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 JF - Applied Research 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 - JOUR A1 - Dittmann, D. A1 - Saal, L. A1 - Zietschmann, F. A1 - Mai, M. A1 - Altmann, Korinna A1 - Al-Sabbagh, Dominik A1 - Schuhmann, P. A1 - Ruhl, A. A1 - Jekel, M. A1 - Braun, U. T1 - Characterization of activated carbons for water treatment using TGA‑FTIR for analysis of oxygen‑containing functional groups JF - Applied Water Science N2 - Water treatment with activated carbon (AC) is an established method for the removal of organic micropollutants and natu ral organic matter. However, it is not yet possible to predict the removal of individual pollutants. An appropriate material characterization, matching adsorption processes in water, might be the missing piece in the puzzle. To this end, this study examined 25 diferent commercially available ACs to evaluate their material properties. Frequently reported analyses, including N2 adsorption/desorption, CHNS(O), point of zero charge (PZC) analysis, and X-ray photoelectron spectroscopy, were conducted on a selected subset of powdered ACs. Inorganic elements examined using X-ray fuorescence and X-ray difraction spectroscopy revealed that relative elemental contents were distinctive to the individual AC’s raw material and activation procedure. This study also is the frst to use thermogravimetric analysis (TGA) coupled to Fourier-transform infrared spectroscopy (FTIR) to conduct quantitative analyses of functional surface oxygen groups (SOGs: carboxylic acid, anhydride, lactone, phenol, carbonyl, and pyrone groups) on such a large number of ACs. The comparably economical TGA method was found to provide good surrogates for the PZC by pyrolytic mass loss up to 600 ◦C (ML600), for the oxygen content by ML1000 and for the carbon content by oxidation. Mass loss profles depict the AC’s chemistry like fngerprints. Furthermore, we found that SOG contents determined by TGA-FTIR covered a wide individual range and depended on the raw material and production process of the AC. TGA and TGA-FTIR might therefore be used to identify the suitability of a particular AC for a variety of target substances in diferent target waters. This can help practitioners to control AC use in waterworks or wastewater treatment plants. KW - Adsorbtion KW - Organic contaminants KW - Temperature-programmed desorption KW - Proximate analysis KW - Principal component analysis PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-555506 DO - https://doi.org/10.1007/s13201-022-01723-2 SN - 2190-5495 VL - 12 SP - 1 EP - 13 PB - Springer CY - Berlin AN - OPUS4-55550 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Goedecke, C. A1 - Eisentraut, Paul A1 - Altmann, Korinna A1 - Elert, Anna Maria A1 - Bannick, C. G. A1 - Ricking, M. A1 - Obermaier, N. A1 - Barthel, A.-K. A1 - Schmitt, T. A1 - Jekel, M. A1 - Braun, U. T1 - Development of a routine screening method for the microplastic mass content in a wastewater treatment plant effluent JF - Frontiers in environmental chemistry N2 - An investigation of microplastic (MP) occurrence in a municipal wastewater treatment plant (WWTP) effluent with tertiary treatment was carried out. Representative sample volumes of 1 m3 were taken by applying a fractionated filtration method (500, 100, and 50 µm mesh sizes). The detection of MP mass fractions by thermal extraction desorption–gas chromatography/mass spectrometry (TED-GC/MS) was achieved without the previously required additional sample pretreatment for the first time. Different types of quantification methods for the evaluation of TED-GC/MS data were tested, and their accuracy and feasibility have been proven for real samples. Polyethylene, polystyrene, and polypropylene were identified in effluent samples. The polymer mass content varied significantly between 5 and 50 mg m−3. A correlation between the MP load and the quantity of suspended matter in the WWTP effluents, particle size distribution, particle type, and operation day (i.e., weekday, season, and capacity) was not found. It can be concluded that a meaningful assessment of WWTPs requires a comprehensive sampling campaign with varying operation conditions. KW - Microplastic KW - Waste water treatment KW - Thermoanalytics PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-550862 DO - https://doi.org/10.3389/fenvc.2022.844633 SN - 2673-4486 VL - 3 SP - 1 EP - 10 PB - Frontiers Media CY - Lausanne AN - OPUS4-55086 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 JF - ACS ES&T Water 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 - TY - JOUR A1 - Lackmann, C. A1 - Velki, M. A1 - Šimić, A. A1 - Müller, Axel A1 - Braun, U. A1 - Ečimović, S. A1 - Hollert, H. T1 - Two types of microplastics (polystyrene-HBCD and car tire abrasion) affect oxidative stress-related biomarkers in earthworm Eisenia andrei in a time-dependent manner JF - Environment International N2 - Microplastics are small plastic fragments that are widely distributed in marine and terrestrial environments. While the soil ecosystem represents a large reservoir for plastic, research so far has focused mainly on the impact on aquatic ecosystems and there is a lack of information on the potentially adverse effects of microplastics on soil biota. Earthworms are key organisms of the soil ecosystem and are due to their crucial role in soil quality and fertility a suitable and popular model organism in soil ecotoxicology. Therefore, the aim of this study was to gain insight into the effects of environmentally relevant concentrations of microplastics on the earthworm Eisenia andrei on multiple levels of biological organization after different exposure periods. Earthworms were exposed to two types of microplastics: (1) polystyrene-HBCD and (2) car tire abrasion in natural soil for 2, 7, 14 and 28 d. Acute and chronic toxicity and all subcellular investigations were conducted for all exposure times, avoidance behavior assessed after 48 h and reproduction after 28 d. Subcellular endpoints included enzymatic biomarker responses, namely, carboxylesterase, glutathione peroxidase, acetylcholinesterase, glutathione reductase, glutathione S-transferase and catalase activities, as well as fluorescence-based measurements of oxidative stress-related markers and multixenobiotic resistance activity. Multiple biomarkers showed significant changes in activity, but a recovery of most enzymatic activities could be observed after 28 d. Overall, only minor effects could be observed on a subcellular level, showing that in this exposure scenario with environmentally relevant concentrations based on German pollution levels the threat to soil biota is minimal. However, in areas with higher concentrations of microplastics in the environment, these results can be interpreted as an early warning signal for more adverse effects. In conclusion, these findings provide new insights regarding the ecotoxicological effects of environmentally relevant concentrations of microplastics on soil organisms. KW - Microplastics KW - Earthworms KW - Toxicity KW - Biomarker KW - oxidative stress PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545423 DO - https://doi.org/10.1016/j.envint.2022.107190 VL - 163 SP - 1 EP - 12 PB - Elsevier Ltd. AN - OPUS4-54542 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 JF - Chemosphere 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 - Richter, S. A1 - Horstmann, J. A1 - Altmann, Korinna A1 - Braun, U. A1 - Hagendorf, C. T1 - A reference methodology for microplastic particle size distribution analysis: Sampling, filtration, and detection by optical microscopy and image processing JF - Applied research N2 - Microplastic (MP) contamination in natural water circulation is a concern for environmental issues and human health. Various types of polymer materials have been identified and were detected in MP analytic test procedures. Beyond MP polymer type, particle size and form play a major role in water analysis due to possible negative toxicologic effects on flora and fauna. However, the correct quantitative measurement of MP size distribution over several orders of magnitude is strongly influenced by sample preparation, filtration materials and processes, and microanalytical techniques, as well as data acquisition and analysis. In this paper, a reference methodology is presented aiming at an improved quantitative analysis of MP particles. An MP analysis workflow is demonstrated including all steps from reference materials to sample preparation, filtration handling, and MP particle size distribution analysis. Background-corrected particle size distributions (1–1000 µm) have been determined for defined polyethylene (PE) and polyethylene terephthalate (PET) reference samples. Microscopically measured particle numbers and errors have been cross-checked with the total initial mass. In particular, defined reference MP samples (PE, PET) are initially characterized and applied to filtration experiments. Optical microscopy imaging on full-area Si filters with subsequent image analysis algorithms is used for statistical particle size distribution analysis. To quantify the effects of handling and filtration, several blind tests with distilled water are carried out to determine the particle background for data evaluation. Particle size distributions of PE and PET reference samples are qualitatively and quantitatively reproduced with respect to symmetry, and maximum and cut-off diameter of the distribution. It is shown that especially MP particles with a radius of >50 µm can be detected and retrieved with high reliability. For particle sizes <50 µm, a significant interference with background contamination is observed. Data from blank samples allows a correction of background contaminations. Furthermore, for enhanced sampling statistics, the recovery of the initial amount of MP will be qualitatively shown. The results are intended as an initial benchmark for MP analytics quality. This quality is based on statistical MP particle distributions and covers the complete analytic workflow starting from sample preparation to filtration and detection. Microscopic particle analysis provides an important supplement for the evaluation of established spectroscopic methods such as Fourier-transform infrared spectroscopy or Raman spectroscopy. KW - Drinking water KW - Filtration KW - Microplastics detection KW - Quality control KW - Statistical particle distribution PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-567625 DO - https://doi.org/10.1002/appl.202200055 SN - 2702-4288 SP - 1 EP - 10 PB - Wiley-VCH CY - Weinheim AN - OPUS4-56762 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Waniek, Tassilo A1 - Braun, U. A1 - Silbernagl, Dorothee A1 - Sturm, Heinz T1 - The impact of water released from boehmite nanoparticles during curing in epoxy-based nanocomposites JF - Journal of Applied Polymer Science N2 - The enhancing effect on mechanical properties of boehmite (γ-AlOOH) nanoparticles (BNP) in epoxy-based nanocomposites on the macroscopic scale encouraged recent research to investigate the micro- and nanoscopic properties. Several studies presented different aspects relatable to an alteration of the epoxy polymer network formation by the BNP with need for further experiments to identify the mode of action. With FTIR-spectroscopic methods this study identifies interactions of the BNP with the epoxy polymer matrix during the curing process as well as in the cured nanocomposite. The data reveals that not the BNP themselves, but the water released from them strongly influences the curing process by hydrolysis of the anhydride hardener or protonation of the amine accelerator. The changes of the curing processes are discussed in detail. The changes of the curing processes enable new explanation for the changed material properties by BNP discussed in recent research like a lowered glass transition temperature region (Tg) and an interphase formation. KW - Spectroscopy KW - Aluminium oxide hydroxide KW - Glass transition temperature KW - Material chemistry KW - Nanocomposites KW - Structure-property relationship PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-527202 DO - https://doi.org/10.1002/app.51006 VL - 138 IS - 39 SP - 51006 PB - Wiley Periodicals LLC CY - Hoboken AN - OPUS4-52720 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -