Pellet Watch :

Global Monitoring of Persistent Organic Pollutants (POPs) using Beached Plastic Resin Pellets

Hideshige TAKADA, Yukie MATA, Satoshi ENDO

Laboratory of Organic Geochemistry Tokyo University of Agriculture and Technology, JAPAN E-mail : shige@cc.tuat.ac.jp Rei YAMASHITA Mohamad Pauzi ZAKARIA
(Hokkaido University, JAPAN) (Universiti Putra Malaysia,, MALAYSIA)

Self-Introduction : Hideshige TAKADA, Ph.D

Laboratory of Organic Geochemistry (LOG), Tokyo University of Agriculture and Technology
H 3C H 2 H 2 H 2 H 2 H2 H 2 H 2 H 2 H2 H 2 C C C C C C C C C C CH 3 C C C C C C C C C C C H 2 H 2 H2 H 2 H 2 H 2 H2 H 2 H 2 H 2 H 2

n-Alkan es

SO3 Na

Linear Alkylbenzenesulfonates (L AS)

J

Linear Alkylbenzenes (L ABs) Tetrapropylene-based alkylbenzenes (TABs)

SO3SO3-

O OH C9H19 C9H19

n N=3 -18

OH

Hopanes

Alkylphenols

Alkylphenolpolyetho xylates (APE)

Br OH HO Br CH 3 C CH 3 Br OH Br OH H

Fluorescent Wh itening Agent

HO

CH 3 C CH 3

Polycyclic Aromatic Hydrocarb ons (PAHs)

Bisphenol A (BPA)
O C C O

Tetrabromo bisphenol A
H HO H

HO

H Copro stano l

O O

C4H 9

Estradiol
Cl Cl

S N

Benzyl n-bu tyl phthalate (BBP)

O C C O C8H 19 C8H 19 Cl

Benzo thiazoles

C Cl C
H

Cl

(Cl)n

(Cl)m

O O

Dioctyl phth alate (DOP)

p,p'-Dichlorodiphenyltrichloroethane (DDT)

Polychlorinated b iphen yls (PCBs)

Plastic Resin Pellets as a Transport Medium for Toxic Chemicals in the Marine Environment

Environmental Science & Technology 2001, vol.35, 318-324

Topics Introduction of marine plastic resin pellets. Types of contaminants detected in marine plastic pellets. Adsorption of contaminants to plastic pellets.

Relationship between contaminant concentrations in beached resin pellets and levels of marine pollution. Proposal of Pellet Watch : Monitoring of POPs using beached plastic resin pellets.

Plastic Resin Pellets

1 cm

Why Plastic Resin Pellets are found in the ocean?

Final Plastic Products
Resin Pellets Chemical Plant Urban runoff Resin Pellets Remelting Molding Factory

River

Ocean
Ingestion by seabird

Beach
Stranded

Contaminants found in marine plastic resin pellets

Additive derived chemicals
OH
HO CH3 C CH3 OH

C9 H19

Nonylphenol Sorption from ambient seawater

Cl Cl Cl Cl Cl Cl

Bisphenol A

CCl2 Cl C

Cl

Polychlorinated biphenyl (PCBs)

DDTs

Polycyclic aromatic hydrocarbons (PAHs)

Nonylphenol concentrations in marine resin pellets on Japanese beaches

Polypropylene (PP) Polyethylene (PE)
Kitakyushu Hiroshima Kobe Imakoura Shirako Kawasaki Kasai-1 Kasai-2 Arakawa TFU1999 TFU2000 n.d.
OH C9H 19 C9H 19 C 9H19 O O PO O C9H 19 O O P O C 9H19

C9H 19

Trisnonylphenylphosphite (TNP) Oxidation

n.d.

Hydrolysis

10

100

1000

10000 100000

+ C9H 19

H 3PO 4

Nonylphenol (ng/g-pellets)

Nonylphenol

Contaminants found in marine plastic resin pellets

Additive derived chemicals
OH
HO CH3 C CH3 OH

C9 H19

Nonylphenol Sorption from ambient seawater

Cl Cl Cl Cl Cl Cl

Bisphenol A

CCl2 Cl C

Cl

Polychlorinated biphenyl (PCBs)

DDTs

Polycyclic aromatic hydrocarbons (PAHs)

Adsorption of PCBs onto plastic resin pellets

PCB concentration (ng/g-pellets)

2
Cl

Cl Cl

Cl Cl Cl

20

PE PP-1 PP-2

0 0

5 10 15 Elapsed time (day)

Applicability of beached plastic resin pellets to monitor coastal pollution by organic micropollutants

Sorbed amounts of contaminants in pellets

Contamination in the sea

Monitoring Tool

Examination of regional difference in PCB concentrations in beached resin pellets. comparison with that in the other monitoring media

Sampling locations of beached resin pellets for monitoring of PCBs

130 E 140 E 45 N X

46 47

11 C

Osaka Bay D 13 12

Japan Sea
18 H 15 14 7,B E 6 8 4 3 5 P Q R S 29,N 30 31 34 M Sagami Bay 33 38 32,O 37,V Kasai Seaside Park Tokyo Bay 35,T 36,U 9 I F 16 17 G 19 45 W 44 43

10

Pacific Ocean

35 N

A 1 2

21 20 Ise Bay 24 25,K,L 22 23 J 26

28

27

39 40

42

41

Sorting and analysis of beached resin pellets for monitoring of PCBs

Sorting PE Yellowing
and/or

Fouled

To exclude sporadic high concentrations of PCBs

10

100

1000

10000

Multiple 10-pellet pools are analyzed for PCBs

Median concentrations

PCB concentration (ng/g-pellet)

Analytical Method
Plastic Resin Pellets
by near-infrared spectroscopy (PlaScan-SH) polyethylene : PE Soxhlet Extraction

Sorting

Dichloromethane

Silica gel column chromatography

5%H O deactivated 2 25% DCM in Hexane 40% DCM in Hexane Wax esters 65% DCM in Hexane 100% DCM Phthalates 30%Acetone in DCM

Hydrocarbons

Alkylphenols

Gas chromatography-mass spectrometry (GC-MS) Fully activated silica gel column chromatography
(Sigma, SIL-A-200 , 0.46 cm i.d. x 18cm) Hexane
6 ml 44 ml

Bisphenol A 17 -Estradiol Estrone

Acetylation

25% DCM in Hexane

8 ml

Alkanes Hopanes

PCBs, DDE & Alkylbenzenes (LABs & TABs)

PAHs DDT, DDD

Gas chromatography-Electron capture detector (GC-ECD)

PCBs concentrations (ng/g-pellet)

10000 1500 20000 1000 500 0

(ng/g-pellet)

Tanegashima Island Pacific Ocean Side of Shikoku

3 4 5

1 2

Seto Inland Sea

6 7 8 9

Osaka Bay and Kii Channel Japan Sea

14 15 16 17 18 19

10 11 12 13

Tokai Region

20 21 22 23 24 25 26 27

Tokyo Bay and its neighboring coasts

28 29 30 31 32 33 34 KS* 35 36 37 38

Izu Islands Tohoku Region and Hokkaido

39 40 41 42 44 45 46 47

PCBs concentration in yellowing and/or fouled PE resin pellets from 47 Japanese beaches.
Each pool is shown as a plot.

PCBs concentrations (ng/g-pellet)

1000

200

400

600

800

Tanegashima Island 1 2

Pacific Ocean Side 4 of Shikoku 5 Seto Inland Sea Osaka Bay and Kii Channel Japan Sea

Tokai Region

Tokyo Bay and its neighboring coasts Izu Islands Tohoku Region and Hokkaido

PCBs concentration in yellowing and/or fouled PE resin pellets from 47 Japanese beaches.

6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47

Median concentrations are plotted for PE pellets.

Mussel Watch?
Mussel Watch
Monitoring methodology of coastal pollution using bivalves as sentinel Buoy Wharf Wall organism

Coastal Water

Organic micropollutants
e.g. Hydrocarbons PCBs Pesticides

Uptake Accumulation

Heavy Metals

MUSSEL (e.g. mytilus edulis) (Mytilus galloprovincialis)

PCBs concentrations (ng/g-lipid)

PCBs concentrations (ng/g-pellet)

1000

200

400

600

800

1000

1500

2000

500

Tanegashima Island Pacific Ocean Side of Shikoku

Seto Inland Sea

C D E FGH I J KL MN O P Q RS T U V

Osaka Bay and Kii Channel Japan Sea

PE Pellet

Mussel

Tokai Region

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27

Tokyo Bay and its neighboring coasts

Izu Islands

PCB concentrations in yellowing and/or fouled PE resin pellets from 47 beaches and in mussels from 24 coasts in Japan.

W X
Tohoku Region and Hokkaido

28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47

Relationship between median concentrations of PCBs in yellowing and/or fouled PE resin pellets and PCBs concentrations in mussels.

PCBs in Mussel (ng/g-lipid)

10000

r2 = 0.37
1000

100

10

1 1 10 100 1000

PCBs in PE Pellets (ng/g)

Conclusion

Beached resin pellets can be used for monitoring of PCBs in seawater. At least 100 pieces per location are necessary for the monitoring. Sorting of yellowing and/or fouled PE pellets is recommended for the monitoring

Pellet Watch
Global Monitoring of Persistent Organic Pollutants (POPs) Using Beached Plastic Resin Pellets

Air Mail

More than 100 pieces (~ 200 pieces) per one location

Laboratory of Organic Geochemistry, Dr. Hideshige Takada, Tokyo University of Agriculture and Technology, Fuchu, Tokyo 183-8509, Japan

Laboratory of Organic Geochemistry Dr. Hideshige Takada, Tokyo University of Agriculture and Technology, Fuchu, Tokyo 183-8509, Japan

More than 100 pieces (~200 pieces) per one location

Sorting PE, yellowing and/or fouled Analysis for POPs (PCBs, organochlorine pesticides)
by GC-ECD, GC-MS more than 3 pools of 10 pellets to exclude sporadic high concentration

Mapping POPs pollution

Example of expected map of PCBs in beached plastic pellets

Sending the data via Internet to the collectors Releasing the results on web

Advantage of Pellet Watch

Extremely low cost for sampling and shipping

No special training is necessary for sampling World citizens can join

Wide area (globe) can be monitored using minimal cost

Thank you for your attention.

Call for pellets!