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 - Tvrdonova, M. A1 - Vlcnovska, M. A1 - Pompeiano Vanickova, L. A1 - Kanicky, V. A1 - Adam, V. A1 - Ascher, Lena A1 - Jakubowski, Norbert A1 - Vaculovicova, M. A1 - Vaculovic, T. T1 - Gold nanoparticles as labels for immunochemical analysis using laser ablation inductively coupled plasma mass spectrometry N2 - In this paper, we describe the labelling of antibodies by gold nanoparticles (AuNPs) with diameters of 10 and 60 nm with detection by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Additionally, the AuNPs labelling strategy is compared with commercially available labelling reagents based on MeCAT (metal coded affinity tagging). Proof of principle experiments based on dot blot experiments were performed. The two labelling methods investigated were compared by sensitivity and limit of detection (LOD). The absolute LODs achieved were in the range of tens of picograms for AuNP labelling compared to a few hundred picograms by the MeCAT labelling. KW - Nanoparticle KW - LA-ICP-MS KW - Labeling PY - 2019 DO - https://doi.org/10.1007/s00216-018-1300-7 SN - 1618-2642 SN - 1618-2650 VL - 411 IS - 3 SP - 559 EP - 564 PB - Springer-Verlag GmbH CY - Berlin, Heidelberg AN - OPUS4-47093 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Roesch, Philipp A1 - Wittwer, Philipp A1 - Piechotta, Christian A1 - Lisec, Jan A1 - Sommerfeld, Thomas A1 - Kluge, Stephanie A1 - Herzel, Hannes A1 - Huthwelker, T. A1 - Borca, C. A1 - Simon, Franz-Georg T1 - Levels of per- and polyfluoroalkyl substances (PFAS) in various wastewater-derived fertilizers – analytical investigations from different perspectives N2 - Solid wastewater-based fertilizers were screened for per- and polyfluoroalkyl substances (PFAS) by the extractable organic fluorine (EOF) sum parameter method. The EOF values for ten sewage sludges from Germany and Switzerland range from 154 to 7209 mg kg−1. For thermal treated sewage sludge and struvite the EOF were lower with values up to 121 mg kg−1. Moreover, the application of PFAS targeted and suspect screening analysis of selected sewage sludge samples showed that only a small part of the EOF sum parameter values can be explained by the usually screened legacy PFAS. The hitherto unknown part of EOF sum parameter contains also fluorinated pesticides, pharmaceutical and aromatic compounds. Because these partly fluorinated compounds can degrade to (ultra-)short PFAS in wastewater treatment plants they should be considered as significant sources of organic fluorine in the environment. The combined results of sum parameter analysis and suspect screening reveal the need to update current regulations, such as the German fertilizer ordinance, to focus not solely on a few selected PFAS such as perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) but consider an additional sum parameter approach as a more holistic alternative. Moreover, diffusion gradient in thin-films (DGT) passive samplers were utilized as an alternative simplified extraction method for PFAS in solid wastewater-based fertilizers and subsequently quantified via combustion ion chromatography. However, the DGT method was less sensitive and only comparable to the EOF values of the fertilizers in samples with >150 mg kg−1, because of different diffusion properties for various PFAS, but also kinetic exchange limitations. KW - Combustion Ion Chromatography KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Sewage sludge KW - Fertilizer PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-583429 DO - https://doi.org/10.1039/d3va00178d VL - 2 IS - 10 SP - 1436 EP - 1445 PB - Royal Society of Chemistry (RSC) AN - OPUS4-58342 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen T1 - The triple-isotope calibration approach: a universal and standard-free calibration approach for obtaining absolute isotope ratios of multi-isotopic elements N2 - The theory of a new calibration approach for obtaining absolute isotope ratios of multi-isotopic elements without the use of any standard has been developed. The calibration approach basically uses the difference in the instrumental isotope fractionation of two different types of mass spectrometers, leading to two different fractionation lines in a three-isotope diagram. When measuring the same sample with both mass spectrometers, the different fractionation lines have one point in common: this is the ‘true’ logarithmized isotope ratio pair of the sample. Thus, the intersection of both fractionation lines provides us with the absolute isotope ratios of the sample. This theory has been tested in practice by measuring Cd and of Pb isotope ratios in the certified reference materials BAM-I012 and NIST SRM981 by thermal ionization mass spectrometry and by inductively coupled plasma mass spectrometry while varying the ionization conditions for both mass spectrometers. With this experiment, the theory could be verified, and absolute isotope ratios were obtained, which were metrologically compatible with the certified isotope ratios. The so-obtained absolute isotope ratios are biased by − 0.5% in average, which should be improved with further developments of the method. This calibration approach is universal, as it can be applied to all elements with three or more isotopes and it is not limited to the type of mass spectrometers applied; it can be applied as well to secondary ion mass spectrometry or others. Additionally, this approach provides information on the fractionation process itself via the triple-isotope fractionation exponent θ. KW - Triple isotope fractionation KW - Absolute isotope ratio KW - Mass