Hazardous chemicals in marine plastics andtheir threat to marine organisms

Shige TAKADA
Laboratory of Organic Geochemistry (LOG)
Tokyo University of Agriculture and Technology
Presented on1International Workshop “The Science of Microplastics in the World Ocean
Woods Hole Oceanographic Institution, Oct. 16, 2019

Major Conclusion

Plastic-mediated chemical exposure does occur
and its significance depends on locations,background pollution, chemicals, species ofbiota, especially trophic levels.

Topicsl

Hazardous chemicals in marine plastics
lll

Chemicals adsorbed from seawater
Additive chemicals

Transfer of the chemicals from ingested plastics tointernal tissue of biotallExperimental evidences
Mechanism

Significance of the plastics as exposure media :Field observations
l Effects of the plastic-mediated chemical exposurelTopicsl

Hazardous chemicals in marine plasticslllChemicals adsorbed from seawater
Additive chemicals

Transfer of the chemicals from ingested plastics tointernal tissue of biotallExperimental evidences
Mechanism

Significance of the plastics as exposure media :Field observations
l Effects of the plastic-mediated chemical exposurelPlastics carry two types of chemicals in marine environment
Additives

Sorption from seawater
OH

Cl Cl

HOCl

Cl

N

C9 H19Cl

Nonylphenol
Br(PCBs)Br

CCl2Cl

Br

Br

Br
Br

N
OC8H17

Benzotriazoles(e.g., UV-328)

Br

O
Br

C

Br

O
C(PBDEs)
Br

DDTs

Cl

Br
Br

Br

C

Br

C2H5O
O

O

Br

CH
CH

C5H11
C5H11

C2H5Br
Br

Br

Br

Br
Br

Polycyclic aromatichydrocarbons (PAHs)

Benzophenones(e.g., BP-12)

Br

Polybrominated diphenyl ethers

BrOH

NCl

Polychlorinated biphenylO

Br

Br

DBDPEHexabromocyclododecanes(HBCDs)BrHO

Phthalates(DEHP)
CH3C
CH3

Bisphenol AOHInternational Pellet Watch demonstrates sorption of POPs
to502 438
405
2970 281
microplasitics
942
328
FranceNetherlands
671
602357225
231
U.K.151 9 Greece
184
92
Belgium
Clm
Cln
307
43274
5112Albania
94
28 94
3046
26
101 62
139
SeattleTurkeyBoston3
China
Ohio3975 140
Azores Italy
Japan
35
San Francisco 20
28
NJ NY
53 Vietnam
Portugal
Los AngelesIsrael
9Bermuda
9Taiwan
17 1317
SanDiego
CanaryIs.
1
Costa
294
10369
HK69
Rica51Hawaii
6 Philippines
India
316Panama 7 24241
82588Thailand
223
12TT
12
Ghana Equatorial
Malaysia
97 Kenya14
Galapagos
7 Guinea
Indonesia Singapore
4241 9593
St. Helena’s 60
1.864
70
34 4
9 Mozambique Cocos
50
25
13Brazil
Easter Is.
0.01
0.26
South Africa
Uruguay
Australia
Chile
New
Argentina
5
http://www.pelletwatch.org/Zealand

PCBs concentrations in beached plastic pellets (ng/g)*sum of concentrations of CB#66, 101, 110, 149, 118, 105, 153, 138, 128, 187, 180, 170, 206

Slow desorption and fast transport may cause sporadic highconcentration of PCBs in plastic from open ocean
Cl Cl~ mmClClClCl

Diffusive transfer in plastic matrix
takes time
Plastic fragment/pellet with 3 mm diameterLong time (~ 1 year) to reach equilibrium
Non-equilibrium : slow sorption/desorption
Open ocean
Polluted waters
slowrapid

Sporadic high concentrations of PCBs found in pellets from remote areas :Microplastics carry contaminants to remote areas

Plastics carry two types of chemicals in marine environment
Additives
OHCl ClHOClClNC9 H19ClNonylphenol
Br(PCBs)BrCCl2Cl

Br

Br

Br
Br

N
OC8H17

Benzotriazoles(e.g., UV-328)

Br

O
Br

C

Br

OC(PBDEs)BrDDTs

Cl

Br
Br

BrCBr

C2H5O
O

O

Br

CH
CH

C5H11
C5H11

C2H5Br
Br

Br

Br

Br
Br

Polycyclic aromatichydrocarbons (PAHs)

Benzophenones(e.g., BP-12)

Br

Polybrominated diphenyl ethers

Br

OH

N

Cl

Polychlorinated biphenyl

O

Br

Br

DBDPE

Hexabromocyclododecanes(HBCDs)Br

HO

Phthalates(DEHP)
CH3C
CH3

Bisphenol AOHBuoyant microplastics from Japan coasts and pacific ocean

Yeo et al. submitted0TB CN.22 2014 July
TB St. P 2014 July
TB CN.22 2015 Sept
TB St.P 2015 Sept
TB IP 2015 Sept
TB Ent 2015 Oct
TB St.1 2015 Oct
TB St.2 2015 Oct
TB St. 1-2 2016 May
TB St. 2 2016 May
TB St. 1-1 2016 Aug
TB St. 2 2016 Aug
TB St. 1 2016 Nov
SB St. 1,4 2016 June
SB St. 2,3 2016 June
SB St. 5 2016 June
SB 2016 Dec
SB 2017 Jan
SB 2017 Feb
CH 2015 July
CH 2016 Aug
NP JMA
NP #7
NP #30Tsushima Strait
Hokkaido Coast
Ise Bay
Shikoku
Suruga Bay
Off Kagoshima
East China Sea
Off Saga
Off Sakata
Off ShakotanOkinotorishima MP3
Okinotorishima MP 6-8
Toyama Bay
Muttsu Bay

Concentration (ng/g-dry weight)

BDE209 was sporadically detected in suspended
microplastics
in seawater
3000
2500

Br 102000

Br 7-91500

1000

Br 1-6Moderate to high conc. –rural and off shore samples –higher BDE/ deca BDE

500

Sagami Bay
Tokyo BayUrban coast
North
Pacific

Rural coast and offshore

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

Detection frequency : ~ 2 %dissected(n=159)

Tanaka, K., van Franeker,
J.A., Deguchi, T., and Takada,H., 2019. Piece-by-piece
analysis of additives andmanufacturing byproducts inplastics ingested by seabirds:
Implication for risk ofexposure to seabirds.

Marine Pollution Bulletin145, 36-41.

(n=35)

PE: polyethylene
PP: polypropylene
PS: polystyrene
PEPD: polyethylene
propylene diene

Bolus

Table3. Ingestion frequency of plastic with additives.
Detection % inIngestion %fragments
Northern fulmar
Deca-BDE
0.6%
9%
HBCDD
1.9%
27%
UV-3280.6%
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%

Topics

Introduction of plastic pollution and microplasticsl Spread of plastics in marine environments:llll

Hazardous chemicals in marine plastics
lllSediment cores
Marine organisms : seabirds, fish, bivalves
Chemicals adsorbed from seawater
Additive chemicals

Transfer of the chemicals from plastics to internal
tissuell

Experimental evidences
Mechanism

Significance of the plastics as exposure media :Field observations
l Effects of the plastic-mediated chemical exposurelHydrophobic and large molecule additive such as BDE209 isdifficult to leach from plastic to water.

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.

,

Stomach oil and fish oil accelerated the leaching of BDE209
DecaBDE(X]

0'!6162Y>8E";6?$(Percent leached BDE209

5555!

DecaZ^J!

Fish oilBDE209in plastic
Stomach oil
Pepsin solution
Sea water
Distilled waterThis suggests that fatty components in digestive tract
facilitates leaching of hydrophobic additives.

2mm?
et al.,? 
2×3×3

Oily components in digestive fluid facilitate leaching ofhydrophobic 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
Polyethylene pellets with 5 additives
Additives:

Br

Brominated flame retardants

BrBr・ BDE209

Br

Br
BrO
Br

Br

Br

Br

Benzotriazole UV-stabilizers (BTs)・ UV-326
・ UV-327
・ UV-328

OHOH
ClN

N

Cl
NN

N

N

Additives+PE powder
mixedmelted,moldedby using extruder

OH
N

N
N

Benzophenone UV-stabilizers (BPs)
OOH

Grid: 5x5mm

・ BP-12
OC8H17

Concentration of each chemical was 0.4 % by weight in polymer.
17Tanaka, K. et al., 2019, Current Biology (under revision)

Field Feeding Experiment of additive-compounded plastic tochicks of streaked shearwater

Exposure group
PE pellets compoundedwith 5 additives

ChicksAdditives
BDE209
UV326, UV327, UV328
BP12(5 pieces/individual)+

Liver
AdiposePreen Gland oil
16 daysnatural dietControl group

Chicksnatural diet
Liver
AdiposePreen Gland oil

natural diet16 daysExposedControl

Concentration (µg/g-lipid)

0.6

0.4

0.2

0.0

0.4

0.3

0.2

0.1

Concentration (µg/g-lipid)

0.5

0.0
Exposed

0.00
0.8

UV-328Control

1.2

Exposed0.05

UV-326

Control

0.10
1.0Concentration (µg/g-lipid)

0.20

Exposed

0.15

Concentration (µg/g-lipid)

BDE209Control

ExposedControl

Concentration (µg/g-lipid)

Results_abdominal adipose (16 day)
UV-327

1.2

1.0

0.8

0.6

0.4

0.2

0.0

BP-12

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

0.00

19

Composition of BDE congeners in seabird adipose, plastics in thestomachs, and their prey.
Abdominal adipose

Prey (lantern-fish)

Plastics in stomach

Lower brominated congeners werederived from natural prey, whereas
higher brominated congeners werederived from ingested plastics.

Topics

Introduction of plastic pollution and microplasticsl Spread of plastics in marine environments:
llllHazardous chemicals in marine plastics
lllSediment cores
Marine organisms : seabirds, fish, bivalves
Chemicals adsorbed from seawater
Additive chemicals

Transfer of the chemicals from plastics to internalorgansllExperimental evidences
Mechanism

Significance of the plastics as exposure media :Field observations Higher trophic level organisms
lLower trophic level organismsl Effects of the plastic-mediated chemical exposurelExposure of contaminants both from plastics and prey
Plastic-derived
chemicals

chemicals from prey

Biomagnification
ClCl ClClClClClCl Cl

POPs in seawater Cl

Significant of ingested
plastics as exposure sourceof chemicals
depend on
target chemicals,
background pollution,
study area, andtarget biota

Summary 1. Plastic contribution to PCBs depends on locations andtrophic levels
Location

AnimalCompounds

SignificanceSeaturtle

Great
Shearwater
Short-tailed
Shearwater
Short-tailed
ShearwaterNorthern
Fulmars
olive ridley,loggerhead
turtles, blueturtle

pelagic fish

lantern fish

PCBs, DDTs

No

pelagic fish

lantern fish

PCBs (HCC))

No

pelagic fish

lantern fish

PCBs (LCC)

Yes

bivalves

clam

PCBs

Yes

Crustacea

coenobita

PCBs

Yes

Gough Island

SeabirdBering Sea

SeabirdBering Sea
CoastalNorwaySeabird

Pacific
South Atlantic
Ocean
North Pacific
Ocean
North Pacific
Ocean
Remoteisland, Japan
Remoteisland, Japan

Species

Seabirds

PCBs

Yes

PCBs (LCC)

Yes

PCBs (HCC)
PCBs, DDTs,PBDEs (LBC)

No
No

PCBs, DDTs,
PBDEs

No

{Ryan, 1988#68}{Yamashita,
2011 #453}{Yamashita,2011 #453}{Herzke, 2016
#654}

{Clukey, 2018
#719}
{Rochman,2014 #718}{Gassel, 2019
#722}
{Gassel, 2019
#722}
Mizukawa et al.,2019
Mizukawa et al.,2019

Summary 2. Plastic contribution to BDE209, phthalates, Benzotriazole
UV-stabilizers is significant in most cases.
Location
Bering Sea
South Atlantic
Ocean

CoastalAustralia

HawaiiMediterraneanRemote island,Japan
Coastal Norway

Pacific

AnimalSeabirds

Species
Short-tailed
Shearwater

Compounds Significance
BDE209pelagic fish

lantern fish
BDE209short-tailed
Shearwater/wed
Phthalates
ged-tailed
shearwater
Seabirds(DEHP)
Black footed
UV-stabilizer
albatross,
Laysan(UV-326, UValbatross
Seabirds328)
Cetorhinus
basking shark
MEHP
maximus
Crustacea
Seabirds

Seaturtle

coenobita
NorthernFulmars
olive ridley,loggerhead
turtles, blueturtle

Yes{Tanaka, 2015
#612}
{Rochman, 2014
#718}

Yes

{Hardesty, 2015#643}

Yes{Tanaka, 2019
#715}

Yes

PBDEs

Yes

BDE209Yes{Fossi, 2014 #610}
Mizukawa et al.,2019
{Herzke, 2016
#654}

No

{Clukey, 2018
#719}

BDE209Yesremote island in Okinawa
Control beachremote island in Okinawa
Plastic contaminated beachMicroplastics in digestive tract of Hermit Crab0 – 13 pieces/g-wet
Controlbeach

293 - 482 pieces/g-wet
Plastic
Plastic
contaminatedcontaminatedbeachPolystyrene
fragment

100μm
Hit ratio:94%

Polyethylene-propylene
fragment

50μm
Hit ratio:73%

50 µm
Images and FTIR spectrum of microplastics found in stomachof Hermit CrabPBDEs concentration (ng/g)

PBDEs (Additives : Brominated flame retardants)
in hepatopancreas of Hermit CrabControlbeach

Plastic
contaminatedbeach

Mizukawa et al.

BDE209 was transferred to internal metabolic system anddebrominatedBDE
209

fragmentationleachingtransfermeta-debromination

Mizukawa et al.

179

202

136

Topics

Introduction of plastic pollution and microplasticsl Spread of plastics in marine environments:
llllHazardous chemicals in marine plastics
lllSediment cores
Marine organisms : seabirds, fish, bivalves
Chemicals adsorbed from seawater
Additive chemicals

Transfer of the chemicals from plastics to internalorgansll

Experimental evidences
Mechanism

Significance of the plastics as exposure media :Field observations
l Effects of the plastic-mediated chemical exposurelConclusions
1. Both sorption- and additive-derived chemicals wereretained in microplastics (PCBs, BDE209; 0.3 mm – 5mm).
2. Sporadic occurrence of microplastics with highconcentrations of additives and sorbed chemicals wereobserved. Their exposure to remote ecosystem wassuggested.
3. Transfer of hydrophobic additives to internal tissue ofmarine organisms was confirmed and it is facilitated byoily components in digestive fluid.
4. Plastic-mediated chemical exposure does occur and its
significance depends on locations, background pollution,
chemicals, species of biota, especially trophic levels.

Microplastic pollution : Acceleration of exposure of additives to human

Human
Indirect exposure

HOClNNNDirect Exposure

OHC9H19leaching accelerated
by digestive fluid
bioaccumulation,
trophic transfer

fragmentation
CCl2ClCCl

ClnClnChemicals inseawater

MP + Chemicals

Additives are transferred tobiological tissue, while MP isexcreted.

Direction of future efforts
Methodology to detect insidious biological effects
on the field and by epidemiological survey
Endocrine disruption of variety of additives
Fate of additives
Leaching from µm-size plastics
transfer to lower trophic level organisms,
biomaginification
More field observations
Nano-size plastics
Measurement
biological effects
Yo-yo-effects of microplastics and legacy pollution

Acknowledgement