SAMPLING, SAMPLE PREPARATION AND DETECTION OF ... - RSC

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

23 May 2018

Outline

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Who we are?

Current activities in the ISO/TC 61/SC14/WG 4

Harmonization progress in Germany

2018-05-23 Microplastic Methodes Workshop, London

Who we are?

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Dr. Claus Gerhard BannickHead of Unit Wastewater Technology Research, coordinator of plastic and environment

German Environment AgencyDepartmental research institute of federal ministry for the environment, nature conservation and nuclear safety

Background: Soil, water and agriculture science

Dr. Ulrike BraunCoordinator of microplastic project

Federal Institute of Material Research and TestingDepartmental research institute of federal ministry for economic affairs and energy

Background: Polymer science

=> Working together in the topic of Microplastics (MP) since 2014


Development of fast MP analysis method:Sampling via fractional filtration

2018-05-23 4

Procedure

• Pumping of water through three sieves (500 µm, 100 µm, 50 µm, …, 10 µm, 5 µm)• Steam sterilization of filter residue• Freeze drying

Sieve tower

Enables sampling of representative amounts in reasonable time (~ 1000 l around 2-3 h on location)

Microplastic Methodes Workshop, London

Development of fast MP analysis method:Detection via TED-GC-MS (ThermoExtraction & Desorption-GC-MS)

2018-05-23 5

• 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


solid phase

Thermo balance TDU-GC-MS

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• Fully automated process

• Sample mass up to 50 mg

• Testing time 2 h 20 min

• Standard deviation less than 5 %

• Almost no sample preparation

2018-05-23

Polymer LOD in µg

PE 1.6

PP 0.44

PS 0.20

PET 0.68

PA6 0.52

PA6.6 2.8

PMMA 0.20

SBR 0.27


Current application of fast MP analysis method:Detection via TED-GC-MS (ThermoExtraction & Desorption-GC-MS)

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Comparison of detection methods

Method Spectroscopic Thermo-analytic ChemicalRamanMicroscopy

FT MIRMicroscopy

NIR Process sensor

Py-GC-MS TED-GC-MS SEC*(Solution)

LC –MS/MS**(Degradation)

Para-meter

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 µgabs.

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), 1256-1264.** 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), 530-534.


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Application of MP analysis method:Waste water treatment plant

Polymer Mass/mg Mass/mg

PE ~59.3 ~19629

PS ~2.5 ~317

PP (only in August)

~4.3 -

Filtration 13 L of influent

Filtration 1000 L of effluent

99 % Retention50 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 influent0

50

100

150

200

250

300

350

400800

30003500

200003000040000 PE

PS PP

Mas

s/m

g


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Application of MP analysis method:Road run off

SBR in all size classes(large < small ?)

Highest SBR fraction in sedimentation sludge

~1% SBR ~ 8 % Tire wear


Filtration 2 L

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Representative water sampling

Particle size class µm 5,000–

1,0001000–

500 500–100 100–50 50–10 10–5 5–1

Averaged particle diameter

µm 3,000 750 300 75 30 7,5 3

Mass of individual particle

mg 14.130 0.221 0.014 2.21E-04 1.41E-05 2.21E-07 1.41E-08

Number of particles in 14.13 mg

items 1 64 1000 6.40E+04 1.00E+06 6,40E+07 1.00E+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


Microplastic screening in terrestrial samples (literature data)

2018-05-23 Microplastic Methodes Workshop, London 11

Source Sample amount Sample preparation Detec-

tion Findings

Sediment (marine)

2 - 30 kg30 – 1000 g Density Separation (NaCl) FTIR/

Raman1 – 2.175 items / kg0,08 – 26,8 g / kg

Sediment (limnic)

2 - 15 kg20 – 4000 g

Density Separation (NaCl)+ H2O2Density Separation (ZnCl2)

FTIR/ Raman 64 – 10.500 items / kg

Sewage sludge (fertilizer)

0,5 - 50 g

Density Separation (NaCl, ZnCl2) Alkaline (NaOH)Enzymatic + H2O2

FTIR/ Raman 80 – 16.700 items / kg

Soil 400 g0,02 - 20 g

Density Separation (H2O, ZnCl2 + FTIR)Thermal Extraction + GC-MSchemical Extraction + FTIR

11 – 7.625 items / kg0,08 – 1,2 g / kg

Agriculture fields

1 m 20,03 - 0,3 g

0,009 g/kg0,003 g/m2

Industry areas 0,02 - 2 g 870 items / kg

0,005 – 34 g/kg

Very low contents per mass in environmental media in terrestrial samples: Need of up-concentration

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There is still no general solution …


…but asking three questions helps to focus a systematic approach:

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Why asking the right questions before matters?

Detection

Samplingpreparation

Sampling Environmental media?water

sedimentssludge

soilair

biota

Goal of investigation?Sort

Particle number, size, formMass fractionAging status

Group of interest?Academia

Regulation / legislatureMonitoring controller

…


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What is standardization?

2018‐05‐23 Microplastic Methodes Workshop, London

Product DIN CEN ISO

Norm DINDIN ENDIN EN ISO

ENEN ISO

ISO

TechnicalSpecification

DIN SPEC(TS)

CEN/TSCen ISO/TS

ISO/TS

Technical Report

DIN SPEC (TR)

CEN/TRCEN ISO/TR

ISO/TR

Open Paper DIN SPEC (PAS)

PAS IWA

Is the scheduled standardization of material and immaterial objects carried out jointly by interested parties in consensus for the benefit of the general public.


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Standardization in “Microplastics” (~ 2016)

2018‐05‐23 Microplastic Methodes Workshop, London

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)



Convener: Claus G. Bannick


=> Foundation of a Sub-Committee ISO/TC 61/SC 14 „Plastics and environment“:pooling of existing and new working groups

=> 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 45Water: ISO/TC 147, CEN/TC 230Soil: ISO/TC 190, CEN/TC 345Fertilizer: ISO/TC 134, CEN/TC 223 and TC 260Sewage sludge: ISO/TC 275, CEN/TC 308Soil improvement: ISO/TC 134, CEN/TC 223Environmental management: ISO/TC 207

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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


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Actual microplastic project in Germany: Plastics in environment

Federal Ministry of Education and Research

18 projects, ~ 35 Mio Euro

Run from summer 2017 up to 2021

12 projects are related to microplastics

Harmonization of data !!! ???

Definition of cross-cutting issues (i.a):

=> Terms and definitions

=> Analytics and reference materials: Living document with recommendation and round robin tests


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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)


1,0001000–

500 500–100 100–50 50–10 10–5 5–1


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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 fractionaging status


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Actual microplastic project in Germany: Definition of first rules for sampling

Sampling of water dependent from suspended particular matter (SPM)- more than 10 mg/L of SPM: 10-20 L- less than 0,5 mg/L of SPM: 10 m3

- between 0,5 and 10 mg/L of SPM: 1-5 m3


1,0001000–

500 500–100 100–50 50–10 10–5 5–1

Sampling of solid environmental media- in progress

Classification of MP sizes


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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


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• Doing research • Be active in standardization• Cross link your national

projects• Cross link people from

different backgrounds (polymer, environmental protection, biology, soil, marine water,…)


Summery

Thanks to the microplastic team at BAM:

Erik Dümichen

Paul Eisentraut

Caroline Goedecke

Daniel Dittmann

Korinna Altmann

Axel Müller

Andrea PaulJana Falkenhagen

Roland BeckerFabian RothHeidi Marx

Financial support

LukasWander

Anna MariaElert

Anne K. BarthelMathias Ricking

Nathan ObermaierThanks to the Microplastics Team at UBA:

2018-05-23 Microplastic Methodes Workshop, London 25

Maria Kittner

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SAMPLING, SAMPLE PREPARATION AND DETECTION OF ... - RSC