spectrometry KW - Calibration KW - Uncertainty PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-516364 DO - https://doi.org/10.1007/s00216-020-03050-4 VL - 413 IS - 3 SP - 821 EP - 826 PB - Springer Verlag AN - OPUS4-51636 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - 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 - 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 - Vogl, Jochen A1 - Rienitz, O. A1 - Pramann, A. A1 - Flierl, L. T1 - Scale Conversion and Uncertainty Calculations in Isotope Delta Measurements N2 - Isotope ratio applications are on the increase and a major part of which are delta measurements, because they are easier to perform than the determination of absolute isotope ratios while offering lower measurement uncertainties. Delta measurements use artefact-based scales and therefore scale conversions are required due to the lack of the scale defining standards. Such scale conversions often form the basis for comparing data being generated in numerous projects andtherefore need to be as accurate as possible. In practice, users are tempted to apply linear approximations, which are not sufficiently exact, because delta values are defined by nonlinear relationships. The bias of such approximations often is beyond typical measurement uncertainties and its extent can hardly be predicted. Therefore, exact calculations are advised. Here, the exact equations and the bias of the approximations are presented, and calculations are illustrated by real-world examples. Measurement uncertainty is indispensable in this context and therefore, its calculation is described as well for determining delta values but also for scale conversions. Approaches for obtaining a single delta measurement and for repeated measurements are presented. For the latter case, a new approach for calculating the measurement uncertainty is presented, which considers covariances between the isotope ratios. KW - Delta isotope standard KW - Delta scale KW - In-house calibration solution KW - Isotope ratios KW - Isotope reference material KW - Measurement uncertainty KW - Scale conversion PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-557254 DO - https://doi.org/10.1111/ggr.12450 SN - 1639-4488 VL - 46 IS - 4 SP - 773 EP - 787 PB - Wiley AN - OPUS4-55725 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Rosner, M. A1 - Curbera, J. A1 - Peltz, U. A1 - Peplinski, Burkhard T1 - Lead isotope analysis in magic artefacts from the Berlin museums N2 - A set of 59 ancient magical artefacts, mainly made of lead, was selected from the collections of the Staatliche Museen zu Berlin in order to unravel their origins. All the selected artefacts have been studied for their Pb isotope compositions, which covered the whole range of the Mediterranean ore deposits. However, the majority (≈86%) were made of lead matching the small compositional range of the Laurion ore deposits. Only eight out of the 59 artefacts were made of recycled lead or lead from other ore deposits. Additionally, all but two were approximately dated based on their inscriptions. The lead isotopic composition together with information obtained from the inscriptions, the resulting dating, the context of the find and the known history of each item allowed us to gain more detailed information about the origins of these magical artefacts. The Attic provenance of 36 curse tablets was confirmed, whereas for 11 curse tablets previously classified as non-Attic, the provenance was either confirmed and specified (six artefacts) or changed to Attic (five artefacts). Surprisingly, the majority (six out of eight) of the analysed curse tablets from the Egyptian collection showed a lead isotopic composition closely matching that of Laurion. A Laurion-like lead isotopic composition was also observed for three of the four analysed oracular tablets from Dodona. Together with the dating information, this points to Laurion as the major and dominant lead source in the Aegean, at least during the fourth–third century B.C. The few curse tablets from earlier than the fourth–third century B.C. point to the use of multiple and thus isotopically more variable lead sources compared with the Roman times. KW - Lead isotopes KW - Pb isotopes KW - Greek curse tablets KW - Antikensammlung Berlin KW - Ägyptisches Museum Berlin PY - 2018 DO - https://doi.org/10.1007/s12520-016-0445-6 SN - 1866-9557 SN - 1866-9565 VL - 10 IS - 5 SP - 1111 EP - 1127 PB - Springer Verlag CY - Berlin AN - OPUS4-45628 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Rosner, M. A1 - Kasemann, S. A. A1 - Kraft, R. A1 - Meixner, A. A1 - Noordmann, J. A1 - Rabb, S. A1 - Rienitz, O. A1 - Schuessler, J. A. A1 - Tatzel, Michael A1 - Vocke, R. D. T1 - Intercalibration of Mg isotope delta scales and realisation of SI traceability for Mg isotope amount ratios and isotope delta values N2 - The continuous improvement of analytical procedures using multi-collector technologies in ICP-mass spectrometry has led to an increased demand for isotope standards with improved homogeneity and reduced measurement uncertainty. For magnesium, this has led to a variety of available standards with different quality levels ranging from artefact standards to isotope reference materials certified for absolute isotope ratios. This required an intercalibration of all standards and reference materials, which we present in this interlaboratory comparison study. The materials Cambridge1, DSM3, ERMAE143, ERM-AE144, ERM-AE145, IRMM-009 and NIST SRM 980 were cross-calibrated with expanded measurement uncertainties (95% confidence level) of less than 0.030‰ for the δ25/24Mg values and less than 0.037‰ for the δ26/24Mg values. Thus, comparability of all magnesium isotope delta (δ) measurements based on these standards and reference materials is established. Further, ERM-AE143 anchors all magnesium δ-scales to absolute isotope ratios and therefore establishes SI traceability, here traceability to the SI base unit mole. This applies especially to the DSM3 scale, which is proposed to be maintained. With ERM-AE144 and ERM-AE145, which are product and educt of a sublimation-condensation process, for the first time a set of isotope reference materials is available with a published value for the apparent triple isotope fractionation exponent θapp, the fractionation relationship ln α(25/24Mg)/ln α(26/24Mg). KW - Delta scale KW - Traceability KW - Scale anchor KW - Absolute isotope ratio KW - Comparability KW - Triple isotope fractionation PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-511557 DO - https://doi.org/10.1111/ggr.12327 SN - 1751-908X VL - 44 IS - 3 SP - 439 EP - 457 PB - Wiley-Blackwell CY - Oxford AN - OPUS4-51155 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - 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 - JOUR A1 - Von der Au, M. A1 - Borovinskaya, O. A1 - Büchel, C. A1 - Meermann, Björn T1 - Der Fingerabdruck der Kieselalge N2 - Elementanalytische Verfahren werden heute zu mehr eingesetzt als bloß zur Bestimmung von Metallgesamtgehalten in diversen Probenmatrizes. Sie stellen heute ein wichtiges Werkzeug zur Beantwortung lebenswissenschaftlicher Fragen aus Umwelt, Medizin und Biologie dar. In der vorliegenden Arbeit kommt die single-cell-ICP-Flugzeitmassenspektrometrie (single-cell-ICP-TOF-MS) zur Multielementanalytik in einzelnen Kieselalgen (Diatomeen) zum Einsatz und wird zukünftig ein wichtiges Werkzeug z.B. bei der Beantwortung ökotoxikologischer Fragestellung sein. KW - Diatomeenanalytik KW - Single cell-ICP-ToF-MS KW - Multielementanalytik in kurzen transienten Signalen PY - 2019 UR - https://q-more.chemie.de/q-more-artikel/299/der-fingerabdruck-der-kieselalge.html SP - 1 EP - 3 PB - LUMITOS AN - OPUS4-49749 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Von der Au, M. A1 - Meermann, Björn T1 - Screening von Organofluorverbindungen im Oberflächenwasser N2 - Organofluorverbindungen kommen in vielen Bereichen zum Einsatz und gelangen in die aquatische Umwelt. Die Belastungssituation der Gewässer ist bisher wenig untersucht – hier kommt die HR-CS GF MAS als leistungsstarkes Screeningtool zum Einsatz. KW - HR-CS-GFMAS KW - Extrahierbar organisch gebundenes Fluor (EOF) KW - Oberflächengewässer PY - 2019 UR - https://analytik.news/Fachartikel/Volltext/bam5.pdf SP - 1 EP - 3 PB - Dr. Beyer Internet-Beratung AN - OPUS4-49750 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von der Au, Marcus A1 - Borovinskaya, O. A1 - Flamigni, L. A1 - Kuhlmeier, K. A1 - Büchel, C. A1 - Meermann, Björn T1 - Single cell-inductively coupled plasma-time of flight-mass spectrometry approach for ecotoxicological testing N2 - Diatoms play a key role in assessing the eco-toxicology of metals and are already part of several national and international guidelines and regulations. Data on metal uptake and its correlation with a natural metal composition of the diatoms are mostly lacking on a cellular basis - mainly due to the lack of a suitable method on both the preparation and detection side. Therefore, within this work a fully automated approach based on the on-line coupling of a high performance liquid chromatograph (HPLC) and an inductively coupled plasma-time of flight-mass spectrometer (ICP-ToF-MS) was applied to analyze single cells of the alga Cyclotella meneghiniana multi-elementally in order to provide a deeper insight into the metal composition and its response to environmental stress. Multi-elemental analysis in single diatoms also enables assessment of combined toxicity of a set of metals. A set of four fingerprint elements, characteristically for diatoms (Mg, P, Si, Fe), were identified and hence the investigation of environmental stress onto the cells was enabled by performing incubation experiments with environmentally relevant toxic elements. It could be shown at moderate environmental stress caused by increasing the metal concentration in the medium (zinc) that the fingerprint element concentrations remained stable and thus the suitability of the selected elements for algae tracing was demonstrated. With regard to further ecotoxicological assessments, a multivariate approach was successfully applied allowing for cell classification upon different incubation concentration levels. This multivariate approach also facilitated an effective identification of three different diatom species (Cyclotella meneghiniana, Thalassiosira weissflogii and Thalassiosira pseudonana). KW - ICP-TOF-MS KW - Ecotoxicological Testing KW - Diatoms PY - 2020 DO - https://doi.org/10.1016/j.algal.2020.101964 VL - 49 SP - 101964 PB - Elsevier B.V. AN - OPUS4-50875 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von der Au, Marcus A1 - Faßbender, Sebastian A1 - Chronakis, Michail A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Size determination of nanoparticles by ICP-ToF-MS using isotope dilution in microdroplets N2 - Within this work, the combination of a microdroplet generator and an ICP-ToF-MS for nanoparticle analysis is presented. For the size determination of platinum nanoparticles an on-line isotope dilution analysis approach was developed. The 194Pt/195Pt isotopic ratio was used for the characterization of the particles, while the 182W/183W isotopic ratio was monitored simultaneously for mass bias correction. The on-line ID-MDG-sp-ICP-ToF-MS approach was deployed for the size determination of three platinum nanoparticle samples (50 nm, 63 nm, 70 nm); for validation, complementary size characterization techniques (sp-ICP-ToF-MS and TEM) were used. The robustness of this technique was evidenced, by using sodium chloride concentrations up to 100 mg L−1 as a matrix component. Our new on-line ID MDG-sp-ICP-ToF-MS approach is a promising tool for the fast and reliable determination of nanoparticles' size in severe matrix concentrations, e.g., environmental samples. KW - ICP-ToF-MS KW - Nanoparticles KW - Isotope Dilution PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-552727 DO - https://doi.org/10.1039/D2JA00072E SN - 0267-9477 VL - 37 IS - 6 SP - 1203 EP - 1207 PB - Royal Society of Chemistry AN - OPUS4-55272 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von der Au, Marcus A1 - Karbach, H. A1 - Bell, A. M. A1 - Bauer, O. B. A1 - Karst, U. A1 - Meermann, Björn T1 - Determination of metal uptake in single organisms, Corophiumvolutator, via complementary electrothermal vaporization/inductively coupled plasma mass spectrometry and laserablation/inductively coupled plasma mass spectrometry N2 - Rationale: (Eco-)toxicological effects are mostly derived empirically and are notcorrelated with metal uptake. Furthermore, if the metal content is determined,mostly bulk analysis of the whole organism population is conducted; thus, biologicalvariability is completely disregarded, and this may lead to misleading results. Toovercome this issue, we compared two different solid sampling techniques for theanalysis of single organisms.Methods: In this study, complementary electrothermal vaporization/inductivelycoupled plasma mass spectrometry (ETV/ICP-MS) , laser ablation/inductivelycoupled plasma mass spectrometry (LA/ICP-MS)-based methods for the analysisof individual organisms were developed and the results obtained were comparedwith the concentrations obtained after digestion and measured using ICP-MS.For this purpose, a common (eco-)toxicological test organism, the mud shrimpCorophium volutator, was selected. As proof-of-concept application, these organismswere incubated with environmentally relevant metals from galvanic anodes, whichare often used for protection against metal corrosion in, for example, offshorewind farms.Results: The bulk analysis revealed that large quantities of the incubated elementswere detectable. Using the ETV/ICP-MS method, we could identify a highbiovariability within the population of organisms tested. Using the LA/ICP-MSmethod, it could be determined that the large quantities of the elements detectedwere due to adsorption of the metals and not due to uptake, which correlates wellwith the absence of (eco-)toxicological effects.Conclusions: The results obtained imply the efficiency of complementary methods toexplain the absence or presence of (eco-)toxicological effects. In particular, methodsthat allow for single-organism analysis or provide even a spatial resolution supportthe interpretation of ecotoxicological findings. KW - ICP-MS KW - Metal toxicity KW - Metal uptake KW - Corophium volutator KW - Seawater PY - 2021 DO - https://doi.org/10.1002/rcm.8953 VL - 35 IS - 2 SP - e8953 AN - OPUS4-52077 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von der Au, Marcus A1 - Schwinn, M. A1 - Kuhlmeier, K. A1 - Büchel, C. A1 - Meermann, Björn T1 - Development of an automated on-line purification HPLC single cell-ICP-MS approach for fast diatom analysis N2 - The most challenging part in performing a single cell ICP-MS (sc-ICP-MS) approach is the sample preparation, in particular the reduction of the ionic background. This step is, in many cases, time-consuming and required for each sample separately. Furthermore, sc-ICP-MS measurements are mostly carried out "manually", given the fact that present systems are not allowing for an automated change of samples. Thus, within this work, we developed an approach based on a HPLC system coupled on-line with sc-ICP-MS via a set of switching valves as well as an in-line filter for automated cell washing. This set-up enables the ionic background removal as well as analysis of single cells completely automated without any manual sample pretreatment. Our approach was applied for the analysis of the single celled diatom species Cyclotella meneghiniana, a marine diatom species, on the basis of Mg24 and facilitates testing in 11 min per sample, requiring only around 10,000 cells in a volume of 10 µL and approx. 10 mL of a 5% MeOH/95% deionized water (v/v) mixture. Even at extremely saline culturing media concentrations (up to 1000 mg L-1 magnesium) our on-line approach worked sufficiently allowing for distinction of ionic and particulate fractions. Furthermore, a set of diatom samples was analyzed completely automated without the need for changing samples manually. So, utilizing this approach enables analyzing a high quantity of samples in a short time and therefore in future the investigation of ecotoxicological effects is simplified for example in terms of metal accumulation by taking biovariability into account. KW - Single cell-ICP-MS KW - Diatoms KW - Ecotoxicology testing KW - Automated system PY - 2019 DO - https://doi.org/10.1016/j.aca.2019.05.045 SN - 1873-4324 VL - 1077 SP - 87 EP - 94 PB - Elsevier AN - OPUS4-48567 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Völzke, Jule L. A1 - Smatty, Sarah A1 - Döring, Sarah A1 - Ewald, Shireen A1 - Oelze, Marcus A1 - Fratzke, Franziska A1 - Flemig, Sabine A1 - Konthur, Zoltán A1 - Weller, Michael G. T1 - Efficient Purification of Polyhistidine-Tagged