Innovative technologies for polymeridentification

Jennifer M. Lynch

1 nm 1 um 1 mm 1 m 1 kmNanoplastics MegaplasticsMeso MacroplasticsMicroplastics

Confirm that particles are plastic polymers

Determine the composition of different polymers in a mixed sample

Importance of polymer identification

PVC

Chemistry

PVC

Uses

PVC

% of U.S. Recycling

PVC

Stratification in ocean

PVC

Stratification in ocean

1 nm 1 um 1 mm 1 m 1 kmNanoplastics MegaplasticsMeso MacroplasticsMicroplastics

By hand

Identify polymers

Chemical/PhysicalChallenging / Unknown

Extract & Purify

Polymer Science (balance, FT-IR, DSC)

Microspectroscopy(µFTIR, µRaman)

Analytical chemistry (pyrolysis GC/MS)

TBD, Promising: AFM-IR, Microfluidic fast Raman, or

pyrolysis GC/MS?

By eyeMicroscopeScanning electron microscope

Visualize

0 10 20 30 40 50

Density separationNile red fluorescence

spectroradiometryXPS

HT-SECDSC

Pyrolysis GC/MSRaman microscopy

FT-IR mode unknownTransmission FT-IR

ATR FT-IR

% of studies

0 50 100 150 200

Density separationNile red fluorescence

spectroradiometryXPS

HT-SECDSC

Pyrolysis GC/MSRaman microscopy

FT-IR microscopyTransmission FT-IR

ATR FT-IR

Instrument cost ($1000)

??

included with ATRRelatively cheap

0 100 200 300 400 500

Density separationNile red fluorescence

spectroradiometryXPS

HT-SECDSC

Pyrolysis GC/MSRaman microscopy

FT-IR microscopyTransmission FT-IR

ATR FT-IR

Analysis time (min)

??

Fast

Open Specy• Free, online• Open source • Spectral analysis tool

• For the microplastics research community

• A growing library of FT-IR and Raman spectra

• Allows users to view, clean, identify, and share their spectra

Website: www.openspecy.org

Website: www.openspecy.org

If interested, email cmdr@hpu.edu

HPU ACC polymer kit PROPOSAL

55

60

65

70

75

80

85

90

95

100

5001000150020002500300035004000

% T

Wavenumber (cm-1)

ATR FT-IR spectrum

DSC melt curve

+

1 nm 1 um 1 mm 1 m 1 kmNanoplastics MegaplasticsMeso MacroplasticsMicroplastics

By hand

Identify polymers

ChemicalChallenging / Unknown

Extract & Purify

Polymer Science (balance, FT-IR, DSC)

Microspectroscopy(µFTIR, µRaman)

Analytical chemistry (pyrolysis GC/MS)

TBD, Promising: AFM-IR, Microfluidic fast Raman, or

pyrolysis GC/MS?

By eyeMicroscopeScanning electron microscope

Visualize

1 nm 1 um 1 mm 1 m 1 kmNanoplastics MegaplasticsMeso MacroplasticsMicroplastics

By hand

Identify polymers

Extract & Purify

Polymer Science (balance, FT-IR, DSC)

By eye

Visualize

1 mm to megaDon’t trust 1377 cm-1 band to differentiate LDPE from HDPE

Benefits of Differential Scanning Calorimetry

LLDPE: 124 oCLDPE: 106 oC HDPE: 135 oC

Differentiate polyethylene densities

Even on particles as small as 0.03 mg (~100 µm)

LDPE vs. HDPE differentiation

• 16 debris pieces had the 1377 cm-1 band in ATR FT-IR spectra = LDPE

• ATR FT-IR is not reliable in differentiating weathered PE

• Weathering affects ATR FT-IR spectra

0

20

40

60

80

100

Mild Moderate Severe%

corr

ect b

y AT

R FT

IR

Extent of Weathering

DSC Confirmation of ATR FT-IR's LDPE

N=4 N=7 N=5

Four-step workflow

1. ATR FT-IR

2. FT-IR total transmission of thin film

3. Differential Scanning Calorimetry

4. Optical or FT-IR microscopy of cross sections

12

4 3

example – Four-Step workflow

1. ATR FT-IR

2. FT-IR total transmission of thin film

3. Differential Scanning Calorimetry

4. Optical or FT-IR microscopy of cross sections

Inner layer is EVA; outer layer is PS

0.45 mils (EVA-PE) 0.16 mils (PE) 0.40 mils (EVOH) 0.28 mils (EVA-tie)

100x

1 mm to mega

Four-Step workflow revealed…

•63 % of HI debris items were made of multiple polymers

•73% of those were not revealed by ATR FT-IR alone

•Multiple methods are required to reveal multi-layer, multi-polymer items, & differentiate PEs

1 mm to mega

1 nm 1 um 1 mm 1 m 1 kmNanoplastics MegaplasticsMeso MacroplasticsMicroplastics

Identify polymers

Physical/Chemical

Extract & Purify

Microspectroscopy

Microscope

Visualize

AbioticBeach Sand

Collection

Extraction

Purification

Separation

Analysis

micro

Quadrat and shovel

Collection

Extraction

Purification

Separation

Analysis

Buoyancy Separation Device (BSD)

2 buckets of sand2 buckets of seawater

micro

www.seed.world

Collection

Extraction

Purification

Separation

Analysis

Buoyancy Separation Device (BSD)micro

Clean Sand

Plastic & Plant

Collection

Extraction

Purification

Separation

Analysis

Trash Time Machine (TTM) aka Debris Separation Vacuum Chamber

micro

Plastic & Plant Plastic

Plant

www.seed.world

Collection

Extraction

Purification

Separation

Analysis

Sieves

>4 mm

> 4 mm 2 - 4 mm

1 -2 mm 0.5 – 1 mm

0.25 – 0.45 mm 0.125 – 0.25mm

0.063 – 0.125 mm <63 µm

Analysis- Tiny (63 µm)Collection

Extraction

Purification

Separation

Analysis

micro

Analysis- Tiny (63 µm)Collection

Extraction

Purification

Separation

Analysis

Plastic

micro

Collection

Extraction

Purification

Separation

Analysis

Analysis- Tiny (63 µm)

PPPENylonnatural polyamides

p ycelluloserubberCarbonatesOther

Plastic

Plant

Sand

micro

1 nm 1 um 1 mm 1 m 1 kmNanoplastics MegaplasticsMeso MacroplasticsMicroplastics

Identify polymers

Microdissection/Chemical

Extract & Purify

Microspectroscopy(µFTIR, µRaman)

Microscope

Visualize

BioticLarval fish

Photos: Jon Whitney, Frank Baensch, Cedric Guigand Gove Whitney et al. 2019 PNAS 116:24143-24149

micro

Polyester

Raman

FT-IR

Gove Whitney et al. 2019 PNAS 116:24143-24149

micro

Jenna Karr

Chemical storage and digestion methods: Are they compatible with polymers?

Jenna Karr

micro

Experimental Design: After Plastic + FilterIn tin tray

Vacuum Pump

Sample Set

Before & AfterMassCountSizeFT-IRPhoto

Experimental Design

Storage95% EtOH1 week1 month

DigestionHNO3KOHFenton’sBleachSonication

micro

microCompatibility Chart

1 nm 1 um 1 mm 1 m 1 kmNanoplastics MegaplasticsMeso MacroplasticsMicroplastics

Identify polymers

Challenging / Unknown

Extract & Purify

TBD, Promising: AFM-IR, Microfluidic fast Raman, or

pyrolysis GC/MS?

Scanning electron microscope

Visualize

NIST Nanoplastics PROPOSAL1. Produce nanoplastic materials of different polymers

• NanoFAB• SPHERE• Possibly with fluorescent or mass-labeled tags

2. Test methods to detect, characterize, or quantify nanoplastics• BCARS• Pyrolysis-GC/MS

3. Test methods to separate, purify, or concentrate nanoplastics• Drinking water• Beach sand

4. Perform in vitro toxicology studies

nano

1. Produce nanoplastic materials of different polymers• NanoFAB• SPHERE• Possibly with fluorescent or mass-labeled tags

2. Test methods to detect, characterize, or quantify nanoplastics• Vector-scan coherent-Raman confocal microspectroscopy• Pyrolysis-GC/MS

3. Test methods to separate, purify, or concentrate nanoplastics• Drinking water• Beach sand

4. Perform in vitro toxicology studies

NIST Nanoplastics PROPOSALnano

1. Produce nanoplastic materials of different polymers• NanoFAB• SPHERE• Possibly with fluorescent or mass-labeled tags

2. Test methods to detect, characterize, or quantify nanoplastics• BCARS• Pyrolysis-GC/MS

3. Test methods to separate, purify, or concentrate nanoplastics• Drinking water• Beach sand

4. Perform in vitro toxicology studies

NIST Nanoplastics PROPOSALnano

1. Produce nanoplastic materials of different polymers• NanoFAB• SPHERE• Possibly with fluorescent or mass-labeled tags

2. Test methods to detect, characterize, or quantify nanoplastics• BCARS• Pyrolysis-GC/MS

3. Test methods to separate, purify, or concentrate nanoplastics• Drinking water• Beach sand

4. Perform in vitro toxicology studies

NIST Nanoplastics PROPOSALnano

Thank you!

• John Kucklick, Kate Beers, Sara Orski, Katy Shaw, Sam Stavis, Li Pinn Sung, A. Pintar, B. Toman, Charlie Camp, Elijah Peterson

• Melissa Jung, Kayla Brignac, Jenna Karr, Brenda Jensen, David Hyrenbach, Keith Korsmeyer

• Rachel Sandquist, Jon Whitney, Jamie Gove, Jana Phipps

• Wanda Weatherford, David Springer, Taanya Ramirez, Ron Abbott, Rick Wagner

• Bridget O’Donnell

• Suja Sukumaran, Matt Cerutti, Brian Bertsch

• Ray Aivazian, Jim Potemra, Anupam Misra, Lloyd Hihara, Jan Kealoha

• Dipak Mainali, Darren Robey

• Brett Howard

• Win Cowger, Andrew Gray, H. Hapich, Chelsea Rochman, Sebastian Primpke, O. Herodotou

Follow us

Website: www.hpu.edu/cncs/cmdr

CENTER FOR MARINE DEBRIS RESEARCH

@MarineDebrisResearch

@debrisresearch

@company/center-for-marine-debris-research