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 -