Rutgers University Rutgers University - Friday, March 29, 2019 · 2019. 4. 17. · Rutgers University - Friday, March 29, 2019. NOAA James J. Howard Marine Sciences Laboratory. Infra-Red

Ashok Deshpande NOAA-NMFS-NEFSC

Keith Cooper, Beth Ravit, Brian Buckley Rutgers University

Rutgers University - Friday, March 29, 2019

NOAA James J. Howard Marine Sciences Laboratory

Infra-RedSpectroscopy

Raman Spectroscopy

MassSpectrometry

Polymer Analysis

Credit: Tsuge, Ohtani and Watanabe

pyrolysis-GC/Ms

• Microplastic sample is heated at high temperature in the pyrolyzer.

• Thermal degradation results in a unique and reproducible signature of fragment molecules that is characteristic to a given polymer.

Pyrogram

CDS 1500 GC-MS InterfaceAgilent 5973 GC-MSCDS 2000 Pyroprobe

Platinum Filament

Anatomy of Pyrolysis GC-MS

Quartz Tube

750ºC=

1382ºF

Pyrogram

Polystyrene+

PMMA

Credit: CDS Analytical

Gas ChromatographMass Spectrometer

Pyrolysis GC-MS

Interface

Pyroprobe

Pyrolysis GC-MS System at the NOAA Sandy Hook Laboratory

Pyroprobe Inlet

Interface Valve

Pyroprobe Placed

Inside of Interface

Platinum Filament

Temp Controller

Systematic and Sequential

Identification of Marker Peaks

That can be later used for

Polymer Characterization

Creation of Pyrolysis GC-MS Database

Involves

Going Above & BeyondJust Peak Comparisons

C-C bonds at different sites along the polymer chain break due to intense heat to yield a variety of short-chain molecules

Pyrolysis

Total Ion Chromatogram (Pyrogram) of High-Density Polyethylene (HDPE)

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

2000000

4000000

6000000

8000000

1e+07

1.2e+07

1.4e+07

1.6e+07

1.8e+07

2e+07

2.2e+07

2.4e+07

2.6e+07

2.8e+07

3e+07

3.2e+07

3.4e+07

3.6e+07

3.8e+07

4e+07

4.2e+07

Time-->

Abundance

TIC: 20170117_06.D

Heavier HydrocarbonsTime

Pyrogram of High-Density Polyethylene (HDPE)

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

2000000

4000000

6000000

8000000

1e+07

1.2e+07

1.4e+07

1.6e+07

1.8e+07

2e+07

2.2e+07

2.4e+07

2.6e+07

2.8e+07

3e+07

3.2e+07

3.4e+07

3.6e+07

3.8e+07

4e+07

4.2e+07

Time-->

Abundance

TIC: 20170117_06.D

“Zoom-In” View is Depicted in the Next Slide

Our goal is to identify all peaks, working with a section at a time.

5.605.806.006.206.406.606.807.007.207.407.607.808.008.208.408.60

5000000

1e+07

1.5e+07

2e+07

2.5e+07

3e+07

Time-->

Abundance

TIC: 20170117_06.D

High-Density Polyethylene (HDPE): “Zoom-In” Part of the Pyrogram

?

25 30 35 40 45 50 55 60 65 70 75 80 85 90 951001051101151200

50000

100000

150000

200000

250000

300000

350000

400000

450000

500000

550000

600000

650000

700000

m/z-->

Abundance

Scan 799 (5.751 min): 20170117_06.D67

5541

81

96

29

50 1099112462 74 103 117864536

High-Density Polyethylene (HDPE)

Mass Spectrum ofPeak at 5.751 min

Library Search: Find Best Match for Mass Spectrum in the NIST Library

1,8-Nonadiene

Mass Spectrum of Unknown Peak

Mass Spectrum in Library Database

Library Match

5.605.806.006.206.406.606.807.007.207.407.607.808.008.208.408.60

5000000

1e+07

1.5e+07

2e+07

2.5e+07

3e+07

Time-->

Abundance

TIC: 20170117_06.D


1,8-Nonadiene

Continue to identify other peaks in this section of the pyrogram..

