TY - JOUR A1 - Brauckmann, C. A1 - Pramann, A. A1 - Rienitz, O. A1 - Schulze, A. A1 - Phukphatthanachai, Pranee A1 - Vogl, Jochen T1 - Combining Isotope Dilution and Standard Addition—Elemental Analysis in Complex Samples N2 - A new method combining isotope dilution mass spectrometry (IDMS) and standard addition has been developed to determine the mass fractions w of different elements in complex matrices: (a) silicon in aqueous tetramethylammonium hydroxide (TMAH), (b) sulfur in biodiesel fuel, and (c) iron bound to transferrin in human serum. All measurements were carried out using inductively coupled plasma mass spectrometry (ICP–MS). The method requires the gravimetric preparation of several blends (bi)—each consisting of roughly the same masses (mx,i) of the sample solution (x) and my,i of a spike solution (y) plus different masses (mz,i) of a reference solution (z). Only these masses and the isotope ratios (Rb,i) in the blends and reference and spike solutions have to be measured. The derivation of the underlying equations based on linear regression is presented and compared to a related concept reported by Pagliano and Meija. The uncertainties achievable, e.g., in the case of the Si blank in extremely pure TMAH of urel (w(Si)) = 90% (linear regression method, this work) and urel (w(Si)) = 150% (the method reported by Pagliano and Meija) seem to suggest better applicability of the new method in practical use due to the higher robustness of regression analysis. KW - Isotope dilution mass spectrometry KW - tandard addition KW - ICP-MS KW - lank characterization KW - Silicon KW - Sulfur KW - Transferrin KW - Tetramethylammonium hydroxide KW - Biodiesel fuel KW - Human serum PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-526376 DO - https://doi.org/10.3390/molecules26092649 VL - 26 IS - 9 SP - 2649 PB - MDPI CY - Basel AN - OPUS4-52637 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wiesner, Yosri A1 - Altmann, Korinna A1 - Braun, U. T1 - Determination of Microplastic Mass Content by Thermal Extraction Desorption Gas Chromatography– Mass Spectrometry N2 - The scientific and practical challenge of detecting microplastics (MPs) in the environment in a targeted and rapid manner is solved by innovative coupling of thermogravimetric analysis with mass spectrometric methods. Fast identification and quantitative determination of most thermoplastic polymers and elastomers is possible by using thermal extraction Desorption gas chromatography–mass spectrometry (TED-GC–MS). KW - Microplastics KW - Mikroplastik KW - TED-GC/MS KW - Microplastics analytic KW - Mikroplastik Massegehalt PY - 2021 VL - 17 IS - 3 SP - 2 EP - 7 PB - MultiMedia (UK) LLC CY - Cranbury AN - OPUS4-52570 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Faßbender, Sebastian A1 - von der Au, Marcus A1 - Koenig, Maren A1 - Pelzer, J. A1 - Piechotta, Christian A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Species-specific isotope dilution analysis of monomethylmercury in sediment using GC/ICP-ToF-MS and comparison with ICP-Q-MS and ICP-SF-MS N2 - A recently introduced inductively coupled plasma-time-of-flight-mass spectrometer (ICP-ToF-MS) shows enhanced sensitivity compared to previous developments and superior isotope ratio precision compared to other ToF and commonly used single-collector ICP-MS instruments. Following this fact, an improvement for isotope dilution ICP-MS using the new instrumentation has been reported. This study aimed at investigating whether this improvement also meets the requirements of species-specific isotope dilution using GC/ICP-MS, where short transient signals are recorded. The results of the analysis of monomethylmercury (MMHg) of a sediment reference material show that isotope ratio precision of ICP-MS instruments equipped with quadrupole, sector-field, and time-of-flight mass analyzers is similar within a broad range of peak signal-to-noise ratio when analyzing one isotopic system. The procedural limit of quantification (LOQ) for MMHg, expressed as mass fraction of Hg being present as MMHg, w(Hg)MMHg, was similar as well for all investigated instruments and ranged between 0.003 and 0.016 μg/kg. Due to the simultaneous detection capability, the ICP-ToF-MS might, however, be more favorable when several isotopic systems are analyzed within one measurement. In a case study, the GC/ICP-ToF-MS coupling was applied for analysis of MMHg in sediments of Finow Canal, a historic German canal heavily polluted with mercury. Mass fractions between 0.180 and 41 μg/kg (w(Hg)MMHg) for MMHg, and 0.056 and 126 mg/kg (w(Hg)total) for total mercury were found in sediment samples taken from the canal upstream and downstream of a former chemical plant. KW - Methylmercury KW - Legacy pollution KW - Finow Canal KW - Isotope dilution KW - Mercury speciation PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-529967 DO - https://doi.org/10.1007/s00216-021-03497-z SN - 1618-2642 VL - 413 IS - 21 SP - 5279 EP - 5289 PB - Springer CY - Berlin AN - OPUS4-52996 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Backes, A. T. A1 - Reinmuth-Selzle, K. A1 - Leifke, A. L. A1 - Ziegler, K. A1 - Krevert, C. S. A1 - Tscheuschner, Georg A1 - Lucas, K. A1 - Weller, Michael G. A1 - Berkemeier, T. A1 - Pöschl, U. A1 - Fröhlich-Nowoisky, J. T1 - Oligomerization and Nitration of the Grass Pollen Allergen Phl p 5 by Ozone, Nitrogen Dioxide, and Peroxynitrite: Reaction Products, Kinetics, and Health Effects N2 - The allergenic and inflammatory potential of proteins can be enhanced by chemical modification upon exposure to atmospheric or physiological oxidants. The molecular mechanisms and kinetics of such modifications, however, have not yet been fully resolved. We investigated the oligomerization and nitration of the grass pollen allergen Phl p 5 by ozone (O3), nitrogen dioxide (NO2), and peroxynitrite (ONOO–). Within several hours of exposure to atmospherically relevant concentration levels of O3 and NO2, up to 50% of Phl p 5 were converted into protein oligomers, likely by formation of dityrosine cross-links. Assuming that tyrosine residues are the preferential site of nitration, up to 10% of the 12 tyrosine residues per protein monomer were nitrated. For the reaction with peroxynitrite, the largest oligomer mass fractions (up to 50%) were found for equimolar concentrations of peroxynitrite over tyrosine residues. With excess peroxynitrite, the nitration degrees increased up to 40% whereas the oligomer mass fractions decreased to 20%. Our results suggest that protein oligomerization and nitration are competing processes, which is consistent with a two-step mechanism involving a reactive oxygen intermediate (ROI), as observed for other proteins. The modified proteins can promote pro-inflammatory cellular signaling that may contribute to chronic inflammation and allergies in response to air pollution. KW - Protein KW - Nitrotyrosine KW - Dityrosine KW - Allergy KW - Hay fever KW - Diesel exhaust KW - Combustion KW - Exhaust PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-529729 DO - https://doi.org/10.3390/ijms22147616 VL - 22 IS - 14 PB - MDPI CY - Basel AN - OPUS4-52972 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Haeckel, A. A1 - Ascher, Lena A1 - Beindorff, N. A1 - Prasad, S. A1 - Garczynska, K. A1 - Guo, J. A1 - Schellenberger, E. T1 - Long‑circulating XTEN864‑annexin A5 fusion protein for phosphatidylserine‑related therapeutic applications N2 - Annexin A5 (anxA5) is a marker for apoptosis, but has also therapeutic potential in cardiovascular diseases, cancer, and, due to apoptotic mimicry, against dangerous viruses, which is limited by the short blood circulation. An 864-amino-acid XTEN polypeptide was fused to anxA5. XTEN864-anxA5 was expressed in Escherichia coli and purified using XTEN as tag. XTEN864-anxA5 was coupled with DTPA and indium-111. After intravenous or subcutaneous injection of 111In-XTEN864-anxA5, mouse blood samples were collected for blood half-life determination and organ samples for biodistribution using a gamma counter. XTEN864-anxA5 was labeled with 6S-IDCC to confirm binding to apoptotic cells using flow cytometry. To demonstrate targeting of atherosclerotic plaques, XTEN864-anxA5 was labeled with MeCAT(Ho) and administered intravenously to atherosclerotic ApoE−/−mice. MeCAT(Ho)-XTEN864-anxA5 was detected together with MeCAT(Tm)-MAC-2 macrophage antibodies by imaging mass cytometry (CyTOF) of aortic root sections. The ability of anxA5 to bind apoptotic cells was not affected by XTEN864. The blood half-life of XTEN864-anxA5 was 13 h in mice after IV injection, markedly longer than the 7-min half-life of anxA5. 96 h after injection, highest amounts of XTEN864-anxA5 were found in liver, spleen, and kidney. XTEN864-anxA5 was found to target the adventitia adjacent to atherosclerotic plaques. XTEN864-anxA5 is a long-circulating fusion protein that can be efficiently produced in E. coli and potentially circulates in humans for several days, making it a promising therapeutic drug. KW - Programmed cell death KW - LA/ICP-MS Imaging KW - Medicinal application PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-533811 DO - https://doi.org/10.1007/s10495-021-01686-w VL - 26 IS - 9-10 SP - 534 EP - 547 PB - Springer AN - OPUS4-53381 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meermann, Björn T1 - The future of elemental analytical chemistry – the sixth special issue dedicated to young analytical scientists N2 - Editorial for a special issue KW - Editorial KW - Special issue, young analytical scientists KW - Elemental analysis PY - 2021 DO - https://doi.org/10.1039/d1ja90038b VL - 36 IS - 9 SP - 1794 EP - 1796 PB - RSC AN - OPUS4-53086 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ogrinc, N. A1 - Rossi, A. M. A1 - Durbiano, F. A1 - Becker, Roland A1 - Milavec, M. A1 - Bogozalec Kosir, A. A1 - Kakoulides, E. A1 - Ozer, H. A1 - Akcadag, F. A1 - Goenaga-Infante, H. A1 - Quaglia, M. A1 - Mallia, S. A1 - Umbricht, G. A1 - O'Connor, G. A1 - Guettler, B. T1 - Support for a European metrology network on food safety Food-MetNet N2 - This paper describes Food-MetNet, a coordinated preparatory initiative to establish the European Metrology Network on Food Safety (EMN-FS). Food-MetNet aims to establish a long-term ongoing dialogue between the metrology community and relevant stakeholders, in particular, European Union Reference Laboratories (EURLs), National Reference Laboratories (NRLs) and the Joint Research Centre (JRC). This dialogue is meant to support the collection of needs from stakeholders, the take-up of metrological research output and the development of the roadmaps needed to navigate future research. KW - Network KW - Metrology KW - Food KW - Safety KW - Stakeholders PY - 2021 DO - https://doi.org/10.1016/j.measen.2021.100285 VL - 18 SP - 1 EP - 4 PB - Elsevier AN - OPUS4-53740 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Becker, Roland A1 - Heyn, L. A1 - Jung, Christian T1 - Indoor exposure to airborne polycyclic aromatic hydrocarbons: A comparison of stir bar sorptive extraction and pump sampling N2 - Stir bar sorptive extraction (SBSE) was compared with standardized pump sampling regarding the prospects to assess airborne levels of polycyclic aromatic hydrocarbons (PAHs) in indoor environments. A historic railway water tower, which will be preserved as a technical monument for museum purposes, was sampled with both approaches because the built-in insulationmaterial was suspected to release PAHs to the indoor air. The 16 PAHs on the US EPA list were quantified using gas chromatography with mass spectrometric detection in filters from pump sampling after solvent extraction and on SBSE devices after thermal desorption. SBSEwas seen to sample detectable PAHmasseswith excellent repeatability and a congener pattern largely similar to that observed with pump sampling. Congener patterns were however significantly different from that in the PAH source because release from the insulation material is largely triggered by the respective congener vapor pressures. Absolute masses in the ng range sampled by SBSE corresponded to airborne concentrations in the ng L−1 range determined by pump sampling. Principle differences between SBSE and pump sampling as well as prospects of SBSE as cost-effective and versatile complement of pump sampling are discussed. KW - Polycyclic aromatic hydrocarbons KW - Adsorption KW - Extraction KW - Indoor air PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537427 DO - https://doi.org/10.1002/eng2.12419 VL - 3 IS - 12 SP - 1 EP - 10 PB - John Wiley & Sons Ltd. AN - OPUS4-53742 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ecke, Alexander A1 - Westphalen, Tanja A1 - Hornung, J. A1 - Voetz, M. A1 - Schneider, Rudolf T1 - A rapid magnetic bead-based immunoassay for sensitive determination of diclofenac N2 - Increasing contamination of environmental waters with pharmaceuticals represents an emerging threat for the drinking water quality and safety. In this regard, fast and reliable analytical methods are required to allow quick countermeasures in case of contamination. Here, we report the development of a magnetic bead-based immunoassay (MBBA) for the fast and cost-effective determination of the analgesic diclofenac (DCF) in water samples, based on diclofenac-coupled magnetic beads and a robust monoclonal anti-DCF antibody. A novel synthetic strategy for preparation of the beads resulted in an assay that enabled for the determination of diclofenac with a significantly lower limit of detection (400 ng/L) than the respective enzyme-linked immunosorbent assay (ELISA). With shorter incubation times and only one manual washing step required, the assay demands for remarkably shorter time to result (< 45 min) and less equipment than ELISA. Evaluation of assay precision and accuracy with a series of spiked water samples yielded results with low to moderate intra- and inter-assay variations and in good agreement with LC–MS/MS reference analysis. The assay principle can be transferred to other, e.g., microfluidic, formats, as well as applied to other analytes and may replace ELISA as the standard immunochemical method. KW - Immunoassay KW - Magnetic beads KW - Diclofenac KW - Water analysis KW - LC-MS/MS PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-542346 DO - https://doi.org/10.1007/s00216-021-03778-7 SN - 1618-2650 VL - 414 SP - 1563 EP - 1573 PB - Springer CY - Heidelberg AN - OPUS4-54234 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lemke, Nora A1 - El-Khatib, Ahmed H. A1 - Tchipilov, Teodor A1 - Jakubowski, N. A1 - Weller, Michael G. A1 - Vogl, Jochen T1 - Procedure providing SI‑traceable results for the calibration of protein standards by sulfur determination and its application on tau N2 - Quantitative proteomics is a growing research area and one of the most important tools in the life sciences. Well-characterized and quantified protein standards are needed to achieve accurate and reliable results. However, only a limited number of sufficiently characterized protein standards are currently available. To fill this gap, a method for traceable protein quantification using sulfur isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) was developed in this study. Gel filtration and membrane filtration were tested for the separation of non-protein-bound sulfur in the protein solution. Membrane filtration demonstrated a better performance due to the lower workload and the very low sulfur blanks of 11 ng, making it well suited for high-purity proteins such as NIST SRM 927, a bovine serum albumin (BSA). The method development was accomplished with NIST SRM 927e and a commercial avidin. The quantified mass fraction of NIST SRM 927e agreed very well with the certified value and showed similar uncertainties (3.6%) as established methods while requiring less sample preparation and no species-specific standards. Finally, the developed procedure was applied to the tau protein, which is a biomarker for a group of neurodegenerative diseases denoted “tauopathies” including, e.g., Alzheimer’s disease and frontotemporal dementia. For the absolute quantification of tau in the brain of transgenic mice overexpressing human tau, a well-defined calibration standard was needed. Therefore, a pure tau solution was quantified, yielding a protein mass fraction of (0.328 ± 0.036) g/kg, which was confirmed by amino acid analysis. KW - Iinductively coupled plasma mass spectrometry KW - Isotope dilution KW - Quantitative protein analysis KW - Sulfur KW - SI traceability PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545200 DO - https://doi.org/10.1007/s00216-022-03974-z VL - 414 SP - 4441 EP - 4455 PB - Springer Verlag AN - OPUS4-54520 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dariz, P. A1 - Wortmann, U. G. A1 - Vogl, Jochen A1 - Schmid, Thomas T1 - Beautiful Pietàs in South Tyrol (Northern Italy): local or imported works of art? N2 - The study, dedicated to Beautiful Pietàs conserved in South Tyrol (Northern Italy), aims to establish, for the first time, a connection between Austroalpine raw materials and the high-fired gypsum mortars constituting the Gothic figure groups in question. The origin and chronology of this stylistically and qualitatively differing ensemble have been subject of art historical debate for nearly a century. The discourse is dominated by three main hypotheses: itinerary of an Austrian artist versus itinerary of the work of art created in an artist’s workshop in Austria versus itinerary of the stylistic vocabulary via graphical or three-dimensional models. The comparison of the δ34S values and the 87Sr/86Sr ratios of the gypsum mortars and Austroalpine sulphate deposits (in a compilation of own reference samples and literature data) points to the exploitation of sediments in the Salzkammergut and possibly also in the evaporite district of the Eastern Calcareous Alps, thus evidencing the import of the sculptures and not the activities of local South Tyrolean or itinerant artists. Two geochronological units are distinguishable: The Pietà in the Church St. Martin in Göflan can be assigned to Upper Permian raw material, whereas the metrologically consistent sculptures in the Church of Our Lady of the Benedictine Abbey Marienberg and in the Chapel St. Ann in Mölten correlate with deposits of the Early Triassic (or the Lower-Middle Triassic transition). The medieval gypsum mortars also differ in their mineralogical characteristics, i.e. in their geologically related minor components, as in the first case, characterised by a significant proportion of primary anhydrite, natural carbonate impurities mainly consist of calcite (partly converted to lime-lump-like aggregates), whereas in the second group dolomite (or rather its hydration products after pyrometamorphic decomposition) predominates, accompanied by celestine, quartz and potassium feldspar. The Pietà in the Cathedral Maria Himmelfahrt in Bozen turned out to be made of Breitenbrunn calcareous sandstone (Leitha Mountains, Burgenland, Austria), which is why the sample is not considered in the geochemical analysis. KW - High-fired gypsum mortar KW - Sulphur isotope KW - Strontium isotope KW - Polarised light microscopy KW - Raman microspectroscopy PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545610 DO - https://doi.org/10.1186/s40494-022-00678-6 SN - 2050-7445 VL - 10 IS - 1 SP - 1 EP - 17 PB - Springer Nature AN - OPUS4-54561 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Casali, C. A1 - Feiler, Torvid A1 - Heilmann, Maria A1 - Braga, D. A1 - Emmerling, Franziska A1 - Grepioni, F. T1 - Too much water? Not enough? In situ monitoring of the mechanochemical reaction of copper salts with dicyandiamide N2 - n situ monitoring of mechanochemical reactions between dicyandiamide (DCD) and CuX2 salts (X = Cl−, NO3−), for the preparation of compounds of agrochemical interest, showed the appearance of a number of phases. It is demonstrated that milling conditions, such as the amount of water added in wet grinding and/or the milling frequency, may affect the course of the mechanochemical reactions, and drive the reaction towards the formation of different products. It has been possible to discover by in situ monitored experiments two novel crystalline forms, namely the neutral complexes [Cu(DCD)2(OH2)2(NO3)2] (2) and [Cu(DCD)2(OH2)Cl2]·H2O (4), in addition to the previously known molecular salt [Cu(DCD)2(OH2)2][NO3]2·2H2O (1, DIVWAG) and neutral complex [Cu(DCD)2(OH2)Cl2] (3, AQCYCU), for which no synthesis conditions were available. Compounds 2 and 4 were fully characterized via a combination of solid-state techniques, including X-ray diffraction, Raman spectroscopy and TGA. KW - Mechanochemistry KW - In situ PY - 2022 DO - https://doi.org/10.1039/d1ce01670a VL - 24 IS - 6 SP - 1292 EP - 1298 PB - RSC AN - OPUS4-54344 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Simon, Fabian A1 - Gehrenkemper, Lennart A1 - von der Au, Marcus A1 - Wittwer, Phillip A1 - Roesch, Philipp A1 - Pfeifer, Jens A1 - Cossmer, Antje A1 - Meermann, Björn T1 - A fast and simple PFAS extraction method utilizing HR–CS–GFMAS for soil samples N2 - Here, we describe an optimized fast and simple extraction method for the determination of per- and polyfluorinated alkyl substances (PFASs) in soils utilizing high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR–CS–GFMAS). To omit the bias of the solid phase extraction (SPE) step commonly used during the analysis of extractable organically bound fluorine (EOF) we optimized a fast and simple SPE-free extraction method. The developed extraction method consists of a liquid-solid extraction using acidified methanol without any additional SPE. Four extraction steps were representative to determine a high proportion of the EOF (>80% of eight extractions). Comparison of the optimized method with and without an additional SPE clean-up step revealed a drastic underestimation of EOF concentrations using SPE. Differences of up to 94% were observed which were not explainable by coextracted inorganic fluoride. Therefore, not only a more accurate but also a more economic as well as ecologic method (bypassing of unnecessary SPE) was developed. The procedural limit of quantification (LOQ) of the developed method was 10.30 μg/kg which was sufficient for quantifying EOF concentrations in all tested samples. For future PFAS monitoring and potential regulative decisions the herein presented optimized extraction method can offer a valuable contribution. KW - Per- and polyfluorinated alkly substances (PFASs) KW - High resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) KW - Soils KW - Solid phase extraction (SPE) KW - Extractable organically bound fluorine (EOF) KW - Solid-liquid extraction PY - 2022 DO - https://doi.org/10.1016/j.chemosphere.2022.133922 VL - 295 SP - 1 EP - 9 PB - Elsevier Ltd. AN - OPUS4-54359 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Frisch, M. A1 - Raza, M. H. A1 - Ye, M.-Y. A1 - Sachse, René A1 - Paul, B. A1 - Gunder, R. A1 - Pinna, N. A1 - Kraehnert, R. T1 - ALD-coated mesoporous iridium-titanium mixed oxides: Maximizing iridium utilization for an outstanding OER performance N2 - With the increasing production of renewable energy and concomitant depletion of fossil resources, the demand for efficient water splitting electrocatalysts continues to grow. Iridium (Ir) and iridium oxides (IrOₓ) are currently the most promising candidates for an efficient oxygen evolution reaction (OER) in acidic medium, which remains the bottleneck in water electrolysis. Yet, the extremely high costs for Ir hamper a widespread production of hydrogen (H₂) on an industrial scale. Herein, the authors report a concept for the synthesis of electrode coatings with template-controlled mesoporosity surface-modified with highly active Ir species. The improved utilization of noble metal species relies on the synthesis of soft-templated metal oxide supports and a subsequent shape-conformal deposition of Ir species via atomic layer deposition (ALD) at two different reaction temperatures. The study reveals that a minimum Ir content in the mesoporous titania-based support is mandatory to provide a sufficient electrical bulk conductivity. After ALD, a significantly enhanced OER activity results in dependency of the ALD cycle number and temperature. The most active developed electrocatalyst film achieves an outstanding mass-specific activity of 2622 mA mg(Ir)⁻¹ at 1.60 V(RHE) in a rotating-disc electrode (RDE) setup at 25 °C using 0.5 m H₂SO₄ as a supporting electrolyte. KW - Acidic oxygen evolution reaction KW - Atomic layer deposition KW - Electrocatalysis KW - Iridium oxide KW - Soft-templated mesoporous films PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-542651 DO - https://doi.org/10.1002/admi.202102035 SN - 2196-7350 SP - 1 EP - 11 PB - Wiley-VCH CY - Weinheim AN - OPUS4-54265 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 - 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 - Spallanzani, Roberta A1 - Koga, K. A1 - Cichy, S. A1 - Wiedenbeck, M. A1 - Schmidt, B. A1 - Oelze, Marcus A1 - Wilke, M. T1 - Lithium and boron difusivity and isotopic fractionation in hydrated rhyolitic melts N2 - Lithium and boron are trace components of magmas, released during exsolution of a gas phase during volcanic activity. In this study, we determine the difusivity and isotopic fractionation of Li and B in hydrous silicate melts. Two glasses were synthesized with the same rhyolitic composition (4.2 wt% water), having diferent Li and B contents; these were studied in difusion-couple experiments that were performed using an internally heated pressure vessel, operated at 300 MPa in the temperature range 700–1250 °C for durations from 0 s to 24 h. From this we determined activation energies for Li and B difusion of 57±4 kJ/mol and 152±15 kJ/mol with pre-exponential factors of 1.53 × 10–7 m2/s and 3.80× 10–8 m2 /s, respectively. Lithium isotopic fractionation during difusion gave β values between 0.15 and 0.20, whereas B showed no clear isotopic fractionation. Our Li difusivities and isotopic fractionation results difer somewhat from earlier published values, but overall confrm that Li difusivity increases with water content. Our results on B difusion show that similarly to Li, B mobility increases in the presence of water. By applying the Eyring relation, we confrm that B difusivity is limited by viscous fow in silicate melts. Our results on Li and B difusion present a new tool for understanding degassing-related processes, ofering a potential geospeedometer to measure volcanic ascent rates. KW - Hydrated silicate melts KW - Stable isotopes KW - Diffusion KW - Isotopic fractionation PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-554496 DO - https://doi.org/10.1007/s00410-022-01937-2 VL - 177 IS - 8 SP - 1 EP - 17 PB - Springer AN - OPUS4-55449 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kittner, Maria A1 - Kerndorff, A. A1 - Ricking, M. A1 - Bednarz, M. A1 - Obermaier, N. A1 - Lukas, M. A1 - Asenova, M. A1 - Bordós, G. A1 - Eisentraut, Paul A1 - Hohenblum, P. A1 - Hudcova, H. A1 - Humer, F. A1 - István, T. G. A1 - Kirchner, M. A1 - Marushevska, O. A1 - Nemejcová, D. A1 - Oswald, P. A1 - Paunovic, M. A1 - Sengl, M. A1 - Slobodnik, J. A1 - Spanowsky, K. A1 - Tudorache, M. A1 - Wagensonner, H. A1 - Liska, I. A1 - Braun, U. A1 - Bannick, C. G. T1 - Microplastics in the Danube River Basin: A First Comprehensive Screening with a Harmonized Analytical Approach N2 - In this study, carried out within the Joint Danube Survey 4, a comprehensive microplastic screening in the water column within a large European river basin from its source to estuary, including major tributaries, was realized. The objective was to develop principles of a systematic and practicable microplastic monitoring strategy using sedimentation boxes for collection of suspended particulate matter followed by its subsequent analysis using thermal extraction desorption-gas chromatography/mass spectrometry. In total, 18 sampling sites in the Danube River Basin were investigated. The obtained suspended particulate matter samples were subdivided into the fractions of >100 μm and <100 μm and subsequently analyzed for microplastic mass contents. The results showed that microplastics were detected in all samples, with polyethylene being the predominant polymer with maximum contents of 22.24 μg/mg, 3.23 μg/mg for polystyrene, 1.03 μg/mg for styrene-butadiene-rubber, and 0.45 μg/mg for polypropylene. Further, polymers such as different sorts of polyester, polyacrylates, polylactide, and natural rubber were not detected or below the detection limit. Additional investigations on possible interference of polyethylene signals by algae-derived fatty acids were assessed. In the context of targeted monitoring, repeated measurements provide more certainty in the interpretation of the results for the individual sites. Nevertheless, it can be stated that the chosen approach using an integrative sampling and determination of total plastic content proved to be successful. KW - Thermal extraction desorption-gas chromatography/mass spectrometry (TED-GC/MS), monitoring KW - Microplastics KW - River KW - Suspended particulate matter (SPM) KW - Sedimentation box (SB) PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-551444 DO - https://doi.org/10.1021/acsestwater.1c00439 VL - 2 IS - 7 SP - 1174 EP - 1181 PB - ACS Publications AN - OPUS4-55144 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Reinmuth-Selzle, K. A1 - Tchipilov, Teodor A1 - Backes, A. T. A1 - Tscheuschner, Georg A1 - Tang, K. A1 - Ziegler, K. A1 - Lucas, K. A1 - Pöschl, U. A1 - Fröhlich-Nowoisky, J. A1 - Weller, Michael G. T1 - Determination of the protein content of complex samples by aromatic amino acid analysis, liquid chromatography-UV absorbance, and colorimetry N2 - Fast and accurate determination of the protein content of a sample is an important and non-trivial task of many biochemical, biomedical, food chemical, pharmaceutical, and environmental research activities. Different methods of total protein determination are used for a wide range of proteins with highly variable properties in complex matrices. These methods usually work reasonably well for proteins under controlled conditions, but the results for non-standard and complex samples are often questionable. Here, we compare new and well-established methods, including traditional amino acid analysis (AAA), aromatic amino acid analysis (AAAA) based on the amino acids phenylalanine and tyrosine, reversed-phase liquid chromatography of intact proteins with UV absorbance measurements at 220 and 280 nm (LC-220, LC-280), and colorimetric assays like Coomassie Blue G-250 dye-binding assay (Bradford) and bicinchoninic acid (BCA) assay. We investigated different samples, including proteins with challenging properties, chemical modifications, mixtures, and complex matrices like air particulate matter and pollen extracts. All methods yielded accurate and precise results for the protein and matrix used for calibration. AAA, AAAA with fluorescence detection, and the LC-220 method yielded robust results even under more challenging conditions (variable analytes and matrices). These methods turned out to be well-suited for reliable determination of the protein content in a wide range of samples, such as air particulate matter and pollen. KW - Air particulate matter KW - Aromatic amino acid analysis KW - Atmospheric aerosol KW - Chemical protein modification KW - Derivatization KW - Nitration KW - Nitrotyrosine KW - LC-UV absorbance KW - Pollen extract KW - Protein quantification KW - Protein test KW - Kjeldahl KW - Tyrosine KW - Phenylalanine KW - Hydrolysis KW - Bradford KW - BCA test KW - 280 nm KW - Air filter samples KW - Fluorescence KW - HPLC KW - Chromatography KW - Protein content KW - 150th anniversary of BAM KW - Topical collection: Analytical Methods and Applications in the Materials and Life Sciences PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545924 UR - https://pubmed.ncbi.nlm.nih.gov/35320366/ DO - https://doi.org/10.1007/s00216-022-03910-1 SP - 1 EP - 14 PB - Springer Nature Limited CY - New York, Heidelberg AN - OPUS4-54592 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