Recombinant Proteins Using Functionalized Corundum Particles N2 - Immobilized metal affinity chromatography (IMAC) is a widely used technique for purifying polyhistidine-tagged recombinant proteins. However, it often has practical limitations that require complex optimizations and additional steps for purification. In this study, we introduce functionalized corundum particles as a novel, efficient, and economical method for purifying recombinant proteins in a column-free format. The corundum surface is modified with amino silane APTES, followed by EDTA dianhydride, and then loaded with nickel ions. We used the Kaiser test to monitor the modification process and ICP-MS to quantify the metal-binding capacity. To evaluate the system, we used His-tagged protein A/G (PAG) mixed with bovine serum albumin (BSA). The corundum particles exhibited a binding capacity of approximately 3 mg of protein per gram of corundum or 2.4 mg per 1 mL of corundum suspension. We also examined cytoplasm obtained from different E. coli strains as an example of a complex matrix. Varying the imidazole concentration in the loading and washing buffers showed that higher concentrations during loading improved purity. Even with sample volumes as large as one liter, we successfully isolated recombinant proteins down to a concentration of 1 µg/mL. We found higher purity levels with corundum when comparing the corundum material to standard Ni–NTA agarose beads. We successfully purified His6-MBP-mSA2, a fusion protein comprising monomeric streptavidin and maltose-binding protein, from E. coli cytoplasm, demonstrating the method's applicability. We also purified SARS-CoV-2-S-RBD-His8 expressed in human Expi293F cells, confirming its suitability for mammalian cell culture supernatants. The material cost of the nickel-loaded corundum material (without regeneration) is estimated to be less than 30 cents per gram of functionalized support or 10 cents per milligram of isolated protein. Another advantage of this system is the exceptional physical and chemical stability of corundum particles. Overall, we have demonstrated that this novel material offers an efficient, robust, and cost-effective purification platform for His-tagged proteins, even in challenging, complex matrices and large sample volumes with low product concentrations. This method has potential applications in both small laboratories and large-scale industrial settings. N2 - Die immobilisierte Metallaffinitätschromatographie (IMAC) ist eine weit verbreitete Technik zur Reinigung von rekombinanten Proteinen mit Polyhistidin-Markierung. Sie hat jedoch oft praktische Einschränkungen, die komplexe Optimierungen und zusätzliche Schritte für die Aufreinigung erfordern. In dieser Studie stellen wir funktionalisierte Korundpartikel als neuartige, effiziente und wirtschaftliche Methode zur Reinigung rekombinanter Proteine in einem säulenfreien Format vor. Die Korundoberfläche wird mit dem Aminosilan APTES und anschließend mit EDTA-Dianhydrid modifiziert und dann mit Nickelionen beladen. Wir haben den Kaiser-Test zur Überwachung des Modifizierungsprozesses und ICP-MS zur Quantifizierung der Metallbindungskapazität verwendet. Zur Charakterisierung des Systems verwendeten wir His-markiertes Protein A/G (PAG) in Kombination mit Rinderserumalbumin (BSA). Die Korundpartikel wiesen eine Bindungskapazität von etwa 3 mg Protein pro Gramm Korund oder 2,4 mg pro 1 ml Korundsuspension auf. Als Beispiel für eine komplexe Matrix untersuchten wir auch Zytoplasma, das aus verschiedenen E. coli-Stämmen gewonnen wurde. Die Variation der Imidazolkonzentration in den Lade- und Waschpuffern zeigte, dass höhere Konzentrationen beim Laden die Reinheit verbesserten. Selbst bei einem Probenvolumen von bis zu einem Liter konnten wir rekombinante Proteine von 1 µg/mL isolieren. Beim Vergleich des Korundmaterials mit Standard-Ni-NTA-Agarose-Beads stellten wir einen höheren Reinheitsgrad mit Korund fest. Wir reinigten erfolgreich His6-MBP-mSA2 aus E. coli-Zytoplasma, ein Fusionsprotein, das aus monomerem Streptavidin und Maltose-bindendem Protein besteht. Wir reinigten auch SARS-CoV-2-S-RBD-His8, das in humanen Expi293F-Zellen exprimiert wurde, und bestätigten damit die Eignung des Materials für Zellkulturüberstände von Säugetieren. Die Materialkosten für nickelbeladenen Korund (ohne Regenerierung) werden auf weniger als 30 Cent pro Gramm funktionalisierten Trägers oder 10 Cent pro Milligramm isolierten Proteins geschätzt. Ein weiterer Vorteil dieses Systems ist die außergewöhnliche physikalische und chemische Stabilität der Korundpartikel. Insgesamt haben wir gezeigt, dass dieses neuartige Material eine effiziente, robuste und kostengünstige Reinigungsplattform für His-markierte Proteine bietet, selbst bei schwierigen, komplexen Matrices und großen Probenmengen mit niedrigen Produktkonzentrationen. Diese Methode könnte sowohl in kleinen Labors als auch in der Großindustrie eingesetzt werden. KW - Aluminum oxide KW - Sapphire KW - Ethylenediaminetetraacetic acid KW - Nickel chelate KW - EDTAD KW - HexaHis-Tag KW - His6 KW - 6xHis KW - His8 KW - Bioseparation KW - IMAC purification KW - Immunocapture KW - Affinity chromatography KW - Carrier KW - Nickel KW - Recombinant protein KW - Escherichia coli KW - Bacterial lysates KW - Cytoplasm KW - Polishing KW - Downstream processing PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-575672 DO - https://doi.org/10.3390/biotech12020031 VL - 12 IS - 2 SP - 1 EP - 18 PB - MDPI CY - Basel, Schweiz AN - OPUS4-57567 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weber, A. A1 - von Randow, M. A1 - Voigt, A.-L. A1 - von der Au, Marcus A1 - Fischer, E. A1 - Meermann, Björn A1 - Wagner, M. T1 - Ingestion and toxicity of microplastics in the freshwater gastropodLymnaea stagnalis: No microplastic-induced effects alone or incombination with copper N2 - The interaction of microplastics with freshwater biota and their interaction with other stressors is still not very well understood. Therefore, we investigated the ingestion, excretion and toxicity of microplastics in the freshwater gastropod Lymnaea stagnalis. MP ingestion was analyzed as tissues levels in L. stagnalis after 6–96 h of exposure to 5–90 μm spherical polystyrene (PS) microplastics. To understand the excretion, tissue levels were determined after 24 h of exposure followed by a 12 h–7 d depuration period. To assess the toxicity, snails were exposed for 28 d to irregular PS microplastics (<63 μm, 6.4–100,000 particles mL−1), both alone and in combination with copper as additional stressor. To compare the toxicity of natural and synthetic particles, we also included diatomite particles. Microplastics ingestion and excretion significantly depended on the particle size and the exposure/depuration duration. An exposure to irregular PS had no effect on survival, reproduction, energy reserves and oxidative stress. However, we observed slight effects on immune cell phagocytosis. Exposure to microplastics did not exacerbate the reproductive toxicity of copper. In addition, there was no pronounced difference between the effects of microplastics and diatomite. The tolerance towards microplastics may originate from an adaptation of L. stagnalis to particle-rich environments or a general stress resilience. In conclusion, despite high uptake rates, PS fragments do not appear to be a relevant stressor for stress tolerant freshwater gastropods considering current environmental levels of microplastics. KW - Lymnaea stagnalis KW - Microplastic-induced effects KW - Mixture toxicity PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-513551 DO - https://doi.org/10.1016/j.chemosphere.2020.128040 VL - 263 SP - 128040 PB - Elsevier Ltd. AN - OPUS4-51355 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weber, K. A1 - Weber, M. A1 - Menneken, M. A1 - Kral, A. G. A1 - Mertz-Kraus, R. A1 - Geisler, T. A1 - Vogl, Jochen A1 - Tütken, T. T1 - Diagenetic stability of non-traditional stable isotope systems (Ca, Sr, Mg, Zn) in teeth – An in-vitro alteration experiment of biogenic apatite in isotopically enriched tracer solution N2 - Stable isotope ratios and trace element concentrations of fossil bones and teeth are important geochemical proxies for the reconstruction of diet and past environment in archaeology and palaeontology. However, since diagenesis can significantly alter primary diet-related isotope signatures and elemental compositions, it is important to understand and quantify alteration processes. Here, we present the results of in-vitro Alteration experiments of dental tissues from a modern African elephant molar reacted in aqueous solutions at 30 °C and 90 °C for 4 to 63 days. Dental cubes with ≈ 3 mm edge length, comprising both enamel and dentin, were placed into 2 mL of acidic aqueous solution enriched in different isotopes (25Mg, 44Ca, 67Zn, 86Sr, initial pH 1). Element and isotope distribution profiles across the reacted cubes were measured with LA-(MC-)ICP-MS and EMPA, while potential effects on the bioapatite crystal structure were characterised by Raman spectroscopy. In all experiments isotope ratios measured by LA-(MC-)ICP-MS revealed an alteration of the enamel in the outer ≈ 200–300 μm. In contrast, dentin was fully altered (≈ 1.4 mm) after one week at 90 °C while the alteration did not exceed a depth of 150–200 μm during the 30 °C experiments. Then, the tracer solution started also to penetrate through the enamel-dentin junction into the innermost enamel, however, leaving the central part of the enamel unaltered, even after three months. The Raman spectra suggest an initial demineralisation in the acidic environment while organic matter (i.e. collagen) is still preserved. In the 90 °C experiment, Raman spectra of the v1 PO4) band of the dentin shift over time towards synthetic hydroxylapatite patterns and the Ca (and Sr) concentrations in the respective solutions decrease. This indicates precipitation of newly formed apatite. Isotope and element concentration profiles across the dental tissues reveal different exchange mechanisms for different isotope systems. Magnesium is leached from enamel and dentin, while Zn is incorporated into the apatite crystal structure. However, the distribution of both elements is not affected in the innermost enamel where their concentrations do not change over the whole duration of the experiments. We found no correlation of reaction depth in the cubes and experimental duration, which might be caused by natural variability of the dental material already at the beginning of the experiment. Our alteration experiments in a closed system at high temperatures ≤90 °C and low initial pH demonstrate that at least the central part of mm-thick mammalian enamel apatite seems to be resistant against alteration preserving its pristine bioapatite mineral structure as well as its in-vivo elemental and isotopic composition. The experiments assess diagenetic alteration in a novel multi-proxy approach using in-situ analyses in high spatial resolution. It is demonstrated that the isotopes of Ca, Sr, Zn and Mg in the dentin are prone for diagenetic alteration, while enamel is more resistant against alteration and could be used for dietary and physiological reconstructions in fossil teeth. KW - Bioapatite