5.605.806.006.206.406.606.807.007.207.407.607.808.008.208.408.60

5000000

1e+07

1.5e+07

2e+07

2.5e+07

3e+07

Time-->

Abundance

TIC: 20170117_06.D


1,8-

Non

adie

ne1-

Non

ene

Non

ane 1,

9-D

ecad

iene

1,10

-Und

ecad

iene

1,11

-Dec

adie

ne

1-Decene1-Undecene

1,-D

odec

ene

Dec

ane

Und

ecan

e

Dod

ecan

e

This pyrogram contains triplets of peaks that are comprised of double-bonded, single bonded, and saturated hydrocarbons.

With a little more patience and perseverance

characterize remaining peaks in the entire pyrogram of



2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

2000000

4000000

6000000

8000000

1e+07

1.2e+07

1.4e+07

1.6e+07

1.8e+07

2e+07

2.2e+07

2.4e+07

2.6e+07

2.8e+07

3e+07

3.2e+07

3.4e+07

3.6e+07

3.8e+07

4e+07

4.2e+07

Time-->

Abundance

TIC: 20170117_06.D

Prop

ene

1-Bu

tene

1-Pe

nten

e1-

Hex

ene

1-H

epte

ne

1-O

cten

e 1-N

onen

e1-

Dec

ene

1-U

ndec

ene

1-D

odec

ene

1-Tr

idec

ene

1-Te

trade

cene

1-Pe

ntad

ecen

e1-

Hex

adec

ene

1-H

epta

dece

ne1-

Oct

adec

ene

1-N

onad

ecen

e1-

Non

adec

ene

1-Ei

cose

ne1-

Hen

eico

sene

1-D

ocos

ene

1-Tr

icos

ene

1-Te

traco

sene

1-Pe

ntac

osen

e1-

Hex

acos

ene

1-H

epta

cose

ne1-

Oct

acos

ene

1-N

onac

osen

e1-

Tric

onte

ne1-

Hen

etric

onte

ne1-

Ditr

icon

tene

1-Tr

itric

onte

ne

HDPE Pyrogram Fully Characterized!!!

Likewise, pyrolysis GC-MS databases are created for other polymers.

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

5000000

1e+07

1.5e+07

2e+07

2.5e+07

3e+07

3.5e+07

4e+07

4.5e+07

5e+07

5.5e+07

6e+07

6.5e+07

7e+07

7.5e+07

8e+07

8.5e+07

9e+07

Time-->

Abundance

TIC: 20170111_04.D

Polyester

6.00 8.00 10.00 12.00 14.00 16.00 18.00

1e+07

2e+07

3e+07

4e+07

5e+07

6e+07

7e+07

8e+07

9e+07

1e+08

1.1e+08

1.2e+08

Time-->

Abundance

TIC: 20170117_04.D

Polystyrene

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

1000000

2000000

3000000

4000000

5000000

6000000

7000000

8000000

9000000

1e+07

1.1e+07

1.2e+07

1.3e+07

1.4e+07

1.5e+07

1.6e+07

1.7e+07

1.8e+07

1.9e+07

2e+07

2.1e+07

2.2e+07

2.3e+07

2.4e+07

Time-->

Abundance

TIC: 20170119_01.D

Polyurethane

2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.00

5000000

1e+07

1.5e+07

2e+07

2.5e+07

Time-->

Abundance

TIC: 20170118_05.D

PVC

2.003.004.005.006.007.008.009.0010.0011.0012.0013.0014.0015.00

1000000

2000000

3000000

4000000

5000000

6000000

7000000

8000000

9000000

1e+07

1.1e+07

1.2e+07

1.3e+07

1.4e+07

1.5e+07

1.6e+07

1.7e+07

1.8e+07

1.9e+07

2e+07

2.1e+07

2.2e+07

Time-->

Abundance

TIC: 20170118_06.D

Nylon 6,6

Examples of Pyrolysis GC-MS Pyrograms of Plastic Polymers

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

2000000

4000000

6000000

8000000

1e+07

1.2e+07

1.4e+07

1.6e+07

1.8e+07

2e+07

2.2e+07

2.4e+07

2.6e+07

2.8e+07

3e+07

3.2e+07

3.4e+07

3.6e+07

3.8e+07

4e+07

4.2e+07

Time-->

Abundance

TIC: 20170117_06.D

High Density Polyethylene(HDPE)

