TY - CONF A1 - Weber, K. T1 - Diagenetic stability of Ca, Mg, Zn and Sr isotopes in teeth 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 in vivo incorporated isotope signatures and elemental compositions, it is important to understand alteration processes. Here, we present the results of in vitro alteration experiments of dental tissues from a modern African elephant molar in aqueous solutions at 30 °C and 90 °C for 4 to 63 days each. Dental cubes with ≈3 mm edge length, comprising both enamel and dentin, were placed into 2 ml of an acidic (HNO3) aqueous solution (pH ≈1) enriched with different isotopes (25Mg, 44Ca, 67Zn, 86Sr). Element and isotope distribution profiles across the different dental cubes were measured with LA-(MC-)ICP-MS and EMPA, while potential changes of the bioapatite crystal structure were characterised by Raman spectroscopy. Isotope ratios measured by LA-(MC-)ICP-MS revealed an alteration of the outer ≈200-300 μm of the enamel in all experiments. Dentin was fully altered after one week (at 90 °C) and the tracer solution started to penetrate through the dentin even into the innermost enamel. However, the central part of the enamel remained unaltered. The Raman spectra suggest a strong recrystallization in the dentin and in the outer ≈40 μm of the enamel and a partial demineralisation of the outer rim of the cubes. Our results indicate that independent of time, temperature or low initial pH, enamel apatite shows a high resistance against the experimental alteration in structure and isotopic composition, in contrast to dentin apatite. T2 - Goldschmidt Conference CY - Online meeting DA - 21.06.2020 KW - Isotope ratio KW - Diagenesis KW - Alteration KW - Bio-apatite PY - 2020 AN - OPUS4-51499 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rienitz, O. A1 - Pramann, A. A1 - Vogl, Jochen A1 - Lee, K.-S. A1 - Yim, Y.-H. A1 - Malinovskiy, D. A1 - Hill, S. A1 - Dunn, P. A1 - Goenaga-Infante, H. A1 - Ren, T. A1 - Wang, J. A1 - Vocke jr., R. D. A1 - Rabb, S: A. A1 - Narukawa, T. A1 - Yang, L. A1 - Mester, Z. A1 - Meija, J. A1 - Aref'ev, D. G. A1 - Marchin, V. A1 - Sharin, A. G. A1 - Bulanov, A. D. A1 - Potapov, A. M. A1 - Otopkova, P. A. A1 - Kessel, R. T1 - The comparability of the determination of the molar mass of silicon highly enriched in 28Si: results of the CCQM-P160 interlaboratory comparison and additional external measurements N2 - An international comparison study on the accurate determination of the molar mass M(Si) of silicon artificially enriched in 28Si (x(28Si) > 0.9999 mol mol−1) has been completed. The measurements were part of the high level CCQM-P160 pilot study assessing the ability of National Metrology Institutes (NMIs) and Designated Institutes (DIs) to make such measurements at the lowest possible levels of measurement uncertainty and to identify possible difficulties when measuring this kind of sample. This study supports the molar mass measurements critical to disseminating the silicon route to realizing the new definitions for the kilogram and the mole. Measurements were also made by one external research institute and an external company. The different institutes were free to choose their experimental (mass spectrometric) set-ups and equipment, thereby enabling also the comparison of different techniques. The investigated material was a chemically pure, polycrystalline silicon material. The subsequent modified single crystalline secondary product of this material was intended for the production of silicon which was used for two additional spheres in the context of the redetermination of the Avogadro constant NA, required for the revision of the International System of Units (SI) via fundamental constants which came into force from May 2019. The CCQM pilot study was organized by Physikalisch-Technische Bundesanstalt (PTB). Aqueous silicon solutions were shipped to all participating institutions. The data analysis as well as the uncertainty modelling and calculation of the results was predefined. The participants were provided with an uncertainty budget as a GUM Workbench® file as well as a free software license for the duration of the comparison. The agreement of the values of the molar mass (M(Si) = 27.976 942 577 g mol−1) was excellent with ten out of 11 results reported within the range of relative uncertainty of 1 × 10−8 required for the revision of the SI. KW - Absolute isotope ratio KW - Molar mass KW - Avogadro constant KW - Revision of the SI PY - 2020 DO - https://doi.org/10.1088/1681-7575/abbdbf VL - 57 IS - 6 SP - 065028 PB - IOP Science CY - Cambridge AN - OPUS4-51500 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gehrenkemper, Lennart A1 - Simon, Fabian A1 - Roesch, Philipp A1 - Fischer, E. A1 - von der Au, Marcus A1 - Pfeifer, Jens A1 - Cossmer, Antje A1 - Wittwer, Philipp A1 - Vogel, Christian A1 - Simon, Franz-Georg A1 - Meermann, Björn T1 - Determination of organically bound fluorine sum parameters in river water samples - Comparison of combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) N2 - In this study, we compare combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) with respect to their applicability for determining organically Bound fluorine sum parameters. Extractable (EOF) and adsorbable (AOF) organically bound fluorine as well as total fluorine (TF) were measured in samples fromriver Spree in Berlin, Germany, to reveal the advantages and disadvantages of the two techniques used as well as the two established fluorine sum Parameters AOF and EOF. TF concentrations determined via HR-CS-GFMAS and CIC were comparable between 148 and 270 μg/L. On average, AOF concentrations were higher than EOF concentrations, with AOF making up 0.14–0.81% of TF (determined using CIC) and EOF 0.04–0.28% of TF (determined using HR-CSGFMAS). The results obtained by the two independent methods were in good agreement. It turned out that HR-CS-GFMAS is a more sensitive and precise method for fluorine analysis compared to CIC. EOF and AOF are comparable tools in Risk evaluation for the emerging pollutants per- and polyfluorinated alkyl substances; however, EOF is much faster to conduct. KW - High resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) KW - Combustion ion chromatography (CIC) KW - Per- and polyfluorinated alkyl substances (PFASs) KW - Adsorbable organically bound fluorine (AOF) KW - Extractable organically bound fluorine (EOF) KW - Surface waters PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-515351 DO - https://doi.org/10.1007/s00216-020-03010-y SN - 1618-2650 VL - 413 IS - 28 SP - 103 EP - 115 PB - Springer CY - Berlin AN - OPUS4-51535 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gaft, M. A1 - Nagli, L. A1 - Gornushkin, Igor B. A1 - Raichlin, Y. T1 - Review on recent advances in analytical applications of molecular emission and modelling N2 - The review mainly deals with two topics that became important in applications of laser-induced breakdown spectroscopy (LIBS) in recent years: the emission of halogen- and rare-earth-containing molecules and selective excitation of molecules by molecular laser-induced fluorescence (MLIF). The first topic is related to the emission of alkaline-earth diatomic halides MX, M = Ca, Mg, Ba, Sr and X = F, Cl, Br, and I and rare-earth element (REE) oxides LaO, YO, and ScO. These molecules form in laser-induced plasma (LIP) soon after its ignition and persist for a long time, emitting broad bands in a visible part of the spectrum. They are best detected after relatively long delay times when emission from interfering plasma species (atoms and ions) has already been quenched. Such behavior of molecular spectra allows of using, for their detection, inexpensive CCD detectors equipped with simple electronic or mechanical shutters and low-resolution spectrometers. A main target for analysis by molecular spectroscopy is halogens; these elements are difficult to detect by atomic spectroscopy because their most intense atomic lines lie in the vacuum UV. Therefore, in many situations, emission from CaF and CaCl may provide a substantially more sensitive detection of F and Cl than emission from elemental F and Cl and their ions. This proved to be important in mining and concrete industries and even Mars exploration. A similar situation is observed for REEs; their detection by atomic spectroscopy sometimes fails even despite the abundance of atomic and ionic REEs' lines in the UV-VIS. For example, in minerals and rocks with low concentrations of REEs, emission from major and minor mineral elements hinders the weak emission from REEs. Many REEs do not form molecules that show strong emission bands in LIP but can still be detected with the aid of LIP. All REEs except La, Y, and Sc exhibit long-lived luminescence in solid matrices that is easily excited by LIP. The luminescence can be detected simultaneously with molecular emission of species in LIP within the same time and spectral window. The second topic is related to the combination of MLIF and LIBS, which is a technique that was proved to be efficient for analysis of isotopic molecules in LIP. For example, the characteristic spectral signals from isotopic molecules containing 10B and 11B are easier to detect with MLIF-LIBS than with laser ablation molecular isotopic spectrometry (LAMIS) because MLIF provides strong resonance excitation of only targeted isotopes. The technique is also very efficient in detection of halogen molecules although it requires an additional tunable laser that makes the experimental setup bulky and more expensive. KW - Plasma induced luminescence KW - Molecular emission KW - Laser induced plasma KW - Plasma modeling KW - Molecular analysis KW - LIBS PY - 2020 DO - https://doi.org/10.1016/j.sab.2020.105989 VL - 173 SP - 105989 PB - Elsevier B. V. AN - OPUS4-51420 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 - CONF A1 - Faßbender, Sebastian T1 - On-line Species-specific Isotopic Analysis of Sulfur by Hyphenation of Capillary Electrophoresis with Multicollector-ICP-MS N2 - In many scientific fields, isotopic analysis can offer valuable information. Up to date, typically bulk analysis is aimed at measuring the isotopic composition of the entire elemental content of the sample. However, the analyte element is usually present under the form of different species. Thus, separating species of interest from one another and from matrix components prior to isotope ratio measurements can provide species-specific isotopic information, which could be used for tracing the origin of environmental pollutants and elucidation of (environmental) speciation. Using on-line hyphenations of