TY - JOUR A1 - Müller, Axel A1 - Altmann, Korinna A1 - Kocher, B. A1 - Braun, U. T1 - Determination of tire wear markers in soil samples and their distribution in a roadside soil N2 - Tire wear (TW) constitutes a significant source of microplastic in terrestrial ecosystems. It is known that particles emitted by roads can have an effect up to 100 m into adjacent areas. Here, we apply for the first-time thermal extraction desorption gas chromatography-mass spectrometry (TED-GC/MS) to determine TW in soil samples by detection of thermal decomposition products of styrene-butadiene rubber (SBR), without additional enrichment. Additionally, zinc contents were determined as an elemental marker for TW. Mixed soil samples were taken along three transects along a German motorway in 0.3, 2.0, and 5.0 m distance from the road. Sampling depths were 0–2, 2–5, 5–10, and 10–20 cm. Four fine fractions, 1 000–500, 500–100, 100–50, and <50 μm, were analyzed. TW contents based on SBR ranged from 155 to 15 898 mg kg−1. TW contents based on zinc were between 413 and 44 812 mg kg−1. Comparison of individual values of SBR and zinc reveals SBR as a more specific marker. Results confirm that most TW ends up in the topsoil within a 2 m distance. The sampling strategy resulted in representative data for a larger area. Standard deviations of quadruple TED-GC/MS determination of SBR were <10% for all grain size fractions. TED-GC/MS is a suitable analytical tool for determining TW in soil samples without the use of toxic chemicals, enrichment, or special sample preparation. KW - Microplastic KW - TED-GC/MS KW - Tire wear PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-543344 DO - https://doi.org/10.1016/j.chemosphere.2022.133653 VL - 294 SP - 1 EP - 8 PB - Elsevier Ltd. AN - OPUS4-54334 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 - Vogel, Christian A1 - Scholz, Philipp A1 - Kalbe, Ute A1 - Caliebe, W. A1 - Tayal, A. A1 - Vasala, S. J. A1 - Simon, Franz-Georg T1 - Speciation of antimony and vanadium in municipal solid waste incineration ashes analyzed by XANES spectroscopy N2 - The use of ashes from municipal solid waste incineration as secondary building materials is an important pillar for the circular economy in Germany. However, leaching of potential toxic elements from these materials must be at environmentally acceptable levels. Normally, a three-month ageing period immobilizes most hazardous heavy metals, but antimony (Sb) and vanadium (V) showed previously unusual leaching. In order to clarify the mechanisms, we analyzed the Sb and V species in various bottom and fly ashes from municipal waste incineration by XANES spectroscopy. Antimony oxidizes from Sb(+ III) species used as flame retardants in plastics to Sb(+ V) compounds during waste incineration. However, owing to the similarity of different Sb(+ V) compound in the Sb K- and L-edge XANES spectra, it was not possible to accurately identify an exact Sb(+ V) species. Moreover, V is mainly present as oxidation state + V compound in the analyzed ashes. However, the coarse and magnetic fraction of the bottom ashes contain larger amounts of V(+ III) and V(+ IV) compounds which might enter the waste incineration from vanadium carbide containing steel tools. Thus, Sb and V could be critical potential toxic elements in secondary building materials and long-term monitoring of the release should be taken into account in the future. KW - Müllverbrennung KW - XANES spectroscopy PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599841 DO - https://doi.org/10.1007/s10163-024-01954-2 SN - 1438-4957 VL - 26 SP - 2152 EP - 72158 PB - Springer Science and Business Media LLC AN - OPUS4-59984 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dittmar, Stefan A1 - Weyrauch, Steffen A1 - Reemtsma, Thorsten A1 - Eisentraut, Paul A1 - Altmann, Korinna A1 - Ruhl, Aki S. A1 - Jekel, Martin T1 - Settling Velocities of Tire and Road Wear Particles: Analyzing Finely Graded Density Fractions of Samples from a Road Simulator and a Highway Tunnel N2 - The terminal settling velocity is considered the most critical parameter determining the transport of tire and road wear particles (TRWP) in aquatic environments. Nonetheless, no respective empirical data has been reported so far. In this study, particle samples from a road simulator and a highway tunnel were investigated with a validated imaging method. Different density and size fractions of both samples were measured separately, acquiring sizes and settling velocities of more than 30,000 individual particles. In addition, tire marker polymers were analyzed for each fraction via thermal extraction desorption-gas chromatography/mass spectrometry. Finally, the acquired particle data was combined according to the fractions’ estimated tire contents in order to deduce detailed probability distributions of particle size and settling velocity for the actual TRWP from both samples. Weighted by TRWP-incorporated tire mass, median diameters of 54 and 44 μm as well as median settling velocities of 0.65 and 0.22 mm/s were found for TRWP from the road simulator and highway tunnel, respectively. This study thus provides the first ever empirical data on TRWP settling velocities in water, which can be highly valuable input for modeling the environmental transport of TRWP and for dimensioning TRWP retention systems. KW - Microplastics KW - TED-GC/MS KW - Sinking velocities KW - Transport PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-635449 DO - https://doi.org/10.1021/acs.est.5c04165 SN - 0013-936X VL - 59 IS - 26 SP - 13434 EP - 13446 PB - American Chemical Society (ACS) AN - OPUS4-63544 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Visileanu, Emilia A1 - Altmann, Korinna A1 - Stepa, Raluca A1 - Haiducu, Maria A1 - Miclea, Paul Tiberiu A1 - Vladu, Alina A1 - Dondea, Felicia A1 - Grosu, Marian Catalin A1 - Scarlat, Razvan T1 - Comparative Analysis of Airborne Particle Concentrations in Textile Industry Environments Throughout the Workday N2 - This paper addresses the growing concern surrounding microplastic pollution, particularly within the textile industry, and the associated potential health risks linked to the inhalation and ingestion of microplastic particles. Microplastics, defined as plastic particles smaller than five millimeters, are increasingly found not only in aquatic environments, but also in soils, air, and food. Although research on the health impacts of microplastics is still emerging, early studies indicate that these particles could contribute to health issues, including oxidative stress, inflammation, and cardiovascular diseases. Notably, individuals with higher concentrations of plastics in arterial plaques are more susceptible to heart attacks and strokes. In the textile industry, synthetic fibers such as polyester, nylon, and acrylic release microplastics into the air during production. The paper discusses a study conducted in a textile company that processes polyester yarns, where airborne microplastic concentrations were measured at various locations throughout the day. Particle sizes ranging from 0.3 nm to 10 nm were analyzed, revealing the presence of polyester polymers in the particulate matter. These findings underscore the widespread nature of microplastic pollution, particularly in industrial settings, and raise concerns about the health risks associated with prolonged exposure to airborne microplastics. While further research is necessary to fully understand the extent of these health impacts, preliminary data suggest a troubling link between microplastic inhalation and cardiovascular conditions. KW - Microplastics KW - Textiles KW - Airborne particles PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-635269 DO - https://doi.org/10.3390/microplastics4020034 SN - 2673-8929 VL - 4 IS - 2 SP - 1 EP - 17 PB - MDPI AG AN - OPUS4-63526 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kalbe, Ute A1 - Piechotta, Christian A1 - Bandow, Nicole T1 - Comparing PFAS analysis in batch leaching and column leaching tests N2 - Laboratory leaching tests are tools to assess the mobility of environmental contaminants released from granular materials. Comparative leaching tests were performed using four PFAS-contaminated soils whose concentration patterns of 10 selected perfluoroalkyl and polyfluoroalkyl substances (PFAS) differed due to the two types of contamination sources. This study aimed to evaluate the equivalence of two usual laboratory-scale leaching test procedures, batch and column percolation tests, at liquid-to-solid ratios (L/S) of 2 l/kg, which is the current practice within the German assessment framework, and 10 l/kg (relevant for some EU regulations such as the landfill directive). The differences between the replicates of leaching tests investigating PFAS were smaller for column percolation tests than for batch tests, probably mainly due to the greater sample size and the better representativeness of the sample portion analyzed. It was observed that batch tests overestimate the release of shorter-chain PFAS, whereby the effect was greater with carboxylic than with sulfonic acids. Currently, the limits of detection of analyses given by the DIN standard with regard to PFCA and PFSA in soils are partly not sufficient to detect very low contents, whereas the detection of selected PFCA and PFSA in eluates is more sensitive, in accordance with the available standards. This results in limitations when calculating mass balances. KW - PFAS KW - Leaching KW - Column percolation test KW - Batch test KW - Soil PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-618187 DO - https://doi.org/10.1007/s11356-024-35510-0 SN - 1614-7499 VL - 31 IS - 57 SP - 65233 EP - 65251 PB - Springer Science and Business Media LLC AN - OPUS4-61818 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fricke, F. A1 - Brandalero, M. A1 - Liehr, Sascha A1 - Kern, Simon A1 - Meyer, Klas A1 - Kowarik, Stefan A1 - Hierzegger, R. A1 - Westerdick, S. A1 - Maiwald, Michael A1 - Hübner, M. T1 - Artificial Intelligence for Mass Spectrometry and Nuclear Magnetic Resonance Spectroscopy Using a Novel Data Augmentation Method N2 - Mass Spectrometry (MS) and Nuclear Magnetic Resonance Spectroscopy (NMR) are valuable analytical and quality control methods for most industrial chemical processes as they provide information on the concentrations of individual compounds and by-products. These processes are traditionally carried out manually and by a specialist, which takes a substantial amount of time and prevents their utilization for real-time closed-loop process control. This paper presents recent advances from two projects that use Artificial Neural Networks (ANNs) to address the challenges of automation and performance-efficient realizations of MS and NMR. In the first part, a complete toolchain has been realized to develop simulated spectra and train ANNs to identify compounds in MS. In the second part, a limited number of experimental NMR spectra have been augmented by simulated spectra, to train an ANN with better prediction performance and speed than state-of-the-art analysis. These results suggest that, in the context of the digital transformation of the process industry, we are now on the threshold of a strongly simplified use of MS and MRS and the accompanying data evaluation by machine-supported procedures, and can utilize both methods much wider for reaction and process monitoring or quality control. KW - Industry 4.0 KW - Cyber-Physical Systems KW - Artificial Neural Networks KW - Mass Spectrometry KW - Nuclear Magnetic Resonance Spectroscopy KW - Modular Production PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-539412 UR - https://ieeexplore.ieee.org/stamp/stamp.jsp?tp=&arnumber=9638378 DO - https://doi.org/10.1109/TETC.2021.3131371 SN - 2168-6750 VL - 10 IS - 1 SP - 87 EP - 98 PB - IEEE AN - OPUS4-53941 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bornemann-Pfeiffer, Martin A1 - Kern, Simon A1 - Maiwald, Michael A1 - Meyer, Klas T1 - Calibration-Free Chemical Process and Quality Control Units as Enablers for Modular Production N2 - Modular chemical production is a tangible translation of the digital transformation of the process industry for specialty chemicals. In particular, it enables the speeding-up of process development and thus a quicker time to market by flexibly connecting and orchestrating standardised physical modules and bringing them to life (i.e., parameterising them) with digitally accumulated process knowledge. We focus on the specific challenges of chemical process and quality control, which in its current form is not well suited for modular production and provide possible approaches and examples of the change towards direct analytical methods, analytical model transfer or machine-supported processes. KW - Modular Production KW - Chemical Process Control KW - Process Analytical Technology KW - Digital Transformation KW - Industry 4.0 PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-517264 DO - https://doi.org/10.1002/cite.202000150 SN - 1522-2640 VL - 93 IS - 1-2 SP - 62 EP - 70 PB - Wiley-VCH CY - Weinheim AN - OPUS4-51726 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gottu Mukkula, A. R. A1 - Kern, Simon A1 - Salge, M. A1 - Holtkamp, M. A1 - Guhl, Svetlana A1 - Fleischer, C. A1 - Meyer, Klas A1 - Remelhe, M. A1 - Maiwald, Michael A1 - Engell, S. T1 - An Application of Modifier Adaptation with Quadratic Approximation on a Pilot Scale Plant in Industrial Environment N2 - The goal of this work is to identify the optimal operating input for a lithiation reaction that is performed in a highly innovative pilot scale continuous flow chemical plant in an industrial environment, taking into account the process and safety constraints. The main challenge is to identify the optimum operation in the absence of information about the reaction mechanism and the reaction kinetics. We employ an iterative real-time optimization scheme called modifier adaptation with quadratic approximation (MAWQA) to identify the plant optimum in the presence of plant-model mismatch and measurement noise. A novel NMR PAT-sensor is used to measure the concentration of the reactants and of the product at the reactor outlet. The experiment results demonstrate the capabilities of the iterative optimization using the MAWQA algorithm in driving a complex real plant to an economically optimal operating point in the presence of plant-model mismatch and of process and measurement uncertainties. KW - Process Analytical Technology KW - Online NMR Spectroscopy KW - Process Industry KW - Iterative real-time optimization KW - Modifier adaptation KW - Plant-model mismatch KW - Reactor control KW - CONSENS PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-524531 DO - https://doi.org/10.1016/j.ifacol.2020.12.685 SN - 1522-2640 VL - 53 IS - 2 SP - 11773 EP - 11779 PB - Elsevier CY - Amsterdam AN - OPUS4-52453 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bruno, Francesco A1 - Fiorucci, Letizia A1 - Vignoli, Alessia A1 - Meyer, Klas A1 - Maiwald, Michael A1 - Ravera, Enrico T1 - pyIHM: Indirect Hard Modeling, in Python N2 - NMR is a powerful analytical technique that combines an exquisite qualitative power, related to the unicity of the spectra of each molecule in a mixture, with an intrinsic quantitativeness, related to the fact that the integral of each peak only depends on the number of nuclei (i.e., the amount of substance times the number of equivalent nuclei in the signal), regardless of the molecule. Signal integration is the most common approach in quantitative NMR but has several drawbacks (vide infra). An alternative is to use hard modeling of the peaks. In this paper, we present pyIHM, a Python package for the quantification of the components of NMR spectra through indirect hard modeling, and we discuss some numerical details of the implementation that make this approach robust and reliable. KW - Algorithms KW - Chemical Structure KW - Deconvolution KW - Mixtures KW - NMR spectroscopy PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626793 DO - https://doi.org/10.1021/acs.analchem.4c06484 SN - 1520-6882 VL - 97 IS - 8 SP - 4598 EP - 4605 PB - ACS Publications CY - Washington D.C. AN - OPUS4-62679 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - You, Zengchao A1 - Akkus, Asli A1 - Weisheit, W. A1 - Giray, Thorsten A1 - Penk, Sibylle A1 - Buttler, Sabine A1 - Recknagel, Sebastian A1 - Abad Andrade, Carlos Enrique T1 - Multielement analysis in soils using nitrogen microwave inductively coupled atmospheric pressure plasma mass spectrometry N2 - In this study, we employed nitrogen microwave inductively coupled atmospheric-pressure plasma (MICAP) combined with quadrupole mass spectrometry (MS) and a liquid sample introduction system to analyze heavy metals in soils. The vanadium, cobalt, nickel, zinc, copper, chromium, arsenic, lead, and cadmium contents in seven reference and three environmental soil samples determined using MICAP-MS were within the uncertainty of the reference values, indicating that MICAP-MS is promising for soil analysis similar to the conventional inductively coupled plasma mass spectrometry (ICP-MS) technique. In addition, the limits of detection (LODs) and sensitivity of both techniques using N2 and Ar plasma were of the same order of magnitude. Furthermore, the performance of MICAP-MS under different N2 purity was investigated, and we found that the plasma formation and ionization efficiency were not influenced by the impurities in the gas. A prominent advantage of MICAP-MS is the low operating cost associated with gas consumption. In this work, MICAP-MS used nitrogen, which is cheaper than argon, and consumed 25% less gas than ICP-MS. Using low-purity N2 can further reduce the gas cost, making MICAP-MS more cost effective than ICP-MS. These results suggest that MICAP-MS is a promising alternative to ICP-MS for the analysis of heavy metals in the soil. KW - Soil KW - Microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) KW - Nitrogen plasma KW - Multi-element analysis PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-561048 DO - https://doi.org/10.1039/d2ja00244b SN - 0267-9477 VL - 37 IS - 12 SP - 2556 EP - 2562 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-56104 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Neamtu, M. A1 - Nadejde, C. A1 - Brinza, L. A1 - Dragos, O. A1 - Gherghel, D. A1 - Paul, Andrea T1 - Iron phthalocyanine-sensitized magnetic catalysts for BPA photodegradation N2 - The catalytic behavior of iron phthalocyanine (FePc)-sensitized magnetic nanocatalysts was evaluated for their application in the oxidative treatment of Bisphenol A (BPA) under mild environmental conditions. Two types of FePc (Fe(II)Pc and Fe(III)Pc), which are highly photosensitive compounds, were immobilized on the surface of functionalized magnetite. The nanomaterials were characterized by high resolution transmission electron microscopy (HR-TEM), X-ray difraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analyses (TGA). The generation of singlet Oxygen by nanomaterials was also investigated. In the presence of UVA light exposure (365nm) and 15mM H2O2, the M@Fe(III)Pc photocatalyst gave the best results; for a catalyst concentration of 2.0gL −1, around 60% BPA was removed after 120min of reaction. These experimental conditions were further tested under natural solar light exposure, for which also M@Fe(III)Pc exhibited enhanced oxidative catalytic activity, being able to remove 83% of BPA in solution. The water samples were less cytotoxic after treatment, this being confrmed by the MCF-7 cell viability assay. KW - Photosensitization KW - magnetic nanocatalysts KW - BPA removal PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-506368 DO - https://doi.org/10.1038/s41598-020-61980-6 VL - 10 IS - 1 SP - 5376 AN - OPUS4-50636 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Eifert, T. A1 - Eisen, K. A1 - Maiwald, Michael A1 - Herwig, C. T1 - Current and future requirements to industrial analytical infrastructure—part 2: smart sensors N2 - Complex processes meet and need Industry 4.0 capabilities. Shorter product cycles, flexible production needs, and direct assessment of product quality attributes and raw material attributes call for an increased need of new process analytical technologies (PAT) concepts. While individual PAT tools may be available since decades, we need holistic concepts to fulfill above industrial needs. In this series of two contributions, we want to present a combined view on the future of PAT (process analytical technology), which is projected in smart labs (Part 1) and smart sensors (Part 2). Part 2 of this feature article series describes the future functionality as well as the ingredients of a smart sensor aiming to eventually fuel full PAT functionality. The smart sensor consists of (i) chemical and process information in the physical twin by smart field devices, by measuring multiple components, and is fully connected in the IIoT 4.0 environment. In addition, (ii) it includes process intelligence in the digital twin, as to being able to generate knowledge from multi-sensor and multi-dimensional data. The cyber-physical system (CPS) combines both elements mentioned above and allows the smart sensor to be self-calibrating and self-optimizing. It maintains its operation autonomously. Furthermore, it allows—as central PAT enabler—a flexible but also target-oriented predictive control strategy and efficient process development and can compensate variations of the process and raw material attributes. Future cyber-physical production systems—like smart sensors—consist of the fusion of two main pillars, the physical and the digital twins. We discuss the individual elements of both pillars, such as connectivity, and chemical analytics on the one hand as well as hybrid models and knowledge workflows on the other. Finally, we discuss its integration needs in a CPS in order to allow is versatile deployment in efficient process development and advanced optimum predictive process control. KW - Smart sensors KW - Industry 4.0 KW - Digital twins KW - Process intelligence KW - Process analytical technology KW - Physical twin KW - Cyber-physical system PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-503980 DO - https://doi.org/10.1007/s00216-020-02421-1 SN - 1618-2642 VL - 412 IS - 9 SP - 2037 EP - 2045 PB - Springer CY - Berlin Heidelberg AN - OPUS4-50398 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Eisen, K A1 - Eifert, T A1 - Herwig, C A1 - Maiwald, Michael T1 - Current and future requirements to industrial analytical infrastructure—part 1: process analytical laboratories N2 - The competitiveness of the chemical and pharmaceutical industry is based on ensuring the required product quality while making optimum use of plants, raw materials, and energy. In this context, effective process control using reliable chemical process analytics secures global competitiveness. The setup of those control strategies often originate in process development but need to be transferable along the whole product life cycle. In this series of two contributions, we want to present a combined view on the future of PAT (process analytical technology), which is projected in smart labs (part 1) and smart sensors (part 2). In laboratories and pilot plants, offline chemical analytical methods are frequently used, where inline methods are also used in production. Here, a transferability from process development to the process in operation would be desirable. This can be obtained by establishing PAT methods for production already during process development or scale-up. However, the current PAT (Bakeev 2005, Org Process Res 19:3–62; Simon et al. 2015, Org Process Res Dev 19:3–62) must become more flexible and smarter. This can be achieved by introducing digitalization-based knowledge management, so that knowledge from product development enables and accelerates the integration of PAT. Conversely, knowledge from the production process will also contribute to product and process development. This contribution describes the future role of the laboratory and develops requirements therefrom. In part 2, we examine the future functionality as well as the ingredients of a smart sensor aiming to eventually fuel full PAT functionality—also within process development or scale-up facilities (Eifert et al. 2020, Anal Bioanal Chem). KW - Smart test laboratories KW - Laboratory 4.0 KW - Sustainable Production KW - Industry 4.0 PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-504020 DO - https://doi.org/10.1007/s00216-020-02420-2 SN - 1618-2642 VL - 412 IS - 9 SP - 2027 EP - 2035 PB - Springer CY - Berlin Heidelberg AN - OPUS4-50402 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Thiele, Isabel A1 - Santolin, Lara A1 - Meyer, Klas A1 - Machatschek, Rainhard A1 - Bölz, Uwe A1 - Tarazona, Natalia A. A1 - Riedel, Sebastian L. T1 - Microbially synthesized poly(hydroxybutyrate-co-hydroxyhexanoate) with low to moderate hydroxyhexanoate content: Properties and applications N2 - Plastic pollution is the biggest environmental concern of our time. Breakdown products like micro- and nanoplastics inevitably enter the food chain and pose unprecedented health risks. In this scenario, bio-based and biodegradable plastic alternatives have been given a momentum aiming to bridge a transition towards a more sustainable future. Polyhydroxyalkanoates (PHAs) are one of the few thermoplastic polymers synthesized 100 % via biotechnological routes which fully biodegrade in common natural environments. Poly(hydroxybutyrate-cohydroxyhexanoate) [P(HB-co-HHx)] is a PHA copolymer with great potential for the commodity polymers industry, as its mechanical properties can be tailored through fine-tuning of its molar HHx content. We have recently developed a strategy that enables for reliable tailoring of the monomer content of P(HB-co-HHx). Nevertheless, there is often a lack of comprehensive investigation of the material properties of PHAs to evaluate whether they actually mimic the functionalities of conventional plastics. We present a detailed study of P(HB-co-HHx) copolymers with low to moderate hydroxyhexanoate content to understand how the HHx monomer content influences the thermal and mechanical properties and to link those to their abiotic degradation. By increasing the HHx fractions in the range of 2 – 14 mol%, we impart an extension of the processing window and application range as the melting temperature (Tm) and glass temperature (Tg) of the copolymers decrease from Tm 165 ◦C to 126 ◦C, Tg 4 ◦C to − 5.9 ◦C, accompanied by reduced crystallinity from 54 % to 20 %. Elongation at break was increased from 5.7 % up to 703 % at 14 mol% HHx content, confirming that the range examined was sufficiently large to obtain ductile and brittle copolymers, while tensile strength was maintained throughout the studied range. Finally, accelerated abiotic degradation was shown to be slowed down with an increasing HHx fraction decreasing from 70 % to 55 % in 12 h. KW - Molecular Biology KW - General Medicine KW - Biochemistry KW - Structural Biology PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595636 DO - https://doi.org/10.1016/j.ijbiomac.2024.130188 VL - 263 SP - 1 EP - 9 PB - Elsevier B.V. AN - OPUS4-59563 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Villajos Collado, José Antonio A1 - Balderas‐Xicohténcatl, Rafael A1 - Al Shakhs, Ali N. A1 - Berenguer‐Murcia, Ángel A1 - Buckley, Craig E. A1 - Cazorla‐Amorós, Diego A1 - Charalambopoulou, Georgia A1 - Couturas, Fabrice A1 - Cuevas, Fermin A1 - Fairen‐Jimenez, David A1 - Heinselman, Karen N. A1 - Humphries, Terry D. A1 - Kaskel, Stefan A1 - Kim, Hyunlim A1 - Marco‐Lozar, Juan P. A1 - Oh, Hyunchul A1 - Parilla, Philip A. A1 - Paskevicius, Mark A1 - Senkovska, Irena A1 - Shulda, Sarah A1 - Silvestre‐Albero, Joaquin A1 - Steriotis, Theodore A1 - Tampaxis, Christos A1 - Hirscher, Michael A1 - Maiwald, Michael T1 - Establishing ZIF‐8 as a reference material for hydrogen cryoadsorption: An interlaboratory study N2 - AbstractHydrogen storage by cryoadsorption on porous materials has the advantages of low material cost, safety, fast kinetics, and high cyclic stability. The further development of this technology requires reliable data on the H2 uptake of the adsorbents, however, even for activated carbons the values between different laboratories show sometimes large discrepancies. So far no reference material for hydrogen cryoadsorption is available. The metal‐organic framework ZIF‐8 is an ideal material possessing high thermal, chemical, and mechanical stability that reduces degradation during handling and activation. Here, we distributed ZIF‐8 pellets synthesized by extrusion to 9 laboratories equipped with 15 different experimental setups including gravimetric and volumetric analyzers. The gravimetric H2 uptake of the pellets was measured at 77 K and up to 100 bar showing a high reproducibility between the different laboratories, with a small relative standard deviation of 3–4 % between pressures of 10–100 bar. The effect of operating variables like the amount of sample or analysis temperature was evaluated, remarking the calibration of devices and other correction procedures as the most significant deviation sources. Overall, the reproducible hydrogen cryoadsorption measurements indicate the robustness of the ZIF‐8 pellets, which we want to propose as a reference material. KW - Physical and theoretical chemistry KW - Atomic and molecular physics, and optics PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594788 DO - https://doi.org/10.1002/cphc.202300794 SN - 1439-7641 SP - 1 EP - 7 PB - Wiley CY - Weinheim AN - OPUS4-59478 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kowalewska, Z. A1 - Abad Andrade, Carlos Enrique A1 - Okruss, M. A1 - Recknagel, Sebastian T1 - Feasibility of high-resolution continuum source molecular absorption spectrometry for vanadium determination N2 - This work aimed to evaluate high-resolution continuum source molecular absorption spectrometry (HR-CS MAS), traditionally used to determine non-metals, for the determination of a new element, metal, vanadium. VO was selected as a target molecule because it is relatively stable and was expected to be spontaneously generated in a flame or a graphite furnace (GF). The high-resolution overview spectra of the molecule were obtained in a wide range of 480–630 nm, and absorption due to the X4Σ−–C4Σ− electronic transition was registered. A unique instrumental setup, comprising a prototype Modular Simultaneous Echelle Spectrograph (MOSES) and a commercial HR-CS MAS apparatus, was applied in the research. Finally, the spectral area centered at 550.6230 nm was selected for analysis. A method was developed to determine V in solutions of catalysts of heavy petroleum oil hydroprocessing using a commercial HR-CS spectrometer in a flame version. Although sensitivity was relatively poor (characteristic concentration 380 mg L−1), an extremely low noise enabled reaching a satisfactory detection limit (20 mg L−1 in solution, i.e. 0.1% m:m in the catalyst). For the first time vanadium was determined using ordinary air-acetylene flame. The obtained results were consistent with the results of atomic absorption spectrometry with N2O-C2H2 flame. Unfortunately, only a small population of VO molecules could have been generated in GF measurements. Furthermore, the observed VO molecules appeared only at unfavorably high temperatures. The work shows the potential of HR-CS MAS as a scientific tool for investigating the mechanism of processes occurring in the GF. This work can inspire other research of new analytes for HR-CS MAS. KW - Vanadium KW - HR-CS-MAS KW - VO KW - High-resolution continuum source molecular absorption spectrometry KW - AAS PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-569899 DO - https://doi.org/10.1039/D2JA00281G SN - 0267-9477 VL - 38 IS - 2 SP - 472 EP - 483 PB - Royal Society of Chemistry AN - OPUS4-56989 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zhuang, Y. A1 - Spahr, S. A1 - Lutze, H.V. A1 - Reith, C.J. A1 - Hagemann, N. A1 - Paul, Andrea A1 - Haderlein, S.B. T1 - Persulfate activation by biochar and iron: Effect of chloride on formation of reactive species and transformation of N,N-diethyl-m-toluamide (DEET) N2 - Fenton-like processes using persulfate for oxidative water treatment and contaminant removal can be enhanced by the addition of redox-active biochar, which accelerates the reduction of Fe(III) to Fe(II) and increases the yield of reactive species that react with organic contaminants. However, available data on the formation of non-radical or radical species in the biochar/Fe(III)/persulfate system are inconsistent, which limits the evaluation of treatment efficiency and applicability in different water matrices. Based on competition kinetics calculations, we employed different scavengers and probe compounds to systematically evaluate the effect of chloride in presence of organic matter on the formation of major reactive species in the biochar/Fe(III)/persulfate system for the transformation of the model compound N,N‑diethyl-m-toluamide (DEET) at pH 2.5. We show that the transformation of methyl phenyl sulfoxide (PMSO) to methyl phenyl sulfone (PMSO2) cannot serve as a reliable indicator for Fe(IV), as previously suggested, because sulfate radicals also induce PMSO2 formation. Although the formation of Fe(IV) cannot be completely excluded, sulfate radicals were identified as the major reactive species in the biochar/Fe(III)/persulfate system in pure water. In the presence of dissolved organic matter, low chloride concentrations (0.1 mM) shifted the major reactive species likely to hydroxyl radicals. Higher chloride concentrations (1 mM), as present in a mining-impacted acidic surface water, resulted in the formation of another reactive species, possibly Cl2•−, and efficient DEET degradation. To tailor the application of this oxidation process, the water matrix must be considered as a decisive factor for reactive species formation and contaminant removal. KW - Water treatment KW - Organic contaminants KW - Fenton-like systems KW - Radicals KW - ESR PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608677 DO - https://doi.org/10.1016/j.watres.2024.122267 SN - 0043-1354 VL - 265 SP - 1 EP - 8 PB - Elsevier Ltd. AN - OPUS4-60867 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - You, Zengchao A1 - Winckelmann, Alexander A1 - Vogl, Jochen A1 - Recknagel, Sebastian A1 - Abad Andrade, Carlos Enrique T1 - Determination of calcium, iron, and selenium in human serum by isotope dilution analysis using nitrogen microwave inductively coupled atmospheric pressure plasma mass spectrometry (MICAP-MS) N2 - In this study, we demonstrate the applicability of nitrogen microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) for Ca, Fe, and Se quantification in human serum using isotope dilution (ID) analysis. The matrix tolerance of MICAP-MS in Na matrix was investigated, uncovering that high Na levels can suppress the signal intensity. This suppression is likely due to the plasma loading and the space charge effect. Moreover, 40Ca and 44Ca isotopic fractionation was noted at elevated Na concentration. Nine certified serum samples were analyzed using both external calibration and ID analysis. Overestimation of Cr, Zn, As, and Se was found in the results of external calibration, which might be resulted from C-induced polyatomic interference and signal enhancement, respectively. Further investigations performed with methanol showed a similar enhancement effect for Zn, As, and Se, potentially supporting this assumption. The mass concentrations determined with ID analysis show metrological compatibility with the reference values, indicating that MICAP-MS combined with ID analysis can be a promising method for precise Ca, Fe, and Se determination. Moreover, this combination reduces the influences of matrix effects, broadening the applicability of MICAP-MS for samples with complex matrix. KW - Selenium KW - Nitrogen microwave inductively coupled atmospheric pressure mass spectrometry KW - Isotope dilution KW - Human serum KW - Calcium KW - Iron PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598664 DO - https://doi.org/10.1007/s00216-024-05274-0 SN - 1618-2642 SP - 3117 EP - 3125 PB - Springer CY - Berlin AN - OPUS4-59866 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tchipilov, Teodor A1 - Meyer, Klas A1 - Weller, Michael G. T1 - Quantitative 1H nuclear magnetic resonance (qNMR) of aromatic amino acids for protein quantification N2 - Hydrolysis of protein samples into amino acids facilitates the use of NMR spectroscopy for protein and peptide quantification. Different conditions have been tested for quantifying aromatic amino acids and proteins. The pH-dependent signal shifts in the aromatic region of amino acid samples were examined. A pH of 12 was found to minimize signal overlap of the four aromatic amino acids. Several aromatic compounds, such as terephthalic acid, sulfoisophthalic acid, and benzene tricarboxylic acid, were applied as internal standards. The quantification of amino acids from an amino acid standard was performed. Using the first two suggested internal standards, recovery was ~97% for histidine, phenylalanine, and tyrosine at a concentration of approximately 1 mM in solution. Acidic hydrolysis of a certified reference material (CRM) of bovine serum albumin (BSA) and subsequent quantification of Phe and Tyr yielded recoveries of 98% ± 2% and 88% ± 4%, respectively, at a protein concentration of 16 g/L or 250 µM. KW - Amino acid analysis KW - Aromatic amino acid analysis KW - AAA KW - AAAA KW - Protein hydrolysis KW - Hydrochloric acid KW - Metrology KW - Traceability KW - NIST KW - Reference materials KW - Internal standard KW - Calibration KW - Compound-independent calibration KW - Histidine KW - Tyrosine KW - Tryptophan KW - Phenylalanine KW - Terephthalic acid KW - Benzene-1,3,5-tricarboxylic acid KW - Bovine serum albumin (BSA) KW - Quantitative protein analysis KW - Phenylketonuria PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-570943 DO - https://doi.org/10.3390/mps6010011 VL - 6 IS - 1 SP - 1 EP - 13 PB - MDPI CY - Basel, Schweiz AN - OPUS4-57094 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Recknagel, Sebastian A1 - Vogel, Kristin T1 - Berechnung und Nutzung von Unsicherheiten zertifizierter Werte von Referenzmaterialien N2 - Referenzmaterialien sind entscheidend für die Qualitätssicherung von Laboratorien. Diese nutzen Referenzmaterialien unter anderem zur Validierung von Messverfahren und zur Kalibrierung von Geräten. Dabei ist zu beachten, dass zertifizierte Merkmalswerte stets eine gewisse Unsicherheit aufweisen. Die Ermittlung dieser Unsicherheitsbeiträge ist Gegenstand des Artikels. Des Weiteren wird ein Vorgehen beschrieben, wie die Unsicherheit von Messverfahren mit Hilfe eines Referenzmaterials bestimmt werden kann. KW - Referenzmaterial KW - Messunsicherheit KW - Qualitätskontrolle PY - 2024 DO - https://doi.org/10.1515/teme-2024-0025 SN - 0171-8096 SP - 1 EP - 7 PB - De Gruyter AN - OPUS4-60564 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mangoufis-Giasin, I. A1 - Piqué, O. A1 - Khanipour, Peyman A1 - Mayrhofer, K. J. J. A1 - Calle-Vallejo, F. A1 - Katsounaros, I. T1 - Different promoting roles of ruthenium for the oxidation of primary and secondary alcohols on PtRu electrocatalysts N2 - This study shows remarkably different features between the oxidation of secondary and primary C₃-C₅ alcohols. The oxidation of primary alcohols is controlled by the oxidative removal of blocking adsorbates, such as CO, formed after the dissociative adsorption of alcohol molecules. Conversely, secondary alcohols do not undergo dissociative adsorption and therefore their oxidation is purely controlled by the energetics of the elementary reaction steps. In this respect, a different role of ruthenium is revealed for the electrooxidation of primary and secondary alcohols on bimetallic platinum-ruthenium catalysts. Ruthenium enhances the oxidation of primary alcohols via the established bifunctional mechanism, in which the adsorption of (hydr)oxide species that are necessary to remove the blocking adsorbates is favored. In contrast, the oxidation of secondary alcohols is enhanced by the Ru-assisted stabilization of an O-bound intermediate that is involved in the potential-limiting step. This alternative pathway enables the oxidation of secondary alcohols close to the equilibrium potential. KW - Electrocatalysis KW - Electrochemical energy conversion KW - Direct alcohol fuel cells KW - Alcohol electrooxidation KW - Secondary alcohols KW - 2-propanol oxidation KW - Electrochemical real-time mass spectrometry KW - Density functional theory PY - 2021 DO - https://doi.org/10.1016/j.jcat.2021.05.028 SN - 0021-9517 VL - 400 SP - 166 EP - 172 PB - Elsevier CY - San Diego, Calif. AN - OPUS4-56999 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fricke, F. A1 - Mahmood, S. A1 - Hoffmann, J. A1 - Brandalero, M. A1 - Liehr, Sascha A1 - Kern, Simon A1 - Meyer, Klas A1 - Kowarik, S. A1 - Westerdick, S. A1 - Maiwald, Michael A1 - Hübner, M. T1 - Artificial Intelligence for Mass Spectrometry and Nuclear Magnetic Resonance Spectroscopy N2 - Mass Spectrometry (MS) and Nuclear Magnetic Resonance Spectroscopy (NMR) are critical components of every industrial chemical process as they provide information on the concentrations of individual compounds and by-products. These processes are carried out manually and by a specialist, which takes a substantial amount of time and prevents their utilization for real-time closed-loop process control. This paper presents recent advances from two projects that use Artificial Neural Networks (ANNs) to address the challenges of automation and performance-efficient realizations of MS and NMR. In the first part, a complete toolchain has been developed to develop simulated spectra and train ANNs to identify compounds in MS. In the second part, a limited number of experimental NMR spectra have been augmented by simulated spectra to train an ANN with better prediction performance and speed than state-of-theart analysis. These results suggest that, in the context of the digital transformation of the process industry, we are now on the threshold of a possible strongly simplified use of MS and MRS and the accompanying data evaluation by machine-supported procedures, and can utilize both methods much wider for reaction and process monitoring or quality control. T2 - 2021 Design, Automation & Test in Europe Conference & Exhibition (DATE) CY - Grenoble, France DA - 01.02.2021 KW - Industry 4.0, KW - Cyber-physical systems KW - Artificial neural networks KW - Mass spectrometry KW - Nuclear magnetic resonance spectroscopy PY - 2021 DO - https://doi.org/10.23919/DATE51398.2021.9473958 SP - 615 EP - 620 PB - IEEE AN - OPUS4-55360 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Anderhalten, L. A1 - Silva, R. V. A1 - Morr, A. A1 - Wang, S. A1 - Smorodchenko, A. A1 - Saatz, Jessica A1 - Traub, Heike A1 - Mueller, S. A1 - Boehm-Sturm, P. A1 - Rodriguez-Sillke, Y. A1 - Kunkel, D. A1 - Hahndorf, J. A1 - Paul, F. A1 - Taupitz, M. A1 - Sack, I. A1 - Infante-Duarte, C. T1 - Different Impact of Gadopentetate and Gadobutrol on Inflammation-Promoted Retention and Toxicity of Gadolinium Within the Mouse Brain N2 - Objectives: Using a murine model of multiple sclerosis, we previously showed that repeated administration of gadopentetate dimeglumine led to retention of gadolinium (Gd) within cerebellar structures and that this process was enhanced with inflammation. This study aimed to compare the kinetics and retention profiles of Gd in inflamed and healthy brains after application of the macrocyclic Gd-based contrast agent (GBCA) gadobutrol or the linear GBCA gadopentetate. Moreover, potential Gd-induced neurotoxicity was investigated in living hippocampal slices ex vivo. Materials and Methods: Mice at peak of experimental autoimmune encephalomyelitis (EAE; n = 29) and healthy control mice (HC; n = 24) were exposed to a cumulative dose of 20 mmol/kg bodyweight of either gadopentetate dimeglumine or gadobutrol (8 injections of 2.5 mmol/kg over 10 days). Magnetic resonance imaging (7 T) was performed at baseline as well as at day 1, 10, and 40 post final injection (pfi) of GBCAs. Mice were sacrificed after magnetic resonance imaging and brain and blood Gd content was assessed by laser ablation-inductively coupled plasma (ICP)-mass spectrometry (MS) and ICP-MS, respectively. In addition, using chronic organotypic hippocampal slice cultures, Gd-induced neurotoxicity was addressed in living brain tissue ex vivo, both under control or inflammatory (tumor necrosis factor α [TNF-α] at 50 ng/μL) conditions. Results: Neuroinflammation promoted a significant decrease in T1 relaxation times after multiple injections of both GBCAs as shown by quantitative T1 mapping of EAE brains compared with HC. This corresponded to higher Gd retention within the EAE brains at 1, 10, and 40 days pfi as determined by laser ablation-ICP-MS. In inflamed cerebellum, in particular in the deep cerebellar nuclei (CN), elevated Gd retention was observed until day 40 after last gadopentetate application (CN: EAE vs HC, 55.06 ± 0.16 μM vs 30.44 ± 4.43 μM). In contrast, gadobutrol application led to a rather diffuse Gd content in the inflamed brains, which strongly diminished until day 40 (CN: EAE vs HC, 0.38 ± 0.08 μM vs 0.17 ± 0.03 μM). The analysis of cytotoxic effects of both GBCAs using living brain tissue revealed an elevated cell death rate after incubation with gadopentetate but not gadobutrol at 50 mM. The cytotoxic effect due to gadopentetate increased in the presence of the inflammatory mediator TNF-α (with vs without TNF-α, 3.15% ± 1.18% vs 2.17% ± 1.14%; P = 0.0345). Conclusions: In the EAE model, neuroinflammation promoted increased Gd retention in the brain for both GBCAs. Whereas in the inflamed brains, efficient clearance of macrocyclic gadobutrol during the investigated time period was observed, the Gd retention after application of linear gadopentetate persisted over the entire observational period. Gadopentetate but not gadubutrol appeared to be neurotoxic in an ex vivo paradigm of neuronal inflammation. KW - Imaging KW - ICP-MS KW - Gadolinium KW - Contrast agent KW - Laser ablation KW - Brain KW - Multiple sclerosis PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546910 DO - https://doi.org/10.1097/RLI.0000000000000884 SN - 0020-9996/22/0000–0000 VL - 57 IS - 10 SP - 677 EP - 688 PB - Wolters Kluwer N.V. CY - Alphen aan den Rijn, The Netherlands AN - OPUS4-54691 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kader, A. A1 - Kaufmann, Jan Ole A1 - Mangarova, D. B. A1 - Moeckel, J. A1 - Brangsch, J. A1 - Adams, L. C. A1 - Zhao, J. A1 - Reimann, C. A1 - Saatz, Jessica A1 - Traub, Heike A1 - Buchholz, R. A1 - Karst, U. A1 - Hamm, B. A1 - Makowski, M. R. T1 - Iron Oxide Nanoparticles for Visualization of Prostate Cancer in MRI N2 - Prostate cancer (PCa) is one of the most common cancers in men. For detection and diagnosis of PCa, non-invasive methods, including magnetic resonance imaging (MRI), can reduce the risk potential of surgical intervention. To explore the molecular characteristics of the tumor, we investigated the applicability of ferumoxytol in PCa in a xenograft mouse model in two different tumor volumes, 500 mm3 and 1000 mm3. Macrophages play a key role in tumor progression, and they are able to internalize iron-oxide particles, such as ferumoxytol. When evaluating T2*-weighted sequences on MRI, a significant decrease of signal intensity between pre- and post-contrast images for each tumor volume (n = 14; p < 0.001) was measured. We, furthermore, observed a higher signal loss for a tumor volume of 500 mm3 than for 1000 mm3. These findings were confirmed by histological examinations and laser ablation inductively coupled plasma-mass spectrometry. The 500 mm3 tumors had 1.5% iron content (n = 14; sigma = 1.1), while the 1000 mm3 tumors contained only 0.4% iron (n = 14; sigma = 0.2). In vivo MRI data demonstrated a correlation with the ex vivo data (R2 = 0.75). The results of elemental analysis by inductively coupled plasma-mass spectrometry correlated strongly with the MRI data (R2 = 0.83) (n = 4). Due to its long retention time in the blood, biodegradability, and low toxicity to patients, ferumoxytol has great potential as a contrast agent for visualization PCa. KW - Imaging KW - Nanoparticle KW - Cancer KW - Iron oxide KW - ICP-MS KW - Magnetic resonance imaging PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-550075 DO - https://doi.org/10.3390/cancers14122909 VL - 14 IS - 12 SP - 1 EP - 13 PB - MDPI CY - Basel, Switzerland AN - OPUS4-55007 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Golusda, L. A1 - Kühl, A. A. A1 - Lehmann, M. A1 - Dahlke, K. A1 - Mueller, S. A1 - Boehm-Sturm, P. A1 - Saatz, Jessica A1 - Traub, Heike A1 - Schnorr, J. A1 - Freise, C. A1 - Taupitz, M. A1 - Biskup, K. A1 - Blanchard, V. A1 - Klein, O. A1 - Sack, I. A1 - Siegmund, B. A1 - Paclik, D. T1 - Visualization of inflammation in experimental colitis by magnetic resonance imaging using very small superparamagnetic iron oxide particles N2 - Inflammatory bowel diseases (IBD) comprise mainly ulcerative colitis (UC) and Crohn´s disease (CD). Both forms present with a chronic inflammation of the (gastro) intestinal tract, which induces excessive changes in the composition of the associated extracellular matrix (ECM). In UC, the inflammation is limited to the colon, whereas it can occur throughout the entire gastrointestinal tract in CD. Tools for early diagnosis of IBD are still very limited and highly invasive and measures for standardized evaluation of structural changes are scarce. To investigate an efficient non-invasive way of diagnosing intestinal inflammation and early changes of the ECM, very small superparamagnetic iron oxide nanoparticles (VSOPs) in magnetic resonance imaging (MRI) were applied in two mouse models of experimental colitis: the dextran sulfate sodium (DSS)-induced colitis and the transfer model of colitis. For further validation of ECM changes and inflammation, tissue sections were analyzed by immunohistochemistry. For in depth ex-vivo investigation of VSOPs localization within the tissue, Europium-doped VSOPs served to visualize the contrast agent by imaging mass cytometry (IMC). VSOPs accumulation in the inflamed colon wall of DSS-induced colitis mice was visualized in T2* weighted MRI scans. Components of the ECM, especially the hyaluronic acid content, were found to influence VSOPs binding. Using IMC, colocalization of VSOPs with macrophages and endothelial cells in colon tissue was shown. In contrast to the DSS model, colonic inflammation could not be visualized with VSOP-enhanced MRI in transfer colitis. VSOPs present a potential contrast agent for contrast-enhanced MRI to detect intestinal inflammation in mice at an early stage and in a less invasive manner depending on hyaluronic acid content. KW - Inflammation KW - Imaging KW - Immunohistochemistry KW - MRI KW - Nanoparticle KW - Extracellular matrix KW - Laser ablation KW - ICP-MS PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-555395 DO - https://doi.org/10.3389/fphys.2022.862212 SN - 1664-042X VL - 13 IS - July 2022 SP - 1 EP - 15 PB - Frontiers Research Foundation CY - Lausanne AN - OPUS4-55539 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Völker, Tobias A1 - Gornushkin, Igor B. T1 - Mass and mole fractions in calibration-free LIBS N2 - This technical note highlights the fact that CF-LIBS algorithms work in mole fractions, while results of spectrochemical analysis are usually reported in mass fractions or mass percent. Ignoring this difference and not converting mole fractions to mass fractions can lead to errors in reported concentrations determined by the CF-LIBS method and inadequate comparison of these concentrations with certified concentrations. Here, the key points of the CF-LIBS algorithm are reproduced and the formulae for converting a mole fraction to a mass fraction and vice versa are given. Several numerical examples are also given, which show that the greater the difference between the molar mass of an individual element in a sample and the average molar mass, the greater the discrepancy between the mole and mass fractions. KW - Spectroscopy KW - Analytical Chemistry KW - LIBS KW - Calibration PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598611 DO - https://doi.org/10.1039/d4ja00028e SN - 0267-9477 VL - 39 IS - 4 SP - 1030 EP - 1032 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59861 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kirilina, E. A1 - Helbling, S. A1 - Morawski, M. A1 - Pine, K. A1 - Reimann, K. A1 - Jankuhn, S. A1 - Dinse, J. A1 - Deistung, A. A1 - Reichenbach, J. R. A1 - Trampel, R. A1 - Geyer, S. A1 - Müller, Larissa A1 - Jakubowski, Norbert A1 - Arendt, T. A1 - Bazin, P.-L. A1 - Weiskopf, N. T1 - Superficial white matter imaging: Contrast mechanisms and whole-brain in vivo mapping N2 - Superficial white matter (SWM) contains the most cortico-cortical white matter connections in the human brain encompassing the short U-shaped association fibers. Despite its importance for brain connectivity, very little is known about SWM in humans, mainly due to the lack of noninvasive imaging methods. Here, we lay the groundwork for systematic in vivo SWM mapping using ultrahigh resolution 7 T magnetic resonance imaging. Using biophysical modeling informed by quantitative ion beam microscopy on postmortem brain tissue, we demonstrate that MR contrast in SWM is driven by iron and can be linked to the microscopic iron distribution. Higher SWM iron concentrations were observed in U-fiber–rich frontal, temporal, and parietal areas, potentially reflecting high fiber density or late myelination in these areas. Our SWM mapping approach provides the foundation for systematic studies of interindividual differences, plasticity, and pathologies of this crucial structure for cortico-cortical connectivity in humans. KW - Magnetic resonance imaging KW - Laser ablation KW - ICP-MS KW - Brain KW - Imaging PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-514430 DO - https://doi.org/10.1126/sciadv.aaz9281 SN - 2375-2548 VL - 6 IS - 41 SP - eaaz9281 PB - American Association for the Advancement of Science (Science/AAAS) CY - Washington, DC, USA AN - OPUS4-51443 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Garcia-Fernandez, J. A1 - Turiel, D. A1 - Bettmer, J. A1 - Jakubowski, Norbert A1 - Panne, Ulrich A1 - Rivas Garcia, L. A1 - Llopis, J. A1 - Sanchez-Gonzalez, C. A1 - Montes-Bayon, M. T1 - In vitro and in situ experiments to evaluate the biodistribution and cellular toxicity of ultrasmall iron oxide nanoparticles potentially used as oral iron supplements N2 - Well-absorbed iron-based nanoparticulated materials are a promise for the oral management of iron deficient anemia. In this work, a battery of in vitro and in situ experiments are combined for the evaluation of the uptake, distribution and toxicity of new synthesized ultrasmall (4 nm core) Fe2O3 nanoparticles coated with tartaric/adipic acid with potential to be used as oral Fe supplements. First, the in vitro simulated gastric acid solubility studies by TEM and HPLC-ICP-MS reveal a partial reduction of the core size of about 40% after 90 min at pH3. Such scenario confirms the arrival of the nanoparticulate material in the small intestine. In the next step, the in vivo absorption through the small intestine by intestinal perfusion experiments is conducted using the sought nanoparticles in Wistar rats. The quantification of Fe in the NPs Suspension before and after perfusion shows Fe absorption levels above 79%, never reported for other Fe treatments. Such high absorption levels do not seem to compromise cell viability, evaluated in enterocytes-like models (Caco-2 and HT-29) using cytotoxicity, ROS production, genotoxicity and lipid peroxidation tests. Moreover, regional differences in terms of Fe concentration are obtained among different parts of the small intestine as duodenum>jejunum>ileum. Complementary transmission electron microscopy (TEM) images show the presence of the intact particles around the intestinal microvilli without significant tissue damage. These studies show the high potential of these NP preparations for their use as oral management of anemia. KW - Iron nanoparticles KW - Anemia KW - ICP-MS KW - In vitro KW - In situ PY - 2020 DO - https://doi.org/10.1080/17435390.2019.1710613 VL - 14 IS - 3 SP - 388 EP - 403 PB - Taylor & Francis Online CY - London AN - OPUS4-50314 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dorgerloh, Ute A1 - Becker, Roland A1 - Freeling, Finnian A1 - Scheurer, Marco A1 - Gökçe, Emine A1 - Strack, Katrin A1 - Sommerfeld, Thomas A1 - Sauer, Andreas A1 - Schneider, Jonas A1 - Härtel, Christoph A1 - Valkov, Vassil A1 - Moser, Lukas A1 - Geiß, Sabine A1 - Junginger, Sabine A1 - Schlittenbauer, Linda A1 - Suess, Elke A1 - Ruth, Katinka T1 - Standardising the quantification of trifluoroacetic acid in water: Interlaboratory validation trial using liquid chromatography-mass spectrometric detection (LC–MS/MS) N2 - The concentration of trifluoroacetic acid in surface and groundwaters and drinking water is subject of increasing concern. Since there is no standardised procedure available, German standardisation body DIN has initiated the first draft standard using liquid chromatography with tandem mass spectrometry (LC–MS/MS) after direct injection for the concentration range between ≥ 0.1 and 3 µg/L. Herein, the interlaboratory comparison as final validation step involving 12 expert laboratories from Germany and Switzerland is described. Two groundwaters, two surface waters, a drinking water, a rainwater, and two fortified groundwater samples displayed relative repeatability standard deviations between 3 and 7% and relative reproducibility standard deviation between 6 and 20% and were included in the draft standard DIN 38407-53. KW - TFA Trifluoroacetic acid KW - LC/MS-MS KW - Validation trial PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-632376 DO - https://doi.org/10.1007/s00769-025-01640-2 SN - 0949-1775 SP - 1 EP - 4 PB - Springer CY - Berlin AN - OPUS4-63237 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rosenkranz, D. A1 - Kriegel, F. L. A1 - Mavrakis, E. A1 - Pergantis, S. A. A1 - Reichardt, P. A1 - Tentschert, J. A1 - Jakubowski, N. A1 - Laux, P. A1 - Panne, Ulrich A1 - Luch, A. T1 - Versatile dual-inlet sample introduction system for multi-mode single particle inductively coupled plasma mass spectrometry N2 - Metal-containing nanoparticles (NP) can be characterized with inductively coupled plasma mass spectrometers (ICP-MS) in terms of their size and number concentration by using the single-particle mode of the instrument (spICP-MS). The accuracy of measurement depends on the setup, operational conditions of the instrument and specific parameters that are set by the user. The transport efficiency of the ICP-MS is crucial for the quantification of the NP and usually requires a reference material with homogenous size distribution and a known particle number concentration. Currently, NP reference materials are available for only a few metals and in limited sizes. If particles are characterized without a reference standard, the results of both size and particle number may be biased. Therefore, a dual-inlet Setup for characterizing nanoparticles with spICP-MS was developed to overcome this problem. This setup is based on a conventional introduction system consisting of a pneumatic nebulizer (PN) for nanoparticle solutions and a microdroplet Generator (μDG) for ionic calibration solutions. A new and flexible interface was developed to facilitate the coupling of μDG, PN and the ICP-MS system. The interface consists of available laboratory components and allows for the calibration, nanoparticle (NP) characterization and cleaning of the arrangement, while the ICP-MS instrument is still running. Three independent analysis modes are available for determining particle size and number concentration. Each mode is based on a different calibration principle. While mode I (counting) and mode III (μDG) are known from the literature, mode II (sensitivity), is used to determine the transport efficiency by inorganic ionic Standard solutions only. It is independent of NP reference materials. The μDG based inlet system described here guarantees superior analyte sensitivities and, therefore, lower detection limits (LOD). The size dependent LODs achieved are less than 15 nm for all NP (Au, Ag, CeO2) investigated. KW - Spectrometer KW - Reference KW - Calibration PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-536121 DO - https://doi.org/10.3791/61653 SN - 1940-087X IS - 163 SP - 1 EP - 19 PB - MyJoVE Corporation CY - Cambridge, MA, USA AN - OPUS4-53612 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hachenberger, Y. U. A1 - Rosenkranz, D. A1 - Kriegel, Fabian L. A1 - Krause, B. A1 - Matschaß, René A1 - Reichardt, P. A1 - Tentschert, J. A1 - Laux, P. A1 - Jakubowski, Norbert A1 - Panne, Ulrich A1 - Luch, A. T1 - Tackling Complex Analytical Tasks: An ISO/TS-Based Validation Approach for Hydrodynamic Chromatography Single Particle Inductively Coupled Plasma Mass Spectrometry N2 - Nano-carrier systems such as liposomes have promising biomedical applications. Nevertheless, characterization of these complex samples is a challenging analytical task. In this study a coupled hydrodynamic chromatography-single particle-inductively coupled plasma mass spectrometry (HDC-spICP-MS) approach was validated based on the technical specification (TS) 19590:2017 of the international organization for standardization (ISO). The TS has been adapted to the hyphenated setup. The quality criteria (QC), e.g., linearity of the calibration, transport efficiency, were investigated. Furthermore, a cross calibration of the particle size was performed with values from dynamic light scattering (DLS) and transmission electron microscopy (TEM). Due to an additional Y-piece, an online-calibration routine was implemented. This approach allows the calibration of the ICP-MS during the dead time of the chromatography run, to reduce the required time and enhance the robustness of the results. The optimized method was tested with different gold nanoparticle (Au-NP) mixtures to investigate the characterization properties of HDC separations for samples with increasing complexity. Additionally, the technique was successfully applied to simultaneously determine both the hydrodynamic radius and the Au-NP content in liposomes. With the established hyphenated setup, it was possible to distinguish between different subpopulations with various NP loads and different hydrodynamic diameters inside the liposome carriers. KW - Single particle ICP-MS KW - Nanoparticle characterization KW - Nano-carrier KW - Iposomes KW - Hydrodynamic chromatography (HDC) KW - Validation PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-506609 DO - https://doi.org/10.3390/ma13061447 VL - 13 IS - 6 SP - 1 EP - 14 CY - Basel, Switzerland AN - OPUS4-50660 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rosenkranz, Daniel A1 - Kriegel, F. L. A1 - Mavrakis, E. A1 - Pergantis, S. A. A1 - Reichardt, Ph. A1 - Tentschert, J. A1 - Jakubowski, Norbert A1 - Laux, P. A1 - Panne, Ulrich T1 - Improved validation for single particle ICP-MS analysis using a pneumatic nebulizer / microdroplet generator sample introduction system for multi-mode nanoparticle determination N2 - This study reports on the development of a single-particle (sp) inductively coupled plasma mass spectrometry (ICP-MS) technique suitable for the multi-mode determination of nanoparticle (NP) metal mass fraction and number concentration. The described technique, which is based on a dual inlet System consisting of a pneumatic nebulizer (PN) and a microdroplet generator (MDG), allows for the sequential introduction of ionic metal calibrant solutions and nanoparticle suspensions via all combinations of the two inlets; thus allowing for a combination of three independent modes of analysis. A novel interface, assembled using standard analytical components (a demountable quartz ICP-MS torch, flexible nonconducting silicon tubing and various connectors), was used to interface the dual inlet system to an ICP-MS. The interface provided improved functionality, compared to a previous design. It is now possible to conveniently exchange and introduce standard solutions and samples via all inlet combinations, analyze them, and also wash the sample inlet systems while the whole setup is still connected to an operating ICP-MS. This setup provided seamless and robust operation in a total of three analysis modes, i.e. three ways to independently determine the metal mass fraction and NP number concentration. All three analyses modes could be carried out within a single analytical run lasting approximately 20 min. The unique feature of the described approach is that each analysis mode is based on a different. KW - Nanomaterials KW - Nanoparticles KW - Single particle ICP-MS KW - Microdroplet generator PY - 2020 DO - https://doi.org/10.1016/j.aca.2019.11.043 VL - 1099 SP - 16 EP - 25 PB - Elsevier B.V. AN - OPUS4-50361 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nourinejhad Zarghani, S. A1 - Monavari, Mehran A1 - Nourinejhad Zarghani, A. A1 - Nouri, S. A1 - Ehlers, J. A1 - Hamacher, J. A1 - Bandte, M. A1 - Büttner, C. T1 - Quantifying plant viruses: Evolution from bioassay to infectivity dilution curves along the model of tobamoviruses N2 - This review describes the development of the bioassay as a means of quantifying plant viruses, with particular attention to tobamovirus. It delves into various models used to establish a correlation between virus particle concentration and the number of induced local lesions (the infectivity dilution curve), including the Poisson, Furumoto and Mickey, Kleczkowski, Growth curve, and modified Poisson models. The parameters of each model are described, and their application or performance in the context of the tobacco mosaic virus is explored. This overview highlights the enduring value of the infectivity dilution curve in tobamovirus quantification, providing valuable insights for researchers or practitioners of bioassays and theoreticians of modeling. KW - Local lesion KW - qRT-PCR KW - Nicotiana KW - ToBRFV KW - TMV KW - CGMMV KW - Disinfection KW - Modeling PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630142 DO - https://doi.org/10.3390/v16030440 SN - 1999-4915 VL - 16 IS - 3 SP - 1 EP - 14 PB - MDPI CY - Basel AN - OPUS4-63014 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Quackatz, Lukas A1 - Gornushkin, Igor B. A1 - Griesche, Axel A1 - Kannengießer, Thomas A1 - Treutler, Kai A1 - Wesling, Volker T1 - In situ chemical analysis of duplex stainless steel weld by laser induced breakdown spectroscopy N2 - The high corrosion resistance and good mechanical properties of duplex stainless steel (DSS) are due to its special chemical composition, which is a balanced phase ratio of ferrite (α) and austenite (γ). Many industrial applications require the integration of DSS components. For this, Gas tungsten arc welding (GTAW) is an excellent choice, as it allows an automated operation with high reproducibility. However, when the weld pool solidifies, critical ratios of α- and γ- phases can occur, which lead to solidification cracking, increased susceptibility to corrosion, and a decrease in ductility and critical strength. Previous studies have shown that these defects can be caused by the accumulation of manganese and chromium in the heat affected zone (HAZ), requiring ongoing monitoring of this accumulation. A suitable method for such monitoring is laser-induced breakdown spectroscopy (LIBS), which can be used in two operating modes: calibration using standard reference samples and calibration-free. Unlike conventional quantitative LIBS measurements, which require reference samples to generate a calibration curve, calibration-free LIBS (CF-LIBS) allows chemical compositions to be determined solely from the emission spectrum of the plasma. Numerous publications show that CF-LIBS is a fast and efficient analytical method for the quantitative analysis of metal samples. In this work, CF-LIBS is applied to spectra obtained during GTAW DSS welding and the result is compared with those obtained by PLS analysis. A good correlation was found between both types of analysis, demonstrating the suitability of the CF-LIBS method for this application. The CF-LIBS method has a significant advantage over conventional LIBS due to the rapid in situ measurement of concentrations of major alloying elements without calibration procedure. This, combined with fast feedback and appropriate adjustment of welding parameters, helps prevent welding defects. KW - Duplex stainless steels KW - In situ measurement KW - LIBS KW - GMAW PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597940 DO - https://doi.org/10.1016/j.sab.2024.106899 SN - 0584-8547 VL - 214 SP - 1 EP - 7 PB - Elsevier B.V. AN - OPUS4-59794 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rabin, Ira A1 - Gordon, Nehemia A1 - Calvillo, Nelson T1 - Coloured Ruling Lines in a Fourteenth-Century Ashkenazi Torah Scroll N2 - Rabbinic halakhah required that Torah scrolls be written with relief ruling, horizontal and vertical lines scored into the writing surface. Coloured ruling with plummet or ink would make a Torah scroll invalid for liturgical use. Ruling lines on some leather fragments of early Oriental Torah scrolls give the impression of being produced with plummet or ink but may be the result of dust in the furrows of relief ruling. Erfurt 9, a fourteenth-century Ashkenazi Torah scroll, has coloured ruling, which is partial secondary re-ruling, on 13 of the 34 surviving sheets, perhaps added when the original relief ruling was difficult to see. The coloured ruling in Erfurt 9 is brown, giving it the visual appearance of iron-gall ink. However, XRF tests showed that the only meaningful metallic component in the coloured ruling was lead (Pb). Lead plummet ruling tends to have a greyish appearance. Black specks under near infrared light are consistent with minium, a lead-based red ink that can turn brown when it degrades. Partial secondary re-ruling added with minium to the original relief ruling comes as a surprise as it would have rendered Erfurt 9 unfit for liturgical use. KW - Hebrew Manuscripts KW - Ruling Lines KW - Coloured Ink PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-628531 DO - https://doi.org/10.25592/uhhfdm.17169 SN - 2410-0951 VL - 10 SP - 9 EP - 32 AN - OPUS4-62853 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fink, Friedrich A1 - Stawski, Tomasz M. A1 - Emmerling, Franziska A1 - Falkenhagen, Jana T1 - A novel machine-learning approach to unlock technical lignin classification by NIR spectroscopy - bench to handheld N2 - In this research, the utilization of near-infrared (NIR) spectroscopy in conjunction with advanced machine learning methods is investigated for categorizing technical lignins obtained from different biomass sources and industrial procedures. Technical lignins, such as kraft, organosolv and lignosulfonates, have different chemical compositions, which continue to make uniform characterization and application in sustainable sectors extremely difficult. Fast, universally accessible analytics combined with data analysis is still an open question. For the first time three distinct NIR spectrometers—a high-performance benchtop system, a mid-priced compact device, and an economical handheld unit—were utilized to record NIR spectra of 31 unique lignin samples. The spectra underwent pre-processing through standard normal variate (SNV) transformation and Savitzky-Golay derivatives to amplify spectral features and decrease noise. Principal component analysis (PCA) was employed to reduce data complexity and extract crucial characteristics for classification purposes. Subsequently, four machine learning algorithms—Support Vector Machines (SVM), Gaussian Naive Bayes (GNB), Gaussian Process Classification (GPC), and Decision Tree Classification (DTC)—were implemented for the classification of the lignin samples. The DTC model exhibited the highest accuracy among them across different spectrometers. Although the benchtop spectrometer produced the most precise outcomes, the compact NeoSpectra system also displayed potential as a cost-efficient option. Nonetheless, the restricted spectral coverage of the handheld NIRONE spectrometer resulted in reduced classification accuracy. Our discoveries highlight the capability of NIR spectroscopy, combined with robust data analysis techniques, for the swift and non-destructive classification of technical lignins, facilitating their improved utilization in sustainable fields. KW - Technical lignins KW - NIR spectroscopy KW - Classification KW - Machine-learning KW - PCA PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-634518 DO - https://doi.org/10.1016/j.chemolab.2025.105467 SN - 0169-7439 VL - 264 SP - 1 EP - 10 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-63451 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - El-Athman, Rukeia A1 - Rädler, Jörg A1 - Löhmann, Oliver A1 - Ariza de Schellenberger, Angela A1 - Muth, Thilo T1 - The BAM Data Store N2 - As a partner in several NFDI consortia, the Bundesanstalt für Materialforschung und -prüfung (BAM, German federal institute for materials science and testing) contributes to research data standardization efforts in various domains of materials science and engineering (MSE). To implement a central research data management (RDM) infrastructure that meets the requirements of MSE groups at BAM, we initiated the Data Store pilot project in 2021. The resulting infrastructure should enable researchers to digitally document research processes and store related data in a standardized and interoperable manner. As a software solution, we chose openBIS, an open-source framework that is increasingly being used for RDM in MSE communities. The pilot project was conducted for one year with five research groups across different organizational units and MSE disciplines. The main results are presented for the use case “nanoPlattform”. The group registered experimental steps and linked associated instruments and chemicals in the Data Store to ensure full traceability of data related to the synthesis of ~400 nanomaterials. The system also supported researchers in implementing RDM practices in their workflows, e.g., by automating data import and documentation and by integrating infrastructure for data analysis. Based on the promising results of the pilot phase, we will roll out the Data Store as the central RDM infrastructure of BAM starting in 2023. We further aim to develop openBIS plugins, metadata standards, and RDM workflows to contribute to the openBIS community and to foster RDM in MSE. T2 - 1st Conference on Research Data Infrastructure DA - 12.09.2023 KW - Research Data Infrastructure KW - Electronic Lab Notebook (ELN) KW - openBIS KW - Research Data Management PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596032 DO - https://doi.org/10.52825/CoRDI.v1i.229 VL - 1 SP - 1 EP - 5 AN - OPUS4-59603 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Drescher, D. A1 - Büchner, T. A1 - Schrade, P. A1 - Traub, Heike A1 - Werner, S. A1 - Guttmann, P. A1 - Bachmann, S. A1 - Kneipp, J. T1 - Influence of Nuclear Localization Sequences on the Intracellular Fate of Gold Nanoparticles N2 - Directing nanoparticles to the nucleus by attachment of nuclear localization sequences (NLS) is an aim in many applications. Gold nanoparticles modified with two different NLS were studied while crossing barriers of intact cells, including uptake, endosomal escape, and nuclear translocation. By imaging of the nanoparticles and by characterization of their molecular interactions with surface-enhanced Raman scattering (SERS), it is shown that nuclear translocation strongly depends on the particular incubation conditions. After an 1 h of incubation followed by a 24 h chase time, 14 nm gold particles carrying an adenoviral NLS are localized in endosomes, in the cytoplasm, and in the nucleus of fibroblast cells. In contrast, the cells display no nanoparticles in the cytoplasm or nucleus when continuously incubated with the nanoparticles for 24 h. The ultrastructural and spectroscopic data indicate different processing of NLS-functionalized particles in endosomes compared to unmodified particles. NLS functionalized nanoparticles form larger intraendosomal aggregates than unmodified gold nanoparticles. SERS spectra of cells with NLS-functionalized gold nanoparticles contain bands assigned to DNA and were clearly different from those with unmodified gold nanoparticles. The different processing in the presence of an NLS is influenced by a continuous exposure of the cells to nanoparticles and an ongoing nanoparticle uptake. This is supported by mass-spectrometry-based quantification that indicates enhanced uptake of NLS-functionalized nanoparticles compared to unmodified particles under the same conditions. The results contribute to the optimization of nanoparticle analysis in cells in a variety of applications, e.g., in theranostics, biotechnology, and bioanalytics. KW - Nanoparticle KW - Laser ablation KW - SERS KW - ICP-MS PY - 2021 DO - https://doi.org/10.1021/acsnano.1c04925 SN - 1936-086X VL - 15 IS - 9 SP - 14838 EP - 14849 PB - American Chemical Society AN - OPUS4-54047 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Theiner, S. A1 - Löhr, Konrad A1 - Köllensperger, G. A1 - Müller, L. A1 - Jakubowski, Norbert T1 - Single-cell analysis by use of ICP-MS N2 - This tutorial review article is highlighting the fundamentals, instrumentation, and most recent trends of single-cell analysis by use of inductively coupled plasma-mass spectrometry (ICP-MS). It is shown that metals and hetero-elements being intrinsically present in cells, taken up by cells (for instance engineered metallic nanoparticles) or binding to a cell can be detected qualitatively by existing ICP-MS Technologies on a single cell level. Adding a quantitative dimension to single-cell analysis by (laser ablation-) ICP-MS requires dedicated calibration and validation strategies, which are currently being established and are being critically discussed. In a tutorial part, the ICP-MS instruments, the measurement conditions, and the sample introduction and preparation techniques are introduced. The application section focuses on the state-of-the-art of single-cell analysis in suspension, using laser ablation or (imaging) mass cytometry. Finally, future trends are critically assessed. KW - Cell KW - ICP KW - ICP-MS KW - Laser ablation PY - 2020 DO - https://doi.org/10.1039/d0ja00194e SN - 0267-9477 VL - 35 IS - 9 SP - 1784 EP - 1813 PB - The Royal Society of Chemistry CY - Cambridge, UK AN - OPUS4-51448 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schannor, Mathias A1 - Oelze, Marcus A1 - Traub, Heike A1 - He, Yubei A1 - Schmidt, Robin A1 - Heidemann, Luisa A1 - Savic, Lynn Jeanette A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Advancing Biomarker Research: In Situ Cu Isotope Analysis in Liver Tumors by LA-MC-ICP-MS N2 - Stable metal isotopes have received increasing attention as medical biomarkers due to their potential to detect changes in metal metabolism related to diseases. In particular, copper stable isotopes are a powerful tool to identify isotopic variation between tumors and healthy tissue, suggesting application in cancer diagnosis. However, potential mechanisms causing isotope fractionation, such as redox- or bond-forming reactions and interactions of metals during transmembrane import and export, are less well understood. Here, we established an in situ method using laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) to advance our understanding of the underlying processes responsible for isotope fractionation between normal and diseased tissues. Gelatin-based bracketing standards and quality control reference materials, crucial for laser ablation analysis, were developed to allow correction for instrumentally induced isotope fractionation during LA-MC-ICP-MS analysis. Using such matrix-matched standards, the method achieved intermediate precisions for delta values of better than 0.15 ‰ (2 s) for inorganic reference materials and of better than 0.17 ‰ (2 s) for biological reference materials. The developed routine was tested on rabbit VX2 liver tumor samples, a model system resembling human hepatocellular carcinoma (HCC) used to study liver cancer. In situ Cu isotope compositions between healthy (𝛿65/63NIST976(Cu) = −1.5 ‰ to 0.2 ‰) and tumorous (𝛿65/63NIST976(Cu) = 0.0 ‰ to 1.3 ‰) liver tissue show distinct differences in their isotope ratios. The observed isotopic dichotomy is consistent with previous solution-based MC-ICP-MS work, showing enrichment of heavy 65Cu in cancer biopsies relative to healthy tissue. KW - Biomarker KW - Laser Ablation KW - Reference Material PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626865 DO - https://doi.org/10.1021/acs.analchem.4c05626 SN - 1520-6882 VL - 97 IS - 8 SP - 4425 EP - 4432 PB - American Chemical Society (ACS) AN - OPUS4-62686 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fogang, S. G. A1 - Temgoua, Ranil C. T. A1 - Deussi Ngaha, M. C. A1 - Kougoum Thieda, V. A1 - Fotsop, C. G. A1 - Averie Vomo, L. A1 - Teikam Kenda, G. A1 - Ngueko Makengue, Y. P. A1 - Deffo, G. A1 - Njanja, E. ED - Teamgoua, Ranil C. T. T1 - Room-Temperature Co-Precipitation Synthesis of Magnetite Nanoparticles and Application as Electrocatalytic Platform for Agricultural Pesticides Sensing in Water N2 - This work presents a straightforward room-temperature co-precipitation method for the synthesis of magnetite nanoparticles (Fe3O4NPs) and application as electrocatalytic material for the simultaneous determination of diuron (DR) and thiabendazole (TBZ) pesticides in water for the first time. The Fe3O4NPs were synthesized using an aqueous-based approach and immobilized onto a glassy carbon electrode (GCE) surface. Comprehensive characterization using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray, cyclic voltammetry (CV), and electrochemical impedance spectroscopy have confirmed the successful formation of well-crystallized Fe3O4NPs with an average crystallinity size of 61.62 nm. Electrochemical studies demonstrated strong electrostatic interactions between GCE/Fe3O4NPs and [Ru(NH3)6]3+. The electrochemical behavior of both pesticides were established by CV, while sensing parameters were optimized through differential pulse voltammetry. Under optimal conditions, the sensor achieved detection limits of 0.398 and 0.480 μM for DR and TBZ, respectively, with good selectivity and reproducibility. The practical utility of the sensor was successfully demonstrated through analysis of real water samples, offering a cost-effective solution for environmental monitoring applications. KW - Nanoparticles KW - Electrochemical sensors KW - Environmental analysis KW - Quality assurance PY - 2025 DO - https://doi.org/10.1002/elan.70022 SN - 1521-4109 VL - 37 IS - 7 SP - 1 EP - 11 PB - Wiley VHC-Verlag AN - OPUS4-63942 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Westwood, S. A1 - Martos, G. A1 - Josephs, R. A1 - Choteau, T. A1 - Wielgosz, R. A1 - Davies, S. A1 - Moawad, M. A1 - Tarrant, G. A1 - Chan, B. A1 - Alamgir, M. A1 - de Rego, E. A1 - Wollinger, W. A1 - Garrido, B. A1 - Fernandes, J. A1 - de Sena, R. A1 - Oliveira, R. A1 - Melanson, J. A1 - Bates, J. A1 - Mai Le, P. A1 - Meija, J. A1 - Quan, C. A1 - Huang, T. A1 - Zhang, W. A1 - Ma, R. A1 - Zhang, S. A1 - Hao, Y. A1 - He, Y. A1 - Song, S. A1 - Wang, H. A1 - Su, F. A1 - Zhang, T. A1 - Li, H. A1 - Lam, W. A1 - Wong, W. A1 - Fung, W. A1 - Philipp, Rosemarie A1 - Dorgerloh, Ute A1 - Meyer, Klas A1 - Piechotta, Christian A1 - Riedel, Juliane A1 - Westphalen, Tanja A1 - Giannikopoulou, P. A1 - Alexopoulos, Ch. A1 - Kakoulides, E. A1 - Kitamaki, Y. A1 - Yamazaki, T. A1 - Shimizu, Y. A1 - Kuroe, M. A1 - Numata, M. A1 - Pérez-Castorena, A. A1 - Balderas-Escamilla, M. A1 - Garcia-Escalante, J. A1 - Krylov, A. A1 - Mikheeva, A. A1 - Beliakov, M. A1 - Palagina, M. A1 - Tkachenko, I. A1 - Spirin, S. A1 - Smirnov, V. A1 - Tang Lin, T. A1 - Pui Sze, C. A1 - Juan, W. A1 - Lingkai, W. A1 - Ting, L. A1 - Quinde, L. A1 - Yizhao, C. A1 - Lay Peng, S. A1 - Fernandes-Whaley, M. A1 - Prevoo-Franzsen, D. A1 - Quinn, L. A1 - Nhlapo, N. A1 - Mkhize, D. A1 - Marajh, D. A1 - Chamane, S. A1 - Ahn, S. A1 - Choi, K. A1 - Lee, S. A1 - Han, J. A1 - Baek, S. A1 - Kim, B. A1 - Marbumrung, S. A1 - Jongmesuk, P. A1 - Shearman, K. A1 - Boonyakong, C. A1 - Bilsel, M. A1 - Gündüz, S. A1 - Ün, I. A1 - Yilmaz, H. A1 - Bilsel, G. A1 - Gökçen, T. A1 - Clarkson, C. A1 - Warren, J. A1 - Achtar, E. T1 - Mass fraction assignment of Bisphenol-A high purity material N2 - The CCQM-K148.a comparison was coordinated by the BIPM on behalf of the CCQM Organic Analysis Working Group for NMIs and DIs which provide measurement services in organic analysis under the CIPM MRA. It was undertaken as a "Track A" comparison within the OAWG strategic plan. CCQM-K148.a demonstrates capabilities for assigning the mass fraction content of a solid organic compound having moderate molecular complexity, where the compound has a molar mass in the range (75 - 500) g/mol and is non-polar (pKow < −2), when present as the primary organic component in a neat organic solid and where the mass fraction content of the primary component in the material is in excess of 950 mg/g. Participants were required to report the mass fraction of Bisphenol A present in one supplied unit of the comparison material. Participants using a mass balance method for the assignment were also required to report their assignments of the impurity components present in the material. Methods used by the seventeen participating NMIs or DIs were predominantly based on either stand-alone mass balance (summation of impurities) or qNMR approaches, or the combination of data obtained using both methods. The results obtained using thermal methods based on freezing-point depression methods were also reported by a limited number of participants. There was excellent agreement between assignments obtained using all three approaches to assign the BPA content. The assignment of the values for the mass fraction content of BPA consistent with the KCRV was achieved by most of the comparison participants with an associated relative standard uncertainty in the assigned value in the range (0.1 - 0.5)%. KW - Bisphenol-A KW - Purity assessment KW - Interlaboratory key comparison KW - Metrology PY - 2021 DO - https://doi.org/10.1088/0026-1394/58/1A/08015 VL - 58 IS - 1A SP - 08015 PB - IOP Publishing AN - OPUS4-54188 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Recknagel, Sebastian T1 - Certified reference material for the determination of hydrolytic resistance of borosilicate glass N2 - The preparation, analysis and certification of a new certified glass reference material (CRM) for the determination of hydrolytic resistance of borosilicate glass with the glass grains test is described. The CRM BAM-S053 is available in the form of glass rods (length: 185 mm, diameter: 9 mm, weight: 27·5 g). Certified properties are the acid consumption determined according to the procedures described in ISO 720, USP<660>, Ph.Eur. 3.2.1, data obtained following the procedure of ISO 719 was scattering too widely. The certified values are based on the results of 15 laboratories which participated in the certification interlaboratory comparison. The CRM is intended for the quality control when applying ISO 720, USP<660>, Ph.Eur. 3.2.1 and with limitations ISO 719. KW - CRM KW - Hydrolytic resistance KW - Borosilicate glass PY - 2021 DO - https://doi.org/10.13036/17533562.62.1.001 VL - 62 IS - 1 SP - 25 EP - 27 AN - OPUS4-52195 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hommel, C. A1 - Hassler, J. A1 - Matschat, Ralf A1 - Vogt, T. A1 - Detcheva, A. K. A1 - Recknagel, Sebastian T1 - A fast and robust direct solid sampling method for the determination of 27 trace, main and minor elements in soda-lime glass based on ETV-ICP OES and using a gaseous halogenating modifier N2 - A method, based on electrothermal vaporization (ETV) coupled to inductively coupled plasma optical emission spectrometry (ICP OES), has been optimized for direct solid sampling analysis of soda-lime glass - the most common type of industrially manufactured glass. This method allows fast and reliable quantification of the main elements - Al, Ca, K, Mg, Na, and Si - and trace elements - As, Ba, Cd, Ce, Co, Cr, Cu, Fe, Mn, Mo, Ni, (P), Pb, Sb, (Se), Sn, Sr, Ti, V, Zn, and Zr. In the presented ETV-ICP OES method, calibration is performed predominantly with matrix-free synthetic samples. This metrological advantage is normally not achieved with direct solid sampling methods and is one of the goals of the present study. In a certification interlaboratory comparison for the soda-lime glass CRM BAM-S005c, 2 out of 16 laboratories employed the ETV-ICP OES method. An improved analytical performance was obtained compared with the results of laboratories that used conventional liquid ICP OES. For both methods, the average relative deviations between the laboratory results and certified values as well as the average values of relative standard deviation were with a few exceptions <10%, in most cases even <5%, which indicated high trueness and precision. KW - ICP-OES KW - ETV KW - Soda-lime glass KW - Reference material PY - 2021 DO - https://doi.org/10.1039/d1ja00081k SN - 0267-9477 SN - 1364-5544 VL - 36 IS - 8 SP - 1683 EP - 1693 PB - Royal Society of Chemistry CY - London AN - OPUS4-53181 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fernandez-Menendez, L. J. A1 - Mendez-Lopez, C. A1 - Abad Andrade, Carlos Enrique A1 - Fandino, J. A1 - Gonzalez-Gago, C. A1 - Pisonero, J. A1 - Bordel, N. T1 - A critical evaluation of the chlorine quantification method based on molecular emission detection in LIBS N2 - The entire process involving the determination of Cl by molecular emission detection in Laser-Induced Breakdown Spectroscopy (LIBS) is thoroughly studied in this paper. This critical evaluation considers how spectra are normalized, how interferences from other molecular species signals are removed, and how signal integration is applied. Moreover, a data treatment protocol is proposed to achieve reliable and accurate Cl determination from the CaCl molecular spectral signal, not requiring the use of more complex numerical approaches. Calcium chloride dihydrate (CaCl2⋅2H2O) and high purity anhydrite samples (CaSO4) are used to optimize the acquisition conditions and data treatment of CaCl emission signal. Using the developed protocol, calibration curves for Cl, covering the concentration range from 0 μg/g to 60,000 μg/g of Cl, are successfully achieved. Finally, the suitability of the proposed methodology for Cl determination is successfully applied in industrial gypsum waste samples, where the results obtained by LIBS are validated using high-resolution molecular absorption spectroscopy (HR-CS-MAS) and potentiometric titration. KW - Laser induced breakdown Spectrocopy (LIBS) KW - Molecular spectra KW - Chlorine determination KW - CaCl emission bands KW - Industrial gypsum PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-544292 DO - https://doi.org/10.1016/j.sab.2022.106390 SN - 0584-8547 VL - 190 SP - 1 EP - 9 PB - Elsevier B.V. CY - Amsterdam, Netherlands AN - OPUS4-54429 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zhuang, Yiling A1 - Haderlein, Stefan B. A1 - Hagemann, Nikolas A1 - Grafmüller, Jannis A1 - Gogler, Karolin A1 - Paul, Andrea A1 - Fink, Friedrich A1 - Spahr, Stephanie T1 - Activation of persulfate by biochar and iron: role of biochar pyrolysis conditions and ash amendments N2 - Redox-active biochars can enhance contaminant transformation in persulfate-based Fenton-like water treatment by facilitating Fe(III) reduction to Fe(II). However, biochar properties vary greatly depending on both feedstock selection and pyrolysis conditions. Best suited biochars for Fe(III) reduction and persulfate activation have yet to be identified. Here, we investigated eight biochars for their ability to activate persulfate with Fe(III) to transform N,N-diethyl-m-toluamide (DEET) in water. Four of the biochars were produced from beech wood under different pyrolysis conditions (450–750 °C, high and low nitrogen flow rate in the reactor) and four biochars were produced from softwood amended with 0 – 43 weight percent (wt%) wood ash prior to pyrolysis at 500 °C. Beech wood biochar produced at 450 °C transformed DEET most efficiently with a half-life time of 39 ± 4 min, likely due to the high concentration of surface oxygen functional groups and persistent free radicals that accelerated Fe(III) reduction and formation of reactive species. Among the ash-amended biochars, biochar with 16 wt% ash amendment showed the most efficient DEET transformation with a half-life time of 27 ± 0.6 min, which is 10-times faster compared to a non-ash-amended biochar produced from the same biomass under similar pyrolysis conditions. Ash amendment led to the formation of crystalline iron minerals in biochars, which likely promoted Fe(III) reduction and persulfate activation. Our results highlight the potential for fine-tuning the redox properties of biochar, e.g., by ash amendment to a woody feedstock, enabling tailored performance for specific water treatment applications. KW - Persistent free radicals KW - Redox-active moieties KW - Fenton-like systems PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-634504 DO - https://doi.org/10.1016/j.seppur.2025.133634 SN - 1383-5866 VL - 374 SP - 1 EP - 8 PB - Elsevier B.V. AN - OPUS4-63450 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sowoidnich, Kay A1 - Pätzold, Stefan A1 - Ostermann, Markus A1 - Sumpf, Bernd A1 - Maiwald, Martin T1 - Qualitative and quantitative soil characterization on an agricultural field using a portable shifted excitation Raman difference spectroscopy instrument N2 - Site-specific farmland management requires comprehensive information about the soil status to derive informed treatment decisions, e.g. for liming or fertilizer recommendations. Standard laboratory methods relying on sample collection have only limited ability to adequately capture the spatial variability of typical agricultural fields. Here, on-site analytical techniques with the potential to measure the soil properties on a substance-specific level and at the required spatial resolution could be very beneficial. Raman spectroscopy is a very promising technique for this purpose as it provides a molecular fingerprint of soil constituents. However, intrinsic soil fluorescence and daylight interference can be major issues masking characteristic Raman signals. Here, we apply an in-house developed portable shifted excitation Raman difference spectroscopy (SERDS) instrument based on a dual-wavelength diode laser emitting around 785 nm to effectively separate the Raman signals of soil from such interferences. SERDS investigations on a selected agricultural field in Germany demonstrate that the Raman spectroscopic signature of 9 soil minerals and organic carbon could successfully be separated from intense backgrounds. Using partial least squares regression against reference analyses, a successful prediction of the soil carbonate (R2 = 0.86, root mean squared error of cross validation RMSECV = 2.49%) and soil organic carbon content (R2 = 0.89, RMSECV = 0.32%) as important soil parameters is realized. The results obtained on-site with the portable instrument were confirmed by SERDS laboratory experiments of collected soil samples thus highlighting the capability and reliability of portable SERDS as promising and complementary tool for precision agriculture KW - XRF KW - Raman spectroscopy KW - Soil KW - SERDS KW - Precision agriculture PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-634597 DO - https://doi.org/10.1039/d5an00178a SN - 0003-2654 VL - 150 IS - 13 SP - 2934 EP - 2944 PB - Royal Society of Chemistry (RSC) AN - OPUS4-63459 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Golub, Tino Petar A1 - Meyer, Klas A1 - Paul, Andrea A1 - Kipphardt, Heinrich A1 - Tuma, Dirk T1 - Exploring the potential of a setup for combined quantification of hydrogen in natural gas – Raman and NMR spectroscopy N2 - An accurate measurement of the amount fraction of hydrogen in gas mixtures is mandatory for practical applications, requiring methods that are fast, continuous, robust, and cost-effective. This study compares the performance of Raman and benchtop NMR process spectroscopy for determining the hydrogen amount fraction in gas mixtures. A setup was designed to integrate both techniques, enabling measurements of the same sample. Tests were conducted with gravimetrically prepared gas mixtures of reference quality ranging from 1.20 cmol/mol to 85.83 cmol/mol of hydrogen. The results demonstrate that Raman spectroscopy provides superior performance, with a minimal root mean square error (RMSE) of 0.22 cmol/mol and excellent linearity. In contrast, benchtop NMR spectroscopy faced challenges, such as overlapping peaks and longer measurement times, resulting in a higher RMSE of 0.71 cmol/mol. Raman spectroscopy proves to be particularly well-suited for practical applications due to its high accuracy and linearity. Meanwhile, benchtop NMR spectroscopy holds potential for future enhancements through ongoing technological advances, such as higher magnetic field strengths. In summary, the results from our study indicate that Raman spectroscopy is already a serviceable method for precise hydrogen quantification, whereas benchtop NMR spectroscopy can be attributed potential for future applications. KW - Hydrogen amount fraction KW - Raman spectroscopy KW - NMR spectroscopy KW - Field applicability PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-610093 DO - https://doi.org/10.1016/j.saa.2024.125087 SN - 1386-1425 VL - 325 SP - 1 EP - 9 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-61009 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Abad Andrade, Carlos Enrique A1 - Mimus, S. A1 - Recknagel, Sebastian A1 - Jakubowski, N. A1 - Panne, Ulrich A1 - Becker-Ross, H. A1 - Huang, M.-D. T1 - Determination of organic chlorine in water via AlCl derivatization and detection by high-resolution continuum source graphite furnace molecular absorption spectrometry N2 - High-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GF-MAS) was employed for determining adsorbable organic chlorine (AOCl) in water. Organic chlorine was indirectly quantified by monitoring the molecular absorption of the transient aluminum monochloride molecule (AlCl) around a wavelength of 261.42 nm in a graphite furnace. An aluminum solution was used as the molecularforming modifier. A zirconium coated graphite furnace, as well as Sr and Ag solutions were applied as modifiers for a maximal enhancement of the absorption signal. The pyrolysis and vaporization temperatures were 600 °C and 2300 °C, respectively. Non-spectral interferences were observed with F, Br, and I at concentrations higher than 6 mg L-1, 50 mg L-1, and 100 mg L-1, respectively. Calibration curves with NaCl, 4-chlorophenol, and trichlorophenol present the same slope and dynamic range, which indicates the chlorine atom specificity of the method. This method was evaluated and validated using synthetic water samples, following the current standard DIN EN ISO 9562:2004 for the determination of the sum parameter adsorbable organic halides (AOX) for water quality. These samples contain 4-chlorophenol as the chlorinated organic standard in an inorganic chloride matrix. Prior to analysis, organic chlorine was extracted from the inorganic matrix via solid-phase extraction with a recovery rate >95%. There were no statistically significant differences observed between measured and known values and for a t-test a confidence level of 95% was achieved. The limits of detection and characteristic mass were found to be 48 and 22 pg, respectively. The calibration curve was linear in the range 0.1–2.5 ng with a correlation coefficient R2 = 0.9986. KW - Chlorides KW - Chlorine KW - Graphite furnace KW - Spectrometry KW - Diatomic molecule KW - Water KW - AlCl PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-534426 DO - https://doi.org/10.1039/D1AY00430A SN - 1759-9660 VL - 13 IS - 33 SP - 3724 EP - 3730 PB - The Royal Society of Chemistry CY - London, UK AN - OPUS4-53442 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -