Hazardous chemicals in marine plastics and their threat to marine … · 2019. 12. 10. · 4. Plastic-mediated chemical exposure does occur and its significance depends on locations,

1

Shige TAKADA

Laboratory of Organic Geochemistry (LOG)

Tokyo University of Agriculture and Technology

Hazardous chemicals in marine plastics and

their threat to marine organisms

Hazardous chemicals in marine plastics Chemicals adsorbed from seawater

Additive chemicals

Transfer of the chemicals from ingested plastics to

internal tissue of biota Experimental evidences

Mechanism

Significance of the plastics as exposure media :

Field observations

Effects of the plastic-mediated chemical exposure

Topics

Plastic-mediated chemical exposure does occur

and its significance depends on locations,

background pollution, chemicals, species of

biota, especially trophic levels.

Major Conclusion


Additive chemicals

Transfer of the chemicals from ingested plastics to

internal tissue of biota Experimental evidences

Mechanism


Field observations


Topics

Nonylphenol

Bisphenol A

Polychlorinated biphenyl (PCBs)

DDTs

Polycyclic aromatic hydrocarbons (PAHs)

Polybrominated diphenyl ethers

(PBDEs)

Hexabromocyclododecanes

(HBCDs)

Phthalates

(DEHP)

DBDPE

NN

N

HO

Benzotriazoles

(e.g., UV-328)

O OH

OC8H17

Benzophenones

(e.g., BP-12)

Additives Sorption from seawater

Plastics carry two types of chemicals in marine environment

International Pellet Watch demonstrates sorption of POPs to

microplasitics 671

12 8

17

94

8 25

9 13

13

6

Vietnam

Japan

HK India

Thailand

Malaysia

Indonesia

Australia

Italy

U.K.

Portugal

South Africa

Mozambique

53

405

Boston

Greece

139 Turkey

46

942

75

9

101

Singapore

7

Costa Rica

6

4

Chile

T T

307 94

Argentina

93

Ghana

Hawaii

62

Taiwan

3 China

50

294

14

5

Cocos

369

Brazil

140

Philippines

41 9

25

France

10 1

2 Panama

7

St. Helena’s

42

0.01

Uruguay

502

Israel

28

2259

34

5

92

112 Albania

17

39 35

43

602

San Francisco

30

Seattle

184

9 San Diego

357

Los Angeles

231

20

64

0.26

New Zealand

70

223

Ohio

NJ

28 274

8 31

69 51

41

Kenya

42

97

60

Equatorial Guinea

2970

151

Netherlands 281

Belgium

5

Galapagos

12

Easter Is.

1.8

Canary Is.

PCBs concentrations in beached plastic pellets (ng/g)

Azores

26

328

438

NY Bermuda

http://www.pelletwatch.org/

*sum of concentrations of CB#66, 101, 110, 149, 118, 105, 153, 138, 128, 187, 180, 170, 206

Non-equilibrium : slow sorption/desorption

Polluted waters Open ocean

slow

rapid

Slow desorption and fast transport may cause sporadic high

concentration of PCBs in plastic from open ocean

Plastic fragment/pellet with 3 mm diameter

Long time (~ 1 year) to reach equilibrium

Diffusive transfer in plastic matrix

takes time

~ mm

Sporadic high concentrations of PCBs found in pellets from remote areas :

Microplastics carry contaminants to remote areas

Nonylphenol

Bisphenol A

Polychlorinated biphenyl (PCBs)

DDTs

Polycyclic aromatic hydrocarbons (PAHs)

Polybrominated diphenyl ethers

(PBDEs)

Hexabromocyclododecanes

(HBCDs)

Phthalates

(DEHP)

DBDPE

NN

N

HO

Benzotriazoles

(e.g., UV-328)

O OH

OC8H17

Benzophenones

(e.g., BP-12)

Additives

Plastics carry two types of chemicals in marine environment

Buoyant microplastics from Japan coasts and pacific ocean

Yeo et al. submitted

0

500

1000

1500

2000

2500

3000TB

CN

.22

20

14

Ju

lyTB

St.

P 2

01

4 J

uly

TB C

N.2

2 2

01

5 S

ept

TB S

t.P

20

15

Sep

tTB

IP 2

01

5 S

ept

TB E

nt

20

15

Oct

TB S

t.1

20

15

Oct

TB S

t.2

20

15

Oct

TB S

t. 1

-2 2

01

6 M

ayTB

St.

2 2

01

6 M

ayTB

St.

1-1

20

16

Au

gTB

St.

2 2

01

6 A

ug

TB S

t. 1

20

16

No

vSB

St.

1,4

20

16

Ju

ne

SB S

t. 2

,3 2

01

6 J

un

eSB

St.

5 2

01

6 J

un

eSB

20

16

Dec

SB 2

01

7 J

anSB

20

17

Feb

CH

20

15

Ju

lyC

H 2

01

6 A

ug

NP

JM

AN

P #

7N

P #

30

Tsu

shim

a St

rait

Ho

kkai

do

Co

ast

Ise

Bay

Shik

oku

Suru

ga B

ayO

ff K

ago

shim

aEa

st C

hin

a Se

aO

ff S

aga

Off

Sak

ata

Off

Sh

ako

tan

Oki

no

tori

shim

a M

P3

Oki

no

tori

shim

a M

P 6

-8To

yam

a B

ayM

utt

su B

ay

Co

nce

ntr

atio

n (

ng/

g-d

ry w

eig

ht)

Br 10

Br 7-9

Br 1-6

Tokyo Bay Sagami Bay

North Pacific

Moderate to high conc. – rural and off shore samples – higher BDE/ deca BDE

Urban coast Rural coast and offshore

BDE209 was sporadically detected in suspended

microplastics in seawater

Additives (e.g., UV-326, UV-327, UV-328, BP-12, BDE209) are sporadically detected in plastics in seabirds’ stomach

PE: polyethylene

PP: polypropylene

PS: polystyrene

PEPD: polyethylene

propylene diene

Table3. Ingestion frequency of plastic with additives.

Detection % in

fragments

Ingestion %

Northern fulmar

Deca-BDE 0.6% 9%

HBCDD 1.9% 27%

UV-328 0.6% 9%

UV-326 1.3% 18%

UV-327 1.9% 27%

BP-12 0.6% 9%

∑ STs 0.6% 9%

Albatross

UV-328 2.9% 17%

UV-327 2.9% 17%

∑ STs 8.6% 50%

(n=159)

(n=35)

Tanaka, K., van Franeker, J.A., Deguchi, T., and Takada,

H., 2019. Piece-by-piece analysis of additives and

manufacturing byproducts in

plastics ingested by seabirds:

Implication for risk of

exposure to seabirds.

Marine Pollution Bulletin 145, 36-41.

Detection frequency : ~ 2 %

dissected

Bolus

Introduction of plastic pollution and microplastics

Spread of plastics in marine environments: Sediment cores

Marine organisms : seabirds, fish, bivalves


Additive chemicals

Transfer of the chemicals from plastics to internal

tissue Experimental evidences

Mechanism


Field observations


Topics

Sun, B., Hu, Y., Cheng, H., and Tao, S., 2019. Releases of brominated flame retardants (BFRs)

from microplastics in aqueous medium: Kinetics and molecular-size dependence of diffusion. Water

Research 151, 215-225.

Hydrophobic and large molecule additive such as BDE209 is

difficult to leach from plastic to water.

Pe

rce

nt le

ach

ed

BD

E2

09

Fish oil

Stomach oil

Pepsin solution

Sea water

Distilled water

Stomach oil and fish oil accelerated the leaching of BDE209

This suggests that fatty components in digestive tract

facilitates leaching of hydrophobic additives.

!!DecaBDE 950ppm !

!!2mm Yamashita

et al.,2011

0.014g

2×3×3mm !

DecaBDE (0.015~0.020g !

!

2013 9

BDE209

in plastic

Oily components in digestive fluid facilitate leaching of

hydrophobic additives and their accumulation in adipose and liver

Tanaka, K., Yamashita, R., and Takada, H., Transfer of hazardous chemicals

from ingested plastics to higher-trophic level organisms, in Hazardous

chemicals associated with plastics in environment, H. Takada and H.K.

Karapanagioti, Editor. 2018, Springer Berlin Heidelberg: p. 267–280.

Plastics compounded with 5 additives

17

Polyethylene pellets with 5 additives

Additives:

・ BDE209

・ UV-326 ・ UV-327 ・ UV-328

・ BP-12 Concentration of each chemical was 0.4 % by weight in polymer.

Brominated flame retardants

Benzotriazole UV-stabilizers (BTs)

Benzophenone UV-stabilizers (BPs)

Grid: 5x5mm

Additives

+

PE powder

mixed

melted,

molded

by using extruder

Tanaka, K. et al., 2019, Current Biology (under revision)

natural diet

natural diet

PE pellets compounded

with 5 additives

Liver

Adipose

Preen Gland oil

BDE209

UV326, UV327, UV328

BP12

Field Feeding Experiment of additive-compounded plastic to

chicks of streaked shearwater

Exposure group

Control group

+

16 days

Liver

Adipose

Preen Gland oil

16 days

Additives

Chicks

Chicks

(5 pieces

/individual)

natural diet

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

Co

ntr

ol

Exp

ose

d

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Co

ntr

ol

Exp

ose

d

0.0

0.1

0.2

0.3

0.4

0.5

Co

ntr

ol

Exp

ose

d

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Co

ntr

ol

Exp

ose

d

0.00

0.05

0.10

0.15

0.20C

on

tro

l

Exp

ose

d

Results_abdominal adipose (16 day)

19

Co

nce

ntr

ation

(µ

g/g

-lip

id)

BDE209 UV-326 UV-328 UV-327

BP-12

Co

nce

ntr

ation

(µ

g/g

-lip

id)

Co

nce

ntr

ation

(µ

g/g

-lip

id)

Co

nce

ntr

ation

(µ

g/g

-lip

id)

Co

nce

ntr

ation

(µ

g/g

-lip

id)

Composition of BDE congeners in seabird adipose, plastics in the

stomachs, and their prey.

Abdominal adipose

Plastics in stomach

Prey (lantern-fish)

Lower brominated congeners were

derived from natural prey, whereas

higher brominated congeners were

derived from ingested plastics.





Additive chemicals


organs Experimental evidences

Mechanism


Field observations Higher trophic level organisms

Lower trophic level organisms


Topics

POPs in seawater

Exposure of contaminants both from plastics and prey

Plastic-derived

chemicals

chemicals from prey

Biomagnification

Significant of ingested

plastics as exposure source

of chemicals

depend on

target chemicals,

background pollution,

study area, and

target biota

Location Animal Species Compounds Significance

Gough Island Seabird

Great

Shearwater PCBs Yes

{Ryan, 1988

#68}

Bering Sea Seabird

Short-tailed

Shearwater PCBs (LCC) Yes

{Yamashita,

2011 #453}

Bering Sea Seabird

Short-tailed

Shearwater PCBs (HCC) No

{Yamashita,

2011 #453}

Coastal

Norway Seabirds

Northern

Fulmars

PCBs, DDTs,

PBDEs (LBC) No

{Herzke, 2016

#654}

Pacific Seaturtle

olive ridley,

loggerhead

turtles, blue

turtle

PCBs, DDTs,

PBDEs No

{Clukey, 2018

#719}

South Atlantic

Ocean pelagic fish lantern fish PCBs, DDTs No

{Rochman,

2014 #718}

North Pacific

Ocean pelagic fish lantern fish PCBs (HCC)) No

{Gassel, 2019

#722}

North Pacific

Ocean pelagic fish lantern fish PCBs (LCC) Yes

{Gassel, 2019

#722}

Remote

island, Japan bivalves clam PCBs Yes

Mizukawa et al.,

2019

Remote

island, Japan Crustacea coenobita PCBs Yes

Mizukawa et al.,

2019

Summary 1. Plastic contribution to PCBs depends on locations and

trophic levels

Summary 2. Plastic contribution to BDE209, phthalates, Benzotriazole

UV-stabilizers is significant in most cases.

