Synthesis of metal doped nanoplastic particles and ... · In collaboration with Ahmed Tlili, Eawag Assess physiological effects on biofilm and snails ... (unpublished scientific data

Eawag: Swiss Federal Institute of Aquatic Science and Technology

Synthesis of metal doped nanoplastic particles and

microplastic fibers and their utility for investigating

plastic fluxes in complex matrices

Dr. Denise M. Mitrano

2

Particulate plastic enters the sewer system

Plastic accumulates in the sewage sludge

or released to streams

Sewage sludge as fertilizer

Particulate plastic in the built environment

Challenges of Microplastic Analysis

3

Natural sample

Time-consuming

Difficulties

Contamination

Expensive

Limited QA/QC

Challenges of Microplastic Analysis

4

Natural sample

Consequences

Limited number of

samples

Mechanistic studies

very time

consuming

Reduced

understanding of

basic processes

Metal Doped Particulate Plastics:

A New Approach

5

Test system

Metal

Analyze metal

as proxy for

plastic

Improved detection limits

Improvements

Faster

Quantitative

Common equipment

Process studies possible

Synthesis and

characterization of

materials

Assessment in small

scale systems

6

Fate, transport and

biological uptake

General Workflow

Synthesis and

characterization of

material

Assessment in small

scale system

Fate, transport and

biological uptake

7

General Workflow

Particulate Plastic Characterization

8

Polystyrene Nanoplastic with Pd

• In-situ polymerization

• Tunable shell morphology

• Density negligibly effected

• No metal leaching over time

Mitrano et al. Nature Nanotechnology 2019 Schmeidgruber, Hufenus, Mitrano Water Research 2019

Polyester Fiber with In

1 mm

• Pilot fiber-spinning plant

• Textile quality

• Distribution similar to releases

after washing textiles

• No metal leaching over time

General Workflow

Synthesis and

characterization of

material

Assessment in small

scale system

Fate, transport and

biological uptake

9

Municipal wastewater treatment

10

Batch Tests to Assess

Particulate Plastic Distribution

11

• Batch tests representing the

activated sludge system

• Attachment affinity

• Estimate association of plastic

to sludge in wastewater

treatment plants

Schmiedgruber, Hufenus, and Mitrano Water Research 2019

Mitrano et al. Nature Nanotechnology 2019



12

Digest

+

Analyze

Mix particulate

plastic and matrix

Supernatant

Settle

Sludge

Sample 1Sample 2Sample 3

Sample n

(…)

?

?





13

Supernatant

Sludge



Synthesis and

characterization of

material

Assessment in small

scale system

Fate, transport and

biological uptake

14

General Workflow

Utility of Metal Doped Plastics

in Complex Systems

15

Retention of plastics in pilot scale WWTP

Photo coutesy Ralf KägiFrehland, Kägi, Hufenus and Mitrano (in preparation)

16

Particulate plastic flux in pilot scale WWTP

Frehland, Kägi, Hufenus and Mitrano (in preparation)

(unpublished scientific data removed from presentation)


in Complex Systems

17

Leaching from sludge and transport in porous media

Keller, Jimminez-Martinez, Mitrano (in preparation)

• Simulate sludge

application on fields

• Quantify leaching of

plastic from sludge

and retention of

plastic in column

• Compare mobility of

particles from sludge

vs. pristine plastic


in Complex Systems

18

Leaching from sludge and transport in porous media

Keller, Jimminez-Martinez, Mitrano (in preparation)



in Complex Systems

19

Uptake of nanoplastics by wheat

In collaboration with Université Grenoble Alpes



in Complex Systems

Trophic transfer of plastics: periphyton to snails

20In collaboration with Ahmed Tlili, Eawag

Assess physiological effects on

biofilm and snails

Growth

Fitness

Offspring


in Complex Systems

21

Trophic transfer of plastics: periphyton to snails

In collaboration with Ahmed Tlili, Eawag


Utility of metal doped plastics:

a tool with many possibilities

22

Suitable materials for mechanistic

process studies made easier

because of faster analysis

Several proof of concept studies

show promise using metal-doped

plastics

Expand to additional systems:

freshwater fate and transport

THANK YOU!Ralf Kägi

Michael Schmiedgruber

Stefan Frehland

Andreas Keller

Felix Schmidt

Ahmed Tlili

Manuel Holzer

Joaquin Jimenez-Martinez

Guieseppi Storti

Francesco Distante

Lucio Isa

Anna Beltzung

Alberto Cingolani

Massimo Morbidelli

Bernd Nowack

Rudolf Hufenus

Markus Hilber

Yaping Kai

Delphine Wegner

Ana-Elena Pradas

Geraldine Sarret

Hiram Castillo

Mohammad Wazne

Roxanne Calais

Questions?

Photo credits: Nowack and Mitrano

Fate and Transport of Particulate Plastic in Technical and Environmental Systems• Removal of nanoplastics in a pilot scale municipal drinking water plant (Dr. Ralf Kägi and Prof. Urs von Gunten; Eawag,

Switzerland) *New funding acquired for project

• Leaching of particulate plastic from sewage sludge and vertical transport through porous media (Dr. Joaquin Jimenez-

Martinez; Eawag/ETH, Switzerland)

• Soil mobility of nanoplastic in column studies and terrestrial mesocosms (Dr. Geert Cornelis; Swedish University of

Agricultural Sciences, Sweden and Dr. Elma Lahive; Centre for Ecology & Hydrology, UK) *New funding acquired

• Validation of large scale sampling techniques for particulate plastic (Dr. Daniel Pröfrock, Helmholz-Zentrum Geesthacht,

Germany)

• Experimental Lakes Area freshwater mesocosms (Prof. Dr. Chelsea Rochman; University of Toronto, Canada)

• Formation and release of microplastic fibers along the textile life-cycle (Prof. Dr. Bernd Nowack; Empa, Switzerland)

• Assessment of microplastic fiber fate in industrial wastewaters (Dr. Curie Park, Cambridge University, UK)

Biological Uptake and Interactions with Particulate Plastic• Trophic transfer of particulate plastic from biofilms to snails (Dr. Ahmed Tlili; Eawag, Switzerland)

• Interaction and uptake of nanoplastics by hydroponically grown wheat plants (Dr. Geraldine Sarret; Universtiy Grenoble

Alpes, France)

• Trophic transfer of nanoplastic in marine systems with mussels (Prof. Dr. Kevin Thomas, University of Queensland)

• Uptake and impacts of particulate plastic on Gammarus (Prof. Dr. Bart Koelmanns; University of Wageningen, the

Netherlands)

• Assessing nanoplastic interactions and transfer across intestinal tissue (Prof. Dr. Bethany Carney Almroth; University of

Gothenburg, Sweden)

• Cellular uptake and effects of nanoplastic (2 separate projects, Dr. Douglas Gilliland, JRC, Italy and Prof. Dr. Melissa

Maurer-Jones, University of Minnesota, USA)

(some) Research Network and collaborative efforts


in Complex Systems

26

nanoparticulate impurities (44, 45, 50, 51), allows the detection of nanoplastic (polystyrene beads of

20 – 500 nm) at trace concentrations and may, thus, be well suited to detect nanoscale plastic particle

in drinking water matrices.

Task 2:

A LIBD system has been developed at Eawag and a comparable system is available at CSEM. In a series of batch experiments the suitability of the LIBD technique for the detection of nanoplastics in drinking water matrices with varying compositions (e.g., different concentrations of Na

+, Ca

2+, Cl

-,

SO42-

) will be assessed. The mobile LIBD available at Eawag will be used to on-line and on-site investigate the removal efficiency (or breakthrough) of polystyrene (PS) beads of different sizes (50 – 100 nm) spiked to the feed waters of the pilot facilities at the WVZ. Expected detection limits of the LIBD system will be in the order of 5x10

9 #/L. Allowing again a reduction of three log units requires a

concentration of 5x1012

#/L in the feed water or 2.5 x 1017

# for a total volume of 50 m3. The stock

suspensions can be obtained at a concentration of 5x1015

#/mL (50 nm) requiring 50 mL of stock suspension for single or 100 mL for duplicate experiments. For the detection of the nanoplastic breakthrough, the LIBD system will be installed at the WVZ and operated in transient mode (time

resolution ~ 5 - 10s).

3.2. Pilot facilities

The following pilot facility is available at the WVZ and will be used to assess the removal efficiency of nanoplastics during drinking water treatment. The pilot facility can be operated at flow rates in the order of a few m

3h

-1 and the suggested runtime are thus a compromise between minimal runtime for

the collection of reliable data and the amount of required (nano) materials.

Figure 1: Schematic of the pilot facilities available at the WVZ.

3.3 Schedule and milestones

The sequence of the proposed project is indicated in Table 2 and the project milestones are listed in Table 3. During the first 6 months, the postdoc will evaluate the stability (aggregation) of the Pt-labeled nanoplastic during ozone treatment and assess whether the ozone treatment results in an increased leaching of the Pd into the water (batch experiments in the lab). In the second half of the first year, the

6

Removal of nanoplastic during drinking water treatment: pilot scale

system available from city of Zürich

Plastic Association with Sludge Flocs Increases

with Longer Contact Times

27Mitrano et al. Nature Nanotechnology 2019

Mix particulate

plastic and

matrix

T= 10 min

Settle 30 min

Settle 30 min

Settle 30 min

Plastic Association with Sludge Flocs Increases

with Longer Contact Times

28Mitrano et al. Nature Nanotechnology 2019

More plastic

attached to

sludge

Less plastic

attached to

sludge

Documents

Synthesis of metal doped nanoplastic particles and ... · In collaboration with Ahmed Tlili, Eawag Assess physiological effects on biofilm and snails ... (unpublished scientific data