TY - JOUR A1 - Faßbender, Sebastian A1 - Rodiouchkina, K. A1 - Vanhaecke, F. A1 - Meermann, Björn T1 - Method development for on-line species-specific sulfur isotopic analysis by means of capillary electrophoresis/multicollector ICP-mass spectrometry N2 - In this work, a method for species-specific isotopic analysis of sulfur via capillary electrophoresis hyphenated on-line with multicollector ICP-MS (CE/MC-ICP-MS) was developed. Correction for the mass bias caused by instrumental mass discrimination was realized via external correction with multiple-injection sample-standard bracketing. By comparing the isotope ratio measurement results obtained using the newly developed on-line CE/MC-ICP-MS method with those obtained via traditional MC-ICP-MS measurement after analyte/matrix separation by anion exchange chromatography for isotopic reference materials and an in-house bracketing standard, the most suitable data evaluation method could be identified. The repeatability for the sulfate-δ34S value (calculated from 18 measurements of a standard conducted over seven measurement sessions) was 0.57‰ (2SD) and thereby only twice that obtained with off-line measurements (0.30‰, n = 68). As a proof of concept for analysis of samples with a real matrix, the determination of the sulfur isotopic composition of naturally present sulfate was performed for different river systems. The CE/MC-ICP-MS results thus obtained agreed with the corresponding off-line MC-ICP-MS results within the 2SD ranges, and the repeatability of consecutive δ34S measurements (n = 3) was between 0.3‰ and 1.3‰ (2SD). Finally, the isotopic analysis of two different S-species in a river water sample spiked with 2-pyridinesulfonic acid (PSA) was also accomplished. KW - River water sulfate KW - Environmental speciation KW - Sulfur isotopes KW - On-line CE/MC-ICP-MS KW - Multiple-injection sample-standard bracketing PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-509549 DO - https://doi.org/10.1007/s00216-020-02781-8 SN - 1618-2642 VL - 412 IS - 23 SP - 5637 EP - 5646 PB - Springer CY - Berlin, Heidelberg AN - OPUS4-50954 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ebel, Kenny A1 - Bald, Ilko T1 - Length and Energy Dependence of Low-Energy Electron-Induced Strand Breaks in Poly(A) DNA N2 - The DNA in living cells can be effectively damaged by high-energy radiation, which can lead to cell death. Through the ionization of water molecules, highly reactive secondary species such as low-energy electrons (LEEs) with the most probable energy around 10 eV are generated, which are able to induce DNA strand breaks via dissociative electron attachment. Absolute DNA strand break cross sections of specific DNA sequences can be efficiently determined using DNA origami nanostructures as platforms exposing the target sequences towards LEEs. In this paper, we systematically study the effect of the oligonucleotide length on the strand break cross section at various irradiation energies. The present work focuses on poly-adenine sequences (d(A4), d(A8), d(A12), d(A16), and d(A20)) irradiated with 5.0, 7.0, 8.4, and 10 eV electrons. Independent of the DNA length, the strand break cross section shows a maximum around 7.0 eV electron energy for all investigated oligonucleotides confirming that strand breakage occurs through the initial formation of negative ion resonances. When going from d(A4) to d(A16), the strand break cross section increases with oligonucleotide length, but only at 7.0 and 8.4 eV, i.e., close to the maximum of the negative ion resonance, the increase in the strand break cross section with the length is similar to the increase of an estimated geometrical cross section. For d(A20), a markedly lower DNA strand break cross section is observed for all electron energies, which is tentatively ascribed to a conformational change of the dA20 sequence. The results indicate that, although there is a general length dependence of strand break cross sections, individual nucleotides do not contribute independently of the absolute strand break cross section of the whole DNA strand. The absolute quantification of sequence specific strand breaks will help develop a more accurate molecular level understanding of radiation induced DNA damage, which can then be used for optimized risk estimates in cancer radiation therapy. KW - DNA origami KW - DNA radiation damage KW - DNA strand breaks KW - Low-energy electrons KW - Sequence dependence PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-503563 DO - https://doi.org/10.3390/ijms21010111 VL - 21 IS - 1 SP - 1 EP - 11 PB - MDPI CY - Basel, Switzerland AN - OPUS4-50356 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 - 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 - 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 - Bröcker, S. A1 - Klaer, R.-H. A1 - Kockmann, N. A1 - Maiwald, Michael T1 - Process Industry United in the Digital World - The current landscape of research for the digitalization of the process industry N2 - The Tutzing Symposium "100 % digital: survival strategies for the process industry" (see 4.1) in April 2018 was characterized by a great momentum which has been taken up and continued until today. The aim was to implement the ideas from the Tutzing Symposium in a coordinated and targeted manner. For this purpose, development needs as well as the numerous currently planned or already started research and development activities in the context of digitalisation were first compiled and analysed. This resulted in the current research landscape for digitalization in the process industry. It now enables to identify open topics and to translate them into research funding programs as well as to define new projects in the dialogue between users, suppliers and research, which are to be meaningfully interlinked and consolidated with existing projects. Due to the strong interest in digitalisation, activities are constantly being added, so that this paper can only provide a snapshot of the situation in the period 2019-2020. KW - Process Industry KW - Digitalisation KW - Tutzing Symposion KW - research landscape KW - Process Control PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-512265 UR - https://processnet.org/en/TAKdigital.html SP - 1 EP - 15 AN - OPUS4-51226 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bhuckory, S. A1 - Wegner, Karl David A1 - Qiu, X. A1 - Wu, Y.T. A1 - Jennings, T. L. A1 - Incamps, A. A1 - Hildebrandt, N. T1 - Triplexed CEA-NSE-PSA Immunoassay Using Time-Gated Terbium-to-Quantum Dot FRET N2 - Time-gated Förster resonance energy transfer (TG-FRET) between Tb complexes and luminescent semiconductor quantum dots (QDs) provides highly advantageous photophysical properties for multiplexed biosensing. Multiplexed Tb-to-QD FRET immunoassays possess a large potential for in vitro diagnostics, but their performance is often insufficient for their application under clinical conditions. Here, we developed a homogeneous TG-FRET immunoassay for the quantification of carcinoembryonic antigen (CEA), neuron-specific enolase (NSE), and prostatespecific antigen (PSA) from a single serum sample by multiplexed Tb-to-QD FRET. Tb–IgG antibody donor conjugates were combined with compact QD-F(ab’)2 antibody acceptor conjugates with three different QDs emitting at 605, 650, and 705 nm. Upon antibody–antigen–antibody Sandwich complex formation, the QD acceptors were sensitized via FRET from Tb, and the FRET ratios of QD and Tb TG luminescence intensities increased specifically with increasing antigen concentrations. Although limits of detection (LoDs: 3.6 ng/mL CEA, 3.5 ng/mL NSE, and 0.3 ng/mL PSA) for the triplexed assay were slightly higher compared to the single-antigen assays, they were still in a clinically relevant concentration range and could be quantified in 50 μL serum samples on a B·R·A·H·M·S KRYPTOR Compact PLUS clinical immunoassay plate reader. The simultaneous quantification of CEA, NSE, and PSA at different concentrations from the same serum sample demonstrated actual multiplexing Tb-to-QD FRET immunoassays and the potential of this technology for translation into clinical diagnostics. KW - Lanthanides KW - Nanoparticles KW - Biosensing KW - Multiplexing KW - FRET KW - Fluorescence KW - PSA KW - NSE KW - CEA PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-512290 DO - https://doi.org/10.3390/molecules25163679 VL - 25 IS - 16 SP - 3679 PB - MDPI AN - OPUS4-51229 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 - Hildebrandt, L. A1 - von der Au, Marcus A1 - Zimmermann, T. A1 - Reese, A. A1 - Ludwig, J. A1 - Pröfrock, D. T1 - A metrologically traceable protocol for the quantification of trace metals in different types of microplastic N2 - The presence of microplastic (MP) particles in aquatic environments raised concern About possible enrichment of organic and inorganic pollutants due to their specific surface and chemical properties. In particular the role of metals within this context is still poorly understood. Therefore, the aim of this work was to develop a fully validated acid digestion protocol for metal analysis in different polymers, which is a prerequisite to study such interactions. The proposed digestion protocol was validated using six different certified reference materials in the microplastic size range consisting of polyethylene, polypropylene, acrylonitrile butadiene styrene and polyvinyl chloride. As ICP-MS/MS enabled time-efficient, sensitive and robust analysis of 56 metals in one measurement, the method was suitable to provide mass fractions for a multitude of other elements beside the certified ones (As, Cd, Cr, Hg, Pb, Sb, Sn and Zn). Three different microwaves, different acid mixtures as well as different temperatures in combination with different hold times were tested for optimization purposes. With the exception of Cr in acrylonitrile butadiene styrene, recovery rates obtained using the optimized protocol for all six certified reference materials fell within a range from 95.9% ± 2.7% to 112% ± 7%. Subsequent optimization further enhanced both precision and recoveries ranging from 103% ± 5% to 107 ± 4% (U; k = 2 (n = 3)) for all certified metals (incl. Cr) in acrylonitrile butadiene styrene. The results clearly show the analytical challenges that come along with metal analysis in chemically resistant plastics. Addressing specific analysis Tools for different sorption scenarios and processes as well as the underlying kinetics was beyond this study’s scope. However, the future application of the two recommended thoroughly validated total acid digestion protocols as a first step in the direction of harmonization of metal analysis in/on MP will enhance the significance and comparability of the generated data. It will contribute to a better understanding of the role of MP as vector for trace metals in the environment. KW - Microplatic KW - Digestion KW - Analytical Chemistry PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-510727 DO - https://doi.org/10.1371/journal.pone.0236120 VL - 15 IS - 7 SP - e0236120 AN - OPUS4-51072 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von Boehn, B. A1 - Scholtz, Lena A1 - Imbihl, R. T1 - Reactivity and Stability of Ultrathin VOx Films on Pt(111) in Catalytic Methanol Oxidation N2 - The growth of ultrathin layers of VOx (<12 monolayers) on Pt(111) and the activity of these layers in catalytic methanol oxidation at 10−4 mbar have been studied with low-energy electron difraction, Auger electron spectroscopy, rate measurements, and with photoemission electron microscopy. Reactive deposition of V in O2 at 670 K obeys a Stranski–Krastanov growth mode with a (√3 × √3)R30° structure representing the limiting case for epitaxial growth of 3D-VOx. The activity of VOx/Pt(111) in catalytic methanol oxidation is very low and no redistribution dynamics is observed lifting the initial spatial homogeneity of the VOx layer. Under reaction conditions, part of the surface vanadium difuses into the Pt subsurface region. Exposure to O2 causes part of the V to difuse back to the surface, but only up to one monolayer of VOx can be stabilized in this way at 10−4 mbar. KW - Vanadium oxide catalysts KW - Pt(111) KW - Supported catalyst KW - Methanol oxidation KW - Stranski–Krastanow growth PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-517376 DO - https://doi.org/10.1007/s11244-020-01321-z SN - 1022-5528 VL - 63 IS - 15-18 SP - 1545 EP - 1556 PB - Springer AN - OPUS4-51737 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Raysyan, Anna A1 - Moerer, R. A1 - Coesfeld, Bianca A1 - Eremin, S. A1 - Schneider, Rudolf T1 - Fluorescence polarization immunoassay for the determination of diclofenac in wastewater N2 - Pharmacologically active compounds are often detected in wastewater and surface waters. The nonsteroidal anti-inflammatory drug diclofenac (DCF) was included in the European watch list of substances that requires its environmental monitoring in the member states. DCF may harmfully influence the ecosystem already at concentrations ≤ 1 μg L−1. The fast and easy quantification of DCF is becoming a subject of global importance. Fluorescence polarization immunoassay (FPIA) is a homogeneous mix-and-read method which does not require the immobilization of reagents. FPIA can be performed in one phase within 20–30 min, making it possible to analyse wastewater without any complicated pre-treatment. In this study, new tracermolecules with different structures, linking fluorophores to derivatives of the analyte, were synthesized, three homologous tracers based on DCF, two including a C6 spacer, and one heterologous tracer derived from 5-hydroxy-DCF. The tracer molecules were thoroughly assessed for performance. Regarding sensitivity of the FPIA, the lowest limit of detection reached was 2.0 μg L−1 with a working range up to 870 μg L−1. The method was validated for real wastewater samples against LC-MS/MS as reference method with good agreement of both methods. KW - Abwasser KW - Umweltschadstoffe KW - Antikörper KW - Antibody PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-518398 DO - https://doi.org/10.1007/s00216-020-03058-w SN - 1618-2642 VL - 413 IS - 4 SP - 999 EP - 107 PB - Springer CY - Heidelberg AN - OPUS4-51839 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 - Bell, A. M. A1 - von der Au, Marcus A1 - Regnery, J. A1 - Schmid, M. A1 - Meermann, Björn A1 - Reifferscheid, G. A1 - Ternes, T. A1 - Buchinger, S. T1 - Does galvanic cathodic protection by aluminum anodes impact marine organisms? N2 - Background: Cathodic protection by sacrifcial anodes composed of aluminum-zinc-indium alloys is often applied to protect ofshore support structures of wind turbines from corrosion. Given the considerable growth of renewable energies and thus ofshore wind farms in Germany over the last decade, increasing levels of aluminum, Indium and zinc are released to the marine environment. Although these metals are ecotoxicologically well-studied, data regarding their impact on marine organisms, especially sediment-dwelling species, as well as possible ecotoxicological efects of galvanic anodes are scarce. To investigate possible ecotoxicological efects to the marine environment, the diatom Phaedactylum tricornutum, the bacterium Aliivibrio fscheri and the amphipod Corophium volutator were exposed to dissolved galvanic anodes and solutions of aluminum and zinc, respectively, in standardized laboratory tests using natural seawater. In addition to acute toxicological efects, the uptake of these elements by C. volutator was investigated. Results: The investigated anode material caused no acute toxicity to the tested bacteria and only weak but signifcant efects on algal growth. In case of the amphipods, the single elements Al and Zn showed signifcant efects only at the highest tested concentrations. Moreover, an accumulation of Al and In was observed in the crustacea species. Conclusions: Overall, the fndings of this study indicated no direct environmental impact on the tested marine organisms by the use of galvanic anodes for cathodic protection. However, the accumulation of metals in, e.g., crustaceans might enhance their trophic transfer within the marine food web. KW - Galvanic anodes KW - Metal toxicity KW - Metal uptake KW - Corophium volutator KW - Seawater PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-520769 DO - https://doi.org/10.1186/s12302-020-00441-3 VL - 32 IS - 1 SP - Article number 157 AN - OPUS4-52076 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Solovyev, N. A1 - El-Khatib, Ahmed A1 - Costas-Rodrigues, M. A1 - Schwab, K. A1 - Griffin, E. A1 - Raab, A. A1 - Platt, B. A1 - Theuring, F. A1 - Vogl, Jochen A1 - Vanhaecke, F. T1 - Cu, Fe and Zn isotope ratios in murine Alzheimer's disease models suggest specific signatures of amyloidogenesis and tauopathy N2 - Alzheimer’s disease (AD) is characterized by accumulation of tau and amyloid-beta in the brain, and recent evidence suggests a correlation between associated protein aggregates and trace elements, such as copper, iron and zinc. In AD, distorted brain redox homeostasis and complexation by amyloid-beta and hyperphosphorylated tau May alter the isotopic composition of essential mineral elements. Therefore, high-precision isotopic analysis may reveal changes in the homeostasis of these elements. We used inductively coupled plasma-mass spectrometry (ICP-MS)-based techniques to determine the total Cu, Fe and Zn contents in the brain, as well as their isotopic compositions in both mouse brain and serum. Results for male transgenic tau (Line 66, L66) and amyloid/presenilin (5xFAD) mice were compared to those for the corresponding age- and gendermatched wild-type control mice (WT). Our data show that L66 brains showed significantly higher Fe levels than the corresponding WT. Significantly less Cu, but more Zn was found in 5xFAD brains. We observed significantly lighter isotopic compositions of Fe (enrichment in the lighter isotopes) in the brain, and in serum of L66 mice compared to WT. For 5xFAD mice, Zn exhibited a trend towards a lighter isotopic composition in brain and a heavier isotopic composition in serum compared to WT. Neither mouse model yielded differences in the isotopic composition of Cu. Our findings indicate significant pathology-specific alterations of Fe and Zn brain homeostasis in mouse models of AD. The associated changes in isotopic composition May serve as a marker for proteinopathies Underlying AD and other types of dementia. KW - Alzheimer’s disease KW - Tau KW - Amyloid-beta KW - Copper KW - Iron KW - Zinc KW - Multi-collector inductively coupled plasma-mass spectrometry (ICP-MS) KW - Brain KW - Serum KW - Isotopic analysis KW - Total element determination PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-520214 DO - https://doi.org/10.1016/j.jbc.2021.100292 VL - 296 SP - 100292 PB - Elsevier Inc. CY - Amsterdam AN - OPUS4-52021 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dorgerloh, Ute A1 - Becker, Roland A1 - Riedel, Juliane A1 - Hofmann, Andrea T1 - Comparison of gas- and liquid chromatography-mass spectrometry for trace analysis of anilines in groundwater N2 - Three chromatographic procedures were