05 PY - 2013 AN - OPUS4-29298 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - CCQM-K72 & P107.1 - Purity of zinc with respect to six metallic analytes T2 - CCQM IAWG Meeting CY - Paris, France DA - 2013-04-15 PY - 2013 AN - OPUS4-30776 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - CCQM-P149 - Purity determination of zinc to be used as primary standard for zinc determination T2 - CCQM IAWG Meeting CY - Paris, France DA - 2014-04-07 PY - 2014 AN - OPUS4-30525 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - CCQM-K72 & P107.1 - Purity of zinc with respect to six metallic analytes T2 - CCQM IAWG Meeting CY - Paris, France DA - 2014-04-07 PY - 2014 AN - OPUS4-30526 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -