TY - JOUR A1 - Müller, Axel A1 - Goedecke, Caroline A1 - Eisentraut, Paul A1 - Piechotta, Christian A1 - Braun, Ulrike T1 - Microplastic analysis using chemical extraction followed by LC‑UV analysis: a straightforward approach to determine PET content in environmental samples N2 - Background: The ubiquitous occurrence of microplastic particles in marine and aquatic ecosystems was intensively investigated in the past decade. However, we know less about the presence, fate, and input paths of microplastic in terrestrial ecosystems. A possible entry path for microplastic into terrestrial ecosystems is the agricultural application of sewage sludge and solid bio-waste as fertilizers. Microplastic contained in sewage sludge also includes Polyethylene terephthalate (PET), which could originate as fiber from textile products or as a fragment from packaging products (foils, bottles, etc.). Information about microplastic content in such environmental samples is limited yet, as most of the used analytical methods are very time-consuming, regarding sample preparation and detection, require sophisticated analytical tools and eventually need high user knowledge. Results: Here, we present a simple, specific tool for the analysis of PET microplastic particles based on alkaline extraction of PET from the environmental matrix and subsequent determination of the monomers, terephthalic acid, using liquid chromatography with UV detection (LC-UV). The applicability of the method is shown for different types of PET in several soil-related, terrestrial environmental samples, e.g., soil, sediment, compost, fermentation residues, but also sewage sludge, suspended particles from urban water management systems, and indoor dust. Recoveries for model samples are between 94.5 and 107.1%. Limit of determination and limit of quantification are absolute masses of 0.031 and 0.121 mg PET, respectively. In order to verify the measured mass contents of the environmental samples, a method comparison with thermal extraction-desorption-gas chromatography–mass spectrometry (TED-GC/MS) was conducted. Both methods deliver similar results and corroborated each other. PET mass contents in environmental samples range from values below LOQ in agriculture soil up to 57,000 mg kg−1 in dust samples. Conclusions: We demonstrate the potential of an integral method based on chemical extraction for the Determination of PET mass contents in solid environmental samples. The method was successfully applied to various matrices and may serve as an analytical tool for further investigations of PET-based microplastic in terrestrial ecosystems. KW - Soil KW - Analysis KW - Microplastic KW - PET KW - LC-UV PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-509060 DO - https://doi.org/10.1186/s12302-020-00358-x IS - 32 SP - 85 PB - Springer Open CY - Berlin AN - OPUS4-50906 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dittmann, Daniel A1 - Eisentraut, Paul A1 - Goedecke, Caroline A1 - Wiesner, Yosri A1 - Jekel, M A1 - Ruhl, A S A1 - Braun, Ulrike T1 - Specific adsorption sites and conditions derived by thermal decomposition of activated carbons and adsorbed carbamazepine N2 - The adsorption of organic micropollutants onto activated carbon is a favourable solution for the treatment of drinking water and wastewater. However, these adsorption processes are not sufficiently understood to allow for the appropriate prediction of removal processes. In this study, thermogravimetric analysis, alongside evolved gas analysis, is proposed for the characterisation of micropollutants adsorbed on activated carbon. Varying amounts of carbamazepine were adsorbed onto three different activated carbons, which were subsequently dried, and their thermal decomposition mechanisms examined. The discovery of 55 different pyrolysis products allowed differentiations to be made between specific adsorption sites and conditions. However, the same adsorption mechanisms were found for all samples, which were enhanced by inorganic constituents and oxygen containing surface groups. Furthermore, increasing the loadings led to the evolution of more hydrated decomposition products, whilst parts of the carbamazepine molecules were also integrated into the carbon structure. It was also found that the chemical composition, especially the degree of dehydration of the activated carbon, plays an important role in the adsorption of carbamazepine. Hence, it is thought that the adsorption sites may have a higher adsorption energy for specific adsorbates, when the activated carbon can then potentially increase its degree of graphitisation. KW - Aktivkohle KW - TED-GC/MS KW - Adsorption KW - Thermoanalytik PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-506946 DO - https://doi.org/10.1038/s41598-020-63481-y VL - 10 IS - 1 SP - 6695 PB - Nature Publishing Group AN - OPUS4-50694 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Usmani, Shirin M. A1 - Plarre, Rüdiger A1 - Hübert, Thomas A1 - Kemnitz, E. ED - Richter, K. ED - Van de Kulien, J.-W. T1 - Termite resistance of pine wood treated with nano metal fluorides N2 - Fluorides are well-known as wood preservatives. One of the limitations of fluoride-based wood preservatives is their high leachability. Alternative to current fluoride salts such as NaF used in wood protection are low water-soluble fluorides. However, impregnation of low water-soluble fluorides into wood poses a challenge. To address this challenge, low water-soluble fluorides like calcium fluoride (CaF2) and magnesium fluoride (MgF2) were synthesized as nanoparticles via the fluorolytic sol−gel synthesis and then impregnated into wood specimens. In this study, the toxicity of nano metal fluorides was assessed by termite mortality, mass loss and visual analysis of treated specimens after eight weeks of exposure to termites, Coptotermes formosanus. Nano metal fluorides with sol concentrations of 0.5 M and higher were found to be effective against termites resulting in 100% termite mortality and significantly inhibited termite feeding. Among the formulations tested, the least damage was found for specimens treated with combinations of CaF2 and MgF2 with an average mass loss less than 1% and visual rating of “1”. These results demonstrate the efficacy of low water-soluble nano metal fluorides to protect wood from termite attack. KW - Holzschutzmittel KW - Nanoparticles KW - Fluorides KW - Termites PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-514325 DO - https://doi.org/10.1007/s00107-020-01522-z VL - 78 SP - 493 EP - 499 PB - Springer CY - Berlin AN - OPUS4-51432 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dittmann, Daniel A1 - Lucke, T. A1 - Ruhl, A. S. A1 - Winzenbacher, R. A1 - Jekel, M. A1 - Braun, Ulrike T1 - Untersuchungen zu biologischen, organischen und anorganischen Veränderungen granulierter Aktivkohlen während der Trinkwasseraufbereitung N2 - Untersuchungen zu biologischen, organischen und anorganischen Veränderungen granulierter Aktivkohlen während der Trinkwasseraufbereitung des Landeswasserversorgers Langenau. KW - Thermogravimetrie KW - Trinkwasser KW - Wasseraufbereitung KW - Aktivkohle PY - 2020 SN - 0083-6915 VL - 118 IS - 2 SP - 47 EP - 50 PB - Wiley-VCH Verlag GmbH & Co. KGaA AN - OPUS4-51434 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Goedecke, Caroline A1 - Dittmann, Daniel A1 - Eisentraut, Paul A1 - Wiesner, Yosri A1 - Schartel, Bernhard A1 - Klack, Patrick A1 - Braun, Ulrike T1 - Evaluation of thermoanalytical methods equipped with evolved gas analysis for the detection of microplastic in environmental samples N2 - Microplastic particles are currently detected in almost all environmental compartments. The results of detection vary widely, as a multitude of very different methods are used with very different requirements for analytical validity. In this work four thermoanalytical methods are compared and their advantages and limitations are discussed. One of them is thermal extraction-desorption gas chromatography mass spectrometry (TED-GC/MS), an analysis method for microplastic detection that has become established in recent years. In addition, thermogravimetric analysis coupled with Fourier-transform infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS) were applied, two methods that are less common in this field but are still used in other research areas. Finally, microscale combustion calorimeter (MCC) was applied, a method not yet used for microplastic detection. The presented results are taken from a recently published interlaboratory comparison test by Becker et al. (2020). Here a reference material consisting of suspended matter and specified added polymer masses was examined, and only the results of the recoveries were presented. In the present paper, however, the results for the individual polymers are discussed in detail and individual perspectives for all instruments are shown. It was found that TED-GC/MS is the most suitable method for samples with unknown matrix and unknown, variable kinds and contents of microplastic. TGA-FTIR is a robust method for samples with known matrix and with defined kinds of microplastic. TGA-MS may offer a solution for the detection of PVC particles in the future. MCC can be used as a very fast and simple screening method for the identification of a potential microplastic load of standard polymers in unknown samples. KW - Microplastic KW - TED-GC/MS KW - TGA-MS KW - TGA-FTIR KW - MCC KW - Thermal analysis PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-516687 DO - https://doi.org/10.1016/j.jaap.2020.104961 VL - 152 SP - 104961 PB - Elsevier B.V. AN - OPUS4-51668 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wiesner, Yosri A1 - Altmann, Korinna A1 - Braun, U. T1 - Determination of Microplastic Mass Content by Thermal Extraction Desorption Gas Chromatography– Mass Spectrometry N2 - The scientific and practical challenge of detecting microplastics (MPs) in the environment in a targeted and rapid manner is solved by innovative coupling of thermogravimetric analysis with mass spectrometric methods. Fast identification and quantitative determination of most thermoplastic polymers and elastomers is possible by using thermal extraction Desorption gas chromatography–mass spectrometry (TED-GC–MS). KW - Microplastics KW - Mikroplastik KW - TED-GC/MS KW - Microplastics analytic KW - Mikroplastik Massegehalt PY - 2021 VL - 17 IS - 3 SP - 2 EP - 7 PB - MultiMedia (UK) LLC CY - Cranbury AN - OPUS4-52570 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - MacLean, J. A1 - Mayanna, S. A1 - Benning, L. G. A1 - Horn, F. A1 - Bartholomäus, A. A1 - Wiesner, Yosri A1 - Wagner, D. A1 - Liebner, S. T1 - The terrestrial plastisphere: Diversity and polymer-colonizing potential of plastic-associated microbial communities in soil N2 - The concept of a ‘plastisphere microbial community’ arose from research on aquatic plastic debris, while the effect of plastics on microbial communities in soils remains poorly understood. Therefore, we examined the inhabiting microbial communities of two plastic debris ecosystems with regard to their diversity and composition relative to plastic-free soils from the same area using 16S rRNA amplicon sequencing. Furthermore, we studied the plastic-colonizing potential of bacteria originating from both study sites as a measure of surface adhesion to UV-weathered polyethylene (PE) using high-magnification field emission scanning electron microscopy (FESEM). The high plastic content of the soils was associated with a reduced alpha diversity and a significantly different structure of the microbial communities. The presence of plastic debris in soils did not specifically enrich bacteria known to degrade plastic, as suggested by earlier studies, but rather shifted the microbial community towards highly abundant autotrophic bacteria potentially tolerant to hydrophobic environments and known to be important for biocrust formation. The bacterial inoculates from both sites formed dense biofilms on the surface and in micrometer-scale surface cracks of the UV-weathered PE chips after 100 days of in vitro incubation with visible threadlike EPS structures and cross-connections enabling surface adhesion. High-resolution FESEM imaging further indicates that the microbial colonization catalyzed some of the surface degradation of PE. In essence, this study suggests the concept of a ‘terrestrial plastisphere’ as a diverse consortium of microorganisms including autotrophs and other pioneering species paving the way for those members of the consortium that may eventually break down the plastic compounds. KW - Soil microbial community KW - Polyethylene colonization KW - Plastic pollution PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-542790 DO - https://doi.org/10.3390/microorganisms9091876 VL - 9 IS - 9 SP - 1 EP - 19 PB - MDPI CY - Basel AN - OPUS4-54279 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Eisentraut, Paul A1 - Altmann, Korinna T1 - Repräsentative Mikroplastik-Detektion in Umweltproben - Weiterentwicklung der TED-GC/MS N2 - Die große Herausforderung in der Detektion von Mikroplastik (MP)‑Partikeln (1-1000 µm) besteht darin, sie neben Millionen von natürlichen Partikeln in Umweltproben nachzuweisen. Zum Aufspüren von Senken, Eintragspfaden und für Monitoring-Kampagnen ist ein schnelles, automatisiertes Verfahren unerlässlich. Ein solches Verfahren wurde an der Bundesanstalt für Materialforschung und -prüfung (BAM) mit der ThermoExtraktion/Desorption-Gaschromatographie-Massenspektrometrie (TED-GC/MS) in den letzten Jahren entwickelt. KW - Mikroplastik KW - TED-GC/MS PY - 2021 UR - https://analyticalscience.wiley.com/do/10.1002/was.0004000195 SN - 0016-3538 SP - 2 EP - 5 PB - Wiley-VCH CY - Weinheim AN - OPUS4-54266 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Cordsmeier, Leo A1 - Hahn, Marc Benjamin T1 - DNA Stability in Biodosimetry, Pharmacy and DNA Based Data-Storage: Optimal Storage and Handling Conditions N2 - DNA long-term stability and integrity is of importance for applications in DNA based bio-dosimetry, data-storage, pharmaceutical quality-control, donor insemination and DNA based functional nanomaterials. Standard protocols for these applications involve repeated freeze-thaw cycles of the DNA, which can cause detrimental damage to the nucleobases, as well as the sugar-phosphate backbone and therefore the whole molecule. Throughout the literature three hypotheses can be found about the underlying mechanisms occurring during freeze-thaw cycles. It is hypothesized that DNA single-strand breaks during freezing can be induced by mechanical stress leading to shearing of the DNA molecule, by acidic pH causing damage through depurination and beta elimination or by the presence of metal ions catalyzing oxidative damage via reactive oxygen species (ROS). Here we test these hypotheses under well defined conditions with plasmid DNA pUC19 in high-purity buffer (1xPBS) at physiological salt and pH 7.4 conditions, under pH 6 and in the presence of metal ions in combination with the radical scavengers DMSO and Ectoine. The results show for the 2686 bp long plasmid DNA, that neither mechanical stress, nor pH 6 lead to degradation during repeated freeze-thaw cycles. In contrast, the presence of metal ions (Fe2+) leads to degradation of DNA via the production of radical species. KW - DNA KW - DNA stability KW - Pharmacy KW - Reference material KW - pUC19 KW - Strand break KW - SSB KW - Dosimetry KW - Biodosimetry KW - Biologisches Dosimeter KW - DNA Dosimeter KW - Quality control KW - Plasmid DNA KW - DNA data storage KW - Nucleobase KW - Base damage KW - Base loss KW - DNA degradation KW - Metal ions KW - ROS KW - OH radical KW - Fenton Reaction KW - H2O2 KW - DNA based data storage KW - Freezing KW - Thawing KW - Mechanical stress KW - pH KW - Beta elimination KW - Ectoine KW - Ectoin KW - THP(B) KW - Radical scavenger KW - DMSO KW - Buffer KW - lN2 KW - DNA vortexing KW - AGE KW - SYBR Gold KW - Gel electrophoresis KW - DNA long term storage KW - DNA reference material PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-557148 DO - https://doi.org/10.1002/cbic.202200391 SP - 1 EP - 9 PB - Wiley-VCH GmbH AN - OPUS4-55714 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kittner, Maria A1 - Kerndorff, A. A1 - Ricking, M. A1 - Bednarz, M. A1 - Obermaier, N. A1 - Lukas, M. A1 - Asenova, M. A1 - Bordós, G. A1 - Eisentraut, Paul A1 - Hohenblum, P. A1 - Hudcova, H. A1 - Humer, F. A1 - István, T. G. A1 - Kirchner, M. A1 - Marushevska, O. A1 - Nemejcová, D. A1 - Oswald, P. A1 - Paunovic, M. A1 - Sengl, M. A1 - Slobodnik, J. A1 - Spanowsky, K. A1 - Tudorache, M. A1 - Wagensonner, H. A1 - Liska, I. A1 - Braun, U. A1 - Bannick, C. G. T1 - Microplastics in the Danube River Basin: A First Comprehensive Screening with a Harmonized Analytical Approach N2 - In this study, carried out within the Joint Danube Survey 4, a comprehensive microplastic screening in the water column within a large European river basin from its source to estuary, including major tributaries, was realized. The objective was to develop principles of a systematic and practicable microplastic monitoring strategy using sedimentation boxes for collection of suspended particulate matter followed by its subsequent analysis using thermal extraction desorption-gas chromatography/mass spectrometry. In total, 18 sampling sites in the Danube River Basin were investigated. The obtained suspended particulate matter samples were subdivided into the fractions of >100 μm and <100 μm and subsequently analyzed for microplastic mass contents. The results showed that microplastics were detected in all samples, with polyethylene being the predominant polymer with maximum contents of 22.24 μg/mg, 3.23 μg/mg for polystyrene, 1.03 μg/mg for styrene-butadiene-rubber, and 0.45 μg/mg for polypropylene. Further, polymers such as different sorts of polyester, polyacrylates, polylactide, and natural rubber were not detected or below the detection limit. Additional investigations on possible interference of polyethylene signals by algae-derived fatty acids were assessed. In the context of targeted monitoring, repeated measurements provide more certainty in the interpretation of the results for the individual sites. Nevertheless, it can be stated that the chosen approach using an integrative sampling and determination of total plastic content proved to be successful. KW - Thermal extraction desorption-gas chromatography/mass spectrometry (TED-GC/MS), monitoring KW - Microplastics KW - River KW - Suspended particulate matter (SPM) KW - Sedimentation box (SB) PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-551444 DO - https://doi.org/10.1021/acsestwater.1c00439 VL - 2 IS - 7 SP - 1174 EP - 1181 PB - ACS Publications AN - OPUS4-55144 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -