1. 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)

2. 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
EMPIR Workshop, Turin, Italy

3. 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
EMPIR Workshop, Turin, Italy

4. 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).
EMPIR Workshop, Turin, Italy

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

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

7. 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
EMPIR Workshop, Turin, Italy

8. 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.
EMPIR Workshop, Turin, Italy

9. 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,
Macroscopic sampling
Adsorber (Twister)
10 mm
Characteristic decomposition products of polymers
Identification via „fingerprint“ or spectra libraries
TDS-GC-MS
Analysis
EMPIR Workshop, Turin, Italy

10. 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
EMPIR Workshop, Turin, Italy

11. 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.
EMPIR Workshop, Turin, Italy

12. 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.
EMPIR Workshop, Turin, Italy

13. Thank you