%0 conference poster %@ %A McCormick Zonderman, A., Ferdinand, M., Hildebrandt, L.M., Pröfrock, D. %D 2024 %J SETAC Europe 34th Annual Meeting %T Detection of Particulate and Metal(loid) Emissions from Offshore Wind Farms %U %X %0 conference poster %@ %A Klein, O., Hildebrandt, L.M., Mara, R., Annika, J., Pröfrock, D. %D 2024 %J SETAC Europe 34th Annual Meeting %T Beyond the Surface: Spotlight on Plastic Metal(loid) Additive Leaching and Unseen Contaminants %U %X %0 journal article %@ 0304-3894 %A Hildebrandt, L., Fischer, M., Klein, O., Zimmermann, T., Fensky, F., Siems, A., Zonderman, A., Hengstmann, E., Kirchgeorg, T., Pröfrock, D. %D 2024 %J Journal of Hazardous Materials %P 134173 %R doi:10.1016/j.jhazmat.2024.134173 %T An analytical strategy for challenging members of the microplastic family: Particles from anti-corrosion coatings %U https://doi.org/10.1016/j.jhazmat.2024.134173 %X Potentially hazardous particles from paints and functional coatings are an overlooked fraction of microplastic (MP) pollution since their accurate identification and quantification in environmental samples remains difficult. We have applied the most relevant techniques from the field of microplastic analysis for their suitability to chemically characterize anti-corrosion coatings containing a variety of polymer binders (LDIR, Raman and FTIR spectroscopy, Py-GC/MS) and inorganic additives (ICP-MS/MS). We present the basis of a possible toolbox to study the release and fate of coating particles in the (marine) environment. Our results indicate that, due to material properties, spectroscopic methods alone appear to be unsuitable for quantification of coating/paint particles and underestimate their environmental abundance. ICP-MS/MS and an optimized Py-GC/MS approach in combination with multivariate statistics enables a straightforward comparison of the multi-elemental and organic additive fingerprints of paint particles. The approach can improve the identification of unknown particles in environmental samples by an assignment to different typically used coating types. In future, this approach may facilitate allocation of emission sources of different environmental paint/coating particles. Indeed, future work will be required to tackle various remaining analytical challenges, such as optimized particle extraction/separation of environmental coating particles. %0 conference poster %@ %A Hildebrandt, L.M., Klein, O., Zimmermann, T., Pröfrock, D. %D 2024 %J SETAC Europe 34 Annual Meeting %T Development and Validation of High-Throughput Methods for the Sampling, Extraction and Analysis of Marine Microplastics %U %X %0 journal article %@ 1618-2642 %A Süssmann, J., Fischer, E.K., Hildebrandt, L., Walz, E., Greiner, R., Rohn, S., Fritsche, J. %D 2024 %J Analytical and Bioanalytical Chemistry %P 3459-3471 %R doi:10.1007/s00216-024-05296-8 %T Nile red-staining for rapid screening of plastic-suspect particles in edible seafood tissues %U https://doi.org/10.1007/s00216-024-05296-8 %X Concerns regarding microplastic (MP) contamination in aquatic ecosystems and its impact on seafood require a better understanding of human dietary MP exposure including extensive monitoring. While conventional techniques for MP analysis like infrared or Raman microspectroscopy provide detailed particle information, they are limited by low sample throughput, particularly when dealing with high particle numbers in seafood due to matrix-related residues. Consequently, more rapid techniques need to be developed to meet the requirements of large-scale monitoring. This study focused on semi-automated fluorescence imaging analysis after Nile red staining for rapid MP screening in seafood. By implementing RGB-based fluorescence threshold values, the need for high operator expertise to prevent misclassification was addressed. Food-relevant MP was identified with over 95% probability and differentiated from natural polymers with a 1% error rate. Comparison with laser direct infrared imaging (LDIR), a state-of-the-art method for rapid MP analysis, showed similar particle counts, indicating plausible results. However, highly variable recovery rates attributed to inhomogeneous particle spiking experiments highlight the need for future development of certified reference material including sample preparation. The proposed method demonstrated suitability of high throughput analysis for seafood samples, requiring 0.02–0.06 h/cm2 filter surface compared to 4.5–14.7 h/cm with LDIR analysis. Overall, the method holds promise as a screening tool for more accurate yet resource-intensive MP analysis methods such as spectroscopic or thermoanalytical techniques. %0 conference poster %@ %A Pohl, F., Hildebrandt, L., O’Dell, J., Talling, P., Baker, M., El Gareb, F., La Nasa, J., De Falco, F., Mattonai, M., Ruffell, S., Eggenhuisen, J., Modugno, F., Proefrock, D., Pope, E., Silva Jacinto, R., Heijnen, M., Hage, S., Simmons, S., Hasenhündl, M., Heerema, C. %D 2023 %J EGU General Assembly 2023 %T The submarine Congo Canyon as a conduit for microplastics to the deep sea %U %X %0 conference lecture %@ %A Zimmermann, T., Hildebrandt, L., Fensky, F., Pröfrock, D. %D 2023 %J European Winter Conference on Plasma Spectrochemistry %T Elemental fingerprint analysis of (micro) plastics via ICP-MS/MS – A possible tool for source tracing? %U %X %0 conference poster %@ %A Klein, O., Zimmermann, T., Hildebrandt, L., Pröfrock, D. %D 2023 %J European Winter Conference on Plasma Spectrochemistry %T Using ICP-MS/MS in complex environments - spatial distribution and possible sources of technology-critical elements %U %X %0 conference lecture %@ %A Hildebrandt, L., Fensky, F., Klein, O., Zimmermann, T., Pröfrock, D. %D 2023 %J Wasser 2023 - Jahrestagung der Wasserchemischen Gesellschaft %T Bestimmung elementarer Fingerabdrücke von Korrosionsschutzbeschichtungen mittels ICP-MS/MS als wichtiger Baustein für die Mikroplastikanalytik %U %X %0 conference lecture %@ %A Pohl, F., De Falco, F., Russell, C., Hildebrandt, L., Miramontes, E. %D 2023 %J EGU General Assembly 2023 %T How could it get any worse? The ecotoxic legacy of plastic pollution and the role of plastic transport and distribution; fragmentation; degradation; and leaching of chemical additives %U %X %0 conference lecture %@ %A Pohl, F., Hildebrandt, L., O’Dell, J., Talling, P., Baker, M., El Gareb, F., La Nasa, J., De Falco, F., Mattonai, M., Ruffell, S., Eggenhuisen, J., Modugno, F., Pröfrock, D., Pope, E., Silva Jacinto, R., Heijnen, M., Hage, S., Simmons, S., Hasenhündl, M., Heerema, C. %D 2023 %J Bouma Deep Water Geoscience Conference %T The submarine Congo Canyon as a conduit for microplastics to the deep sea %U %X %0 conference lecture %@ %A Pröfrock, D., Przibilla, A., Klein, O., Hildebrandt, L., Ebeling, A., el Gareb, F., Rohrweber, A., Witthoff, C., Zimmermann, T. %D 2023 %J European Winter Conference on Plasma Spectrochemistry %T New Applications of ICP-MS/MS and MC ICP-MS to study the chemical anthropocene %U %X %0 journal article %@ 1618-2642 %A Hildebrandt, L., Zimmermann, T., Pröfrock, D. %D 2023 %J Analytical and Bioanalytical Chemistry %P 3041-3049 %R doi:10.1007/s00216-023-04611-z %T Laser microdissection pressure catapulting (LMPC): a new technique to handle single microplastic particles for number-based validation strategies %U https://doi.org/10.1007/s00216-023-04611-z %X This study examines laser microdissection pressure catapulting (LMPC) as an innovative method for microplastic research. Laser pressure catapulting as part of commercially available LMPC microscopes enables the precise handling of microplastic particles without any mechanical contact. In fact, individual particles with sizes between several micrometers and several hundred micrometers can be transported over centimeter-wide distances into a collection vial. Therefore, the technology enables the exact handling of defined numbers of small microplastics (or even individual ones) with the greatest precision. Herewith, it allows the production of particle number-based spike suspensions for method validation. Proof-of-principle LMPC experiments with polyethylene and polyethylene terephthalate model particles in the size range from 20 to 63 µm and polystyrene microspheres (10 µm diameter) demonstrated precise particle handling without fragmentation. Furthermore, the ablated particles showed no evidence of chemical alteration as seen in the particles’ IR spectra acquired via laser direct infrared analysis. We propose LMPC as a promising new tool to produce future microplastic reference materials such as particle-number spiked suspensions, since LMPC circumvents the uncertainties resulting from the potentially heterogeneous behavior or inappropriate sampling from microplastic suspensions. Furthermore, LMPC could be advantageous for the generation of very accurate calibration series of spherical particles for microplastic analysis via pyrolysis–gas chromatography–mass spectrometry (down to 0.54 ng), as it omits the dissolution of bulk polymers. %0 journal article %@ 0025-326X %A Hansen, J., Hildebrandt, L., Zimmermann, T., El Gareb, F., Fischer, E.K., Pröfrock, D. %D 2023 %J Marine Pollution Bulletin %P 114880 %R doi:10.1016/j.marpolbul.2023.114880 %T Quantification and characterization of microplastics in surface water samples from the Northeast Atlantic Ocean using Laser Direct Infrared Imaging %U https://doi.org/10.1016/j.marpolbul.2023.114880 %X Total number concentrations ranged from 47 to 2154 microplastic particles per m3 (average for all stations: 500 ± 700 microplastic particles m−3 (1 SD; n = 8)). In total, 20 polymer types were identified. The most common polymer types were polyethylene terephthalate (20 %) and acrylates/polyurethane/varnish (15 %). 93 % of the detected microplastics were smaller than 100 μm in length. Analysis of sample replicates indicates high spatio-temporal variations in microplastic pollution within the investigated region. %0 conference lecture %@ %A Hildebrandt, L., Pröfrock, D. %D 2023 %J SETAC Europe 2023 %T Microplastic analysis of complex marine water and sediment samples %U %X %0 conference lecture %@ %A Römerscheid, M. %A Lips, S., Hildebrandt, L., Schmitt-Jansen, M., Pröfrock, D., Jahnke, A. %D 2023 %J SETAC Europe 2023 %T Prioritization of consumer plastics for further testing based on artificial weathering combined with bioanalytical and chemical screening %U %X %0 online contribution %@ %A Hildebrandt, L., Pröfrock, D. %D 2023 %J Agilent LDIR 8700 User Community Meeting 2023 %T Development and validation of methods for the sampling; extraction and analysis of marine microplastics %U %X %0 conference lecture %@ %A Hildebrandt, L., Pröfrock, D. %D 2023 %J Agilent Microplastics Virtual Symposium 2023 %T Release of plastic additives and microplastic particles from different consumer products into water under accelerated UV weathering conditions %U %X %0 conference lecture %@ %A Menger, F., Römerscheid, M., Nabi, D., Hildebrandt, L., Lips, S., Bedulina, D., Huber, C., Gandrass, J., Jahnke, A., Krauss, M., Beck, A., Joerss, H. %D 2023 %J International Conference on Non-Target Screening (ICNTS 23) %T Plastic, water & the sun – Characterization of chemicals leaching from plastic under UV light treatment %U %X %0 conference lecture %@ %A Hildebrandt, L., Pohl, F., Mitrano, D., Zimmermann, T. %D 2023 %J SETAC North America 44th Annual Meeting %T The standardized Micro- and Nanoplastic Planet: Degradation; Fragmentation and Leaching %U %X %0 online contribution %@ %A Hildebrandt, L., El Gareb, F., Hansen, J., Takyar, H., Lange, M., Zimmermann, T., Jahnke, A., Bergmann, M., Peeken, I., Tekman, M., Gerdts, G., Bellou, N., Pohl, F., Baldewein, L., Pröfrock, D., Ebinghaus, R. %D 2022 %J Coastal Pollution Toolbox %T Microplastic Compendium %U %X URL: www.microplastic-compendium.eu %0 conference lecture %@ %A Zimmermann, T., Hildebrandt, L., El Gareb, F., Mitrano, D., Pröfrock, D. %D 2022 %J 28. ICP-MS Anwender*innentreffen und 14. Symposium massenspektrometrische Verfahren der Elementspurenanalyse %T ICP-MS-basierte Elementanalytik zur Entwicklung neuer Probenahmetechniken für die Mikroplastikanalytik %U %X %0 conference lecture (invited) %@ %A Pröfrock, D., Przibilla, A., Klein, O., Hildebrandt, L., Ebeling, A., El Gareb, F., Zimmermann, T. %D 2022 %J 28. ICP-MS Anwender*innentreffen und 14. Symposium massenspektrometrische Verfahren der Elementspurenanalyse %T More than trace elements – New Applications for ICP-MS to investigate the chemical anthropocene %U %X %0 journal article %@ %A Klein, O., Zimmermann, T., Hildebrandt, L., Pröfrock, D. %D 2022 %J Science of the Total Environment %P 158464 %R doi:10.1016/j.scitotenv.2022.158464 %T Technology-critical elements in Rhine sediments - A case study on occurrence and spatial distribution %U https://doi.org/10.1016/j.scitotenv.2022.158464 %X Obtained mass fractions in conjunction with corresponding geoaccumulation indices (Igeo) provide first indications of a possible enrichment along the Rhine for the TCEs of interest (Ga, Ge, Nb, In, Te, rare earth elements, and Ta). Especially the mass fractions of Zn, Ge, In, La, Sm, and Gd exhibit significant anthropogenic inputs. For stations characterized by high Ge and In mass fractions, element fingerprints imply possible atmospheric deposition stemming from e.g. combustion processes. Distinct anomalies of La and Sm most likely originate from discharges located at the city of Worms into the Upper Rhine. Statistical analysis of all analyzed 55 elemental mass fractions revealed similar behavior of TCEs compared to classical heavy metals. Diffuse as well as point sources of TCEs are likely. As a result, this study provides further insight into the role of TCEs as potential emerging contaminants in the environment. %0 conference lecture (invited) %@ %A Pröfrock, D., Hildebrandt, L., El Gareb, F., Nack, F., Zimmermann, T., Klein, O. %D 2022 %J Analytic Conference %T ICP-MS/MS and LDIR as complementary technique in small micro- and nanoplastic Research - From method optimization to the study of environmentally relevant polymers as vector for trace metals %U %X %0 journal article %@ 0269-7491 %A Hildebrandt, L., El Gareb, F., Zimmermann, T., Klein, O., Kerstan, A., Emeis, K., Pröfrock, D. %D 2022 %J Environmental Pollution %P 119547 %R doi:10.1016/j.envpol.2022.119547 %T Spatial distribution of microplastics in the tropical Indian Ocean based on laser direct infrared imaging and microwave-assisted matrix digestion %U https://doi.org/10.1016/j.envpol.2022.119547 %X The mean microplastic concentration of the analyzed samples was 50 ± 30 particles/fibers m−3 (1 SD, n = 21). Number concentrations ranged from 8 to 132 particles/fibers m−3 (20–300 μm). The most abundant polymer clusters were acrylates/polyurethane/varnish (49%), polyethylene terephthalate (26%), polypropylene (8%), polyethylene (4%) and ethylene-vinyl acetate (4%). 96% of the microplastic particles had a diameter <100 μm. Though inter-study comparison is difficult, the investigated area exhibits a high contamination with particulate plastics compared to other open ocean regions. A distinct spatial trend was observed with an increasing share of the size class 20–50 μm from east to west. %0 journal article %@ 1618-3258 %A Hildebrandt, L., Nack, F., Zimmermann, T., El Gareb, F., Pröfrock, D. %D 2022 %J Mitteilungen der Fachgruppe Umweltchemie und Oekotoxikologie %N 1 %P 7-10 %T Mikroplastik als Trojanisches Pferd für Spurenmetalle %U 1 %X giert auch als Trojanisches Pferd für gelöste Metallkationen. %0 conference lecture %@ %A El Gareb, F., Hildebrandt, L., Zimmermann, T., Klein, O., Kerstan, A., Emeis, K., Pröfrock, D. %D 2022 %J Wasser 2022 - Jahrestagung der Wasserchemischen Gesellschaft %T Analyse des Vorkommens und der Verteilung von Mikrokunststoffen im tropischen Indischen Ozean mittels Laser Direct Infrared (LDIR) Chemical Imaging und mikrowellenunterstützter Probenaufbereitung %U %X %0 conference lecture %@ %A Hildebrandt, L., Nack, F., Zimmermann, T., Pröfrock, D. %D 2022 %J Wasser 2022 - Jahrestagung der Wasserchemischen Gesellschaft %T Mikroplastikpartikel als Sorbens für Metall- und Halbmetallionen %U %X %0 lecture %@ %A Hildebrandt, L., El Gareb, F., Nack, F., Zimmermann, T., Pröfrock, D. %D 2022 %J %T Nano-; microplastics and metals - how are they related? %U %X %0 conference poster %@ %A El Gareb, F., Hildebrandt, L., Kerstan, A., Zimmermann, T., Emeis, K., Pröfrock, D. %D 2022 %J SETAC Europe 2022 - annual meeting Copenhagen %T Investigation of microplastics in the tropical Indian Ocean using Laser Direct Infrared (LDIR) Chemical Imaging and microwave-assisted sample preparation %U %X %0 doctoral thesis %@ %A Hildebrandt, L. %D 2021 %J %T Development and application of analytical methods to sample; isolate and characterize nano- and microplastics in aquatic environments and associated trace metals %U %X %0 conference lecture %@ %A Hildebrandt, L., Zimmermann, T., El Gareb, F., Pröfrock, D. %D 2021 %J Agilent - Microplastics in the Environment Virtual Symposium %T Nano- and Microplastics Analysis via LDIR and ICP-MS %U %X %0 journal article %@ 2666-9110 %A Hildebrandt, L., Nack, F., Zimmermann, T., Pröfrock, D. %D 2021 %J Journal of Hazardous Materials Letters %P 100035 %R doi:10.1016/j.hazl.2021.100035 %T Microplastics as a Trojan horse for trace metals %U https://doi.org/10.1016/j.hazl.2021.100035 %X Due to an assumed lack of anionic binding sites (most plastics are non-polar), scientists long considered virgin particulate plastics inert towards metal ions. However, we proved significant metal sorption to microplastics at neutral pH and release in a solution mimicking gastrointestinal chemistry serving as a proof-of-principle for environmental and human bioavailability. Competitive ion-exchange incubation experiments comprised 55 metals and metalloids. Fast kinetics were observed with 45 %–75 % of As, Be, Bi, Cr, Fe, In, Pb, Th, Sn and the rare-earth element ions being sorbed after 1 h. The investigated metal and metalloid cations showed significant differences in the extent of sorption, based upon which a distinct categorization was possible. Microplastics are not only a potential danger for aquatic and human life, but - as demonstrated in this paper - also serve as a Trojan Horse for dissolved metal cations. The corresponding effects on aquatic and human health will gain higher importance in the near future due to the predicted increases of marine plastic litter and microplastic sorbents. %0 lecture %@ %A Hildebrandt, L., Zimmermann, T., Nack, F., El Gareb, F., Mitrano, D., Pröfrock, D. %D 2021 %J %T Nano-; microplastics and metals - how are they related? %U %X %0 conference lecture %@ %A Hildebrandt, L., El Gareb, F., Pröfrock, D. %D 2021 %J Agilent Analytik-Forum 2021 %T Nano- und Mikroplastik-Analytik mittels ICP-MS/MS und LDIR Imaging - Zwei Anwendungsbeispiele %U %X %0 journal article %@ 0304-3894 %A Hildebrandt, L., Zimmermann, T., Primpke, S., Fischer, D., Gerdts, G., Pröfrock, D. %D 2021 %J Journal of Hazardous Materials %P 125482 %R doi:10.1016/j.jhazmat.2021.125482 %T Comparison and uncertainty evaluation of two centrifugal separators for microplastic sampling %U https://doi.org/10.1016/j.jhazmat.2021.125482 %X For the first time in microplastic research, an expanded uncertainty was calculated according to the “Guide to the expression of Uncertainty in Measurement” (JCGM 100:2008). Bottom-up uncertainty evaluation revealed the different sampling methods (~ 44%), sample replicates (~ 26%) and the different detection techniques (~ 16%) as the major sources of uncertainty. Depending on the number of particles detected in the samples, the relative expanded uncertainty (Urel (k =2)) ranged from 24% up to > 200% underpinning tremendous importance of sound uncertainty evaluation. Our results indicate that scientist should rethink many “observed patterns” in the literature due to being insignificant and herewith not real. %0 conference lecture %@ %A Hildebrandt, L., Zimmermann, T., Mitrano, D., Proefrock, D. %D 2020 %J SETAC Europe Meeting %T First lab-scale feasibility study on the enrichment of nanoplastic particles from water samples by continuous flow centrifugation using metal-doped nanoplastics and ICP-MS/MS detection %U %X %0 journal article %@ 2296-665X %A Hildebrandt, L., Mitrano, D., Zimmermann, T., Pröfrock, D. %D 2020 %J Frontiers in Environmental Science %P 89 %R doi:10.3389/fenvs.2020.00089 %T A Nanoplastic Sampling and Enrichment Approach by Continuous Flow Centrifugation %U https://doi.org/10.3389/fenvs.2020.00089 %X Substantial efforts have been undertaken to isolate and characterize plastic contaminants in different sample matrices in the last years as the ubiquitous presence of particulate plastic in the environment has become evident. In comparison, plastic particles <1 µm (nanoplastic) in the environment remain mostly unexplored. Adequate techniques for the enrichment, as well as the detection of nanoplastic, are lacking but are urgently needed to assess the full scope of (potential) nanoplastic pollution. Use of Pd-doped nanoplastic particles constitutes a powerful tool to develop new analytical approaches, as they can be traced accurately and with ease in a variety of complex matrices by highly sensitive, time-efficient and robust ICP-MS(/MS) techniques. In this lab-scale study, for the first time, the capability of continuous flow centrifugation to retain nanoplastic particles (∼160 nm) from ultrapure water, as well as from filtered and unfiltered water from the German Elbe River was evaluated. Depending on the pump rate, the retention efficiency for the nanoplastic particles in ultrapure water ranged from 92% ± 8% (1 L h−1) to 53% ± 5% (5 L h−1) [uc (n = 3)] and from 75% ± 5% to 65% ± 6% (uc) (2.5 L h−1) in river water. Recirculating the water through the system two and three times at the highest tested flow rate led to retention efficiencies >90%. In a proof-of-principle setup, it was demonstrated that operating two continuous flow centrifuges sequentially at different rotational speeds bears the potential to enable size- and density-selective sampling of the colloidal fraction. A significant fraction of the spiked nanoplastic particles [76% ± 5% (uc)] could be separated from a model mixture of natural particles with a well-defined mean size of approximately 3 µm. While the certified reference plankton material used here was quantitatively retained in the first centrifuge rotor together with 23.0% ± 2.2% of the effective dose of the spiked nanoplastic, the remaining fraction of the nanoplastic could be recovered in the second rotor (53% ± 5%) and the effluent [24.4% ± 2.4% (uc)]. Based on the good retention efficiencies and the demonstrated separation potential, continuous flow centrifugation has proven to be a very promising technique for nanoplastic sampling and enrichment from natural water samples. %0 journal article %@ 1759-9660 %A Zimmermann, T., von der Au, M., Reese, A., Klein, O., Hildebrandt, L., Pröfrock, D. %D 2020 %J Analytical Methods %N 30 %P 3778-3787 %R doi:10.1039/D0AY01049A %T Substituting HF by HBF4 – an optimized digestion method for multi-elemental sediment analysis via ICP-MS/MS %U https://doi.org/10.1039/D0AY01049A 30 %X Determination of elemental mass fractions in sediments plays a major role in evaluating the environmental status of aquatic ecosystems. Herewith, the optimization of a new total digestion protocol and the subsequent analysis of 48 elements in different sediment reference materials (NIST SRM 2702, GBW 07313, GBW 07311 and JMC-2) based on ICP-MS/MS detection is presented. The developed method applies microwave acid digestion and utilizes HBF4 as fluoride source for silicate decomposition. Similar to established protocols based on HF, HBF4 ensures the dissolution of the silicate matrix, as well as other refractory oxides. As HBF4 is not acutely toxic; no special precautions have to be made and digests can be directly measured via ICP-MS without specific sample inlet systems, evaporation steps or the addition of e.g. H3BO3, in order to mask excess HF. Different acid mixtures with and without HBF4 were evaluated in terms of digestion efficiency based on the trace metal recovery. The optimized protocol (5 mL HNO3, 2 mL HCL, 1 mL HBF4) allows a complete dissolution of the analyzed reference materials, as well as quantitative recoveries for a wide variety of certified analytes. Low recoveries for e.g. Sr, Ba and rare earth elements due to fluoride precipitation of HF-based digestions protocols, can be avoided by the usage of HBF4 instead. Based on the usage of high purity HBF4 all relevant trace, as well as matrix elements can be analyzed with sufficiently low LOQs (0.002 μg L−1 for U up to 6.7 μg L−1 for Al). In total, 34 elements were within a recovery range of 80%–120% for all three analyzed reference materials GBW 07313, GBW 07311 and JMC-2. 14 elements were outside a recovery range of 80%–120% for at least one of the analyzed reference materials. %0 conference lecture %@ %A Hildebrandt, L., Proefrock, D., Kerstan, A. %D 2020 %J 37. Agilent Forum Analytik Wien 2020 %T First steps in applying Quantum-Cascade-Laser Imaging for microplastic analysis in environmental samples %U %X Nevertheless, first results show that there are still some challenges to master. Especially, when it comes to the analysis of environmental samples bearing a highly complex matrix. To demonstrate the capabilities of the new QCL system it has been applied for the analysis of suspended particlulate matter sample from the German Elbe River estuary, which have been obtained during the testing of two new water-sampling approaches for microplastic. After an iterative optimization process of the spectral library, first results agree with the results obtained by the FPA-based FTIR approach. %0 journal article %@ 1759-9660 %A Lechthaler, S., Hildebrandt, L., Stauch, G., Schüttrumpf, H. %D 2020 %J Analytical Methods %N 42 %P 5128-5139 %R doi:10.1039/D0AY01574A %T Canola Oil Extraction in Conjunction with a Plastic Free Separation Unit Optimises Microplastics Monitoring in Water and Sediment %U https://doi.org/10.1039/D0AY01574A 42 %X Microplastics are widely distributed in the environment and to define contamination hot spots, environmental samples have to be analysed by means of cost- as well as time-efficient and reliable standardised protocols. Due to the lipophilic characteristics of plastic, oil extraction as a fast and density-independent separation is beneficial for the crucial extraction step. It was extensively validated (480 experiments) in two test setups by using canola oil and a cost-effective, plastic-free separation unit with spiked microplastic (19 different polymer types) in the density range from ρ = 11 - 1,760 kg/m³ and in the size range from 0.02 mm - 4.4 mm. Thus, an innovative, new method combination was developed and profoundly validated for water and sediment samples using only a short settling time of 15 minutes. Some experiments were also carried out with zinc chloride to obtain additional reference data (particles ≤ 359 µm). The total mean recovery rate was 89.3%, 91.7% within the larger microplastic fraction and 85.7% for the small fraction. Compared to zinc chloride (87.6%), recovery rates differed not significantly with oil (87.1%). Furthermore, size limits were set, since the method works best with particles 0.02 mm ≥ d ≤ 3 mm. The proposed method exhibits higher efficiency (84.8% for 20 - 63 µm) for the potentially most harmful microplastic size fraction than the classic setup using brine solution. As a result, oil is a comparably effective separation medium and offers further advantages for separating water and sediment samples due to its density independence, simple and fast application and environmental friendliness. Based on this, a new extraction protocol is presented here that confirms oil separation as a sound and effective separation in microplastic analysis and identifies previously missing information. %0 journal article %@ 1932-6203 %A Hildebrandt, L., von der Au, M., Zimmermann, T., Reese, A., Ludwig, J., Pröfrock, D. %D 2020 %J PLoS One %N 7 %P e0236120 %R doi:10.1371/journal.pone.0236120 %T A metrologically traceable protocol for the quantification of trace metals in different types of microplastic %U https://doi.org/10.1371/journal.pone.0236120 7 %X The presence of microplastic (MP) particles in aquatic environments raised concern about possible enrichment of organic and inorganic pollutants due to their specific surface and chemical properties. In particular the role of metals within this context is still poorly understood. Therefore, the aim of this work was to develop a fully validated acid digestion protocol for metal analysis in different polymers, which is a prerequisite to study such interactions. The proposed digestion protocol was validated using six different certified reference materials in the microplastic size range consisting of polyethylene, polypropylene, acrylonitrile butadiene styrene and polyvinyl chloride. As ICP-MS/MS enabled time-efficient, sensitive and robust analysis of 56 metals in one measurement, the method was suitable to provide mass fractions for a multitude of other elements beside the certified ones (As, Cd, Cr, Hg, Pb, Sb, Sn and Zn). Three different microwaves, different acid mixtures as well as different temperatures in combination with different hold times were tested for optimization purposes. With the exception of Cr in acrylonitrile butadiene styrene, recovery rates obtained using the optimized protocol for all six certified reference materials fell within a range from 95.9% ± 2.7% to 112% ± 7%. Subsequent optimization further enhanced both precision and recoveries ranging from 103% ± 5% to 107 ± 4% (U; k = 2 (n = 3)) for all certified metals (incl. Cr) in acrylonitrile butadiene styrene. The results clearly show the analytical challenges that come along with metal analysis in chemically resistant plastics. Addressing specific analysis tools for different sorption scenarios and processes as well as the underlying kinetics was beyond this study’s scope. However, the future application of the two recommended thoroughly validated total acid digestion protocols as a first step in the direction of harmonization of metal analysis in/on MP will enhance the significance and comparability of the generated data. It will contribute to a better understanding of the role of MP as vector for trace metals in the environment. %0 conference lecture %@ %A El Gareb, F., Hildebrandt, L., Kerstan, A., Zimmermann, T., Emeis, K., Pröfrock, D. %D 2020 %J YOUMARES 11 %T Microplastics in the Indian Ocean - Analyzed by Quantum Cascade laser- based infrared imaging %U %X %0 other %@ %A Hildebrandt, L., El Gareb, F., Zimmermann, T., Klein, O., Emeis, K., Pröfrock, D., Kerstan, A. %D 2020 %J %T Fast, Automated Microplastics Analysis Using Laser Direct Chemical Imaging : Characterizing and quantifying microplastics in water samples from marine environments %U %X It is estimated that more than 75% of the 8.3 billion metric tons of plastic produced over the last 65 years have turned into waste (1). Up to 13 million metric tons of this waste ends up in the ocean every year (2) and recent calculations estimate that more than 5.25 trillion plastic particles float in the world’s oceans (3). Scientists have demonstrated the alarming environmental ubiquity and persistence of particulate plastic in aquatic ecosystems (4). Models predict that approximately 14% of the plastic debris in the ocean surface layer can be classified as so-called microplastics (often referred to as particles between 1 μm and 5 mm in size) (5). These ingestible and potentially harmful particles have been formed by UV-induced, mechanical, or biological degradation of larger debris items (6). To verify the estimates and to meet upcoming regulatory measures (e.g., California Senate Bill 1422) and directives (MSFD, 2008/56/EC), accurate, time-efficient, and robust analytical workflows and techniques are required. %0 conference lecture %@ %A Hildebrandt, L., Voigt, N., Proefrock, D. %D 2019 %J Goldschmidt 2019 %T First evaluation of continuous flow centrifugation as a novel straightforward and non-size-disriminating sampling technique for microplastic in waters %U %X %0 conference poster %@ %A Nack, F., Hildebrandt, L., Zimmermann, T., Reese, A., Proefrock, D. %D 2019 %J SETAC Europe 29th Annual Meeting %T Studying the sorption of 60 different metals to virgin and UV exposed small PE and PET microplastic using ICP-MS/MS %U %X %0 conference poster %@ %A Hildebrandt, L., Voigt, N., Proefrock, D. %D 2019 %J SETAC Europe 29th Annual Meeting %T First evaluation of continuous flow centrifugation as a novel straightforward and non-size-discriminating sampling technique for microplastic in waters %U %X %0 conference lecture %@ %A Hildebrandt, L., Voigt, N., Proefrock, D. %D 2019 %J International Conference on Microplastic Pollution in the Mediterranean Sea %T First evaluation of continuous flow centrifugation as a novel straightforward and non-size-discriminating sampling technique for microplastic in waters %U %X %0 journal article %@ 0269-7491 %A Lorenz, C., Roscher, L., Meyer, M.S., Hildebrandt, L., Prume, J., Loeder, M.G.J., Primpke, S., Gerdts, G. %D 2019 %J Environmental Pollution %P 1719-1729 %R doi:10.1016/j.envpol.2019.06.093 %T Spatial distribution of microplastics in sediments and surface waters of the southern North Sea %U https://doi.org/10.1016/j.envpol.2019.06.093 %X Microplastic pollution within the marine environment is of pressing concern globally. Accordingly, spatial monitoring of microplastic concentrations, composition and size distribution may help to identify sources and entry pathways, and hence allow initiating focused mitigation. Spatial distribution patterns of microplastics were investigated in two compartments of the southern North Sea by collecting sublittoral sediment and surface water samples from 24 stations. Large microplastics (500−5000 μm) were detected visually and identified using attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy. The remaining sample was digested enzymatically, concentrated onto filters and analyzed for small microplastics (11−500 μm) using Focal Plane Array (FPA) FTIR imaging. Microplastics were detected in all samples with concentrations ranging between 2.8 and 1188.8 particles kg−1 for sediments and 0.1–245.4 particles m−3 for surface waters. On average 98% of microplastics were <100 μm in sediments and 86% in surface waters. The most prevalent polymer types in both compartments were polypropylene, acrylates/polyurethane/varnish, and polyamide. However, polymer composition differed significantly between sediment and surface water samples as well as between the Frisian Islands and the English Channel sites. These results show that microplastics are not evenly distributed, in neither location nor size, which is illuminating regarding the development of monitoring protocols. %0 journal article %@ 0141-1136 %A Hildebrandt, L., Voigt, N., Zimmermann, T., Reese, A., Proefrock, D. %D 2019 %J Marine Environmental Research %P 104768 %R doi:10.1016/j.marenvres.2019.104768 %T Evaluation of continuous flow centrifugation as an alternative technique to sample microplastic from water bodies %U https://doi.org/10.1016/j.marenvres.2019.104768 %X The scientific and public interest regarding environmental pollution with microplastic has considerably increased within the last 15 years. Nevertheless, up to now there is no widely applied standard operation procedure for microplastic sampling, resulting in a lack of inter-study comparability. In addition, many studies on microplastic occurrences do not indicate a sound methodological validation of the applied methods and procedures. This study presents an alternative volume-reduced sampling technique to sample the entire load of suspended particulate matter including microplastic particles in natural waters, based on continuous flow centrifugation. For the lab-scale validation of the proposed instrumental setup, six different microplastic types (PE, PET, PS, PVDC, EPS and PP) were used. The particles covered a size range from 1 μm to 1 mm and a density range from 0.94 g mL−1 to 1.63 g mL−1. Recoveries ranged from 95.0% ± 2.3%–99.1% ± 0.3% for virgin powders and from 96.1% ± 0.6%–99.4% ± 0.2% (1 SD, n = 2–3) for microplastic suspended in river water for 40 days. Gravimetric and microscopic analysis of the effluent indicates efficient removal of microplastic from the suspensions. Static light scattering analysis of the microplastic suspensions prior to and after centrifugation confirmed that no change of the particle size distribution has occurred – neither through aggregation nor through size-discrimination during centrifugation. Moreover, the system was tested in the field and used twice to sample suspended particulate matter from the Elbe estuary directly on site. Based on these first lab-scale experiments, continuous flow centrifugation proves a promising technique bearing potential to alleviate drawbacks such as contamination, filter clogging and particle size-discrimination of commonly used volume-reduced microplastic sampling approaches. %0 lecture %@ %A Hildebrandt, L. %D 2019 %J %T Mikro-, Nanoplastik und Metalle – Wie hängt das zusammen? : Ringvorlesung "Ausgewählte Kapitel der Toxikologie und Umweltmedizin %U %X %0 conference poster %@ %A Hildebrandt, L., Zimmermann, T., Reese, A., Proefrock, D. %D 2019 %J European Winter Conference on Plasma Spectrochemistry 2019 %T Development of a microwave-assisted digestion protocol for trace metal analysis in different types of polymers using ICP-MS/MS %U %X