Hazardous chemicals in plastics in marine environments and their potential effects on

marine organisms

11

（Tokyo University of Agriculture and Technology）

Hideshige Takada, Kosuke Tanaka, Rei Yamashita

Yutaka Watanuki （Hokkaido University）

2

Marine organisms ingest plastics

Albatross

T/V Wakatake Maru (Hokkaido Pref.) By-catch in driftnet June-July 2003, 2005

Sampling area 40˚00’N−47˚30’N, 180˚00’ 55˚30’N−58˚30’N, 178˚00’ E−178˚00’ W

Short-tailed shearwater from Northern pacific

Resin pellets Fragments of plastic

Fiber

Styrofoam Plastic sheets 1 cm n=41

Plastic sheets

9%

Styrofoam 1%

Fiber 5%

Fragments of plastic 59%

Resin pellets 26%

Type and composition of plastics found in the stomachs of short-tailed shearwater.

Short-tailed shearwater Puffinus tenuirostris

Plastics found in digestive tracts of the seabirds

Yamashita et al. 2011

Plastics detected in digestive tract of short-tailed shearwater

0.1 g – 0.6 g per an individual

6

More than 180 species of animals are known to have ingested plastic debris, including birds, fish, turtles and marine mammals. Physical impacts of the ingested plastics have been reported for many species of organisms (Wright et al., 2013).

Marine organisms ingest plastics

Plastics in Seabird

Plastics carry two types of chemicals in marine environment

C9H19

OH

C

CH3

CH3

OHHO

Cl

Cl

Cl

ClCl

Cl

C

CCl2

Cl

Cl

Nonylphenol

Bisphenol A

Polychlorinated biphenyl (PCBs)

DDTs  

Polycyclic aromatic hydrocarbons (PAHs)

Polybrominated diphenyl ethers (PBDEs)

O

Br Br

Br

BrBrBr

BrBr

Br

Br

Hexabromocyclododecanes (HBCDs)

Additive-derived chemicals

BrBr

Br

Br Br

Br

Sorption from ambient seawater Sorption from ambient seawater

Plastics carry two types of chemicals in marine environment

C9H19

OH

C

CH3

CH3

OHHO

Cl

Cl

Cl

ClCl

Cl

C

CCl2

Cl

Cl

Nonylphenol

Bisphenol A

Polychlorinated biphenyl (PCBs)

DDTs  

Polycyclic aromatic hydrocarbons (PAHs)

Polybrominated diphenyl ethers (PBDEs)

O

Br Br

Br

BrBrBr

BrBr

Br

Br

Hexabromocyclododecanes (HBCDs)

Additive-derived chemicals

BrBr

Br

Br Br

Br

C9H19

OH

Nonylphenol : Endocrine disrupting chemicals

Additives to plastic Antioxidants Antistatic agents

l disorders in the reproductive system l vaginal clear cell adenocarcinoma l decreased ability to reproduce

250

200

150

100

50

0

Endocrine disrupting chemicals released from plastic caps of mineral water bottles

World Cap 2012

applied in various electric products and fabrics.

PBDEs : Flame retardants

Penta  BDE(Br4,  Br5)

e.g.,  BDE47

O

Br

Br

Br

Br O

BrBr Br

Br

Br

BrBr

Br

Br

Br

Octa  BDE(Br7,8)

DecaBDE(Br10)

3  technical  products  (mixtures  of  congeners)  

e.g.,  BDE209

O

Br Br

Br

Br Br

Br

Br

e.g.,  BDE183

Kanagawa, Japan

Tonkin Bay, Vietnam

Long Beach, USA

Northern Pacific Central Gyre

Atlan*c

Marbella, Costa Rica

Tokyo, Japan

Central Pacific

Urban beach Rural beach Open ocean

Sampling locations of user plastic fragments

BDE209 and BDE183 were sporadically detected in marine plastics even from open ocean

Distributions of PBDE congeners in marine plastic fragments

Hirai et al., 2011

Plastics carry two types of chemicals in marine environment

C9H19

OH

C

CH3

CH3

OHHO

Cl

Cl

Cl

ClCl

Cl

C

CCl2

Cl

Cl

Nonylphenol

Bisphenol A

Polychlorinated biphenyl (PCBs)

DDTs  

Polycyclic aromatic hydrocarbons (PAHs)

Polybrominated diphenyl ethers (PBDEs)

O

Br Br

Br

BrBrBr

BrBr

Br

Br

Hexabromocyclododecanes (HBCDs)

BrBr

Br

Br Br

Br

Sorption from ambient seawater Sorption from ambient seawater

Persistent organic pollutants (POPs)

PCBs

･Industrial products for a variety of uses including dielectric fluid, heat medium, and lubricants. ･ Endocrine disrupting chemicals

ClnCln

DDTs

･DDT and its metabolites such as DDE and DDD. ･DDT was used as insecticides ･Endocrine disrupting chemicals

CHCCl3

Cl

Cl CCCl2

Cl

Cl

CHCHCl2

Cl

Cl

HCH

･Insecticide

H H

H

HH

H

Cl

Cl

ClCl

Cl

Cl

DDT DDE DDD

ü Man-made chemicals ü Persistent (stable, resistant to degradation) ü Toxic to human and marine organisms ü Hydrophobic (lipophilic) ü Bioaccumulative

Regulated by Stockholm convention

DDTs PCBs

HCH Plastics

･DDT and its metabolites such as DDE and DDD. ･DDT was used as insecticides ･Endocrine disrupting chemicals

･Industrial products for a variety of uses including dielectric fluid, heat medium, and lubricants. ･ Endocrine disrupting chemicals

･Insecticide

Pellets accumulate POPs from seawater

ClnClnCH

CCl3

Cl

Cl CCCl2

Cl

Cl

CHCHCl2

Cl

Cl

DDT DDE DDD

H H

H

HH

H

Cl

Cl

ClCl

Cl

Cl

PAHs

adsorption from ambient seawater

Concentration factor is estimated to be ~ 105 to ~106. 16

Laboratory of Organic Geochemistry, Dr. Hideshige Takada, Tokyo University of Agriculture and Technology,

Fuchu, Tokyo 183-8509, Japan

Air Mail

More than 50 pieces (~ 100 pieces) per one location

International Pellet Watch Global Monitoring of Persistent Organic Pollutants (POPs)

Using Beached Plastic Resin Pellets

17

Plastic resin pellet from various areas in the world

Analysis for persistent organic pollutants (POPs)

l Feed the data back to the collaborators via e-mail l Releasing the results on web 19 http://www.pelletwatch.org/

Chemical Analysis

Chemical hazardousness of marine plastics

Status of Global pollution

169  

12  10  

20  

94  

8  217  

24  

9  16  

26  

 6  

Vietnam  Japan  

HK  India  

Thailand  Malaysia  Indonesia  

Australia  

Italy  

U.K.  

Portugal  

South  Africa  

Mozambique  

43  

416  

Boston  

Greece  

International Pellet Watch : monitoring of POPs Plastics carry hazardous chemicals in marine environments

141  Turkey  53  

453  

73  

10  

107  

Singapore  

7  

Costa    Rica  

7  

7  

Chile  

T  T  

294  

253  

94  

Argen*na  

88  

Ghana  

Hawaii  

85  

Taiwan  

2China  

51  

297  

16  7  Cocos  

387  

Brazil  

143  

Philippines  

45   9  

25  

2746  France  

9   0.74  

1.49  

Panama  

314  

7  

St.  Helena’s  43  

0.01  Uruguay  

131  

573  Ohio  

Israel  28  

209  

43  

5   Sweden  

94  

112  

Albania  

17  

33  38  

73  41  

605  

San  Francisco  

32  

SeaNle  

182  

10   San  Diego  

341  

Los  Angeles  

253  

23  

0.01  Henderson  

Island  

Concentration of PCBs* in beached plastic resin pellet (ng/g-pellet)

60

0.26

New  Zealand  

0.9 0.2 119  

70  

207  

Ohio  

New  Jersey  

30  265  

8   47  

73  63  

11  Kenya  

52  

97  

61  

Plastics carry two types of chemicals in marine environment

C9H19

OH

C

CH3

CH3

OHHO

Cl

Cl

Cl

ClCl

Cl

C

CCl2

Cl

Cl

Nonylphenol Bisphenol A

Polychlorinated biphenyl (PCBs)

DDTs  

Polycyclic aromatic hydrocarbons (PAHs)

Polybrominated diphenyl ethers

(PBDEs)

O

Br Br

Br

BrBrBr

BrBr

Br

Br

Sorption from ambient seawater

C8H17

OH

Octylphenol

Additive-derived chemicals

Transfer of chemicals from ingested plastics to biological tissue was of concern.

Transfer of chemicals from ingested plastics to biological tissue

O

Br Br

Br

BrBrBr

BrBr

Br

Br

O

Br Br

Br

BrBrBr

BrBr

Br

Br

?

?

T/V Wakatake Maru (Hokkaido Pref.) By-catch in driftnet June-July 2003, 2005

Sampling area 40˚00’N−47˚30’N, 180˚00’ 55˚30’N−58˚30’N, 178˚00’ E−178˚00’ W

Short-tailed shearwater from Northern pacific

Proventriculus

Gizzard

Resin pellets Fragments

of plastic Fiber

Styrofoam Plastic sheets

1 cm

Abdominal adipose of circus of short-tailed shearwater by-catch

l Amount of plastics found in stomach l PBDEs concentrations in abdominal adipose

abdominal adipose

26

Increased pollutants concentrations with increasing plastic ingestion

PCBs in seawater

Cl Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Exposure of contaminants both from plastics and prey

Plastic-derived PCBs

PCBs from prey

Biomagnification

Takada 2013 “Accumulation”

applied in various electric products and fabrics.

PBDEs : Flame retardants

Lower  brominated  

BDE47

O

Br

Br

Br

Br O

BrBr Br

Br

Br

BrBr

Br

Br

Br

BDE209

O

Br Br

Br

Br Br

Br

Br

BDE183

(Br7  -‐‑‒  10)(Br4,  Br5)

Higher  brominated  

Less biomagnified

Plastic-derived Higher brominated congeners could have more impact on exposure of the contaminants to oceanic seabird

Lower brominated congeners (Br1 – Br6)

BDE209

No detection in pelagic fish

O

BrBr Br

Br

Br

BrBr

Br

Br

Br

Higher brominated congeners (Br7 – Br10)

O

Br

Br

Br

Br O

Br Br

Br

Br Br

Br

Br

BDE183 BDE47

T/V Wakatake Maru (Hokkaido Pref.) By-catch in driftnet June-July 2003, 2005

Sampling area 40˚00’N−47˚30’N, 180˚00’ 55˚30’N−58˚30’N, 178˚00’ E−178˚00’ W

Short-tailed shearwater from Northern pacific

Proventriculus

Gizzard

Resin pellets Fragments

of plastic Fiber

Styrofoam Plastic sheets

1 cm

Abdominal adipose of circus of short-tailed shearwater by-catch

l Amount of plastics found in stomach l PBDEs concentrations in abdominal adipose

abdominal adipose

Blank BDE#47 : 0.0006 ng/g-lipid BDE#209 :0.03 ng/g-lipid

PBDEs were detected in abdominal adipose of �all the individuals.

Higher concentrations of PBDEs were detected sporadically in fatty tissue of the seabird

Composition of BDE congeners in seabird adipose, plastics in the stomachs, and their prey.

Abdominal adipose

Plastics in stomach

Prey (lantern-fish)

Higher brominated congeners were derived from ingested plastics, whereas lower brominated congeners were derived from natural prey

Transfer of chemicals from ingested plastics to biological tissue has been confirmed.

Transfer of chemicals from ingested plastics to biological tissue

O

Br Br

Br

BrBrBr

BrBr

Br

Br

O

Br Br

Br

BrBrBr

BrBr

Br

Br

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Distilled water Sea water 　　　 Pepsin solution 　20℃ Pepsin solution 　38℃ Fish oil from walleye pollack, Stomach oil collected from Streaked Shearwater 　　　　　　　　　　　

BDE209 was industrially compounded into polyethlene (PE)

Leaching experiment to test bioavailability of additives in plastic

Conclusion and Questions to be addressed

Transfer of the chemicals from ingested plastics to internal system of the biota was confirmed for a species of seabird.

Magnitude of the plastic-associated transfer of chemicals.

The other areas? The other species?

Biological response (adverse effects on the marine organisms)

Conclusions

Questions

The other animals?

169  

12  10  

20  

94  

8  217  

24  

9  16  

26  

 6  

Vietnam  Japan  

HK  India  

Thailand  Malaysia  Indonesia  

Australia  

Italy  

U.K.  

Portugal  

South  Africa  

Mozambique  

43  

416  

Boston  

Greece  

Call for pellets from PICES member countries!

141  Turkey  53  

453  

73  

10  

107  

Singapore  

7  

Costa    Rica  

7  

7  

Chile  

T  T  

294  

253  

94  

Argen*na  

88  

Ghana  

Hawaii  

85  

Taiwan  

2China  

51  

297  

16  7  Cocos  

387  

Brazil  

143  

Philippines  

45   9  

25  

2746  France  

9   0.74  

1.49  

Panama  

314  

7  

St.  Helena’s  43  

0.01  Uruguay  

131  

573  Ohio  

Israel  28  

209  

43  

5   Sweden  

94  

112  

Albania  

17  

33  38  

73  41  

605  

San  Francisco  

32  

SeaNle  

182  

10   San  Diego  

341  

Los  Angeles  

253  

23  

0.01  Henderson  

Island  

Concentration of PCBs* in beached plastic resin pellet (ng/g-pellet)

60

0.26

New  Zealand  

0.9 0.2 119  

70  

207  

Ohio  

New  Jersey  

30  265  

8   47  

73  63  

11  Kenya  

52  

97  

61