KW - Isotopes KW - Raman spectroscopy KW - Diagenesis KW - LA-(MC-)ICP-MS KW - EPMA PY - 2021 DO - https://doi.org/10.1016/j.chemgeo.2021.120196 VL - 572 SP - 120196 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-52447 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - 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 - 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 - JOUR A1 - Xiao, J. A1 - Vogl, Jochen A1 - Rosner, M. A1 - Jin, Z. T1 - Boron isotope fractionation in soil-plant systems and its influence on biogeochemical cycling N2 - Boron (B) is an essential mineral nutrient for higher plants. Although B plant nutrition is well studied, the B isotope fractionation at the soil-plant interface, within plant metabolism, and its influence on biogeochemical cycling is not fully understood. Boron concentrations and isotope variations (δ11B) of the dicotyledonous plants of Chenopodium album and Brassica napus and their growing soils along a climatic gradient were analyzed to decipher these unresolved issues of the B behavior. The boron concentrations and δ11B values show an increasing trend from roots to leaves for both plants, while a decreasing trend from flower to shell and to seed for Brassica napus. A large boron isotope fractionation occurs within the plants with median Δ11Bleaf-root ≈ +20‰, which is related to different boron transporters and transportation ways. Formation of borate dimerized rhamnogalacturonan II in cell and B(OH)3 transportation in xylem lead to heavier δ11B values from root to stem and leaf while B(OH)4􀀀 transportation in phloem lead to lighter δ11B values from flower to shell and seed. Although samples cover a distinct transect with systematically different climatic conditions, Δδ11B within the individual plant compartments and between the bulk plants and the soil available B do not show any systematic variation. This suggests that B uptake from the soil into Chenopodium album and Brassica napus occurs without a distinct isotope fractionation at the soil-plant interface (median Δ11Bbulkplant-soil = 􀀀 0.2‰) and plants are able to regulate boron uptake. Both the observed large B fractionation within plant and low or absent B isotope fractionation at the soil-plant interface may have profound implications for the biological and geological B cycle. If this observed boron behavior also exists in other plants, their litters would be an important source for exporting 11B-rich biological material from continental ecosystems via rivers to the global oceans. This may be helpful for the explanation of ocean B cycle and the increasing δ11B values over the Cenozoic. KW - Boron isotopic composition KW - Boron isotope fractionation KW - Soil available boron KW - Biological boron recycling KW - Chenopodium album KW - Brassica napus PY - 2022 DO - https://doi.org/10.1016/j.chemgeo.2022.120972 SN - 0009-2541 VL - 606 SP - 1 EP - 8 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-55031 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yang, L. A1 - Vogl, Jochen A1 - Mann, J. A1 - Kraft, R. A1 - Vocke, R. A1 - Pramann, A. A1 - Eberhardt, J. A1 - Rienitz, O. A1 - Lee, K.-S. A1 - Lim, J. S. A1 - Sobina, E. A1 - Song, P. A1 - Wang, J. A1 - Mester, Z. A1 - Meija, J. T1 - Copper isotope delta measurements in high purity materials: CCQM-P213 pilot study N2 - Accurate and precise isotope ratio measurements of heavy elements are playing an increasinglyimportant role in modern analytical sciences and have numerous applications. Today, isotope ratio measurements are typically performed with two principal techniques: thermal ionization mass spectrometry (TIMS) and multiple collector-inductively coupled plasma mass spectrometry (MC-ICP-MS). To obtain accurate results by mass spectrometry, isotopic certified reference materials (iCRMs) are needed for mass bias correction and for the validation of the method used for analysis.Thus, it is of paramount importance to achieve measurement comparability of all data reported, and to assess measurement capability of each CRM producer/National Metrology Institute (NMI). Therefore, the international comparison (CCQM-P213) was performed to assess the analytical capabilities of NMIs for the accurate determination of copper isotope ratio delta values in high purity materials. The study was proposed by the coordinating laboratories, National Research Council Canada (NRC), National Institute of Standards and Technology (NIST), Bundesanstalt für Materialforschung und -prüfung (BAM) and Physikalisch-Technische Bundesanstalt (PTB), as an activity of the Isotope Ratio Working Group (IRWG) of the Consultative Committee for Amount of Substance - Metrology in Chemistry and Biology (CCQM). Participants included six NMIs and one designated institute (DI) from the six countries. Although no measurement method was prescribed by the coordinating laboratories, MC-ICP-MS with either standard-sample bracketing (SSB) or combined SSB with internal normalization (C-SSBIN) models for mass bias correction were recommended. Results obtained from the six NMIs and one DI were in good agreement. KW - Comparability KW - Traceability KW - Metrology KW - Isotope delta KW - Copper PY - 2023 DO - https://doi.org/10.1088/0026-1394/60/1A/08019 VL - 60 IS - 1A SP - 1 EP - 23 PB - IOP Science AN - OPUS4-58040 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - You, Zengchao A1 - Winckelmann, Alexander A1 - Vogl, Jochen A1 - Recknagel, Sebastian A1 - Abad Andrade, Carlos Enrique T1 - Determination of calcium, iron, and selenium in human serum by isotope dilution analysis using nitrogen microwave inductively coupled atmospheric