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 - GEN A1 - Dittmann, Daniel T1 - Experimental raw data for "Specific adsorption sites and conditions derived by thermal decomposition of activated carbons and adsorbed carbamazepine" N2 - This is the repository of all experimental raw data used in the Scientific Reports publication "Specific adsorption sites and conditions derived by thermal decomposition of activated carbons and adsorbed carbamazepine" by Daniel Dittmann, Paul Eisentraut, Caroline Goedecke, Yosri Wiesner, Martin Jekel, Aki Sebastian Ruhl, and Ulrike Braun. It includes - overview_measurements.xlsx and overview_measurements.ods containing a list of all TGA experiments (TGA, TGA-FTIR, TED-GC-MS, and ramp-kinetics) - TED-GC-MS.zip containing gas chromatography-mass spectrometry experimtent files for the Chemstation and OpenChrom - TGA.zip containing thermogravimetric analyses raw data on evolved gas analyses experiments (TGA-FTIR and TED-GC-MS) - TGA_kinetics.zip containing thermogravimetric analyses raw data on decomposition kinetic experiments (ramp-kinetics) - TGA-FTIR.zip containing Fourier-transform infrared spectroscopy series files for OMNIC - XRF.zip containing x-ray flourescence data on elemental composition KW - Adsorption KW - Aktivkohle KW - TED-GC/MS KW - Thermoanalytik PY - 2020 DO - https://doi.org/10.5281/zenodo.3716316 PB - Zenodo CY - Geneva AN - OPUS4-51902 LA - eng 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 - 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 - CONF A1 - Drago, Claudia T1 - Sweetening the (microplastics) pill: PET tablets (1-100µm) as candidate reference material for the validation of microplastics measurement N2 - The lack of validation and standard procedures in microplastics studies has led to the inability to compare and harmonise data from different analytical methods, laboratories and time scales. To monitor and regulate exposure to microplastics in the environment and in food for human health, it is crucial to ensure their comparability and to validate the analytical methods used in microplastics studies. Monitoring microplastics requires complex approaches for accurate determination otherwise it can lead to an over- or underestimation in environmental and food-relevant matrices. Moreover, to support the need of reliable measurement required by the European legislation directive on drinking water (EU 2020/2184) or the revision of the urban waste water directive, which will be finalised in 2024 the production and validation of polymeric reference materials with environmentally relevant concentrations, irregular shapes, defined aging status and different sizes is essential. The production of reference material with acceptable uncertainties in homogeneity need to be balanced, considering the low microplastics concentrations detected in the environment and in food. The aim of the project PLASTICTRACE and of this study, is to propose a “easy-to-use PET tablet ” (PET particle size mainly 1-100 µm) for routine applications as a candidate general reference material for detection methods. Batches of water-soluble matrix containing different concentrations of PET powder were produced. Results of imaging and counting methods (SEM, Laser diffraction), including production´s challenges; together with thermo-analytical methods (TED-GC/MS and Py-GC/MS) and vibrational spectroscopy (µ-Raman and µ-FTIR), will be presented. These data are useful to assess homogeneity and stability of the particles over time according to ISO 33405:2024. In addition, we will show some insights on the application of the PET-tablets in complex matrices, as milk powder and suspended solid from surface water, that could be easily used for routine microplastics analysis. T2 - MICRO 2024 CY - Arrecife, Spain DA - 23.09.2024 KW - Microplastics KW - Reference materials KW - Polymer 3R KW - TED-GC/MS PY - 2024 AN - OPUS4-61274 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - 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 - 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 - CONF A1 - Miclea, P-T T1 - Evaluation of Toxicological Characteristics of Airborne Nano/Microplastic Particles From the Industrial Environment N2 - Micro and nano plastic (MNPs) particles and fibres represent a global scale contamination source with hazard potential. They can be identified all around our environment, even in air, soil and water. One of the major global MNPs polluters is the textile industry, which generates plastic particles (nylon, polyester, polyurethane, polyolefin, acrylic etc.) during the manufacturing processes. The study analyses the level of particle concentration outside a company that processes textile yarns, but also from the proximity of workplaces using an online air samplers with cascade and mono filter holders for silicon (Si) and quartz filters, respectively. A laser detector was used for real- time counting of particles of six size classes (PM0.3-PM10). Silicon (Si) filters with a diameter of 9 mm and pore sizes of 10 µm and 1 µm and quartz filters with a diameter of 25 mm and a pore size of 1.2 µm were used for particle sampling. A special holder was designed and made for selective sampling (PM10 and PM1.0) on Si filters. Quartz filters were pre-calcined (8000C) before collection. Sampling parameters: airflow (GilAir Plus pump) -2 l/m3, collection time -3 hours; starting time 7.00 am (T1)/2.00 pm (T2), intermittent natural ventilation, average temperature and humidity: 23.3 0C, RH: 52.5%. The weight of particles collected (µg) on the quart filters was 4.9E-05 (T1) and 5.1E-05 (T2) and on the Si filters 3,2 E-05(T1) and 5E-06(T2). The total number of the outside particles (PM0,3-PM10) was situated between 3584,58 (T1)-15165,05(T2) and inside 9901(T1) and 12921,61(T2). The highest number of PM 10 particles inside was 72/m3 and of PM0.3 particles 71979/m3. The samples were characterized using electron microscopy and µRaman spectroscopy. All samples showed a high concentration of particles on the filter. Samples show only particles with irregular shapes. The equivalent particle diameter was for PM10: 1-5 µm and PM1<1 µm. The total Ion Chromatogram shows the presence of PET-type polymer and the TED GS-MS analysis shows that the weight of the collected particles is PET. After extracting the particles from the quartz filters, they were tested for evaluation of the cytotoxic potential of preparations on human monocyte-macrophage cell cultures and peripheral lymphocytes. In the first case, the level of cytotoxicity was at the border between non-cytotoxic and cytotoxic and in the second test the result was moderate cytotoxic. T2 - SETAC Europe 2025 CY - Vienna, Austria DA - 11.05.2025 KW - Microplastics KW - TED-GC/MS KW - Nanoplastics KW - Raman microscopy PY - 2025 AN - OPUS4-63378 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Altmann, Korinna A1 - Goedecke, Caroline A1 - Bannick, C.-G. A1 - Abusafia, A. A1 - Scheid, C. A1 - Steinmetz, H. A1 - Paul, Andrea A1 - Beleites, C. A1 - Braun, U. T1 - Identification of microplastic pathways within a typical European urban wastewater system N2 - In recent years, thermoextraction/desorption-gas chromatography/mass spectrometry (TED-GC/MS) has been developed as a rapid detection method for the determination of microplastics (MP) mass contents in numerous environmentally relevant matrices and, in particular, for the measurement of polymers in water samples without time-consuming sample preparation. The TED-GC/MS method was applied to investigate a typical European municipal wastewater system for possible MP masses. Such investigations are important in view of the recent revision of the Urban Wastewater Treatment Directive. Four different representative sampling sites were selected: greywater (domestic wastewater without toilet), combined sewer, and influent and effluent of a wastewater treatment plant (WWTP). All samples were collected by fractional filtration. Filtration was carried out over mesh sizes of 500, 100, 50, and in some cases, 5 µm. Polyethylene (PE), polypropylene (PP), and polystyrene (PS) were detected in all samples, with the PE fraction dominating in all cases. Styrene-butadiene rubber which serves as an indication of tire abrasion, was only found in the influent of the WWTP. The highest MP mass contents were found in the combined sewer, so MP can become a source of pollution during heavy rain events when the capacity limits of the effluent are reached, and the polluted effluent is released uncontrolled into the environment. Based on the studies, MP retention from the WWTP could be estimated to be approximately 96%. Few trends in polymer type or mass contents were detected within the different fractions of the samples or when comparing samples to each other. KW - Microplastics KW - Microplastic analysis KW - TED-GC/MS KW - Microplastic pathways KW - Mass contents PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-568289 DO - https://doi.org/doi.org/10.1002/appl.202200078 SP - 1 EP - 10 PB - Wiley-VCH CY - Weinheim AN - OPUS4-56828 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Braun, U. T1 - Detection of plastics in soil N2 - Soil acts as a final sink for pollutants. Microplastics from different sources such as plastic mulching, littering, compost, sewage sludge, sedimentary deposition, and tyre abrasion are expected to be found in soil. However, representative and comprehensive information is missing on the sources, transport, and fate. Therefore, a reliable analysis method for microplastics in soils needs to be developed. The presented work describes the development of a procedure for microplastics analysis in soils. A representative sampling based on the on-site conditions and a sample preparation method was established and comprised of a drying step, the separation of microplastic particles > 1 mm, and a density separation for particles < 1 mm. The detection of the large microplastic particles (> 1 mm) was conducted with Attenuated Total Reflection - Fourier Transform infrared Spectroscopy (ATR-FTIR) , while Thermal Extraction Desorption - Gas Chromatography / Mass Spectrometry (TED-GC/MS) was applied for particles < 1 mm, gaining information on the type of polymer and mass fraction. Based on the established method, 14 environmental soil samples ? with different exposure of microplastics from agriculture, industrial sites, roads, and floods were investigated. Due to the arbitrary microplastic particle distribution among the samples for large microplastics, it was reasoned that the found particles were unrepresentative. In contrast, microplastic particles < 1 mm were discovered in a high mass in soil samples exposed to plastic mulching or fertilization with sewage sludge or compost (0 – 115 mg/kg). On average, microplastic contents detected in soil samples taken from a construction site and an inner-city lake were higher (13 – 238 mg/kg). As expected, microplastic content in soil sampled in proximity to roads was more pronounced in the upper soil layers. In contrast, very remote sampling sites, expectably uncontaminated, did not lead to the detection of microplastic regarding to thermoanalytical detection method. In a proof of concept experiment several in vivo and in vitro ecotoxicological tests were applied to evaluate the effect of microplastics (tyre abrasion, polystyrene containing hexabromocyclododecane) in natural soils. In summary, while no effects of the examined probes could be detected on higher levels of biological organization after exposures to earthworm E. andrei, significant changes in several oxidative stress related biomarkers were observed. T2 - SETAC Europe 2022 CY - Kopenhagen, Denmark DA - 15.05.2022 KW - Microplastic KW - TED-GC/MS KW - Soil PY - 2022 AN - OPUS4-55872 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -