SAMPLING, SAMPLE PREPARATION AND DETECTION OF MICROPLASTICS, CURRENT ACTIVITIES IN THE ISO/TC 61/SC14/WG 4

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1 23 May 2018 SAMPLING, SAMPLE PREPARATION AND DETECTION OF MICROPLASTICS, CURRENT ACTIVITIES IN THE ISO/TC 61/SC14/WG 4 Ulrike Braun, Bundesanstalt für Materialforschung und prüfung (BAM), Berlin, Germany Claus G. Bannick, Umweltbundesamt (UBA), Berlin, Germany

2 Outline Who we are? Current activities in the ISO/TC 61/SC14/WG 4 Harmonization progress in Germany 2

3 Who we are? Dr. Claus Gerhard Bannick Head of Unit Wastewater Technology Research, coordinator of plastic and environment German Environment Agency Departmental research institute of federal ministry for the environment, nature conservation and nuclear safety Background: Soil, water and agriculture science Dr. Ulrike Braun Coordinator of microplastic project Federal Institute of Material Research and Testing Departmental research institute of federal ministry for economic affairs and energy Background: Polymer science => Working together in the topic of Microplastics (MP) since

4 Development of fast MP analysis method: Sampling via fractional filtration Enables sampling of representative amounts in reasonable time (~ 1000 l around 2-3 h on location) Sieve tower Procedure Pumping of water through three sieves (500 µm, 100 µm, 50 µm,, 10 µm, 5 µm) Steam sterilization of filter residue Freeze drying 4

5 Development of fast MP analysis method: Detection via TED-GC-MS (ThermoExtraction & Desorption-GC-MS) solid phase Thermo balance TDU-GC-MS Measurement principle: thermal degradation products were collected on the solid phase, desorbed und analyzed via GC-MS Identification through specific degradation products Determination of mass fractions is possible 5

6 Current application of fast MP analysis method: Detection via TED-GC-MS (ThermoExtraction & Desorption-GC-MS) Polymer LOD in µg PE 1.6 PP 0.44 PS 0.20 PET 0.68 Fully automated process Sample mass up to 50 mg Testing time 2 h 20 min Standard deviation less than 5 % Almost no sample preparation PA PA PMMA 0.20 SBR Microplastic Methodes Workshop, London 6

7 Comparison of detection methods Method Spectroscopic Thermo-analytic Chemical Parameter Raman Microscopy FT MIR Microscopy NIR Process sensor Py-GC-MS TED-GC-MS SEC* (Solution) Sample mass µg µg mg µg mg mg mg Resolution / Detection limit > 10 µm > 20 µm 0,5-1 wt.% 1 ppm 0,5 2,5 µg abs. LC MS/MS** (Degradation) 8-50 µg/kg Preparation As received As received As received Isolated particles As received As received As received Measurement time d d min h h h h Result Identification Yes Yes Yes Yes Yes Only PS, PET Only PET, PC Mass fraction No No Yes Yes Yes Yes Degradation Yes No No Yes No (Yes) No Particle size Yes Yes No No No No No * Elert, A. M.; Becker, R.; Duemichen, E.; Eisentraut, P.; Falkenhagen, J.; Sturm, H.; Braun, U., Comparison of different methods for MP detection: What can we learn from them, and why asking the right question before measurements matters? Environmental Pollution 2017, 231, (Part 2), ** Wang, L.; Zhang, J.; Hou, S.; Sun, H., A Simple Method for Quantifying Polycarbonate and Polyethylene Terephthalate Microplastics in Environmental Samples by Liquid Chromatography Tandem Mass Spectrometry. Environmental Science & Technology Letters 2017, 4, (12),

8 Application of MP analysis method: Waste water treatment plant Mass/mg PE PS PP Polymer Mass/mg Mass/mg PE ~59.3 ~19629 PS ~2.5 ~317 PP (only in August) Filtration 1000 L of effluent ~4.3 - Filtration 13 L of influent µm 100 µm 500 µm 50 µm 100 µm 500 µm 50 µm 100 µm 500 µm 50 µm 100 µm 500 µm 50 µm 100 µm 500 µm 50 µm 100 µm 500 µm 50 µm 100 µm 500 µm 50 µm 100 µm 500 µm 50 µm 100 µm 500 µm 16/8/4 16/8/8 16/8/10 16/8/12 16/11/22 16/11/23 16/11/24 16/11/25 influent 99 % Retention 8

9 Application of MP analysis method: Road run off Filtration 2L SBR in all size classes (large < small?) Highest SBR fraction in sedimentation sludge ~1% SBR ~ 8 % Tire wear 9

10 Representative water sampling Particle size class Averaged particle diameter Mass of individual particle Number of particles in mg µm 5,000 1, µm 3, ,5 3 mg E E E E-08 items E E+06 6,40E E+09 Mass of large particles will dominate the mass of small particles Less contaminated water needs higher sampling volumes for representative result Representative water volume for detection of large particles >> small particles 10

11 Microplastic screening in terrestrial samples (literature data) Source Sample amount Sample preparation Detection Findings Sediment (marine) 2-30 kg g Density Separation (NaCl) FTIR/ Raman items / kg 0,08 26,8 g / kg Sediment (limnic) 2-15 kg g Density Separation (NaCl)+ H 2 O 2 Density Separation (ZnCl 2 ) FTIR/ Raman items / kg Sewage sludge (fertilizer) Soil Agriculture fields Industry areas 0,5-50 g 400 g 0,02-20 g 1 m 2 0,03-0,3 g 0,02-2 g Density Separation (NaCl, ZnCl 2 ) Alkaline (NaOH) Enzymatic + H 2 O 2 FTIR/ Raman Density Separation (H 2 O, ZnCl 2 + FTIR) Thermal Extraction + GC-MS chemical Extraction + FTIR items / kg items / kg 0,08 1,2 g / kg 0,009 g/kg 0,003 g/m2 870 items / kg 0, g/kg Very low contents per mass in environmental media in terrestrial samples: Need of up-concentration 11

12 There is still no general solution but asking three questions helps to focus a systematic approach: 12

13 Why asking the right questions before matters? Group of interest? Academia Regulation / legislature Monitoring controller Goal of investigation? Sort Particle number, size, form Mass fraction Aging status Detection Sampling preparation Sampling Environmental media? water sediments sludge soil air biota 13

14 What is standardization? Is the scheduled standardization of material and immaterial objects carried out jointly by interested parties in consensus for the benefit of the general public. Product DIN CEN ISO Norm DIN DIN EN DIN EN ISO EN EN ISO ISO Technical Specification DIN SPEC (TS) CEN/TS Cen ISO/TS ISO/TS Technical Report DIN SPEC (TR) CEN/TR CEN ISO/TR ISO/TR Open Paper DIN SPEC (PAS) PAS IWA Microplastic Methodes Workshop, London 14 13

15 Standardization in Microplastics (~ 2016) Challenge: As this is an international problem, solutions can and should only be created through international bodies/ at international level. Goal: Development of standards for the investigation and evaluation of plastics in environmentally relevant liquids and solids => Start of international standardization activities in ISO/TC 61 "Plastics (ad hoc group): Plastics in the Environment Current state of knowledge and methodologies (Technical Report 21960) Microplastic Methodes Workshop, London 15 14

16 Standardization in Microplastics (~ 2017) => Foundation of a Sub-Committee ISO/TC 61/SC 14 Plastics and environment : pooling of existing and new working groups Convener: Claus G. Bannick 16

17 Standardization in Microplastics (~ 2018) => Cooperation with other ISO or CEN/TCs and consideration of already existing standards, standards in progress and standards to be expected and framework specifications (Vienna Agreement): 11 positive, 0 negative, 8 abstentions => The following international and European Technical Committees of ISO and CEN have already dealt with partial aspects which must be taken into account in the overall concept: Rubber: ISO/TC 45 Water: ISO/TC 147, CEN/TC 230 Soil: ISO/TC 190, CEN/TC 345 Fertilizer: ISO/TC 134, CEN/TC 223 and TC 260 Sewage sludge: ISO/TC 275, CEN/TC 308 Soil improvement: ISO/TC 134, CEN/TC 223 Environmental management: ISO/TC

18 ISO/NP TR 21960: The document Terms and definitions Applications of plastic materials Occurrence of plastics in environment (water, sediments, sludge, soil, air, biota) Testing methods with focus microplastics (sampling, sampling preparation, analysis) Entry pathways, environmental assessment 18

19 Actual microplastic project in Germany: Plastics in environment Definition of cross-cutting issues (i.a): => Terms and definitions Federal Ministry of Education and Research 18 projects, ~ 35 Mio Euro Run from summer 2017 up to projects are related to microplastics Harmonization of data!!!??? => Analytics and reference materials: Living document with recommendation and round robin tests 19

20 Actual microplastic project in Germany: Definition of first, general rules Working without plastic equipment (only silicone) Working in laminar flow boxes, especially during sampling preparation Documentation of blanc values, recovery rates with reference materials Hygenisation of samples from critical sources (WWTP) Result documentation in particle numbers per volume (or dry mass) or in mass fraction per volume (or dry mass) Classification of MP sizes (practical aspects during sampling and detection, effect assessment) Particle size class µm 5,000 1,

21 Actual microplastic project in Germany: Definition of first rules for detection No visual methods without chemical identification Considering the requirement for detection methods: - dimension of analyzed sample mass (with respect to the representativeness of sample) - measurement time (with respect to monitoring processes) - lower detection limit (with respect to expected MP findings) Considering the results of detection methods - sort of polymer - number, size and form of particles - mass fraction - aging status 21

22 Actual microplastic project in Germany: Definition of first rules for sampling Classification of MP sizes Particle size class µm 5,000 1, Sampling of water dependent from suspended particular matter (SPM) - more than 10 mg/l of SPM: L - less than 0,5 mg/l of SPM: 10 m 3 - between 0,5 and 10 mg/l of SPM: 1-5 m 3 Sampling of solid environmental media - in progress 22

23 Actual microplastic project in Germany: Definition of first rules for sample preparation Dependent on sample source and detection method Working in laminar flow boxes Chemical, physical or enzymatic steps - recommendation in progress 23

24 Summery Doing research Be active in standardization Cross link your national projects Cross link people from different backgrounds (polymer, environmental protection, biology, soil, marine water, ) 24

25 Thanks to the microplastic team at BAM: Andrea Paul Jana Falkenhagen Roland Becker Fabian Roth Heidi Marx Erik Dümichen Korinna Altmann Anna Maria Elert Paul Eisentraut Caroline Goedecke Daniel Dittmann Axel Müller Lukas Wander Maria Kittner Financial support Thanks to the Microplastics Team at UBA: Anne K. Barthel Mathias Ricking Nathan Obermaier 25