1st December 2015 Microplastic in Environmental Samples: Quantitative Determination and Metrological Traceability Ulrike Braun1, Roland Becker1 Claus G. Bannick2 Rainer Stosch3 1 Bundesanstalt für Materialforschung und –prüfung (BAM) 2 Umweltbundesamt (UBA) 3 Physikalisch-Technische Bundesanstalt (PTB)

Facts Microplastics (MP) Increasing plastic production (300 mio t/a): founds in environment nearly everywhere Microplastics (few µm up to 5mm) Primary microplastic: cosmetics, technical abrasives (~ 0,5 kilo t/a) Secondary microplastic: degradated polymers by UV, O2, mechanics (~ 8-10 mio t/a) 10 mm 2015-12-01 EMPIR Workshop, Turin, Italy

MP Particles: Possible Risks Release of toxic decomposition products to environment during degradation (decomposition products of polymer, additives) Adsorption of persistent pollutants, ingestion to animals and accumulation of pollution in food chain Carrier for vectors of different biologic species No verified data exist about the kind and amount, the source and the fate as well as the behaviour of microplastic particles in the environment. Analytic problem: a few synthetic polymer particles with different material characteristics (density, solubility) beside many natural, macromolecular particles in various environmental matrices 2015-12-01 EMPIR Workshop, Turin, Italy

MP Particles in Environment: Analysis Harmonized sampling /sample preparation from various environmental matrices (water, soil, biota). Routine analysis for identification, quantitative determination and metrological traceability. Assessment of risks (persistent pollutants, microbiology). 2015-12-01 EMPIR Workshop, Turin, Italy

MP Particles in Environment: Analysis Routine analysis for identification, quantitative determination and metrological traceability. 2015-12-01 EMPIR Workshop, Turin, Italy

Raman Spectroscopy Mapping Example: Sand + 2wt% PE, laser wavelength 488 nm Spectra PE Spectra sand Mapping 2888 cm-1 Mapping 472 cm-1 2015-12-01 EMPIR Workshop, Turin, Italy

metrological AFM (PTB) Raman Mapping Quantification PTB Raman calibration standard traceability to length (m) metrological AFM (PTB) fcal,x/y 2 µm py px Raman mapping of calibrated „chessboard“ pattern surface coverage: (x ± Ux) % px , py: structure period 2015-12-01 EMPIR Workshop, Turin, Italy

Conclusion Raman Mapping Certain identification is possible, determination of particle sizes (microbiologic interaction). Non destructive method. Major disadvantage: fluorescence of matrix and high resolution /black matrix can lead to the melting of polymers. Automatisation by use of calibration standard and quantitative result. 2015-12-01 EMPIR Workshop, Turin, Italy

Thermo-Analytic Methods Assessment of a new method for the analysis of decomposition gases of polymers by a combining thermogravimetric solid-phase extraction and thermal desorption gas chromatography mass spectrometry, E. Duemichen, U. Braun, R. Senz, G. Fabian, H. Sturm, Journal of Chromatography A 2014, 1354, 117-128. Macroscopic sampling Adsorber (Twister) 10 mm Characteristic decomposition products of polymers Identification via „fingerprint“ or spectra libraries TDS-GC-MS Analysis 2015-12-01 EMPIR Workshop, Turin, Italy

PE in Environmental Samples Analysis of polyethylene microplastics in environmental samples, using a thermal decomposition method, E. Dümichen, A.-K. Barthel, U. Braun, C. G. Bannick, K. Brand, M. Jekel, R. Senz Water Research Vol. 85, 2015, 451–457. Abundance Retention time / min Certain identification of PE in sample 2015-12-01 EMPIR Workshop, Turin, Italy

Conclusion Thermo-Analytic Methods Identification of polymers in environmental samples (PE, PP) Quantification (bulk method) is possible by use of calibration standards. Major disadvantages: destructive method, no information about particle contribution Improvement of method, automatisation, limit of detection. 2015-12-01 EMPIR Workshop, Turin, Italy

Possible objective for a project contribution Standardisation of methods for microplastic analysis in environmental samples: Raman Mapping, Thermo-analytic methods, ... Assessment of metrological traceability. Development and provision of reference materials. 2015-12-01 EMPIR Workshop, Turin, Italy

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