We have to do this work only once to create the library!!!

After creation of the library, the next step is to test the..

• Common Plastic Items

• Weathered Plastics

Common Plastic Items

4.00 5.00 6.00 7.00 8.00 9.00 10.00

1e+07

2e+07

3e+07

4e+07

5e+07

6e+07

7e+07

8e+07

9e+07

1e+08

1.1e+08

Time-->

Abundance

TIC: 20161219_02.D

12" Hard Plastic Ruler

Styrene Styrene Dimer

Styrene Trimer

Polystyrene

2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.0011.0012.00

5000000

1e+07

1.5e+07

2e+07

2.5e+07

3e+07

3.5e+07

4e+07

4.5e+07

5e+07

Time-->

Abundance

TIC: 20161205_01.D

Micropipette Tip (100 µl)

2,4-Dimethyl-1-heptene

(A Marker Compound of Polypropylene)

Polypropylene

Hair Comb

PolypropylenePolystyrene

2,4-Dimethyl-1-heptene

(A Marker Compound of Polypropylene)

Styrene

(A Marker Compound of Polystyrene)

Mixed polymer

Weed Wacker Trimmer Line

Ɛ-Caprolactam

Nylon-6(Polycaprolactam)

The final step in microplastics method development is

to test the real-world, weathered plastic fragments:

• Microplastics on Beach

• Microplastics in River/Estuary

• Microplastics in Ocean

Plastic Fragments from a Beach in Long Branch, New Jersey

Fish shaped beach plastic

Found on Long Branch, NJ Beach

PolyethyleneEvenly spaced triplets containing dienes,

monoenes, and saturated alkanes

Blue Fragment of Plastic

Found on Long Branch, NJ Beach

Polypropylene

2,4-Dimethyl-1-heptene(A marker of polypropylene)

Microplastics fromPassaic River, New Jersey

Dr. Keith Cooper and Dr. Beth Ravit (Rutgers University)

Dr. Brian Buckley (Rutgers University)

Rutgers Field Collection P9A

Polystyrene

Styrene

Rutgers Field Collection P3A

Polyethylene

Evenly spaced triplets containing dienes, monoenes,

and saturated alkanes

Dr. Frank HernandezUniversity of Southern Mississippi

Microplastics in Sargassum Mats

NOAA Restore CruiseGulf of Mexico

NOAA Restore Cruise PS-17-07 Sample 7

Gulf of Mexico Surface Water Dip Net

Polypropylene

2,4-Dimethyl-1-heptene(A marker of polypropylene)

NOAA Restore Cruise PS-17-07 Sample 3

Gulf of Mexico Surface Water Dip Net

Polyethylene

Evenly spaced triplets containing dienes, monoenes, and saturated alkanes

NOAA-Rutgers University Collaborative Study

Raritan Bay

RR1 - Sayreville - Ken Buchanan Riverfront Park

RR3 - Edison - Boat Basin & River Walk

RR4 - Highland Park – Donaldson Park

RR8 - Bridgewater - Old York Road

RR6 - Piscataway – Riverside Park

MCUA

Raritan River Watershed Sampling Sites(Freshwater and Tidally Influenced)

P8 - PVSC - Newark

P1 - Kearny

P7 - Riverfront Park - Newark

P6 - Elmwood Park - Above Dundee Dam

P10 - Lyndhurst

P5 - Livingston

P9 - Fairfield

Newark Bay

Passaic River Watershed Sampling Sites(Freshwater and Tidally Influenced)

New York Bay

• River Sampling: At each location, and in each river, a 330µ mesh manta trawl net was held in a stationary position at water surface for fifteen minutes.

• Bay Sampling: Bay samples were collected by pulling the manta trawl net with the attached flow meter with a boat.

• Collected sample was filtered to remove the materials larger than 330µ.

Microplastics Sampling

Two types of climate-related samples were collected:

• Dry Samples: These samples were collected under dry weather conditions -defined as a period without rain for at least 48 hours.

• Wet Samples: These samples were collected under wet weather conditions - defined as a period of 24 hours or less after a rain event of 2.2 cm.

Selection of Sites for the Pyrolysis GC-MS Analyses:

• Microplastics samples were first analyzed for the persistent organic pollutants (POPs) by Dr. Brian Buckley’s Laboratory by using headspace solid-phase micro-extraction coupled with gas chromatography/ion-trap mass spectrometry (HS-SPME/GC-ITMS).

• Pyrolysis GC-MS analyses were then performed on a total of 143 microplastics samples from those locations that showed the elevated levels of adsorbed POPs in the HS-SPME/GC-ITMS analyses.

0

1

2

3

4

5

6

7

8

Number of Microplastics Analyzed for Each Raritan River Location

RR6: Piscataway Riverside Park

DOWN

RR8: Bridgewater Old York Road

DOWN

RR4: Highland Park Donaldson Park

UP

No particular trend was observed in the mobilization of microplastics due to the wet weather.

0

10

20

30

40

50

60No. of Microplastics Analyzed for Each Passaic River Location

P5: Livingston

UP(n = 8)

P10: Lyndhurst

SIGNIFICANTLY UP

Number of microplastics at Lyndhurst appeared to be highly significantly mobilized due to wet weather.

(n = 55)

A few examples of microplastics pyrograms..

Rutgers Sample RR4 6/29Tiny greenish blue fragment/fiber

E:\Microplastics\Rutgers II\20180830_11.D

PolyethyleneEvenly spaced triplets containing dienes, monoenes, and saturated alkanes

Rutgers Sample RR3 8/25off-white nurdle


PolyethyleneEvenly spaced triplets containing dienes, monoenes, and saturated alkanes

Rutgers Sample June 10 Bay 1 Baykeeper Patrol BoatOrange brown plastic piece


2,4-Dimethyl-1-heptene(A marker compound of polypropylene)

Polypropylene

Rutgers Sample RR3 8/25semi-transparent nurdle


2,4-Dimethyl-1-hepteneA marker compound of polypropylene

Polypropylene

Rutgers Sample P5ASoft off-white foam fragments


2,4-Dimethyl-1-HepteneA marker compound of polypropylene

PolypropylenePolyethylene (minor)

The pyrogram also appears to contain evenly spaced triplets possibly containing dienes, monoenes, and saturated alkanes.

It was difficult to get good mass spectra of different peaks at the low concentrations. Therefore the pattern was used instead to guess the presence of polyethylene.

Styr

ene

Styr

ene

Dim

er

Styr

ene

Trim

er

Polystyrene

Rutgers Sample RR3 8/25small round off-white foam


Rutgers Sample P10 Stormpale yellow transparent film

E:\Microplastics\Rutgers II\20180830_106R.D

Benz

oic

acid

Viny

l ben

zoat

e

Div

inyl

tere

phth

alat

e

Acet

ophe

none

4-(V

inyl

oxyc

arbo

nyl)

benz

oic

acid

Phth

alic

anh

ydrid

e

Benz

ene

Acet

alde

hyde

Polyethylene terephthalate (PET)

Cyc

lope

ntan

one

Rutgers Sample P10AVery tiny red fragment


Acet

alde

hyde

2-H

ydro

xyet

hyl m

etha

cryl

ate

Isop

horo

ne d

iisoc

yana

te

Poly(2-hydroxyethyl methacrylate); PHEMANylon-6,6Isophorone diisocyanate Polyurethane

Rutgers Sample RR8 6/29black thin peel


Met

hyl m

etha

cryl

ate

n-Bu

tyl a

cryl

ate

tribu

tyl h

ex-5

-ene

-1,3

,5-tr

icar

boxy

late

(trim

er)

dibu

tyl 2

-met

hyle

nepe

ntan

edio

ate

(dim

er)

dibu

tyl g

luta

rate

1-Bu

tano

ln-

buta

nal

1-Bu

tene

Polybutyl acrylate; PBAPolymethyl methacrylate; PMMA

Furfu

ral

5-m

ethy

l fur

fura

lPh

enol

2-M

ethy

lcyc

lope

ntan

one

Xyle

ne

Cre

sol

Levo

gluc

osen

one

Ethy

lphe

nol

4-Vi

nylp

heno

l

2-M

etho

xy-4

-vin

ylph

enol

3-m

ethy

l-,2

-ben

zene

diol

Levo

gluc

osan

Rutgers Sample RR8 5/15/17 Bridgewaterblack peel


2-M

etho

xyph

enol

Cellulose(+Polycarbonate?)

Bisp

heno

l-A ?

Quantitative Analyses

Microplastics in Raritan River/ MCUA System (n=46)

Microplastics in Raritan River/ (n=41)

Polyethylene >>> Polypropylene >> Polystyrene*if multiple pieces of polystyrene foams were encountered, not all were counted or analyzed

Microplastics in Passaic River/ Newark Bay System (n=92)

Microplastics in Passaic River (n=85)

Polypropylene ~ Polyethylene >> Polystyrene*

*if multiple pieces of polystyrene foams were encountered, not all were counted or analyzed

Polymers in P10 Dry Microplastics Samples

Lyndhurst (n=8)

Minor Polymers: One each of Polyethylene; Polystyrene; Wood Fragment; Poly(2-hydroxyethyl methacrylate) (PHEMA) + Nylon-6,6 + Polyurethane of Isophoronediisocyanate; one unidentified polymer (not detected)

Polypropylene = 3

Polymers in P10 Storm Microplastics Samples

Lyndhurst (n=55)

Minor Polymers: One each of Polyethylene terephthalate; Polyaminobismaleimide; Cellulose + Cellulose Acetate

During the storm events, polypropylene, polyethylene, and styrene appear to be significantly mobilized from the land-based sources in and around Lyndhurst area.

Polyethylene was prominent polymer in both water bodies.

-- Sinkers and Floaters --

• Microplastics collected for this study were surface samples.• Therefore, the presence of lighter polymers like polyethylene,

propylene, and expanded polystyrene was not too surprising.

Floaters

Sinkers

Distribution of plastic marine debris collected in 6136 surface plankton net tows from 1986-2008 in the western North Atlantic Ocean and Caribbean Sea.

Kara Lavender Law, Skye Moret-Ferguson, Nikolai A. Maximenko, Giora Proskurowski, Emily E. Peacock, Jan Hafner, and Christopher M. Reddy. Plastic Accumulation in the North Atlantic Subtropical Gyre. Science, 2010; DOI: 10.1126/science.1192321

Question: Since these were surface water microplastics samples, it would be interesting and important to know how representative are these microplastics polymers of the respective river ecosystems?

Do they represent:

• Surface water only?

• Entire water column?

• Bottom water?

• Bottom sediments?

Future Research:

• Density-based microplastics polymer distribution, and abundance in the upper, middle and deeper sections of water column.

• Chronology of microplastics deposition in the sediment cores.

• Temporal and seasonal trends in polymer composition - this information could shed light on the diversity of microplastics sources.

Microplastics found in Passaic River at Lyndhurst, NJ after a storm event..

Documents

Rutgers University Rutgers University - Friday, March 29, 2019 · 2019. 4. 17. · Rutgers University - Friday, March 29, 2019. NOAA James J. Howard Marine Sciences Laboratory. Infra-Red