investigated regarding their potential for the quantification of aniline and 19 of its methylated and chlorinated derivatives in groundwater. These methods were based on liquid-liquid-extraction in combination with gas chromatography and single quadrupole mass spectrometry (GC/MS) according to German standard DIN 38407-16:1999 and its extension using tandem mass spectrometry (GC/MS-MS), both following liquid-liquid extraction, and as third alternative the direct injection of the water sample into a liquid chromatograph coupled to tandem mass spectrometry (LC/MS-MS). Results were compared using fortified water and real-world contaminated groundwater used in an interlaboratory comparison. It could be shown that GC/MS and GC/MS-MS yielded results deviating less than 10% from each other while all three procedure displayed quantification results deviating less than 15% from the intercomparison reference values in case of each analyte in the concentration range between 1 and 45 µg L-1. Though GC/MS-MS displays a ten-fold higher sensitivity than single quadrupole GC/MS, the precision of both methods in the concentration range was similar. LC/MS-MS has the advantage of no further sample preparation due to the direct injection and leads for methylanilines and meta-, para- substituted chloroanilines to results sufficiently equivalent to the standardised GC/MS method. However, LC/MS-MS is not suitable for ortho-chloroaniline derivates due to significantly lower ion yields than meta- and para-substituted chloroanilines. KW - Interlaboratory comparison KW - Aniline KW - Chloroanilines KW - Methylanilines KW - Groundwater KW - GC/MS KW - GC/MS-MS KW - LC/MS-MS PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-535793 DO - https://doi.org/10.1080/03067319.2021.1987423 VL - 103 IS - 19 SP - 8465 EP - 8477 PB - Taylor & Francis CY - London AN - OPUS4-53579 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Raysyan, Anna A1 - Schneider, Rudolf T1 - Development of a Lateral Flow Immunoassay (LFIA) to Screen for the Release of the Endocrine Disruptor Bisphenol A from Polymer Materials and Products N2 - One of the most important chemicals used in the production of polymer plastics and coatings is bisphenol A. However, despite the large number of studies on the toxicity and hormonal activity of BPA, there are still open questions and thus considerable media attention regarding BPA toxicity. Hence, it is necessary to develop a sensitive, simple, cost-efficient, specific, portable, and rapid method for monitoring bisphenol A and for high sample throughput and on-site screening analysis. Lateral flow immunoassays have potential as rapid tests for on-site screening. To meet sensitivity criteria, they must be carefully optimized. A latex microparticle-based LFIA for detection of BPA was developed. The sensitivity of the assay was improved by non-contact printing of spot grids as the control and test lines with careful parameter optimization. Results of the test could be visually evaluated within 10 min with a visual cut-off of 10 µg/L (vLOD). Alternatively, photographs were taken, and image analysis performed to set up a calibration, which allowed for a calculated limit of detection (cLOD) of 0.14 µg/L. The method was validated for thermal paper samples against ELISA and LC–MS/MS as reference methods, showing good agreement with both methods KW - Endokrine Disruptoren KW - Polymere KW - Schnelltest KW - Endocrine disruptor KW - Bisphenol A KW - LFIA KW - Immunoassay PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-540492 DO - https://doi.org/10.3390/bios11070231 VL - 11 IS - 7 SP - 1 EP - 11 PB - MDPI CY - Basel AN - OPUS4-54049 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ecke, Alexander A1 - Bohm, Konrad A1 - Schneider, Rudolf T1 - Magnetpartikelbasierte Immunoassays als vielseitiges Werkzeug für die Umweltanalytik N2 - Der Bedarf nach schnellen und kostengünstigen Analysemethoden in der (Trink-)Wasseranalytik steigt mit dem zunehmenden Eintrag pharmazeutisch aktiver Substanzen in die Umwelt. Insbesondere die Kontamination mit Antibiotika erscheint neben ökotoxikologischen Effekten vor allem in Hinblick auf die Evolution resistenter Keime im Wasser besorgniserregend. Wir berichten hier über die Entwicklung eines magnetpartikelbasierten Immunoassays (MBBA) zur Detektion des Breitbandantibiotikums Amoxicillin (AMX) in Wasserproben, der im Vergleich zum entsprechenden Enzyme-linked Immunosorbent Assay (ELISA) eine wesentlich kürzere Analysendauer sowie einen breiteren Messbereich mit niedrigerer Nachweisgrenze aufweist. Das angewendete Assayprinzip ist dabei leicht auf weitere Analyten übertragbar und ermöglicht die Implementierung in einen Immunosensor. KW - Magnetpartikel KW - Amoxicillin KW - Immunoassay KW - Wasser KW - Antikörper PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-527366 UR - https://www.gdch.de/netzwerk-strukturen/fachstrukturen/umweltchemie-und-oekotoxikologie/publikationen/mitteilungen/archiv/2021.html SN - 1618-3258 VL - 27 IS - 2 SP - 48 EP - 51 PB - Gesellschaft Deutscher Chemiker (GDCh) CY - Frankfurt/Main AN - OPUS4-52736 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ecke, Alexander A1 - Schneider, Rudolf T1 - Pitfalls in the Immunochemical Determination of β-Lactam Antibiotics in Water N2 - Contamination of waters with pharmaceuticals is an alarming problem as it may support the evolution of antimicrobial resistance. Therefore, fast and cost-effective analytical methods for potential on-site analysis are desired in order to control the water quality and assure the safety of its use as a source of drinking water. Antibody-based methods, such as the enzyme-linked immunosorbent assay (ELISA), can be helpful in this regard but can also have certain pitfalls in store, depending on the analyte. As shown here for the class of β-lactam antibiotics, hydrolysis of the β-lactam ring is a key factor in the immunochemical analysis as it influences antibody recognition. With the antibody used in this study, the limit of detection (LOD) in the immunoassay could be significantly reduced by hydrolysis for the five tested penicillins, with the lowest LOD for carbenicillin (0.2 nmol/L) and the greatest impact on penicillins G and V (reduction by 85%). In addition to enhanced quantification, our strategy also provides access to information about the degree of hydrolysis in water samples as shown for the most abundant penicillin amoxicillin. KW - ELISA KW - Immunoassay KW - β-Lactam KW - Amoxicillin KW - Hydrolysis PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-522832 DO - https://doi.org/10.3390/antibiotics10030298 SN - 2079-6382 VL - 10 IS - 3 SP - 298 PB - MDPI CY - Basel, CH AN - OPUS4-52283 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lange, M. A. A1 - Khan, I. A1 - Opitz, P. A1 - Hartmann, J: A1 - Ashraf, M. A1 - Qurashi, A. A1 - Prädel, L. A1 - Panthöfer, M. A1 - Cossmer, Antje A1 - Pfeifer, Jens A1 - Simon, Fabian A1 - von der Au, Marcus A1 - Meermann, Björn A1 - Mondeshki, M. A1 - Tahir, M. N. A1 - Tremel, W. T1 - A Generalized Method for High-Speed Fluorination of Metal Oxides by Spark Plasma Sintering Yields Ta3O7F and TaO2F with High Photocatalytic Activity for Oxygen Evolution from Water N2 - A general method to carry out the fluorination of metal oxides with poly(tetrafluoroethylene) (PTFE, Teflon) waste by spark plasma sintering (SPS) on a minute scale with Teflon is reported. The potential of this new approach is highlighted by the following results. i) The tantalum oxyfluorides Ta3O7F and TaO2F are obtained from plastic scrap without using toxic or caustic chemicals for fluorination. ii) Short reaction times (minutes rather than days) reduce the process time the energy costs by almost three orders of magnitude. iii) The oxyfluorides Ta3O7F and TaO2F are produced in gram amounts of nanoparticles. Their synthesis can be upscaled to the kg range with industrial sintering equipment. iv) SPS processing changes the catalytic properties: while conventionally prepared Ta3O7F and TaO2F show little catalytic activity, SPS-prepared Ta3O7F and TaO2F exhibit high activity for photocatalytic oxygen evolution, reaching photoconversion efficiencies up to 24.7% and applied bias to photoconversion values of 0.86%. This study shows that the materials properties are dictated by the processing which poses new challenges to understand and predict the underlying factors. KW - Fluorination KW - Oxygen evolution reaction KW - Photocatalysis KW - Spark plasma sintering KW - Tantalum oxyfluorides PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-524329 DO - https://doi.org/10.1002/adma.202007434 VL - 23 IS - 20 SP - 7434 PB - Wiley‐VCH GmbH AN - OPUS4-52432 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hernandez-Castillo, A. O. A1 - Bischoff, J. A1 - Lee, J. H. A1 - Langenhan, Jennifer A1 - Karra, M. A1 - Meijer, G. A1 - Eibenberger-Arias, S. T1 - High-resolution UV spectroscopy of 1-indanol N2 - We report on rotationally resolved laser induced fluorescence (LIF) and vibrationally resolved resonanceenhanced multiphoton ionization (REMPI) spectroscopy of the chiral molecule 1-indanol. Spectra of the S1 ’ S0 electronic transition are recorded in a jet-cooled, pulsed molecular beam. Using two timedelayed pulsed lasers, the lifetimes of the S1 state of the two most stable conformers, referred to as eq1 and ax2, have been determined. The S1 ’ S0 origin bands of these conformers as well as the Transition to a vibrationally excited level in the S1 state of eq1 are recorded with full rotational resolution (25 MHz observed linewidth) by measuring the LIF intensity following excitation with a tuneable, narrowband cw laser. On selected rotationally resolved electronic transitions, Lamb-dips are measured to confirm the Lorentzian lifetime-contribution to the observed lineshapes. The rotationally resolved S1 ’ S0 origin band of a neon-complex of eq1 is measured via LIF as well. The fit of the rotationally resolved LIF spectra of the origin bands to those of an asymmetric rotor yields a standard deviation of about 6 MHz. The resulting spectroscopic parameters are tabulated and compared to the outcome of ab initio calculations. For both conformers as well as for the Ne-eq1 complex, the geometric structures in the S0 and S1 states are discussed. For all systems, the transition dipole moment is mainly along the a-axis, the contributions along the b- and c-axes being about one order of magnitude smaller. KW - REMPI KW - LIF KW - 1-indanol PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-525056 DO - https://doi.org/10.1039/d0cp06170k VL - 23 IS - 12 SP - 7048 EP - 7056 PB - Royal Society of Chemistry AN - OPUS4-52505 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - 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 - 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 - Marklein, B. A1 - Jenning, M. A1 - Konthur, Zoltán A1 - Häupl, T. A1 - Welzel, F. A1 - Nonhoff, U. A1 - Krobitsch, S. A1 - Mulder, D. M. A1 - Koenders, M. I. A1 - Joshua, V. A1 - Cope, A. P. A1 - Shlomchik, M. J. A1 - Anders, H.-J. A1 - Burmester, G. R. A1 - Hensvold, A. A1 - Catrina, A. I. A1 - Rönnelid, J. A1 - Steiner, G. A1 - Skriner, K. T1 - The citrullinated/native index of autoantibodies against hnRNP-DL predicts an individual "window of treatment success" in RA patients N2 - Background: There is a need for biomarker to identify patients “at risk” for rheumatoid arthritis (risk-RA) and to better predict the therapeutic response and in this study we tested the hypothesis that novel native and citrullinated heterogeneous nuclear ribonucleoprotein (hnRNP)-DL autoantibodies could be possible biomarkers. Methods: Using protein macroarray and ELISA, epitope recognition against hnRNP-DL was analysed in sera from different developed RA disease and diagnosed SLE patients. Toll-like receptor (TLR) 7/9 and myeloid Differentiation primary response gene 88 (MyD88)-dependency were studied in sera from murine disease models. HnRNP-DL expression in cultivated cells and synovial tissue was analysed by indirect immunofluorescence, immunoblot and immunohistochemistry. KW - Citrullinated KW - Rheumatoid arthritis KW - Protein-modification KW - Autoantibodies KW - Antigens PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-533682 DO - https://doi.org/10.1186/s13075-021-02603-x SN - 1478-6362 VL - 23 SP - 1 EP - 16 PB - BioMed Central CY - London AN - OPUS4-53368 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 - Dariz, P. A1 - Schmid, Thomas T1 - Trace compounds in Early Medieval Egyptian blue carry information on provenance, manufacture, application, and ageing N2 - Only a few scientific evidences for the use of Egyptian blue in Early Medieval wall paintings in Central and Southern Europe have been reported so far. The monochrome blue fragment discussed here belongs to the second church building of St. Peter above Gratsch (South Tyrol, Northern Italy, fifth/ sixth century A.D.). Beyond cuprorivaite and carbon black (underpainting), 26 accessory minerals down to trace levels were detected by means of Raman microspectroscopy, providing unprecedented insights into the raw materials blend and conversion reactions during preparation, application, and ageing of the pigment. In conjunction with archaeological evidences for the manufacture of Egyptian blue in Cumae and Liternum and the concordant statements of the antique Roman writers Vitruvius and Pliny the Elder, natural impurities of the quartz sand speak for a pigment produced at the northern Phlegrean Fields (Campania, Southern Italy). Chalcocite (and chalcopyrite) suggest the use of a sulphidic copper ore, and water-insoluble salts a mixed-alkaline flux in the form of plant ash. Not fully reacted quartz crystals partly intergrown with cuprorivaite and only minimal traces of silicate glass portend solid-state reactions predominating the chemical reactions during synthesis, while the melting of the raw materials into glass most likely played a negligible role. KW - Egyptian blue KW - Raman microspectroscopy KW - Spectoscopic imaging KW - Cuprorivaite KW - Amorphous carbon PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537591 DO - https://doi.org/10.1038/s41598-021-90759-6 VL - 11 SP - 1 EP - 12 PB - Nature Portfolio AN - OPUS4-53759 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmid, Thomas A1 - Kraft, Ronja A1 - Dariz, P. T1 - Shedding light onto the spectra of lime - Part 2: Raman spectra of Ca and Mg carbonates and the role of d-block element luminescence N2 - We previously described the observation of a characteristic narrowband red luminescence emission of burnt lime (CaO), whose reason was unknown so far. This study presents Raman spectra of Mg5 CO3)4(OH)2∙4H2O, Mg5(CO3)4(OH)2, MgCO3, CaMgCO3 and CaCO3 (in limestone powder) as well as luminescence spectra of their calcination products. Comparison of the latter revealed MgO:Cr3+ as the source of the red lime luminescence in all studied samples, containing magnesium oxide as major component, minor component or trace. Spectral characteristics and theoretical background of the luminescence emission of d-block elements integrated in crystal lattices are discussed with the aim of sharpening the awareness for this effect in the Raman community and promoting its application in materials analysis. The latter is demonstrated by the Raman microspectroscopic imaging of the distributions of both Raman-active and Raman-inactive phases in clinker remnants in a 19th-century meso Portland cement mortar sample, which contain relatively high amounts of free lime detected in the form of both luminescing CaO and Raman-scattering Ca(OH)2, owing to exposure of the surface of the thin section to humid air. A combination of light and Raman spectroscopy revealed a calcium–magnesium–iron sulphide phase, indicating sulphurous raw materials and/or solid fuels employed in the calcination process, which in contrast to previously described morphologies of sulphides in cement clinker form extensive greenish black layers on free lime crystals. KW - Calcium carbonates KW - Raman spectroscopy KW - Luminescence KW - Magnesium carbonates KW - Meso Portland cement PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537611 DO - https://doi.org/10.1002/jrs.6174 SN - 0377-0486 VL - 52 IS - 8 SP - 1462 EP - 1472 PB - Wiley Analytical Science AN - OPUS4-53761 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmid, Thomas A1 - Hidde, Julia A1 - Grünier, Sophie A1 - Jungnickel, Robert A1 - Dariz, P. A1 - Riedel, Jens A1 - Neuhaus, B. T1 - Ageing effects in mountig media of microscope slide samples from natural history collections: A case study with Canada balsam and Permount™ N2 - Microscope slide collections represent extremely valuable depositories of research material in a natural history, forensic, veterinary, and medical context. Unfortunately, most mounting media of these slides deteriorate over time, with the reason for this not yet understood at all. In this study, Raman spectroscopy, ultraviolet–visible (UV–Vis) spectroscopy, and different types of light microscopy were used to investigate the ageing behaviour of naturally aged slides from museum collections and the experimentally aged media of Canada balsam and Permount™, representing a natural and a synthetic resin, respectively, with both being based on mixtures of various terpenes. Whereas Canada balsam clearly revealed chemical ageing processes, visible as increasing colouration, Permount™ showed physical deterioration recognisable by the increasing number of cracks, which even often impacted a mounted specimen. Noticeable changes to the chemical and physical properties of these mounting media take decades in the case of Canada balsam but just a few years in the case of Permount™. Our results question whether or not Canada balsam should really be regarded as a mounting medium that lasts for centuries, if its increasing degree of polymerisation can lead to a mount which is no longer restorable. KW - Deterioration KW - Microscope slides KW - Mounting media KW - Raman spectroscopy KW - UV–Vis spectroscopy PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537632 DO - https://doi.org/10.3390/polym13132112 VL - 13 IS - 13 SP - 1 EP - 27 PB - MDPI CY - Basel AN - OPUS4-53763 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 - 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 - Kang, Y. A1 - Nack, L. M. A1 - Liu, Y. A1 - Qi, B. A1 - Huang, Y. A1 - Liu, Z. A1 - Chakraborty, I. A1 - Schulz, F. A1 - Ahmed, A. A. A. A1 - Poveda, M. C. A1 - Hafizi, F. A1 - Roy, S. A1 - Mutas, M. A1 - Holzapfel, M. A1 - Sanchez-Cano, C. A1 - Wegner, Karl David A1 - Feliu, N. A1 - Parak, W. J. T1 - Quantitative considerations about the size dependence of cellular entry and excretion of colloidal nanoparticles for different cell types N2 - Most studies about the interaction of nanoparticles (NPs) with cells have focused on how the physicochemical properties of NPs will influence their uptake by cells. However, much less is known about their potential excretion from cells. However, to control and manipulate the number of NPs in a cell, both cellular uptake and excretion must be studied quantitatively. Monitoring the intracellular and extracellular amount of NPs over time (after residual noninternalized NPs have been removed) enables one to disentangle the influences of cell proliferation and exocytosis, the major pathways for the reduction of NPs per cell. Proliferation depends on the type of cells, while exocytosis depends in addition on properties of the NPs, such as their size. Examples are given herein on the role of these two different processes for different cells and NPs. KW - Cell proliferation KW - Exocytosis KW - Gold nanoparticles KW - Quantum dots KW - Fluorescence KW - Uptake studies PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-543476 DO - https://doi.org/10.1007/s40828-021-00159-6 SN - 2199-3793 VL - 8 IS - 1 SP - 1 EP - 8 PB - Springer CY - Berlin AN - OPUS4-54347 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Prohaska, T. A1 - Irrgeher, J. A1 - Benefield, J. A1 - Böhlke, J. K. A1 - Chesson, L. A. A1 - Coplen, T. B. A1 - Ding, T. A1 - Dunn, P. J. H. A1 - Gröning, M. A1 - Holden, N. E. A1 - Meijer, H. A. J. A1 - Moossen, H. A1 - Possolo, A. A1 - Takahashi, Y. A1 - Vogl, Jochen A1 - Walczyk, T. A1 - Wang, J. A1 - Wieser, M. E. A1 - Yoneda, S. A1 - Zhu, X.-K. A1 - Meija, J. T1 - Standard atomic weights of the elements 2021 (IUPAC Technical Report) N2 - Following the reviews of atomic-weight determinations and other cognate data in 2015, 2017, 2019 and 2021, the IUPAC (International Union of Pure and Applied Chemistry) Commission on Isotopic Abundances and Atomic Weights (CIAAW) reports changes of standard atomic weights. The symbol Ar(E) was selected for standard atomic weight of an element to distinguish it from the atomic weight of an element E in a specific substance P, designated Ar(E, P). The CIAAW has changed the values of the standard atomic weights of five elements based on recent determinations of terrestrial isotopic abundances: Ar (argon): from 39.948 ± 0.001 to [39.792, 39.963] Hf (hafnium): from 178.49 ± 0.02 to 178.486 ± 0.006 Ir (iridium): from 192.217 ± 0.003 to 192.217 ± 0.002 Pb (lead): from 207.2 ± 0.1 to [206.14, 207.94] Yb (ytterbium): from 173.054 ± 0.005 to 173.045 ± 0.010 The standard atomic weight of argon and lead have changed to an interval to reflect that the natural variation in isotopic composition exceeds the measurement uncertainty of Ar(Ar) and Ar(Pb) in a specific substance. The standard atomic weights and/or the uncertainties of fourteen elements have been changed based on the Atomic Mass Evaluations 2016 and 2020 accomplished under the auspices of the International Union of Pure and Applied Physics (IUPAP). Ar of Ho, Tb, Tm and Y were changed in 2017 and again updated in 2021: Al (aluminium), 2017: from 26.981 5385 ± 0.000 0007 to 26.981 5384 ± 0.000 0003 Au (gold), 2017: from 196.966 569 ± 0.000 005 to 196.966 570 ± 0.000 004 Co (cobalt), 2017: from 58.933 194 ± 0.000 004 to 58.933 194 ± 0.000 003 F (fluorine), 2021: from 18.998 403 163 ± 0.000 000 006 to 18.998 403 162 ± 0.000 000 005 (Ho (holmium), 2017: from 164.930 33 ± 0.000 02 to 164.930 328 ± 0.000 007) Ho (holmium), 2021: from 164.930 328 ± 0.000 007 to 164.930 329 ± 0.000 005 Mn (manganese), 2017: from 54.938 044 ± 0.000 003 to 54.938 043 ± 0.000 002 Nb (niobium), 2017: from 92.906 37 ± 0.000 02 to 92.906 37 ± 0.000 01 Pa (protactinium), 2017: from 231.035 88 ± 0.000 02 to 231.035 88 ± 0.000 01 Pr (praseodymium), 2017: from 140.907 66 ± 0.000 02 to 140.907 66 ± 0.000 01 Rh (rhodium), 2017: from 102.905 50 ± 0.000 02 to 102.905 49 ± 0.000 02 Sc (scandium), 2021: from 44.955 908 ± 0.000 005 to 44.955 907 ± 0.000 004 (Tb (terbium), 2017: from 158.925 35 ± 0.000 02 to 158.925 354 ± 0.000 008) Tb (terbium), 2021: from 158.925 354 ± 0.000 008 to 158.925 354 ± 0.000 007 (Tm (thulium), 2017: from 168.934 22 ± 0.000 02 to 168.934 218 ± 0.000 006) Tm (thulium), 2021: from 168.934 218 ± 0.000 006 to 168.934 219 ± 0.000 005 (Y (yttrium), 2017: from 88.905 84 ± 0.000 02 to 88.905 84 ± 0.000 01) Y (yttrium), 2021: from 88.905 84 ± 0.000 01 to 88.905 838 ± 0.000 002 KW - Argon KW - Ciaaw.org KW - Hafnium KW - Iridium KW - Lead KW - LSVEC KW - Ytterbium PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-548443 DO - https://doi.org/10.1515/pac-2019-0603 SN - 0033-4545 VL - 94 IS - 5 SP - 573 EP - 600 PB - De Gruyter Verlag CY - Berlin AN - OPUS4-54844 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 - Veico, V. P. A1 - Karlagina, Yu. Yu. A1 - Samokhvalov, A. A. A1 - Polyakov, D. S. A1 - Manokhin, S. S. A1 - Radaev, M. M. A1 - Odintsova, G. V. A1 - Gornushkin, Igor B. T1 - Surface Structuring and Reverse Deposition of Nanoporous Titanium Oxides by Laser Ablation of Titanium in Air N2 - The deposition of titanium oxides during titanium laser ablation in air has been experimentally and numerically investigated. A titanium sample was irradiated by nanosecond pulses from an Yb-fber laser with a beam scanned across the sample surface for its texturing. As a result, the hierarchical structure was observed consisting of a microrelief formed by the laser ablation and a nanoporous coating formed by the reverse deposition from the laser induced plasma plume. The chemical and phase composition of the nanoporous coating, as well as the morphology and structure of the surface, were studied using scanning electron microscopy, atomic force microscopy, and X-ray microanalysis. It was found that the deposit consists mostly of porous TiO2 with 26% porosity and inclusions of TiO, Ti2O3, and Ti2O3N. Optical emission spectroscopy was used to control the plasma composition and estimate the effective temperature of plasma plume. The chemical-hydrodynamic model of laser induced plasma was developed to get a deeper insight into the deposition process. The model predicts that condensed titanium oxides, formed in peripheral plasma zones, gradually accumulate on the surface during the plasma plume evolution. A satisfactory agreement between the experimental and calculated chemical composition of the plasma plume as well as between the experimental and calculated composition and thickness of the deposited film was demonstrated. This allows a cautious conclusion that the formation of condensed oxides in the plasma and their consequent deposition onto the ablation surface are among the key mechanisms of formation of porous surface films. KW - Laser ablation KW - Laser induced plasma deposition KW - Surface coating KW - Titanium dioxide KW - Hydrodynamic model KW - Plasma chemistry KW - Emission spectroscopy PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-548555 DO - https://doi.org/10.1007/s11090-022-10256-0 VL - 42 IS - 4 SP - 923 EP - 937 PB - Springer AN - OPUS4-54855 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 - Gornushkin, Igor B. A1 - Völker, Tobias T1 - Intrinsic Performance of Monte Carlo Calibration-Free Algorithm for Laser-Induced Breakdown Spectroscopy N2 - The performance of the Monte Carlo (MC) algorithm for calibration-free LIBS was studied on the example of a simulated spectrum that mimics a metallurgical slag sample. The underlying model is that of a uniform, isothermal, and stationary plasma in local thermodynamical equilibrium. Based on the model, the algorithm generates from hundreds of thousands to several millions of simultaneous configurations of plasma parameters and the corresponding number of spectra. The parameters are temperature, plasma size, and concentrations of species. They are iterated until a cost function, which indicates a difference between synthetic and simulated slag spectra, reaches its minimum. After finding the minimum, the concentrations of species are read from the model and compared to the certified values. The algorithm is parallelized on a graphical processing unit (GPU) to reduce computational time. The minimization of the cost function takes several minutes on the GPU NVIDIA Tesla K40 card and depends on the number of elements to be iterated. The intrinsic accuracy of the MC calibration-free method is found to be around 1% for the eight elements tested. For a real experimental spectrum, however, the efficiency may turn out to be worse due to the idealistic nature of the model, as well as incorrectly chosen experimental conditions. Factors influencing the performance of the method are discussed. KW - Laser induced breakdown spectroscopy KW - Calibration-free analysis KW - Monte Carlo algorithm PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-558016 DO - https://doi.org/10.3390/s22197149 VL - 22 IS - 19 SP - 7149 PB - MDPI AN - OPUS4-55801 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Völker, Tobias A1 - Gornushkin, Igor B. T1 - Importance of physical units in the Boltzmann plot method N2 - The Boltzmann plot is one of the most widely used methods for determining the temperature in different types of laboratory plasmas. It operates on the logarithm as a function of the dimensional argument, which assumes that the correct physical units are used. In many works using the Boltzmann method, there is no analysis of the dimension of this argument, which may be the cause of a potential error. This technical note offers a brief description of the method and shows how to correctly use physical units when using transcendental functions like the logarithm. KW - Boltzmann plot KW - Laser induced plasma PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-558039 DO - https://doi.org/10.1039/d2ja00241h SP - 1 EP - 3 PB - Royal Society of Chemistry AN - OPUS4-55803 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 - Coplen, T. B. A1 - Holden, N. E. A1 - Ding, T. A1 - Meijer, H. A. J. A1 - Vogl, Jochen A1 - Zhu, X. T1 - The Table of Standard Atomic Weights—An exercise in consensus N2 - The present Table of Standard Atomic Weights (TSAW) of the elements is perhaps one of the most familiar data sets in science. Unlike most parameters in physical science whose values and uncertainties are evaluated using the “Guide to the Expression of Uncertainty in Measurement” (GUM), the majority of standard atomic weight values and their uncertainties are consensus values, not GUM-evaluated values. The Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) regularly evaluates the literature for new isotopic-abundance measurements that can lead to revised standard atomic-weight values, Ar(E) for element E. The Commission strives to provide utmost clarity in products it disseminates, namely the TSAW and the Table of Isotopic Compositions of the Elements (TICE). In 2016, the Commission recognized that a guideline recommending the expression of uncertainty listed in parentheses following the standard atomic-weight value, for example, Ar(Se) = 78.971(8), did not agree with the GUM, which suggests that this parenthetic notation be reserved to express standard uncertainty, not the expanded uncertainty used in the TSAW and TICE. In 2017, to eliminate this noncompliance with the GUM, a new format was adopted in which the uncertainty value is specified by the “±” symbol, for example, Ar(Se) = 78.971 ± 0.008. To clarify the definition of uncertainty, a new footnote has been added to the TSAW. This footnote emphasizes that an atomic-weight uncertainty is a consensus (decisional) uncertainty. Not only has the Commission shielded users of the TSAW and TICE from unreliable measurements that appear in the literature as a result of unduly small uncertainties, but the aim of IUPAC has been fulfilled by which any scientist, taking any natural sample from commerce or research, can expect the sample atomic weight to lie within Ar(E) ± its uncertainty almost all of the time. KW - Atomic weight KW - Standard atomic weight KW - Uncertainty PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-551299 DO - https://doi.org/10.1002/rcm.8864 SN - 1097-0231 VL - 36 IS - 15 SP - 1 EP - 15 PB - Wiley AN - OPUS4-55129 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Raysyan, Anna A1 - Zwigart, S. A1 - Eremin, S. A. A1 - Schneider, Rudolf T1 - BPA Endocrine Disruptor Detection at the Cutting Edge: FPIA and ELISA Immunoassays N2 - BPA is a chemical commonly used in the production of polymer-based materials that can have detrimental effects on the thyroid gland and impact human reproductive health. Various expensive methods, such as liquid and gas chromatography, have been suggested for detecting BPA. The fluorescence polarization immunoassay (FPIA) is an inexpensive and efficient homogeneous mix-and-read method that allows for high-throughput screening. FPIA offers high specificity and sensitivity and can be carried out in a single phase within a timeframe of 20–30 min. In this study, new tracer molecules were designed that linked the fluorescein fluorophore with and without a spacer to the bisphenol A moiety. To assess the influence of the C6 spacer on the sensitivity of an assay based on the respective antibody, hapten–protein conjugates were synthesized and assessed for performance in an ELISA setup, and this resulted in a highly sensitive assay with a detection limit of 0.05 µg/L. The lowest limit of detection was reached by employing the spacer derivate in the FPIA and was 1.0 µg/L, working range from 2 to 155 µg/L. The validation of the methods was conducted using actual samples compared to LC–MS/MS, which served as the reference method. The FPIA and ELISA both demonstrated satisfactory concordance. KW - Fluorescence Polarization KW - Enzyme-Linked Immunosorbent Assay KW - Endokriner Disruptor KW - Bisphenol A KW - Freisetzung PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-579497 DO - https://doi.org/10.3390/bios13060664 VL - 13 IS - 6 SP - 1 EP - 12 PB - MDPI CY - Basel AN - OPUS4-57949 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stratulat, C. A1 - Ginghina, R. E. A1 - Bratu, A. E. A1 - Isleyen, A. A1 - Tunc, M. A1 - Hafner-Vuk, K. A1 - Frey, A. M. A1 - Kjeldsen, H. A1 - Vogl, Jochen T1 - Development- and Validation-Improved Metrological Methods for the Determination of Inorganic Impurities and Ash Content from Biofuels N2 - In this study, five laboratories, namely, BRML (Romania), TUBITAK UME (Turkey), IMBIH (Bosnia and Herzegovina), BAM (Germany), and DTI (Denmark), developed and validated analytical procedures by ICP-MS, ICP-OES, MWP-AES, WD-XRF, and ID-MS for the determination of inorganic impurities in solid and liquid biofuels, established the budget of uncertainties, and developed the method for determining the amount of ash in the measurement range 0–1.2% with absolute repeatability less than 0.1% and absolute reproducibility of 0.2% (according to EN ISO 18122). In order to create homogeneous certified reference materials, improved methodologies for the measurement and characterization of solid and liquid biofuels were developed. Thus, information regarding the precision, accuracy, and bias of the method, and identifying the factors that intervened in the measurement of uncertainty were experimentally determined, supplementing the information from the existing standards in the field. KW - Development KW - Validate method KW - Biodiesel KW - ICP-MS KW - ICP-OES KW - MW-AES KW - WD-XRF KW - ID-MS KW - Inorganic impurities KW - Ash content KW - Wood chips PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-578743 DO - https://doi.org/10.3390/en16135221 VL - 16 IS - 13 SP - 1 EP - 14 PB - MDPI AN - OPUS4-57874 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Menero-Valdés, P. A1 - Chronakis, Michail Ioannis A1 - Fernández, B. A1 - Quarles Jr., C. D. A1 - González-Iglesias, H. A1 - Meermann, Björn A1 - Pereiro, R. T1 - Single Cell–ICP–ToF-MS for the Multiplexed Determination of Proteins: Evaluation of the Cellular Stress Response N2 - An automated and straightforward detection and data treatment strategy for the determination of the protein relative concentration in individual human cells by single cell–inductively coupled plasma–time-of-flight mass spectrometry (sc-ICP-ToF-MS) is proposed. Metal nanocluster (NC)-labeled specific antibodies for the target proteins were employed, and ruthenium red (RR) staining, which binds to the cells surface, was used to determine the number of cell events as well as to evaluate the relative volume of the cells. As a proof of concept, the expression of hepcidin, metallothionein-2, and ferroportin employing specific antibodies labeled with IrNCs, PtNCs, and AuNCs, respectively, was investigated by sc-ICP-ToF-MS in human ARPE-19 cells. Taking into account that ARPE-19 cells are spherical in suspension and RR binds to the surface of the cells, the Ru intensity was related to the cell volume (i.e., the cell volume is directly proportional to (Ru intensity)3/2), making it possible to determine not only the mass of the target proteins in each individual cell but also the relative concentration. The proposed approach is of particular interest in comparing cell cultures subjected to different supplementations. ARPE-19 cell cultures under two stress conditions were compared: a hyperglycemic model and an oxidative stress model. The comparison of the control with treated cells shows not only the mass of analyzed species but also the relative changes in the cell volume and concentration of target proteins, clearly allowing the identification of subpopulations under the respective treatment. KW - Peptides and Proteins KW - Immunology KW - Metals PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-581630 DO - https://doi.org/10.1021/acs.analchem.3c02558 VL - 95 IS - 35 SP - 13322 EP - 13329 PB - ACS Publications AN - OPUS4-58163 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Martusevich, A. A1 - Kornev, R. A1 - Ermakov, A. A1 - Gornushkin, Igor B. A1 - Nazarov, V. A1 - Shabarova, L. A1 - Shkrunin, V. T1 - Spectroscopy of Laser-Induced Dielectric Breakdown Plasma in Mixtures of Air with Inert Gases Ar, He, Kr, and Xe N2 - The generation of ozone and nitrogen oxides by laser-induced dielectric breakdown (LIDB) in mixtures of air with noble gases Ar, He, Kr, and Xe is investigated using OES and IR spectroscopy, mass spectrometry, and absorption spectrophotometry. It is shown that the formation of NO and NO2 noticeably depends on the type of inert gas; the more complex electronic configuration and the lower ionization potential of the inert gas led to increased production of NO and NO2. The formation of ozone occurs mainly due to the photolytic reaction outside the gas discharge zone. Equilibrium thermodynamic analysis showed that the formation of NO in mixtures of air with inert gases does not depend on the choice of an inert gas, while the equilibrium concentration of the NO+ ion decreases with increasing complexity of the electronic configuration of an inert gas. KW - Laser-induced dielectric breakdown (LIDB) KW - Nitrogen monoxide KW - Nitrogen dioxide KW - Ozone KW - Emission spectroscopy KW - Inert gases KW - Thermodynamic analysis PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-568258 DO - https://doi.org/10.3390/s23020932 SN - 1424-8220 VL - 23 IS - 2 SP - 1 EP - 13 PB - MDPI CY - Basel, Switzerland AN - OPUS4-56825 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kazlagić, Anera A1 - Rosner, M. A1 - Cipriani, A. A1 - Frick, D. A. A1 - Glodny, J. A1 - Hoffmann, E. J. A1 - Hora, J. M. A1 - Irrgeher, J. A1 - Lugli, F. A1 - Magna, T. A1 - Meisel, T. C. A1 - Meixner, A. A1 - Possolo, A. A1 - Pramann, A. A1 - Pribil, M. J. A1 - Prohaska, T. A1 - Retzmann, Anika A1 - Rienitz, O. A1 - Rutherford, D. A1 - Paula-Santos, G. M. A1 - Tatzel, M. A1 - Widhalm, S. A1 - Willbold, M. A1 - Zuliani, T. A1 - Vogl, Jochen T1 - Characterisation of conventional 87Sr/86Sr isotope ratios in cement, limestone and slate reference materials based on an interlaboratory comparison study N2 - An interlaboratory comparison (ILC)was organised to characterise 87Sr/86Sr isotope ratios in geological and industrial reference materials by applying the so-called conventional method for determining 87Sr/86Sr isotope ratios. Four cements (VDZ 100a,VDZ 200a, VDZ 300a, IAG OPC-1), one limestone (IAG CGL ML-3) and one slate (IAG OU-6) reference materials were selected, covering a wide range of naturally occurring Sr isotopic signatures. Thirteen laboratories received aliquots of these six reference materials together with a detailed technical protocol. The consensus values for the six reference materials and their associated measurement uncertainties were obtained by applying a Gaussian, linear mixed effects model fitted to all the measurement results. By combining the consensus values and their uncertainties with an uncertainty contribution for potential heterogeneity, reference values ranging from 0.708134 mol mol-1 to 0.729778 mol mol-1 were obtained with relative expanded uncertainties of ≤ 0.007 %. This study represents an ILC on conventional 87Sr/86Sr isotope ratios, within which metrological principles were considered and the compatibility of measurement results obtained by MC-ICP-MS and by MC-TIMS is demonstrated. The materials characterised in this study can be used as reference materials for validation and quality control purposes and to estimate measurement uncertainties in conventional 87Sr/86Sr isotope ratio measurement. KW - Sr isotope analysis KW - Isotope ratios KW - Cement KW - Geological material KW - MC-TIMS KW - MC-ICP-MS KW - Interlaboratory comparison KW - Measurement uncertainty KW - Cconventional method PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-579836 DO - https://doi.org/10.1111/ggr.12517 SN - 1639-4488 VL - 47 IS - 4 SP - 821 EP - 840 PB - Wiley online library AN - OPUS4-57983 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nxumalo, T. A1 - Akhdhar, A. A1 - Mueller, V. A1 - Simon, Fabian A1 - von der Au, Marcus A1 - Cossmer, Antje A1 - Pfeifer, Jens A1 - Krupp, E. A1 - Meermann, Björn A1 - Kindness, A. A1 - Feldmann, J. T1 - EOF and target PFAS analysis in surface waters affected by sewage treatment effluents in Berlin, Germany N2 - Per- and polyfuoroalkyl substances (PFAS) are emerging organic pollutants and can occur in surface and groundwater. To identify the degree of pollution in surface water with PFAS, often targeted HPLC–ESI–MS/MS has been employed in which commonly 30–40 compounds are analyzed. However, other PFAS and organofuorines remain undetected. We sampled surface water of the river Spree and the Teltow Canal in Berlin, Germany, which are afected by the efuent discharge of wastewater treatment plants. Here, we employed high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) for measuring extractable organofuorines (EOF) and compared in a mass balance approach the total fuorine to the identifed and quantifed PFAS from the targeted analysis. The analysis highlights that the EOF are in the range expected for an urban river system (Winchell et al. in Sci Total Environ 774, 2021). However, downstream of an efuent discharge, the EOF increased by one order of magnitude, e.g., 40.3 to 574 ng F L−1, along the Teltow Canal. From our target analytes, mostly short-chained perfuorinated carboxylic acids and sulfonates occur in the water, which however makes up less than 10% of the EOF. The increase in EOF in the Teltow Canal correlates well with the increase of perfuorohexanoic acid (PFHxA), indicating that PFHxA is characteristic for the discharged EOF but not responsible for the increase. Hence, it points to PFHxA precursor discharge. The study highlights that EOF screening using HR-CS-GFMAS is necessary to identify the full scale of pollution with regard to PFAS and other organofuorines such as pharmaceutical compounds from the efuent of WWTPs. KW - PFAS KW - WWTP KW - GF-MAS PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-580341 DO - https://doi.org/10.1007/s00216-022-04500-x VL - 415 SP - 1195 EP - 1204 PB - Springer AN - OPUS4-58034 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hendriks, L. A1 - Brunjes, R. A1 - Taskula, S. A1 - Kocic, J. A1 - Hattendorf, B. A1 - Bland, G. A1 - Lowry, G. A1 - Bolea-Fernandez, E. A1 - Vanhaecke, F. A1 - Wang, J. A1 - Baalousha, M. A1 - von der Au, Marcus A1 - Meermann, Björn A1 - Holbrook, T. A1 - Wagner, S. A1 - Harycki, S. A1 - Gundlach-Graham, A. A1 - von der Kammer, F. T1 - Results of an interlaboratory comparison for characterization of Pt nanoparticles using single-particle ICP-TOFMS N2 - This study describes an interlaboratory comparison (ILC) among nine (9) laboratories to evaluate and validate the standard operation procedure (SOP) for single-particle (sp) ICP-TOFMS developed within the context of the Horizon 2020 project ACEnano. The ILC was based on the characterization of two different Pt nanoparticle (NP) suspensions in terms of particle mass, particle number concentration, and isotopic composition. The two Pt NP suspensions were measured using icpTOF instruments (TOFWERK AG, Switzerland). Two Pt NP samples were characterized and mass equivalent spherical sizes (MESSs) of 40.4 ± 7 nm and 58.8 ± 8 nm were obtained, respectively. MESSs showed <16% relative standard deviation (RSD) among all participating labs and <4% RSD after exclusion of the two outliers. A good agreement was achieved between the different participating laboratories regarding particle mass, but the particle number concentration results were more scattered, with <53% RSD among all laboratories, which is consistent with results from previous ILC studies conducted using ICP-MS instrumentation equipped with a sequential mass spectrometer. Additionally, the capabilities of sp-ICP-TOFMS to determine masses on a particle basis are discussed with respect to the potential for particle density determination. Finally, because quasi-simultaneous multi-isotope and multielement determinations are a strength of ICP-TOFMS instrumentation, the precision and trueness of isotope ratio determinations were assessed. The average of 1000 measured particles yielded a precision of below ±1% for intensity ratios of the most abundant Pt isotopes, i.e. 194Pt and 195Pt, while the accuracy of isotope ratios with the lower abundant isotopes was limited by counting statistics. KW - ILC KW - spICP-MS KW - PtNP KW - Nanopartikel PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-580353 DO - https://doi.org/10.1039/d3nr00435j SN - 2040-3364 VL - 15 IS - 26 SP - 11268 EP - 11279 PB - Royal Society of Chemistry (RSC) AN - OPUS4-58035 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Michail Ioannis, Chronakis A1 - von der Au, Marcus A1 - Meermann, Björn T1 - Single cell-asymmetrical flow field-flow fractionation/ICP-time of flight-mass spectrometry (sc-AF4/ICP-ToF-MS): an efficient alternative for the cleaning and multielemental analysis of individual cells N2 - Asymmetrical Flow Field-Flow Fractionation (AF4), as a cleaning technique, was combined on-line with the multielemental analytical capabilities of an Inductively Coupled Plasma-Time of Flight-Mass Spectrometer (ICP-ToF-MS). In that manner, the heavy ionic matrix effect of untreated cells' samples can be significantly reduced. As a proof of concept, commercial baker's yeast cells were analysed. KW - AF4 KW - Single Cell KW - Cleaning PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-576419 DO - https://doi.org/10.1039/d2ja00264g SN - 0267-9477 VL - 37 IS - 12 SP - 2691 EP - 2700 PB - Royal Society of Chemistry AN - OPUS4-57641 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Retzmann, Anika A1 - Faßbender, Sebastian A1 - Rosner, M. A1 - von der Au, Marcus A1 - Vogl, Jochen T1 - Performance of second generation ICP-TOFMS for (multi-)isotope ratio analysis: a case study on B, Sr and Pb and their isotope fractionation behavior during the measurements N2 - The performance of second generation ICP-TOFMS, equipped with a micro-channel plate (MCP) enabling multi-isotope detection, in terms of isotope ratio precision and instrumental isotopic fractionation (IIF) for (multi-)isotope ratio analysis was thoroughly assessed for B, Sr and Pb. Experimental isotope ratio precision of 0.14 % for 11B/10B intensity ratio, 0.15 % for 87Sr/86Sr intensity ratio and 0.07% for 208Pb/206Pb intensity ratio were obtained at high signal levels ($500 mg L−1) which is comparable to first generation ICP-TOFMS. The long-term stability of isotope ratios, measured over several hours and expressed as repeatability, is between 0.05 % and 1.8 % for B, Sr and Pb. The observed IIF per mass unit is negative for B (i.e., −11 % for 11B/10B) which is in accordance with measurements using sector field (MC) ICP-MS. But the observed IIF per mass unit is positive for Sr (i.e., 2 % for 87Sr/86Sr) and Pb (i.e., 4.5 % for 208Pb/206Pb) which is not in accordance with measurements using sector field (MC) ICP-MS. Furthermore, different IIFs per mass unit were observed for different isotope pairs of the same isotopic system (i.e., Sr, Pb) and adjacent isotopic systems (i.e., Pb vs. Tl). This and the observations from three-isotope plots for Sr and Pb show that ion formation, ion extraction, ion transmission, ion separation and ion detection in second generation ICP-TOFMS is subject to IIF that does not follow the known mass dependent fractionation laws and is possibly caused by mass independent fractionation and/or multiple (contradictory) fractionation processes with varying contributions. The non-mass dependent IIF behavior observed for second generation ICP TOFMS has profound consequences for the IIF correction of isotope raw data, including application of multi-isotope dilution mass spectrometry (IDMS) using ICP-TOFMS. Hence, only IIF correction models that correct also for mass independent fractionation are applicable to calculate reliable isotope ratios using second generation ICP-TOFMS. In the present study, reliable d11B values, and absolute B, Sr and Pb isotope ratios could be determined using the SSB approach in single-element solutions as well as in a mixture of B, Sr and Pb, where the isotopes were measured simultaneously. KW - ICP-TOFMS KW - Isotope delta value KW - Isotope amount ratio KW - Conventional isotope ratio KW - Instrumental isotope fractionation PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-582239 DO - https://doi.org/10.1039/d3ja00084b SN - 0267-9477 VL - 38 IS - 10 SP - 2144 EP - 2158 PB - Royal Society of Chemistry AN - OPUS4-58223 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Temgoua, Ranil C.T. A1 - Dontsi, Fabiola T. A1 - Lebègue, Estelle A1 - Thobie-Gautier, Christine A1 - Tonlé, Ignas K. A1 - Boujtita, Mohammed T1 - Understanding the behavior of phenylurazole-tyrosine-click electrochemical reaction using hybrid electroanalytical techniques N2 - In this work, the electrochemical behavior of 4-phenylurazole (Ph-Ur) was studied and the latter was used as a molecular anchor for the electrochemical bioconjugation of tyrosine (Y). Cyclic voltammetry (CV) and controlled potential coulometry (CPC) allowed the in-situ generation of the PTAD (4-phenyl-3 H-1,2,4-triazole-3,5(4 H)-dione) species from phenylurazole on demand for tyrosine electrolabeling. The chemoselectivity of the reaction was studied with another amino acid (lysine, Lys) and no changes in Lys were observed. To evaluate the performance of tyrosine electrolabeling, coulometric analyses at controlled potentials were performed on solutions of phenylurazole and the phenylurazole-tyrosine mixture in different proportions (2:1, 1:1, and 1:2). The electrolysis of the phenylurazole-tyrosine mixture in the ratio (1:2) produced a charge of 2.07 C, very close to the theoretical value (1.93 C), with high reaction kinetics, a result obtained here for the first time. The products obtained were identified and characterized by liquid chromatography coupled to high-resolution electrospray ionization mass spectrometry (LC-HRMS and LC- HRMS2). Two products were formed from the click reactions, one of which was the majority. Another part of this work was to study the electrochemical degradation of the molecular anchor 4-phenylazole (Ph-Ur). Four stable degradation products of phenylurazole were identified (C7H9N2O, C6H8N, C6H8NO, C14H13N4O2) based on chromatographic profiles and mass spectrometry results. The charge generated during the electrolysis of phenylurazole (two-electron process) (2.85 C) is inconsistent with the theoretical or calculated charge (1.93 C), indicating that secondary/parasitic reactions occurred during the electrolysis of the latter. In conclusion, the electrochemically promoted click phenylurazole-tyrosine reactions give rise to click products with high reaction kinetics and yields in the (1:2) phenylurazole-tyrosine ratios, and the presence of side reactions is likely to affect the yield of the click phenylurazole-tyrosine reaction. KW - Clinical Biochemistry KW - Spectroscopy KW - Drug Discovery KW - Pharmaceutical Science KW - Analytical Chemistry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599267 DO - https://doi.org/10.1016/j.jpba.2024.116147 VL - 245 SP - 1 EP - 8 PB - Elsevier BV AN - OPUS4-59926 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von Törne, Wipert Jannik A1 - Steinhäuser, Lorin A1 - Klyk-Seitz, Urszula-Anna A1 - Piechotta, Christian T1 - High-resolution mass spectrometric elucidation of electron ionization induced fragmentation pathways of methylated warfarin and selected hydroxylated species N2 - The plant secondary metabolite families of coumarin and 4-hydroxy coumarin have a broad pharmacological spectrum ranging from antibacterial to anticancer properties. One prominent member of this substance class is the synthetic but naturally inspired anticoagulant drug and rodenticide warfarin (coumadin). A vast number of publications focus on the identification of warfarin and its major cytochrome P450-mediated phase I metabolites by liquid chromatography (LC) with mass spectrometry (MS) and tandem mass spectrometric (MS/MS) detection techniques. For the first time, electron ionization (EI) induced high-resolution quadrupole time-of-flight mass spectrometric (HR-qToF-MS) data of in-liner derivatized warfarin and selected hydroxylated species is provided in this study as an alternative to LC-MS/MS approaches. Furthermore, the characteristic fragments and fragmentation pathways of the analyzed methyl ethers are concluded. The obtained data of analytical standards, specific deuterated and 13C-labeled compounds prove inductive cleavage of the acyl or acetonyl side chain, methyl migration, and H-migration, along with consequential inductive cleavage as predominant fragmentation routes. Based on the HR-spectral data, commonalities and differences between the analyzed compounds and fragment groups were evaluated with future applicability in structure elucidation and spectra prediction of related compounds. KW - High-resolution mass spectrometry KW - Warfarin KW - Hydroxy warfarin KW - Fragmentation pathway PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596025 DO - https://doi.org/10.1016/j.ijms.2024.117220 SN - 1387-3806 VL - 499 SP - 1 EP - 7 PB - Elsevier B.V. AN - OPUS4-59602 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von Törne, Wipert Jannik A1 - Klyk-Seitz, Urszula-Anna A1 - Piechotta, Christian T1 - Developing a GC-EI-MS/MS method for quantifying warfarin and five hydroxylated metabolites generated by the Fenton reaction N2 - AbstractSince the 1950s, Warfarin has been used globally as both a prescription drug and a rodenticide. Research has shown that warfarin and other rodenticides are present in the environment and food chain. However, emerging contaminants are subject to degradation by biotic and abiotic processes and advanced oxidation processes. In some cases, detecting the parent compound may not be possible due to the formation of structurally changed species. This approach aims to identify hydroxylated transformation products of warfarin in a laboratory setting, even after the parent compound has undergone degradation. Therefore, the Fenton reaction is utilized to insert hydroxylation into the parent compound, warfarin, by hydroxyl and hydroperoxyl radicals generated by Fe2+/Fe3+ redox reaction with hydrogen peroxide. Using multiple reaction monitoring, a GC–MS/MS method, incorporating isotopically labeled reference compounds, is used to quantify the expected derivatized species. The analytes are derivatized using trimethyl-3-trifluoromethyl phenyl ammonium hydroxide, and the derivatization yield of warfarin is determined by using isotopically labeled reference compounds. The method has a linear working range of 30 to 1800 ng/mL, with detection limits ranging from 18.7 to 67.0 ng/mL. The analytes are enriched using a C18-SPE step, and the recovery for each compound is calculated. The Fenton reaction generates all preselected hydroxylated transformation products of warfarin. The method successfully identifies that 4′-Me-O-WAR forms preferentially under the specified experimental conditions. By further optimizing the SPE clean-up procedures, this GC–MS-based method will be suitable for detecting transformation products in more complex matrices, such as environmental water samples. Overall, this study provides a better understanding of warfarin’s degradation and offers a robust analytical tool for investigating its transformation products. KW - Health, Toxicology and Mutagenesis KW - Pollution KW - Environmental Chemistry KW - General Medicine PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595737 DO - https://doi.org/10.1007/s11356-024-32133-3 SN - 0944-1344 VL - 31 SP - 16986 EP - 16994 PB - Springer Science and Business Media LLC AN - OPUS4-59573 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kornev, Roman A1 - Gornushkin, Igor B. A1 - Shabarova, Lubov A1 - Kadomtseva, Alena A1 - Mochalov, Georgy A1 - Rekunov, Nikita A1 - Romanov, Sergey A1 - Medov, Vitaly A1 - Belousova, Darya A1 - Maleev, Nikita T1 - Plasma-Chemical Disposal of Silicon and Germanium Tetrachlorides Waste by Hydrogen Reduction N2 - The processes of hydrogen reduction of silicon and germanium chlorides under the conditions of high-frequency (40.68 MHz) counteracted arc discharge stabilized between two rod electrodes are investigated. The main gas-phase and solid products of plasma-chemical transformations are determined. Thermodynamic analysis of SiCl4 + H2 and GeCl4 + H2 systems for optimal process parameters was carried out. Using the example of hydrogen reduction of SiCl4 by the method of numerical modeling, gas-dynamic and thermal processes for this type of discharge are investigated. The impurity composition of gas-phase and solid reaction products is investigated. The possibility of single-stage production of high-purity Si and Ge mainly in the form of compact ingots, as well as high-purity chlorosilanes and trichlorogermane, is shown. KW - High-frequency arc discharge KW - Hydrogen reduction KW - Silicon chlorides KW - Germanium chlorides PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594454 DO - https://doi.org/10.3390/sci6010001 VL - 6 IS - 1 SP - 1 EP - 12 PB - MDPI AG AN - OPUS4-59445 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gehrenkemper, Lennart A1 - Rühl, Isabel A1 - Westphalen, Tanja A1 - Simon, Fabian A1 - von der Au, Marcus A1 - Cossmer, Antje A1 - Meermann, Björn T1 - Investigating the uptake and fate of per- and polyfluoroalkylated substances (PFAS) in bean plants (Phaseolus vulgaris): comparison between target MS and sum parameter analysis via HR-CS-GFMAS N2 - AbstractIn this study, we present a screening method based on molecular absorption spectrometry to study PFAS uptake and fate in plants. To evaluate the suitability of this method we analyzed plant extracts with molecular absorption spectrometry (MAS) as well as liquid chromatography–tandem mass spectrometry (LC–MS/MS) for mass balance studies (w(F)). French bean plants (Phaseolus vulgaris) were grown on soil spiked using eight PFAS substances that vary in chain length and functional group composition. Specifically, these include three short-chained (C4–C5), five long-chained (C7–C10) carboxylic acids, one sulfonic acid and one sulfonic amide moieties. To investigate substance-specific PFAS uptake systematically, PFAS were spiked as single substance spike. Additionally, we studied one mixture of the investigated substances in equal proportions regarding w(F) and four PFAS mixtures of unknown composition. After 6 weeks, the plants were separated into four compartments. We analyzed the four compartments as well as the soil for extractable organically bound fluorine (EOF) by high resolution-continuum source-graphite furnace-molecular absorption spectrometry (HR-CS-GFMAS) as well as for sum of ten target-PFAS by LC–MS/MS. All three short-chained PFAS perfluorobutanoic acid (PFBA), perfluorobutanoic sulfonic acid (PFBS) and perfluoropentanoic acid (PFPeA) were determined in high concentrations mainly in the fruits of the investigated plants while long-chained PFAS perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were mainly determined in roots. PFBS was determined in remarkably high concentrations in leaves compartment by both quantification methods. Overall, comprehensive results of single substance spikes were in good agreement for both methods except for a few cases. Hence, two phenomena were identified: for mixed PFAS spikes of unknown composition huge differences between EOF and sum of target PFAS were observed with systematically higher EOF values. Overall, both methods indicate comparable results with MS being more reliable for known PFAS contamination and MAS being more valuable to identify PFAS exposure of unknown composition. Graphical Abstract KW - Pollution PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-589394 DO - https://doi.org/10.1186/s12302-023-00811-7 VL - 35 IS - 104 SP - 1 EP - 13 PB - Springer Science and Business Media LLC AN - OPUS4-58939 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rieger, Philip A1 - Magnall, Joseph M. A1 - Gleeson, Sarah A. A1 - Oelze, Marcus T1 - Pyrite chemistry records a multistage ore forming system at the Proterozoic George Fisher massive sulfide Zn-Pb-Ag deposit, Mount Isa, Australia N2 - Trace element (TE) analysis of pyrite via LA-ICP-MS can be used to reconstruct the conditions of pyrite formation in complex mineral systems. The Carpentaria province in northern Australia is host to some of the world’s highest value Zn-Pb (+Ag, Cu) deposits. The genesis of many of these deposits is controversial, with competing models of single-vs. multi-stage ore formation. In this study, LA-ICP-MS data of paragenetically constrained pyrite from the George Fisher Zn-Pb-Ag deposit has been analysed to investigate the chemistry of different stages of ore formation. Pyrite from correlative unmineralized host rocks has also been analysed to investigate evidence of distal hydrothermal anomalism. All LA-ICP-MS data have been statistically evaluated (principal component analysis) and interpreted together with whole rock lithogeochemical data of the same samples. Pre-ore diagenetic pyrite is compositionally similar to other Proterozoic diagenetic pyrite, with some evidence of minor hydrothermal anomalism that with further analysis could help define distal alteration. Pyrite from the different ore stages are compositionally distinct, consistent with a multi-stage system. Ore stage 1 pyrite exceeds background contents of Co, Cu, Zn, As, Ag, Sb, Tl, and Pb and has elevated Co/Ni ratios, whereas only Ni and Co are above background abundances in ore stage 2 and 3 pyrite, of which only ore stage 3 pyrite has high Co/Ni ratios. Ore stage 1 pyrite has a similar composition to hydrothermal pyrite in the undeformed northern Carpentaria CD-type deposits and was likely syn-diagenesis. Ore stage 2 was syn-deformation, and resulted in replacement and recrystallization of pre-existing pyrite, and the expulsion of incompatible TEs. Ore stage 3 formed via a later Cu-Zn-Pb mineralizing event that resulted in a new geochemically distinct generation of Co-rich pyrite. Overall, this study demonstrates the value of paragenetically-constrained pyrite TE data for refining genetic models in complex sediment hosted mineral systems. KW - General Earth and Planetary Sciences PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-590407 DO - https://doi.org/10.3389/feart.2023.892759 VL - 11 SP - 1 EP - 19 PB - Frontiers Media SA AN - OPUS4-59040 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Inostroza, Manuel A1 - Fernandez, Bárbara A1 - Aguilera, Felipe A1 - Layana, Susana A1 - Walter, Thomas R. A1 - Zimmer, Martin A1 - Rodríguez-Díaz, Augusto A1 - Oelze, Marcus T1 - Physical and chemical characteristics of active sulfur flows observed at Lastarria volcano (northern Chile) in January 2019 N2 - Molten sulfur is found in various subaerial volcanoes. However, limited records of the pools and flows of molten sulfur have been reported: therefore, questions remain regarding the physicochemical processes behind this phenomenon. A suite of new sulfur flows, some of which active, was identified at the Lastarria volcano (northern Chile) and studied using satellite imagery, in situ probing, and temperature and video recording. This finding provides a unique opportunity to better understand the emplacement mechanisms and mineral and chemical compositions of molten sulfur, in addition to gaining insight into its origin. Molten sulfur presented temperatures of 124–158°C, with the most prolonged sulfur flow reaching 12 m from the source. Photogrammetric tools permitted the identification of levees and channel structures, with an estimated average flow speed of 0.069 m/s. Field measurements yielded a total volume of 1.45 ± 0.29 m3 of sulfur (equivalent to ∼2.07 tons) mobilized during the January 2019 event for at least 408 min. Solidified sulfur was composed of native sulfur with minor galena and arsenic- and iodine-bearing minerals. Trace element analysis indicated substantial enrichment of Bi, Sb, Sn, Cd, as well as a very high concentration of As (&gt;40.000 ppm). The January 2019 molten sulfur manifestations in Lastarria appear to be more enriched in As compared to the worldwide known volcanoes with molten sulfur records, such as the Shiretoko-Iozan and Poás volcanoes. Furthermore, their rheological properties suggest that the “time of activity” in events such as this could be underestimated as flows in Lastarria have moved significantly slower than previously thought. The origin of molten sulfur is ascribed to the favorable S-rich chemistry of fumarolic gases and changes in host rock permeability (fracture opening). Molten sulfur in Lastarria correlates with a peak in activity characterized by high emissions of SO2 and other acid species, such as HF and HCl, in addition to ground deformation. Consequently, molten sulfur was framed within a period of volcanic unrest in Lastarria, triggered by changes in the magmatic-hydrothermal system. The appearance of molten sulfur is related to physicochemical perturbations inside the volcanic system and is perhaps a precursor of eruptive activity, as observed in the Poás and Turrialba volcanoes. KW - General Earth and Planetary Sciences PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-590331 DO - https://doi.org/10.3389/feart.2023.1197363 VL - 11 SP - 1 EP - 18 PB - Frontiers Media SA AN - OPUS4-59033 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Völker, Tobias A1 - Gornushkin, Igor B. T1 - Investigation of a method for the correction of self-absorption by Planck function in laser induced breakdown spectroscopy N2 - The electron density and temperature of a laser-induced plasma can be determined from the width and intensity of the spectral lines, provided that the corresponding optical transitions are optically thin. However, the lines in laser induced plasma are often self-absorbed. One of the methods of correction of this effect is based on the use of the Planck function and an iterative numerical calculation of the plasma temperature. In this study, the method is further explored and its inherent errors and limitations are evaluated. For this, synthetic spectra are used that fully correspond to the assumed conditions of a homogeneous isothermal plasma at local thermodynamic equilibrium. Based on the error analysis, the advantages and disadvantages of the method are discussed in comparison with other methods of self-absorption correction. KW - LIBS KW - Self-absorption KW - Planck function PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-572677 DO - https://doi.org/10.1039/D2JA00352J SN - 0267-9477 SP - 1 EP - 6 PB - Royal Society of Chemistry (RSC) AN - OPUS4-57267 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Riedel, Soraya A1 - Jaut, Valerie A1 - Schneider, Rudolf T1 - Ergometrine sensing in rye flour by a magnetic bead-based immunoassay followed by flow injection analysis with amperometric detection N2 - A certain group of mycotoxins, the ergot alkaloids, has caused countless deaths throughout human history. They are found in rye and other cereals and ingesting contaminated foods can cause serious health problems. To identify contaminated food exceeding the legal limits for ergot alkaloids, a portable and cost-effective test system is of great interest to the food industry. Rapid analysis can be achieved by screening for a marker compound, for which we chose ergometrine. We developed a magnetic bead-based immunoassay for ergometrine with amperometric detection in a flow injection system using a handheld potentiostat and a smartphone. With this assay a limit of detection of 3 nM (1 μg/L) was achieved. In spiked rye flour, ergometrine levels from 25 to 250 μg/kg could be quantified. All results could be verified by optical detection. The developed assay offers great promise to meet the demand for on-site ergometrine detection in the food industry. KW - Ergot alkaloids KW - Amperometry KW - Magnetic beads KW - Immunoassay KW - Food analysis KW - Fow injection analysis KW - Mycotoxins PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565906 DO - https://doi.org/10.1016/j.talanta.2022.124172 SN - 0039-9140 N1 - Geburtsname von Riedel, Soraya: Höfs, S. - Birth name of Riedel, Soraya: Höfs, S. VL - 254 IS - 124172 SP - 1 EP - 8 PB - Elsevier B.V. AN - OPUS4-56590 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Flierl, Lukas A1 - Rienitz, Olaf A1 - Vogl, Jochen A1 - Pramann, Axel T1 - An advancement of the gravimetric isotope mixture method rendering the knowledge of the spike purity superfluous N2 - The gravimetric isotope mixture method is the primary method to determine absolute isotope ratios. This method, however, depends on the existence of suitable spike materials and knowledge of their purities. Determining the purity of the spikes can be tedious and labour-intensive. In this publication, an advancement of the gravimetric isotope mixture method, rendering the determination of the purity of the spike materials unnecessary, is presented. The advancement combines mass spectrometry and ion chromatography leading to an approach being independent of the purity of the spike materials. In the manuscript the mathematical background and the basic idea of the novel approach are described using a two-isotope system like copper or lithium. KW - Isotope amount ratios KW - Metrology KW - Mass spectrometry KW - Ion chromatography PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608726 DO - https://doi.org/10.1007/s00216-024-05465-9 SP - 5325 EP - 5333 PB - Springer Science and Business Media LLC AN - OPUS4-60872 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wegner, Karl David A1 - Hildebrandt, N. T1 - Near infrared quantum dots for biosensing and bioimaging N2 - Quantum dots (QDs) possess unique optoelectronic properties, which make them very attractive to be used as optical probes in biosensing and bioimaging applications. The strong absorbance and light scattering of biological compounds like tissue and blood in the visible range pose a problem. However, if optical probes emitting in the near-infrared (NIR) range are used, scattering, absorption, and autofluorescence of biological components are strongly reduced. This allows for an increased light penetration depth and higher spatial and temporal resolution for the investigation of biological processes. The synthesis and application of NIR emitting QDs is a fast-growing research field and the benefits of using QDs were demonstrated for a variety of applications, such as photoelectrochemical biosensor, in vivo vascular imaging, and fluorescence-guided surgery. This article reviews the state-of-the-art developments in the preparation of NIR/IR QDs and highlights the latest research about their utilization in biosensing and bioimaging applications. KW - Quantum dots KW - Near-infrared KW - Biosensing KW - Bioimaging KW - NIR-II / SWIR KW - Advanced nanomaterials PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-609708 SN - 0165-9936 DO - https://doi.org/10.1016/j.trac.2024.117922 VL - 180 SP - 1 EP - 19 PB - Elsevier B.V. AN - OPUS4-60970 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Simon, Fabian A1 - von der Au, Marcus A1 - Gehrenkemper, Lennart A1 - Meermann, Björn T1 - An optimized method for PFAS analysis using HR–CS–GFMAS via GaF detection N2 - The analysis of per- and polyfluoroalkyl substances (PFAS) via sum parameters like extractable organic fluorine (EOF) in combination with high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR–CS–GFMAS) is highly promising regarding fluorine sensitivity and selectivity. However, the HR–CS–GFMAS method includes several drying and heating steps which can lead to losses of volatile PFAS before the molecular formation step using e.g., GaF formation. Hence, the method leads to a strong discrimination of PFAS within the EOF depending on their physical/chemical properties and is therefore associated with reduced accuracy. To reduce this discrepancy and to indicate realistic PFAS pollution values, an optimization of the HR–CS–GFMAS method for PFAS analysis is needed. Hence, we determined fluorine response factors of several PFAS with different physical/chemical properties upon application of systematic optimization steps. We could therefore improve the method's sensitivity for PFAS analysis using a modifier drying pre-treatment step followed by a sequential injection of sample solutions. The highest improvement in sensitivity of volatile PFAS was shown upon addition of a Mg modifier during drying pre-treatment. Thereby, during optimization the relative standard deviation of fluorine response factors could be reduced from 55 % (initial method) to 27 % (optimized method) leading to a more accurate determination of organofluorine sum parameters. The method provides an instrumental LOD and LOQ of β(F) 1.71 μg/L and 5.13 μg/L, respectively. Further validation aimed to investigate several matrix effects with respect to water matrices. Here, substance-specific behavior was observed. For example, perfluorooctanoic acid (PFOA) which was used as calibrator, showed signal suppressions upon high chloride concentrations (>50 mg/L). Hence, a thorough separation of Cl from analytes during sample preparation is needed for accurate sum parameter analysis. KW - PFAS KW - GF-AAS KW - Method optimization PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-610522 DO - https://doi.org/10.1016/j.talanta.2024.126811 VL - 281 SP - 1 EP - 11 PB - Elsevier B.V. AN - OPUS4-61052 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chronakis, Michail Ioannis A1 - Meermann, Björn A1 - von der Au, Marcus T1 - The evolution of data treatment tools in single-particle and single-cell ICP-MS analytics N2 - Single-particle inductively coupled plasma-mass spectrometry (sp-ICP-MS) is one of the most powerful tools in the thriving field of nanomaterial analysis. Along the same lines, single-cell ICP-MS (sc-ICP-MS) has become an invaluable tool in the study of the variances of cell populations down to a per-cell basis. Their importance and application fields have been listed numerous times, across various reports and reviews. However, not enough attention has been paid to the immense and ongoing development of the tools that are currently available to the analytical community for the acquisition, and more importantly, the treatment of single-particle and single-cell-related data. Due to the ever-increasing demands of modern research, the efficient and dependable treatment of the data has become more important than ever. In addition, the field of single-particle and single-cell analysis suffers due to a large number of approaches for the generated data—with varying levels of specificity and applicability. As a result, finding the appropriate tool or approach, or even comparing results, can be challenging. This article will attempt to bridge these gaps, by covering the evolution and current state of the tools at the disposal of sp-ICP-MS users. Graphical Abstract KW - Trend Article KW - spICP-MS KW - Data Tools KW - scICP-MS PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-610539 DO - https://doi.org/10.1007/s00216-024-05513-4 SP - 1 EP - 7 PB - Springer Science and Business Media LLC AN - OPUS4-61053 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dariz, P. A1 - Schmid, Thomas T1 - Raman focal point on Roman Egyptian blue elucidates disordered cuprorivaite, green glass phase and trace compounds N2 - The discussed comparative analyses of Roman Imperial pigment balls and fragmentary murals unearthed in the ancient cities of Aventicum and Augusta Raurica (Switzerland) by means of Raman microspectroscopy pertain to a predecessor study on trace compounds in Early Medieval Egyptian blue (St. Peter, Gratsch, South Tyrol, Northern Italy). The plethora of newly detected associated minerals of the raw materials surviving the synthesis procedure validate the use of quartz sand matching the composition of sediments transported by the Volturno river into the Gulf of Gaeta (Campania, Southern Italy) with a roasted sulphidic copper ore and a mixed-alkaline plant ash as fluxing agent. Thus, the results corroborate a monopolised pigment production site located in the northern Phlegrean Fields persisting over the first centuries A.D., this in line with statements of the antique Roman writers Vitruvius and Pliny the Elder and recent archaeological evidences. Beyond that, Raman spectra reveal through gradual peak shifts and changes of band width locally divergent process conditions and compositional inhomogeneities provoking crystal lattice disorder in the chromophoric cuprorivaite as well as the formation of a copper-bearing green glass phase, the latter probably in dependency of the concentration of alkali flux, notwithstanding that otherwise solid-state reactions predominate the synthesis. KW - Raman microspectroscopy KW - Egyptian blue KW - Cuprorivaite PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-559028 DO - https://doi.org/10.1038/s41598-022-19923-w SN - 2045-2322 VL - 12 IS - 1 SP - 1 EP - 12 PB - Nature Publishing Group CY - London AN - OPUS4-55902 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sieber, M. J. A1 - Wilke, M. A1 - Appelt, O. A1 - Oelze, Marcus A1 - Koch-Müller, M. T1 - Melting relations of Ca–Mg carbonates and trace element signature of carbonate melts up to 9 GPa – A proxy for melting of carbonated mantle lithologies N2 - The most profound consequences of the presence of Ca–Mg carbonates (CaCO3–MgCO3) in the Earth’s upper mantle may be to lower the melting temperatures of the mantle and control the melt composition. Low-degree partial melting of a carbonate-bearing mantle produces CO2-rich, silica-poor melts compositionally imposed by the melting relations of carbonates. Thus, understanding the melting relations in the CaCO3–MgCO3 system facilitates the interpretation of natural carbonate-bearing silicate systems. We report the melting relations of the CaCO3–MgCO3 system and the partition coefficient of trace elements between carbonates and carbonate melt from experiments at high pressure (6 and 9 GPa) and temperature (1300–1800 ◦C) using a rocking multi-anvil press. In the absence of water, Ca–Mg carbonates are stable along geothermal gradients typical of subducting slabs. Ca–Mg carbonates (∼ Mg0.1–0.9Ca0.9–0.1CO3) partially melt beneath mid-ocean ridges and in plume settings. Ca–Mg carbonates melt incongruently, forming periclase crystals and carbonate melt between 4 and 9 GPa. Furthermore, we show that the rare earth element (REE) signature of Group-I kimberlites, namely strong REE fractionation and depletion of heavy REE relative to the primitive mantle, is resembled by carbonate melt in equilibrium with Ca-bearing magnesite and periclase at 6 and 9 GPa. This suggests that the dolomite–magnesite join of the CaCO3–MgCO3 system might be useful to approximate the REE signature of carbonate-rich melts parental to kimberlites. KW - High pressure experiments KW - Laser Ablation PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-561197 DO - https://doi.org/10.5194/ejm-34-411-2022 SN - 0935-1221 VL - 34 IS - 5 SP - 411 EP - 424 PB - Copernicus Publications CY - Göttingen AN - OPUS4-56119 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Steinhäuser, Lorin A1 - Piechotta, Christian A1 - Westphalen, Tanja A1 - Kaminski, Katja T1 - Evaluation, comparison and combination of molecularly imprinted polymer solid phase extraction and classical solid phase extraction for the preconcentration of endocrine disrupting chemicals from representative whole water samples N2 - Estrogens are endocrine disrupting chemicals and of high concerns due to demonstrated harmful effects on the environment and low effect levels. For monitoring and risk assessment, several estrogens were included in the "watch list" of the EU Water Framework Directive which sets very low environmental quality standard (EQS) levels for Estrone (E1) and 17β-Estradiol (E2) of 0.4 ng L−1 and for 17α-Ethinylestradiol (EE2) of 0.035 ng L−1 requiring sensitive detection methods, as well as extensive sample preparation. A sensitive, derivatization-free, isotope dilution calibration HPLC-MS/MS method for a panel of 5 selected estrogens (including the 3 estrogens of the EU WFD watchlist), and a procedure for the reproducible preparation of a representative whole water matrix including mineral water, humic acids and solid particulate matter are presented. These are used in a diligent comparison of classical solid phase extraction (SPE) on hydrophilic-lipophilic balanced (HLB) phase to SPE on an estrogen-specific molecularly imprinted polymer phase (MISPE) for ultra-trace levels of the analytes (1–10 ng L−1). Additionally, a two-step procedure combining HLB SPE disks followed by MISPE is evaluated. The tow-step procedure provides superior enrichment, matrix removal and sample throughput while maintaining comparable recovery rates to simple cartridge SPE. Estimated method quantification limits (MQLs) range from 0.109–0.184 ng L−1 and thus meet EQS-levels for E1 and E2, but not EE2. The representative whole water matrix provides a reproducible comparison of sample preparation methods and lays the foundation for a certified reference material for estrogen analysis. The presented method will serve as the basis for an extended validation study to assess its use for estrogen monitoring in the environment. KW - Estrogens KW - Whole water samples KW - Molecular imprinted polymers KW - EU-WFD PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-563547 DO - https://doi.org/10.1016/j.talo.2022.100163 SN - 2666-8319 VL - 6 SP - 1 EP - 5 PB - Elsevier B.V. CY - Amsterdam, Niederlande AN - OPUS4-56354 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tatzel, M. A1 - Frings, P. J. A1 - Oelze, Marcus A1 - Herwartz, D. A1 - Lünsdorf, K. A1 - Wiedenbeck, M. T1 - Chert oxygen isotope ratios are driven by Earth's thermal evolution N2 - The 18O/16O ratio of cherts (δ18Ochert) increases nearly monotonically by ~15‰ from the Archean to present. Two end-member explanations have emerged: cooling seawater temperature (TSW) and increasing seawater δ18O (δ18Osw). Yet despite decades of work, there is no consensus, leading some to view the δ18Ochert record as pervasively altered. Here, we demonstrate that cherts are a robust archive of diagenetic temperatures, despite metamorphism and exposure to meteoric fluids, and show that the timing and temperature of quartz precipitation and thus δ18Ochert are determined by the kinetics of silica diagenesis. A diagenetic model shows that δ18Ochert is influenced by heat flow through the sediment column. Heat flow has decreased over time as planetary heat is dissipated, and reasonable Archean-modern heat flow changes account for ~5‰ of the increase in δ18Ochert, obviating the need for extreme TSW or δ18Osw reconstructions. The seawater oxygen isotope budget is also influenced by solid Earth cooling, with a recent reconstruction placing Archean δ18OSW 5 to 10‰ lower than today. Together, this provides an internally consistent view of the δ18Ochert record as driven by solid Earth cooling over billion-year timescales that is compatible with Precambrian glaciations and biological. KW - Climate KW - Oxygen isotope ratios KW - Silica diagenesis KW - Early Earth KW - Heat flow PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-569359 DO - https://doi.org/10.1073/pnas.2213076119 SN - 0027-8424 VL - 119 IS - 51 SP - 1 EP - 7 PB - National Academy of Sciences CY - Washington, DC AN - OPUS4-56935 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Breuninger, Esther S. A1 - Tolu, Julie A1 - Aemisegger, Franziska A1 - Thurnherr, Iris A1 - Bouchet, Sylvain A1 - Mestrot, Adrien A1 - Ossola, Rachele A1 - McNeill, Kristopher A1 - Tukhmetova, Dariya A1 - Vogl, Jochen A1 - Meermann, Björn A1 - Sonke, Jeroen E. A1 - Winkel, Lenny H. E. T1 - Marine and terrestrial contributions to atmospheric deposition fluxes of methylated arsenic species N2 - Arsenic, a toxic element from both anthropogenic and natural sources, reaches surface environments through atmospheric cycling and dry and wet deposition. Biomethylation volatilizes arsenic into the atmosphere and deposition cycles it back to the surface, affecting soil-plant systems. Chemical speciation of deposited arsenic is important for understanding further processing in soils and bioavailability. However, the range of atmospheric transport and source signature of arsenic species remain understudied. Here we report significant levels ofmethylated arsenic in precipitation, cloudwater and aerosols collected under free tropospheric conditions at Pic du Midi Observatory (France) indicating long-range transport, which is crucial for atmospheric budgets. Through chemical analyses andmoisture source diagnostics, we identify terrestrial and marine sources for distinct arsenic species. Estimated atmospheric deposition fluxes of methylated arsenic are similar to reported methylation rates in soils, highlighting atmospheric deposition as a significant, overlooked source of potentially bioavailable methylated arsenic species impacting plant uptake in soils. KW - Arsenic KW - Speciation KW - Fluxes KW - Marine KW - Terrestrial KW - Sulfur isotopes PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-615551 DO - https://doi.org/10.1038/s41467-024-53974-z SN - 2041-1723 VL - 15 IS - 1 SP - 1 EP - 13 PB - Springer Science and Business Media LLC AN - OPUS4-61555 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zweigle, J. A1 - Schmidt, A. A1 - Bugsel, B. A1 - Vogel, Christian A1 - Simon, Fabian A1 - Zwiener, C. T1 - Perfluoroalkyl acid precursor or weakly fluorinated organic compound? A proof of concept for oxidative fractionation of PFAS and organofluorines N2 - Organofluorine mass balance approaches are increasingly applied to investigate the occurrence of per- and polyfluoroalkyl substances (PFAS) and other organofluorines in environmental samples more comprehensively. Usually, complex samples prevent the identification and quantification of every fluorine-containing molecule. Consequently, large unidentified fractions between fluorine sum parameters such as extractable organic fluorine (EOF) and the sum of quantified analytes are frequently reported. We propose using oxidative conversion to separate (unidentified) weakly fluorinated compounds (e.g., pesticides, pharmaceuticals) from PFAA-precursors (perfluoroalkyl chain lengths ≥ C6). We show with three organofluorine model substances (flufenamic acid, diflufenican, pantoprazole) that CF3-groups or aromatic fluorine can be quantitatively converted to inorganic fluoride and trifluoroacetic acid (TFA) by applying PhotoTOP oxidation (UV/TiO2). The principle of fluorine separation in mixtures is demonstrated by the oxidation of the three weakly fluorinated compounds together with the PFAA-precursor 6:2/6:2 fluorotelomer mercaptoalkyl phosphate diester (FTMAP). After oxidation, the products F− and TFA were separated from PFCAs ( C4) by SPE, and the fractions were analyzed individually. Closed mass balances both with and without the addition of organic matrix were achieved. Eventually, the fluorine balance was verified by total fluorine measurements with combustion ion chromatography (CIC). The proposed methods should be considered a proof of concept to potentially explain unidentified fractions of the EOF, especially if compounds with low fluorine content such as pesticides, pharmaceuticals, and their transformation products contribute largely to the EOF. Future studies are needed to show the applicability to the complexity of environmental samples. Graphical Abstract KW - Combustion Ion Chromatography KW - Per- and Polyfluoroalkyl substances (PFAS) PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-613429 DO - https://doi.org/10.1007/s00216-024-05590-5 SP - 1 EP - 10 PB - Springer Science and Business Media LLC AN - OPUS4-61342 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - D'Agostino, Giancarlo A1 - Oelze, Marcus A1 - Vogl, Jochen A1 - Ghestem, Jean-Philippe A1 - Lafaurie, Nicolas A1 - Klein, Ole A1 - Pröfrock, Daniel A1 - Di Luzio, Marco A1 - Bergamaschi, Luigi A1 - Jaćimović, Radojko A1 - Oster, Caroline A1 - Irrgeher, Johanna A1 - Lancaster, Shaun T. A1 - Walch, Anna A1 - Röthke, Anita A1 - Michaliszyn, Lena A1 - Pramann, Axel A1 - Rienitz, Olaf A1 - Sara-Aho, Timo A1 - Cankur, Oktay A1 - Kutan, Derya A1 - Noireaux, Johanna T1 - Development and application of reference and routine analytical methods providing SI-traceable results for the determination of technology-critical elements in PCB from WEEE N2 - The recovery and reprocessing of technology-critical elements (TCE) present in printed circuit boards (PCB) from electrical and electronic waste is essential both for recycling valuable materials subject to supply risk and for reducing the environmental impact. Although the quantitative knowledge of TCE amounts in endof- life PCB plays a key role, there are neither matrix certified reference materials nor harmonized analytical methods available to establish the traceability of the results to the International System of Units. To fill these gaps, we developed and applied five reference analytical methods based on ICP-MS standard addition calibrations and INAA k0- and relative calibrations suitable to certify reference materials. In addition, we developed and tested six analytical methods based on more commonly used ICP-MS external standard calibrations to provide industry with routine analysis methods. Twenty TCE (Ag, Au, Co, Cu, Dy, Ga, Gd, Ge, In, La, Li, Nd, Ni, Pd, Pr, Pt, Rh, Sm, Ta and Ti) were selected as target analytes and a batch of powdered PCB was used as measurement material. An overall mutual agreement was observed among data collected by reference methods at a few percent relative uncertainty levels. Moreover, all but one of the methods developed for routine analysis demonstrated their suitability in industrial applications by producing data within ± 20% of the values established with reference methods. KW - Technology critical elements KW - Electronic waste KW - Printed circuit boards KW - Traceability KW - Uncertainty PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612416 DO - https://doi.org/10.1039/d4ja00235k SN - 1364-5544 VL - 39 IS - 11 SP - 2809 EP - 2823 PB - Royal Society of Chemistry (RSC) AN - OPUS4-61241 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lancaster, Shaun T. A1 - Sahlin, Eskil A1 - Oelze, Marcus A1 - Ostermann, Markus A1 - Vogl, Jochen A1 - Laperche, Valérie A1 - Touze, Solène A1 - Ghestem, Jean-Philippe A1 - Dalencourt, Claire A1 - Gendre, Régine A1 - Stammeier, Jessica A1 - Klein, Ole A1 - Pröfrock, Daniel A1 - Košarac, Gala A1 - Jotanovic, Aida A1 - Bergamaschi, Luigi A1 - Di Luzio, Marco A1 - D’Agostino, Giancarlo A1 - Jaćimović, Radojko A1 - Eberhard, Melissa A1 - Feiner, Laura A1 - Trimmel, Simone A1 - Rachetti, Alessandra A1 - Sara-Aho, Timo A1 - Roethke, Anita A1 - Michaliszyn, Lena A1 - Pramann, Axel A1 - Rienitz, Olaf A1 - Irrgeher, Johanna T1 - Evaluation of X-ray fluorescence for analysing critical elements in three electronic waste matrices: A comprehensive comparison of analytical techniques N2 - As the drive towards recycling electronic waste increases, demand for rapid and reliable analytical methodology to analyse the metal content of the waste is increasing, e.g. to assess the value of the waste and to decide the correct recycling routes. Here, we comprehensively assess the suitability of different x-ray fluorescence spectroscopy (XRF)-based techniques as rapid analytical tools for the determination of critical raw materials, such as Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Nb, Pd and Au, in three electronic waste matrices: printed circuit boards (PCB), light emitting diodes (LED), and lithium (Li)-ion batteries. As validated reference methods and materials to establish metrological traceability are lacking, several laboratories measured test samples of each matrix using XRF as well as other independent complementary techniques (instrumental neutron activation analysis (INAA), inductively coupled plasma mass spectrometry (ICP-MS) and ICP optical emission spectrometry (OES)) as an inter-laboratory comparison (ILC). Results highlighted key aspects of sample preparation, limits of detection, and spectral interferences that affect the reliability of XRF, while additionally highlighting that XRF can provide more reliable data for certain elements compared to digestion-based approaches followed by ICP-MS analysis (e.g. group 4 and 5 metals). A clear distinction was observed in data processing methodologies for wavelength dispersive XRF, highlighting that considering the metals present as elements (rather than oxides) induces overestimations of the mass fractions when compared to other techniques. Eventually, the effect of sample particle size was studied and indicated that smaller particle size (<200 μm) is essential for reliable determinations. KW - XRF KW - WEEE KW - PCB KW - Battery KW - LED KW - Recycling PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-614060 DO - https://doi.org/10.1016/j.wasman.2024.10.015 VL - 190 SP - 496 EP - 505 PB - Elsevier B.V. AN - OPUS4-61406 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gregório, Bruno J.R. A1 - Ramos, Inês I. A1 - Marques, Sara S. A1 - Barreiros, Luísa A1 - Magalhães, Luís M. A1 - Schneider, Rudolf A1 - Segundo, Marcela A. T1 - Microcarrier-based fluorescent yeast estrogen screen assay for fast determination of endocrine disrupting compounds N2 - The presence of endocrine-disrupting compounds (EDCs) in water poses a significant threat to human and animal health, as recognized by regulatory agencies throughout the world. The Yeast Estrogen Screen (YES) assay is an excellent method to evaluate the presence of these compounds in water due to its simplicity and capacity to assess the bioaccessible forms/fractions of these compounds. In the presence of a compound with estrogenic activity, Saccharomyces cerevisiae cells, containing a lacZ reporter gene encoding the enzyme β-galactosidase, are induced, the enzyme is synthesised, and released to the extracellular medium. In this work, a YES-based approach encompassing the use of a lacZ reporter gene modified strain of S. cerevisiae, microcarriers as solid support, and a fluorescent substrate, fluorescein di-β-D-galactopyranoside, is proposed, allowing for the assessment of EDCs’ presence after only 2 h of incubation. The proposed method provided an EC50 of 0.17 ± 0.03 nM and an LLOQ of 0.03 nM, expressed as 17β-estradiol. The assessment of different EDCs provided EC50 values between 0.16 and 1.2 × 103 nM. After application to wastewaters, similar results were obtained for EDCs screening, much faster, compared to the conventional 45 h spectrophotometric procedure using a commercial kit, showing potential for onsite high-throughput screening of environmental contamination. KW - Biosensoren KW - YES assay KW - Endokrine Disruptoren PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-602315 DO - https://doi.org/10.1016/j.talanta.2024.125665 VL - 271 SP - 1 EP - 7 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-60231 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Braymer, Joseph J. A1 - Stehling, Oliver A1 - Stümpfig, Martin A1 - Rösser, Ralf A1 - Spantgar, Farah A1 - Blinn, Catharina M. A1 - Mühlenhoff, Ulrich A1 - Pierik, Antonio J. A1 - Lill, Roland T1 - Requirements for the biogenesis of [2Fe-2S] proteins in the human and yeast cytosol N2 - The biogenesis of iron–sulfur (Fe/S) proteins entails the synthesis and trafficking of Fe/S clusters, followed by their insertion into target apoproteins. In eukaryotes, the multiple steps of biogenesis are accomplished by complex protein machineries in both mitochondria and cytosol. The underlying biochemical pathways have been elucidated over the past decades, yet the mechanisms of cytosolic [2Fe-2S] protein assembly have remained ill-defined. Similarly, the precise site of glutathione (GSH) requirement in cytosolic and nuclear Fe/S protein biogenesis is unclear, as is the molecular role of the GSH-dependent cytosolic monothiol glutaredoxins (cGrxs). Here, we investigated these questions in human and yeast cells by various in vivo approaches. [2Fe-2S] cluster assembly of cytosolic target apoproteins required the mitochondrial ISC machinery, the mitochondrial transporter Atm1/ABCB7 and GSH, yet occurred independently of both the CIA system and cGrxs. This mechanism was strikingly different from the ISC-, Atm1/ABCB7-, GSH-, and CIA-dependent assembly of cytosolic–nuclear [4Fe-4S] proteins. One notable exception to this cytosolic [2Fe-2S] protein maturation pathway defined here was yeast Apd1 which used the CIA system via binding to the CIA targeting complex through its C-terminal tryptophan. cGrxs, although attributed as [2Fe-2S] cluster chaperones or trafficking proteins, were not essential in vivo for delivering [2Fe-2S] clusters to either CIA components or target apoproteins. Finally, the most critical GSH requirement was assigned to Atm1-dependent export, i.e. a step before GSH-dependent cGrxs function. Our findings extend the general model of eukaryotic Fe/S protein biogenesis by adding the molecular requirements for cytosolic [2Fe-2S] protein maturation. KW - Biokorrosion KW - Hydrogenasen KW - Microbially Induced Corrosion PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-602328 DO - https://doi.org/10.1073/pnas.2400740121 SN - 0027-8424 VL - 121 IS - 21 SP - 1 EP - 12 PB - Proceedings of the National Academy of Sciences CY - Washington D.C. AN - OPUS4-60232 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Groschke, Matthias A1 - Becker, Roland T1 - Comparison of carrier gases for the separation and quantification of mineral oil hydrocarbon (MOH) fractions using online coupled high performance liquid chromatography-gas chromatography-flame ionisation detection N2 - On-line coupled high performance liquid chromatography-gas chromatography-flame ionisation detection (HPLC-GC-FID) was used to compare the effect of hydrogen, helium and nitrogen as carrier gases on the chromatographic characteristics for the quantification of mineral oil hydrocarbon (MOH) traces in food related matrices. After optimisation of chromatographic parameters nitrogen carrier gas exhibited characteristics equivalent to hydrogen and helium regarding requirements set by current guidelines and standardisation such as linear range, quantification limit and carry over. Though nitrogen expectedly led to greater peak widths, all required separations of standard compounds were sufficient and humps of saturated mineral oil hydrocarbons (MOSH) and aromatic mineral oil hydrocarbons (MOAH) were appropriate to enable quantitation similar to situations where hydrogen or helium had been used. Slightly increased peak widths of individual hump components did not affect shapes and widths of the MOSH and MOAH humps were not significantly affected by the use of nitrogen as carrier gas. Notably, nitrogen carrier gas led to less solvent peak tailing and smaller baseline offset. Overall, nitrogen may be regarded as viable alternative to hydrogen or helium and may even extend the range of quantifiable compounds to highly volatile hydrocarbon eluting directly after the solvent peak. KW - Mineral oil hydrocarobons KW - Food KW - Liquid chromatography KW - Gas chromatography KW - MOSH/MOAH PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601450 DO - https://doi.org/10.1016/j.chroma.2024.464946 SN - 0021-9673 VL - 1726 SP - 1 EP - 7 PB - Elsevier CY - New York, NY AN - OPUS4-60145 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmidt, Stephan A1 - Hoffmann, Holger A1 - Garbe, Leif-Alexander A1 - Harrer, Andrea A1 - Steiner, Markus A1 - Himly, Martin A1 - Schneider, Rudolf T1 - Re-assessment of monoclonal antibodies against diclofenac for their application in the analysis of environmental waters N2 - The non-steroidal anti-inflammatory drug (NSAID) diclofenac (DCF) is an important environmental contaminant occurring in surface waters all over the world, because, after excretion, it is not adequately removed from wastewater in sewage treatment plants. To be able to monitor this pollutant, highly efficient analytical methods are needed, including immunoassays. In a medical research project, monoclonal antibodies against diclofenac and its metabolites had been produced. Based on this monoclonal anti-DCF antibody, a new indirect competitive enzyme-linked immunosorbent assay (ELISA) was developed and applied for environmental samples. The introduction of a spacer between diclofenac and the carrier protein in the coating conjugate led to higher sensitivity. With a test midpoint of 3 mg L−1 and a measurement range of 1–30 mg L−1, the system is not sensitive enough for direct analysis of surface water. However, this assay is quite robust against matrix influences and can be used for wastewater. Without adjustment of the calibration, organic solvents up to 5%, natural organic matter (NOM) up to 10 mg L−1, humic acids up to 2.5 mg L−1, and salt concentrations up to 6 g L−1 NaCl and 75 mg L−1 CaCl2 are tolerated. The antibody is also stable in a pH range from 3 to 12. Cross-reactivity (CR) of 1% or less was determined for the metabolites 40-hydroxydiclofenac (40-OH-DCF), 5-hydroxydiclofenac (5-OH-DCF), DCF lactam, and other NSAIDs. Relevant cross-reactivity occurred only with an amide derivative of DCF, 6-aminohexanoic acid (DCF-Ahx), aceclofenac (ACF) and DCF methyl ester (DCF-Me) with 150%, 61% and 44%, respectively. These substances, however, have not been found in samples. Only DCF-acyl glucuronide with a cross-reactivity of 57% is of some relevance. For the first time, photodegradation products were tested for cross-reactivity. With the ELISA based on this antibody, water samples were analysed. In sewage treatment plant effluents, concentrations in the range of 1.9–5.2 mg L−1 were determined directly, with recoveries compared to HPLC-MS/MS averaging 136%. Concentrations in lakes ranged from 3 to 4.4 ng L−1 and were, after pre-concentration, determined with an average recovery of 100% KW - Antikörper KW - Immunoassay KW - Wasser PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-602280 DO - https://doi.org/10.1039/d3ay01333b VL - 16 IS - 21 SP - 3349 EP - 3363 PB - Royal Society of Chemistry (RSC) CY - London AN - OPUS4-60228 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tatzel, Michael A1 - Oelze, Marcus A1 - Frick, Daniel A. A1 - Di Rocco, Tommaso A1 - Liesegang, Moritz A1 - Stuff, Maria A1 - Wiedenbeck, Michael T1 - Silicon and oxygen isotope fractionation in a silicified carbonate rock N2 - Silicon isotope fractionation during silicification is poorly understood and impedes our ability to decipher paleoenvironmental conditions from Si isotopes in ancient cherts. To investigate isotope fractionation during silica-for-carbonate replacement we analyzed the microscale Si and O isotope composition in different silica phases in a silicified zebra dolostone as well as their bulk δ18O and Δ’17O compositions. The subsequent replacement of carbonate layers is mimicked by decreasing δ18O and δ30Si. The textural relationship and magnitude of Si and O isotope fractionation is best explained by near-quantitative silica precipitation in an open system with finite Si. A Rayleigh model for silicification suggests positive Ɛ30/28Si during silicification, conforming with predictions for isotope distribution at chemical equilibrium from ab-initio models. Application of the modelled Ɛ30Si-T relationship yields silicification temperatures of approx. 50°C. To reconcile the δ18Ochert composition with these temperatures, the δ18O of the fluid must have been between -2.5 and -4 ‰, compositions for which the quartz phases fall close to the oxygen equilibrium fractionation line in three-isotope space. Diagenetic silica replacement appears to occur in O and Si isotopic equilibrium allowing reconstructions of temperatures of silicification from Si isotopes and derive the δ18O composition of the fluid – a highly desired value needed for accurate reconstructions of the temperature- and δ18O histories of the oceans. KW - Silicon isotopes PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-603430 DO - https://doi.org/10.1016/j.chemgeo.2024.122120 SN - 0009-2541 VL - 658 SP - 1 EP - 13 PB - Elsevier B.V. AN - OPUS4-60343 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tukhmetova, Dariya A1 - Langhammer, Nicole A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Online Isotope Analysis of Sulfur in Proteins via Capillary Electrophoresis Coupled With Multicollector ICP‐MS (CE/MC‐ICP‐MS): A Proof of Concept Study N2 - Isotope ratio analysis of sulfur in biological samples using inductively coupled plasma-mass spectrometry (ICP-MS) has gained significant interest for applications in quantitative proteomics. Advancements like coupling separation techniques with multicollector ICP-MS (MC-ICP-MS) enhance the throughput of species-specific sulfur isotope ratio measurements, fostering new avenues for studying sulfur metabolism in complex biological matrices. This proof-of-concept study investigates the feasibility of online CE/MC-ICP-MS for directly analyzing sulfur isotope ratios in proteins (albumin). Leveraging our previous work on the applicability of CE/ICP-MS for quantifying sulfur-containing biological molecules, we explore its potential for sulfur isotope analysis. Our results demonstrate that direct analysis of sulfur isotopes in albumin protein using online capillary electrophoresis MC-ICP-MS (CE/MC-ICP-MS) eliminates the need for laborious pretreatment steps, while yielding isotope ratios comparable to the reference values. Although initial precision can be improved through further system optimization and protein injection techniques, this approach paves the way for future analysis of mixtures of various biological compounds in, for example, clinical diagnosis studies. KW - Isotope analysis KW - Sulfur KW - CE/MC-ICP-MS PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612439 DO - https://doi.org/10.1002/elps.202400128 SN - 0173-0835 SP - 1 EP - 6 PB - Wiley-Blackwell CY - Weinheim AN - OPUS4-61243 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Westwood, Steven A1 - Lippa, Katrice A1 - Shimuzu, Yoshitaka A1 - Lalerle, Beatrice A1 - Saito, Takeshi A1 - Duewer, David A1 - Dai, Xinhua A1 - Davies, Stephen A1 - Ricci, Marina A1 - Baldan, Annarita A1 - Lang, Brian A1 - Sarge, Stefan A1 - Wang, Haifeng A1 - Pratt, Ken A1 - Josephs, Ralf A1 - Mariassy, Mikael A1 - Pfeifer, Dietmar A1 - Warren, John A1 - Bremser, Wolfram A1 - Ellison, Stephen A1 - Toman, Blaza A1 - Nelson, Michael A1 - Huang, Ting A1 - Fajgelj, Ales A1 - Gören, Ahmet A1 - Mackay, Lindsey A1 - Wielgosz, Robert T1 - Methods for the SI-traceable value assignment of the purity of organic compounds (IUPAC Technical Report) N2 - The “purity” of an organic compound typically refers, in practice, to an assignment of the mass fraction content of the primary organic component present in the material. The “purity” value of an organic primary calibrator material is the ultimate source of metrological traceability of any quantitative measurement of the content of that compound in a given matrix. The primary calibrator may consist of a Certified Reference Material (CRM) whose purity has been assigned by the CRM producer or a laboratory may choose to value-assign a material to the extent necessary for their intended application by using appropriately valid methods. This report provides an overview of the approach, performance and applicability of the principal methods used to determine organic purity including mass balance, quantitative NMR, thermal methods and direct-assay techniques. A statistical section reviews best practice for combination of data, value assignment as the upper limit values corresponding to 100 % purity are approached and how to report and propagate the standard uncertainty associated with the assigned values. KW - Calibration hierarchy KW - Certified reference materials KW - Mass balance KW - Measurement uncertainty KW - Organic purity KW - Primary calibrators KW - Primary reference materials KW - qNMR KW - Related-structure impurities KW - Thermal analysis KW - Titrimetry KW - Traceability KW - Uncertainty propagation KW - Volatile organic compounds KW - Water content PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-627932 DO - https://doi.org/10.1515/pac-2020-0804 SN - 0033-4545 SN - 1365-3075 VL - 95 IS - 1 SP - 1 EP - 77 PB - de Gruyter CY - Berlin AN - OPUS4-62793 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zöllner, Moritz T. A1 - Dariz, Petra A1 - Riedel, Jens A1 - Schmid, Thomas T1 - Dolomite and Mg Calcite as Mineral Thermometers in Mortar Binders. A High Resolution Raman Spectroscopic Study N2 - This paper suggests the use of high‐resolution Raman scattering bands of MgCa carbonates as posteriori thermometer minerals in archaeometric studies. Therefore, the thermal behavior of two dolomite samples and the hydration and carbonation reaction in air of the decomposition products were investigated by Raman microspectroscopy. The increase in the calcination temperature resulted in the formation of – Raman silent MgO and – inert Mg calcite at 700°C–750°C. In contrast, the decarbonation, hydration, and recarbonation of sample material exposed to 750°C–900°C in a muffle furnace led to the appearance of Mg‐free calcite. High spectral resolution Raman spectroscopy enabled a spectral distinction between these two groups due to differences in the band parameters (peak position, bandwidth) of the vibrational (v1, v4, L) modes of calcite. In combination with Raman microspectroscopic mapping, this spectral information represents a new approach for the estimation of burning temperatures of medieval high‐fired gypsum mortars via natural dolomite impurities. Thus, the results of this work highlight the importance and potential of Raman microspectroscopy as a thermometric tool for elucidating the thermal history of anthropogenic fired materials, with potential applications for archaeometry and art technology, as well as for quality controls in the frame of the production of mineral mortar binders and ceramics or bricks, respectively. KW - Mineral thermometry KW - Raman spectroscopy KW - Dolomite KW - High-fired gypsum mortar PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630270 DO - https://doi.org/10.1002/jrs.6810 SN - 1097-4555 SP - 1 EP - 13 PB - Wiley AN - OPUS4-63027 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mugani, R. A1 - El Khalloufi, F. A1 - Kasada, M. A1 - Redouane, E. M. A1 - Haida, M. A1 - Aba, R. P. A1 - Essadki, Y. A1 - Zerrifi, S. E. A. A1 - Herter, Sven-Oliver A1 - Hejjaj, A. A1 - Aziz, F. A1 - Ouazzani, N. A1 - Azevedo, J. A1 - Campos, A. A1 - Putschew, A. A1 - Grossart, H.-P. A1 - Mandi, L. A1 - Vasconcelos, V. A1 - Oudra, B. T1 - Monitoring of toxic cyanobacterial blooms in Lalla Takerkoust reservoir by satellite imagery and microcystin transfer to surrounding farms N2 - Cyanobacterial harmful algal blooms (CyanoHABs) threaten public health and freshwater ecosystems worldwide. In this study, our main goal was to explore the dynamics of cyanobacterial blooms and how microcystins (MCs) move from the Lalla Takerkoust reservoir to the nearby farms. We used Landsat imagery, molecular analysis, collecting and analyzing physicochemical data, and assessing toxins using HPLC. Our investigation identified two cyanobacterial species responsible for the blooms: Microcystis sp. and Synechococcus sp. Our Microcystis strain produced three MC variants (MC-RR, MC-YR, and MC-LR), with MC-RR exhibiting the highest concentrations in dissolved and intracellular toxins. In contrast, our Synechococcus strain did not produce any detectable toxins. To validate our Normalized Difference Vegetation Index (NDVI) results, we utilized limnological data, including algal cell counts, and quantified MCs in freeze-dried Microcystis bloom samples collected from the reservoir. Our study revealed patterns and trends in cyanobacterial proliferation in the reservoir over 30 years and presented a historical map of the area of cyanobacterial infestation using the NDVI method. The study found that MC-LR accumulates near the water surface due to the buoyancy of Microcystis. The maximum concentration of MC-LR in the reservoir water was 160 μg/L. In contrast, 4 km downstream of the reservoir, the concentration decreased by a factor of 5.39 to 29.63 μg/L, indicating a decrease in MC-LR concentration with increasing distance from the bloom source. Similarly, the MC-YR concentration decreased by a factor of 2.98 for the same distance. Interestingly, the MC distribution varied with depth, with MC-LR dominating at the water surface and MC-YR at the reservoir outlet at a water depth of 10 m. Our findings highlight the impact of nutrient concentrations, environmental factors, and transfer processes on bloom dynamics and MC distribution. We emphasize the need for effective management strategies to minimize toxin transfer and ensure public health and safety. KW - Cyanotoxin KW - HPLC-MS/MS KW - Surface water PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-623672 DO - https://doi.org/10.1016/j.hal.2024.102631 SN - 1568-9883 VL - 135 SP - 1 EP - 14 PB - Elsevier CY - Amsterdam AN - OPUS4-62367 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - McGonigle, Rebecca A1 - Glasgow, Jodie A1 - Houston, Catriona A1 - Cameron, Iain A1 - Homann, Christian A1 - Black, Dominic J. A1 - Pal, Robert A1 - MacKenzie, Lewis E. ED - MacKenzie, Lewis E. T1 - Autoclave reactor synthesis of upconversion nanoparticles, unreported variables, and safety considerations N2 - Autoclave reactors are widely used across chemical and biological sciences, including for the synthesis of upconversion nanoparticles (UCNPs) and other nanomaterials. Yet, the details of how autoclave reactors are used in such synthesis are rarely reported in the literature, leaving several key synthesis variables widely unreported and thereby hampering experimental reproducibility. In this perspective, we discuss the safety considerations of autoclave reactors and note that autoclaves should only be used if they are (a) purchased from reputable suppliers/manufacturers and (b) have been certified compliant with relevant safety standards. Ultimately, using unsuitable autoclave equipment can pose a severe physical hazard and may breach legal safety requirements. In addition, we highlight several parameters in autoclave synthesis that should be reported as standard to maximise the reproducibility of autoclave synthesis experiments across materials and chemistry research. We encourage users of autoclave synthesis vessels to: (1) adopt high-safety autoclaves and (2) report the many experimental variables involved to enhance experimental reproducibility. KW - Reference material KW - Nano KW - Particle KW - Shell KW - Fluorescence KW - Lifetime KW - Decay kinetics KW - Synthesis KW - Quality assurance KW - Method KW - Energy transfer KW - Upconversion KW - Autoclave synthesis KW - Data comparability PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-625672 DO - https://doi.org/10.1038/s42004-025-01415-3 VL - 8 IS - 1 SP - 1 EP - 7 PB - Springer Science and Business Media LLC AN - OPUS4-62567 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fiedler, Saskia A1 - Ton-That, C. A1 - Phillips, M. R. T1 - Defect-free ZnO nanorods with high angular distribution for enhanced excitonic emission N2 - AbstractLow-temperature hydrothermal growth has emerged as a popular method for the fabrication of ZnO nanorods (NRs), increasing the functionality and utility of ZnO-based devices. In this work, we study the influence of growth time, temperature and seed layer on the dimensions and angular distribution of ZnO NRs. High-quality NRs with a crisscrossed 60° angular distribution have been grown with a 20–60 nm diameter and 600 nm length. We show that, within the ideal range of growth parameters, the growth time and temperature have no controllable influence on NR diameter and length, while the deposition method and size of the pre-growth deposited ZnO seeds affects diameter and NR angular alignment. We demonstrate advantages of using crisscross-aligned NRs over planar ZnO for the enhancement of ZnO excitonic emission by optical coupling with gold nanoparticles. These results can be readily adapted for applications that involve surface coating-mediated enhancement of both light emission and injection. KW - ZnO nanorod KW - Hydrothermal growth KW - Seed layer KW - Angular distribution KW - Cathodoluminescence KW - Luminescence enhancement PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-618176 DO - https://doi.org/10.1557/s43578-023-00941-x SN - 0884-2914 SN - 2044-5326 VL - 38 IS - 8 SP - 2145 EP - 2155 PB - Springer CY - Berlin AN - OPUS4-61817 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schardt, Annika A1 - Schmitt, Johannes A1 - Engelhard, Carsten T1 - Single particle inductively coupled plasma mass spectrometry with nanosecond time resolution N2 - In this proof-of-principle study, we present our contribution to single particle inductively coupled plasma mass spectrometry (spICP-MS) developments with a novel in-house built data acquisition system with nanosecond time resolution (nanoDAQ) and a matching data processing approach. The new system can continuously sample the secondary electron multiplier (SEM) detector signal and enables the detection of gold nanoparticles (AuNP) as small as 7.5 nm with the commercial single quadrupole ICP-MS instrument used in this study. Recording of the SEM signal by the nanoDAQ is performed with a dwell time of approximately 4 ns. A tailored method was developed to process this type of transient data, which is based on determining the temporal distance between detector events that is denoted as event gap (EG). We found that the inverse logarithm of EG is proportional to the particle size and that the number of detector events corresponding to a particle signal distribution can be used to calibrate and determine the particle number concentration (PNC) of a nanoparticle dispersion. Due to the high data acquisition frequency, a statistically significant number of data points can be obtained in 60 s or less and the main time limitation for analyses is merely the sample uptake time and rinsing step between analyte solutions. At this stage, the data processing method provides average information on complete data sets only and will be adapted to enable particle-by-particle analysis with future hardware/software revision. KW - ICP-MS KW - Nanoparticles KW - Nanosecond time resolution KW - Single particle detection PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612706 DO - https://doi.org/10.1039/d3ja00373f SN - 1364-5544 SN - 0267-9477 VL - 39 IS - 2 SP - 389 EP - 400 PB - Royal Society of Chemistry (RSC) CY - Cambridge AN - OPUS4-61270 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Santos, C.I.L. A1 - Machado, W.S. A1 - Wegner, Karl David A1 - Gontijo, L.A.P. A1 - Bettini, J. A1 - Schiavon, M.A. A1 - Reiss, P. A1 - Aldakov, D. T1 - Hydrothermal Synthesis of Aqueous-Soluble Copper Indium Sulfide Nanocrystals and Their Use in Quantum Dot Sensitized Solar Cells N2 - facile hydrothermal method to synthesize water-soluble copper indium sulfide (CIS) nanocrystals (NCs) at 150 degrees C is presented. The obtained samples exhibited three distinct photoluminescence peaks in the red, green and blue spectral regions, corresponding to three size fractions, which could be separated by means of size-selective precipitation. While the red and green emitting fractions consist of 4.5 and 2.5 nm CIS NCs, the blue fraction was identified as in situ formed carbon nanodots showing excitation wavelength dependent emission. When used as light absorbers in quantum dot sensitized solar cells, the individual green and red fractions yielded power conversion efficiencies of 2.9% and 2.6%, respectively. With the unfractionated samples, the efficiency values approaching 5% were obtained. This improvement was mainly due to a significantly enhanced photocurrent arising from complementary panchromatic absorption. KW - Aqueous quantum dot KW - Solar cells KW - CUINS2 nanocrystals KW - Colloidal semiconductor nanocrystals PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-517983 DO - https://doi.org/10.3390/nano10071252 VL - 10 IS - 7 SP - 1252 PB - MDPI AN - OPUS4-51798 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Duarte Bernardino, Carolina A1 - Lee, Mihyun A1 - Ren, Qun A1 - Ruehle, Bastian T1 - Facile Spray-Coating of Antimicrobial Silica Nanoparticles for High-Touch Surface Protection N2 - The rising threat from infectious pathogens poses an ever-growing challenge. Metal-based nanomaterials have gained a great deal of attention as active components in antimicrobial coatings. Here, we report on the development of readily deployable, sprayable antimicrobial surface coatings for high-touch stainless steel surfaces that are ubiquitous in many healthcare facilities to combat the spread of pathogens. We synthesized mesoporous silica nanoparticles (MSNs) with different surface functional groups, namely, amine (MSN-NH2), carboxy (MSN-COOH), and thiol groups (MSN-SH). These were chosen specifically due to their high affinity to copper and silver ions, which were used as antimicrobial payloads and could be incorporated into the mesoporous structure through favorable host−guest interactions, allowing us to find the most favorable combinations to achieve antimicrobial efficacy against various microbes on dry or semidry high-touch surfaces. The antimicrobial MSNs were firmly immobilized on stainless steel through a simple two-step spray-coating process. First, the stainless steel surfaces are primed with sprayable polyelectrolyte solutions acting as adhesion layers, and then, the loaded nanoparticle dispersions are spray-coated on top. The employed polyelectrolytes were selected and functionalized specifically to adhere well to stainless steel substrates while at the same time being complementary to the MSN surface groups to enhance the adhesion, wettability, homogeneity, and stability of the coatings. The antimicrobial properties of the nanoparticle suspension and the coatings were tested against three commonly found pathogenic bacteria, Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli, as well as a fungal pathogen, Candida albicans. Especially MSN-SH loaded with silver ions showed excellent antimicrobial efficacy against all tested pathogens under application-relevant, (semi)dry conditions. The findings obtained here facilitate our understanding of the correlation between the surface properties, payloads, and antimicrobial activity and show a new pathway toward simple and easily deployable solutions to combat the spread of pathogens with the help of sprayable antimicrobial surface coatings. KW - Mesoporous silica nanoparticles KW - Thin films KW - Antimicrobial coatings KW - Spray-coating KW - Infectious diseases KW - Pathogen transmission KW - High-touch surfaces PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626269 DO - https://doi.org/10.1021/acsami.4c18916 SN - 1944-8252 SP - 1 EP - 13 PB - ACS Publications CY - Washington, DC AN - OPUS4-62626 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ruehle, Bastian T1 - Natural language processing for automated workflow and knowledge graph generation in self-driving labs N2 - Natural language processing with the help of large language models such as ChatGPT has become ubiquitous in many software applications and allows users to interact even with complex hardware or software in an intuitive way. The recent concepts of Self-Driving Labs and Material Acceleration Platforms stand to benefit greatly from making them more accessible to a broader scientific community through enhanced user-friendliness or even completely automated ways of generating experimental workflows that can be run on the complex hardware of the platform from user input or previously published procedures. Here, two new datasets with over 1.5 million experimental procedures and their (semi)automatic annotations as action graphs, i.e., structured output, were created and used for training two different transformer-based large language models. These models strike a balance between performance, generality, and fitness for purpose and can be hosted and run on standard consumer-grade hardware. Furthermore, the generation of node graphs from these action graphs as a user-friendly and intuitive way of visualizing and modifying synthesis workflows that can be run on the hardware of a Self-Driving Lab or Material Acceleration Platform is explored. Lastly, it is discussed how knowledge graphs – following an ontology imposed by the underlying node setup and software architecture – can be generated from the node graphs. All resources, including the datasets, the fully trained large language models, the node editor, and scripts for querying and visualizing the knowledge graphs are made publicly available. KW - Natural Language Processing KW - Large Language Models KW - Self-Driving Labs KW - Materials Acceleration Platforms KW - Workflows KW - Nanomaterials KW - Advanced Materials PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-631947 UR - https://github.com/BAMresearch/MAPz_at_BAM/tree/main/Minerva-Workflow-Generator DO - https://doi.org/10.1039/d5dd00063g SN - 2635-098X SP - 1 EP - 10 PB - Royal Society of Chemistry (RSC) AN - OPUS4-63194 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ecke, Alexander A1 - Bell, Jérémy A1 - Schneider, Rudolf T1 - A three-dimensional microfluidic flow cell and system integration for improved electrochemical substrate detection in HRP/TMB-based immunoassays N2 - Immunoassays, based on the recognition and capture of analytes by highly selective antibodies, are now used extensively in all areas of diagnostics, but the challenge is to further integrate them into online sensors. To improve the transition from laboratory immunoassays to immunosensors, we have developed a complete flow system, based on a microfluidic core flow cell to enable automated detection of one of the most commonly used immunoassay substrates, TMB, by chronoamperometry. The architecture and fluidic optimisation of the system showed that a specially designed 3D flow cell allows higher flow rates (500 μL min−1) than a standard enlarged microfluidic channel (50 μL min−1) resulting in a significantly shorter detection time of 30 seconds per sample and making the system more robust against interferences due to bubble formation in the chip. The electrochemical measurements showed an improved signal-to-noise ratio (SNR) and thus higher sensitivity for a model immunoassay for diclofenac (SNR = 59), compared to the analytical performance of a conventional laboratory microplate-based assay with optical detection (SNR = 19). In general, this system facilitates the conversion of any conventional immunoassay into an immunosensor with automatic and continuous detection. KW - Microfluidic KW - Immunoassay KW - Electrochemical KW - Mikrofluidik KW - Immunassay KW - Elektrochemie PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-580159 DO - https://doi.org/10.1039/d3sd00095h VL - 2 SP - 887 EP - 892 PB - Royal Society of Chemistry CY - London, United Kingdom AN - OPUS4-58015 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Roesch, Philipp A1 - Vogel, Christian A1 - Wittwer, Philipp A1 - Huthwelker, T. A1 - Borca, C. A1 - Sommerfeld, Thomas A1 - Kluge, Stephanie A1 - Piechotta, Christian A1 - Kalbe, Ute A1 - Simon, Franz-Georg T1 - Taking a Look at the Surface: µ-XRF Mapping and Fluorine K-edge µ-XANES Spectroscopy of Organofluorinated Compounds in Environmental Samples and Consumer Products N2 - For the first time, µ-X-ray fluorescence (µ-XRF) mapping combined with fluorine K-edge µ-X-ray absorption near-edge structure (µ-XANES) spectroscopy was applied to depict per- and polyfluoroalkyl substances (PFAS) contamination and inorganic fluoride in samples concentrations down to 100 µg/kg fluoride. To demonstrate the matrix tolerance of the method, several PFAS contaminated soil and sludge samples as well as selected consumer product samples (textiles, food contact paper and permanent baking sheet) were investigated. µ-XRF mapping allows for a unique element-specific visualisation at the sample surface and enables localisation of fluorine containing compounds to a depth of 1 µm. Manually selected fluorine rich spots were subsequently analysed via fluorine K-edge µ-XANES spectroscopy. To support spectral interpretation with respect to inorganic and organic chemical distribution and compound class determination, linear combination (LC) fitting was applied to all recorded µ-XANES spectra. Complementarily, solvent extracts of all samples were target-analysed via LC-MS/MS spectrometry. The detected PFAS sum values range from 20 to 1136 µg/kg dry weight (dw). All environmentally exposed samples revealed higher concentration of PFAS with a chain length >C8 (e.g. 580 µg/kg dw PFOS for Soil1), whereas the consumer product samples showed a more uniform distribution with regard to chain lengths from C4 to C8. Independent from quantified PFAS amounts via target analysis, µ-XRF mapping combined with µ-XANES spectroscopy was successfully applied to detect both point-specific concentration maxima and evenly distributed surface coatings of fluorinated organic contaminants in the corresponding samples. KW - PFAS KW - XRF KW - LC-MS/MS KW - XANES KW - Fluoride KW - Soil PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-576109 DO - https://doi.org/10.1039/D3EM00107E SN - 2050-7887 SP - 1 EP - 12 PB - Royal Society of Chemistry AN - OPUS4-57610 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Roesch, Philipp A1 - Wittwer, Philipp A1 - Sommerfeld, Thomas A1 - Riedel, Maren A1 - Leube, Peter A1 - Kalbe, Ute A1 - Schoknecht, Ute A1 - Simon, Franz-Georg T1 - Per- and Polyfluoroalkyl Substances (PFAS) in Ski Waxes and Snow from Cross-Country Skiing in Germany - Comparative study of Sum Parameter and Target Analysis N2 - Per- and polyfluoroalkyl substances (PFAS) are often environmentally exposed via discharge through human consumer products, such as ski waxes. In our study we analyzed various ski waxes from the 1980s and 2020s, to determine both the sum parameter values total fluorine (TF), extractable organically bound fluorine (EOF), hydrolysable organically bound fluorine (HOF) as well as targeted PFAS analysis. This showed that modern high-performance waxes contain up to 6 % TF, but also PFAS-free labelled ski waxes contain traces of PFAS with EOF/HOF values in the low mg kg-1 range. With the ban of all fluorine-based waxes with the start of the 2023/2024 winter season this will probably change soon. Moreover, we applied our analysis methods to snow samples from a frequently used cross country ski trail (Kammloipe) in the Ore Mountain region in Germany, assessing the potential PFAS entry/discharge through ski waxes. Melted snow samples from different spots were analyzed by the adsorbable organically bound fluorine (AOF) sum parameter and PFAS target analysis and confirmed the abrasion of the ski waxes into the snow. Moreover, on a PFAS hotspot also soil samples were analyzed, which indicate that PFAS from the ski waxes adsorb after snow melting into the soil. KW - Combustion Ion Chromatography KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Consumer Products PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612760 DO - https://doi.org/10.1016/j.hazadv.2024.100484 VL - 16 SP - 1 EP - 5 PB - Elsevier B.V. AN - OPUS4-61276 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Roesch, Philipp A1 - Schinnen, Andrea A1 - Riedel, Maren A1 - Sommerfeld, Thomas A1 - Sawal, G. A1 - Bandow, N. A1 - Vogel, Christian A1 - Kalbe, Ute A1 - Simon, Franz-Georg T1 - Investigation of pH-dependent extraction methods for PFAS in (fluoropolymer-based) consumer products: A comparative study between targeted and sum parameter analysis N2 - Here, we report a comparative study of different sum parameter analysis methods for the extraction of per- and polyfluoroalkyl substances (PFAS) from manufactured consumer products, which can be measured by combustion ion chromatography (CIC). Therefore, a hydrolysis-based extraction method was further developed, which accounts for the addition of hydrolyzable covalently bound polyfluoroalkylated side-chain polymers (SFPs) to the extractable organic fluorine portion of the mass balance proposed as "hydrolyzable organically bound fluorine" (HOF). To test this hypothesis, the method was applied to 39 different consumer products containing fluoropolymers or monomeric PFAS taken from four different categories: outdoor textiles, paper packaging, carpeting, and permanent baking sheets. We also evaluated the method's efficiency by extracting four synthesized fluorotelomer polyacrylate reference compounds. The total fluorine (TF) and extractable organically bound fluorine (EOF) values were measured through CIC using established protocols. The TF values ranged from sub-ppb to %-levels, depending on the compound class. All samples showed results for hydrolyzed organofluorine (HOF) between 0.03 and 76.3 μg/g, while most EOF values were lower (