pressure plasma mass spectrometry (MICAP-MS) N2 - In this study, we demonstrate the applicability of nitrogen microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) for Ca, Fe, and Se quantification in human serum using isotope dilution (ID) analysis. The matrix tolerance of MICAP-MS in Na matrix was investigated, uncovering that high Na levels can suppress the signal intensity. This suppression is likely due to the plasma loading and the space charge effect. Moreover, 40Ca and 44Ca isotopic fractionation was noted at elevated Na concentration. Nine certified serum samples were analyzed using both external calibration and ID analysis. Overestimation of Cr, Zn, As, and Se was found in the results of external calibration, which might be resulted from C-induced polyatomic interference and signal enhancement, respectively. Further investigations performed with methanol showed a similar enhancement effect for Zn, As, and Se, potentially supporting this assumption. The mass concentrations determined with ID analysis show metrological compatibility with the reference values, indicating that MICAP-MS combined with ID analysis can be a promising method for precise Ca, Fe, and Se determination. Moreover, this combination reduces the influences of matrix effects, broadening the applicability of MICAP-MS for samples with complex matrix. KW - Selenium KW - Nitrogen microwave inductively coupled atmospheric pressure mass spectrometry KW - Isotope dilution KW - Human serum KW - Calcium KW - Iron PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598664 DO - https://doi.org/10.1007/s00216-024-05274-0 SN - 1618-2642 SP - 3117 EP - 3125 PB - Springer CY - Berlin AN - OPUS4-59866 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zimmermann, T. A1 - von der Au, Marcus A1 - Reese, A. A1 - Klein, O. A1 - Hildebrandt, L. A1 - Pröfrock, D. T1 - Substituting HF by HBF4 – an optimized digestion method for multi-elemental sediment analysis via ICP-MS/MS N2 - Determination of elemental mass fractions in sediments plays a major role in evaluating the environmental status of aquatic ecosystems. Herewith, the optimization of a new total digestion protocol and the subsequent analysis of 48 elements in different sediment reference materials (NIST SRM 2702, GBW 07313, GBW 07311 and JMC-2) based on ICP-MS/MS detection is presented. The developed method applies microwave acid digestion and utilizes HBF4 as fluoride source for silicate decomposition. Similar to established protocols based on HF, HBF4 ensures the dissolution of the silicate matrix, as well as other refractory oxides. As HBF4 is not acutely toxic; no special precautions have to be made and digests can be directly measured via ICP-MS without specific sample inlet systems, evaporation steps or the addition of e.g. H3BO3, in order to mask excess HF. Different acid mixtures with and without HBF4 were evaluated in terms of digestion efficiency based on the trace metal recovery. The optimized protocol (5 mL HNO3, 2 mL HCL, 1 mL HBF4) allows a complete dissolution of the analyzed reference materials, as well as quantitative recoveries for a wide variety of certified analytes. Low recoveries for e.g. Sr, Ba and rare earth elements due to fluoride precipitation of HF-based digestions protocols, can be avoided by the usage of HBF4 instead. Based on the usage of high purity HBF4 all relevant trace, as well as matrix elements can be analyzed with sufficiently low LOQs (0.002 μg L−1 for U up to 6.7 μg L−1 for Al). In total, 34 elements were within a recovery range of 80%–120% for all three analyzed reference materials GBW 07313, GBW 07311 and JMC-2. 14 elements were outside a recovery range of 80%–120% for at least one of the analyzed reference materials. KW - Reference Materials KW - Sediment KW - HF free Digestion PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-510480 DO - https://doi.org/10.1039/D0AY01049A SP - 1 EP - 10 PB - Royal Society of Chemistry AN - OPUS4-51048 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zweigle, J. A1 - Capitain, C. A1 - Simon, Fabian Michael A1 - Roesch, Philipp A1 - Bugsel, B. A1 - Zwiener, C. T1 - Non-extractable PFAS in functional textiles − Characterization by complementary methods: oxidation, hydrolysis, and fluorine sum parameters N2 - Per- and polyfluoroalkyl substances (PFAS) are widely used for durable water-repellent finishing of different fabrics and textiles like outdoor clothing, carpets, medical textiles and more. Existing PFAS extraction techniques followed by target analysis are often insufficient in detecting widely used side-chain fluorinated polymers (SFPs) that are barely or non-extractable. SFPs are typically copolymers consisting of a non-fluorinated backbone with perfluoroalkyl side-chains to obtain desired properties. We compared the accessible analytical information and performance of complementary techniques based on oxidation (dTOP assay, PhotoTOP), hydrolysis (THP assay), standard extraction, extractable organic fluorine (EOF), and total fluorine (TF) with five functional textiles and characterized 7 further textiles only by PhotoTOP oxidation. The results show that when applied directly to textile samples, oxidation by dTOP and PhotoTOP and also hydrolysis by the THP are able to capture large fractions of the TF in form of perfluoroalkyl side-chains present in the textiles while methods relying on extracts (EOF, target and non-target analysis) were much lower (e.g., factor ~25-50 lower). The conversion of large fractions of the measured TF into PFCAs or FTOHs from fluorinated side chains is in contrast to previous studies. Concentrations ranged from