Location Animal Species Compounds Significance

Bering Sea Seabirds

Short-tailed

Shearwater BDE209 Yes

{Tanaka, 2015

#612}

South Atlantic

Ocean pelagic fish lantern fish BDE209 Yes

{Rochman, 2014

#718}

Coastal

Australia Seabirds

short-tailed

Shearwater/wed

ged-tailed

shearwater

Phthalates

(DEHP) Yes

{Hardesty, 2015

#643}

Hawaii Seabirds

Black footed

albatross,

Laysan

albatross

UV-stabilizer

(UV-326, UV-

328) Yes

{Tanaka, 2019

#715}

Mediterranean basking shark

Cetorhinus

maximus MEHP Yes {Fossi, 2014 #610}

Remote island,

Japan Crustacea coenobita PBDEs Yes

Mizukawa et al.,

2019

Coastal Norway Seabirds

Northern

Fulmars BDE209 Yes

{Herzke, 2016

#654}

Pacific Seaturtle

olive ridley,

loggerhead

turtles, blue

turtle BDE209 No

{Clukey, 2018

#719}

remote island in Okinawa

Control beach

remote island in Okinawa

Plastic contaminated beach

Microplastics in digestive tract of Hermit Crab

Plastic

contaminated Plastic

contaminated

beach

Control

beach

293 - 482 pieces/g-wet 0 – 13 pieces/g-wet

Polystyrene fragment

100μm Hit ratio:94%

Polyethylene-propylene fragment

50μm Hit ratio:73%

50 µm

Images and FTIR spectrum of microplastics found in stomach

of Hermit Crab

BDE209

BDE206

BDE203

BDE202

BDE179

BDE184

BDE183

BDE153

6Br③(BDE146)

6Br②(BDE133/136)

PB

DE

s c

oncentr

atio

n (

ng/g

)

PBDEs (Additives : Brominated flame retardants)

in hepatopancreas of Hermit Crab

Plastic

contaminated

beach

Control

beach

Mizukawa et al.

BDE 209

179

202 meta-debromination

fragmentation

leaching

transfer

BDE209 was transferred to internal metabolic system and

debrominated

136 Mizukawa et al.





Additive chemicals


organs Experimental evidences

Mechanism


Field observations


Topics

Flesh-footed shearwater from Southern pacific

Conclusions

1. Both sorption- and additive-derived chemicals were

retained in microplastics (PCBs, BDE209; 0.3 mm –

5mm).

2. Sporadic occurrence of microplastics with high

concentrations of additives and sorbed chemicals were

observed. Their exposure to remote ecosystem was

suggested.

4. Plastic-mediated chemical exposure does occur and its

significance depends on locations, background pollution,

chemicals, species of biota, especially trophic levels.

3. Transfer of hydrophobic additives to internal tissue of

marine organisms was confirmed and it is facilitated by

oily components in digestive fluid.

Chemicals in

seawater MP + Chemicals

Additives are transferred to

biological tissue

Human

Direct Exposure

Indirect exposure

fragmentation,

leaching,

bioaccumulation,

trophic transfer

N

N

N

HO

Cl

Microplastic pollution : Acceleration of exposure of additives to human

More field observations

Methodology to detect insidious biological effects

on the field and by epidemiological survey

Endocrine disruption of variety of additives

Direction of future efforts

Fate of additives

Leaching from µm-size plastics

transfer to lower trophic level organisms,

biomaginification

Measurement

biological effects

Yo-yo-effects of microplastics and legacy pollution

Nano-size plastics

Acknowledgement

Documents

Hazardous chemicals in marine plastics and their threat to marine … · 2019. 12. 10. · 4. Plastic-mediated chemical exposure does occur and its significance depends on locations,