separation techniques with multicollector-ICP-MS (MC-ICP-MS) can save time and effort and enables the analysis of different species during a single measurement. Whereas some works hyphenating GC and IC with MC-ICP-MS have already been reported, LC and CE hyphenations are still inadequately represented based on the capabilities of these separation techniques. In this work, we developed an on-line hyphenation of CE with multicollector-ICP-MS (CE/MC-ICP-MS) for isotopic analysis of sulfur species using a multiple-injection approach for instrumental mass bias correction by standard-sample bracketing. With this method, the isotopic composition of sulfur in sulfate originating from river water could be analyzed without sample preparation. The results were compared to data from off-line analysis of the same samples for validation. The repeatability of the results of the on-line measurements was promising regarding the differentiation of the river systems by the isotopic signature of river water sulfate. The great potential of this method is based on the versatility of the applied separation technique, not only in the environmental field but also for, e.g., biomolecules because sulfur is the only covalently bound constituent of proteins that can be analyzed by MC-ICP-MS. T2 - SciX 2020 CY - Online meeting DA - 12.10.2020 KW - Capillary electrophoresis KW - Hyphenated techniques KW - Isotopic analysis KW - Speciation analysis PY - 2020 AN - OPUS4-51402 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Dittmann, Daniel T1 - Aktivkohlecharakterisierung von GAK-Filtern bei unterschiedlichen Laufzeiten N2 - Eine umfangreich ausgestaltete Trinkwasseraufbereitung als Multibarrieren-System ist notwendig, wenn das Rohwasser direkt aus Fließgewässern entnommen wird (z. B. für das Mülheimer Verfahren). Eine der Barrieren wird, als gezielte Behandlungs- oder Sicherheitsstufe, oft als Filter mit granulierter Aktivkohle (GAK-Filter) realisiert. Ihre Standzeit kann bei geringer Wasserbelastung (DOC < 2 mg/L), z. B. bei der Landeswasserversorgung Langenau, bis zu 5 Jahre betragen. Bei Rohwasser mit höherem Organikgehalt (DOC > 7 mg/L), wie bei der Nordwasser in Rostock, wird hingegen mindestens alle drei Jahre die GAK in den Filterkolonnen ausgetauscht. Die Rest-Adsorptionskapazität der GAK kann durch verschiedene Verfahren abgeschätzt werden, ist aber nach wie vor Gegenstand aktueller Forschung. Die weitergehende Charakterisierung der beladenen GAK kann hierbei helfen. Auf dem Poster sollen erste Ergebnisse zu den in Langenau und Rostock eingesetzten Aktivkohlen präsentiert werden. Hierzu wurden die frischen und nach unterschiedlichen Laufzeiten beladenen GAK untersucht. Die Zusammensetzung der Anorganik und der adsorbierten Organik, welche mittels Zersetzungs¬gasanalyse charakterisiert wurde, zeigt deutliche Unterschiede. Bspw. nimmt der Calcium-Gehalt der GAK in Langenau kontinuierlich zu, wohingegen dieser in den Proben aus Rostock mit zunehmender Laufzeit zurückgeht. Umgekehrt verhält es sich mit der Organik: Die GAK aus Rostock zeigen Hinweise auf biologische Besiedelung, während diese in Langenau trotz längerer Filterlaufzeit auszubleiben scheint. T2 - 4. Mülheimer Wasseranalytisches Seminar (MWAS2020) CY - Mülheim an der Ruhr, Germany DA - 16.09.2020 KW - Thermogravimetrie KW - Trinkwasser KW - Wasseraufbereitung KW - Aktivkohle PY - 2020 AN - OPUS4-51433 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dittmann, Daniel A1 - Lucke, T. A1 - Ruhl, A. S. A1 - Winzenbacher, R. A1 - Jekel, M. A1 - Braun, Ulrike T1 - Untersuchungen zu biologischen, organischen und anorganischen Veränderungen granulierter Aktivkohlen während der Trinkwasseraufbereitung N2 - Untersuchungen zu biologischen, organischen und anorganischen Veränderungen granulierter Aktivkohlen während der Trinkwasseraufbereitung des Landeswasserversorgers Langenau. KW - Thermogravimetrie KW - Trinkwasser KW - Wasseraufbereitung KW - Aktivkohle PY - 2020 SN - 0083-6915 VL - 118 IS - 2 SP - 47 EP - 50 PB - Wiley-VCH Verlag GmbH & Co. KGaA AN - OPUS4-51434 LA - deu 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 - Liaskos, C. A1 - Rhoderick, G. A1 - Hodges, J. A1 - Possolo, A. A1 - Wilke, Olaf T1 - Pilot comparison CCQM-P177 - monoterpenes in nitrogen at 2.5 nmol/mol - final report N2 - Growing awareness of the impact of monoterpenes on climate, atmospheric chemistry, and indoor air quality has necessitated the development of measurement standards to globally monitor and control their emissions. For National Metrology Institutes to develop such standards, it is essential that they demonstrate measurement equivalence for assigned values at the highest levels of accuracy. This report describes the results of a pilot comparison for 4 key monoterpene species: α-pinene, 3-carene, R-limonene and 1,8-cineole, at a nominal amount-of-substance fraction of 2.5 nmol mol-1. The objective of this comparison is to evaluate participant capabilities to measure trace-level monoterpenes using their own calibration techniques. KW - Pilot comparison KW - CCQM KW - Monoterpene KW - Accuracy PY - 2020 DO - https://doi.org/10.1088/0026-1394/57/1A/08018 SN - 0026-1394 SN - 1681-7575 VL - 57 IS - 1A SP - 08018-1 EP - 08018-21 PB - IOP Science AN - OPUS4-51111 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -