Polybrominated Diphenyl Ether

(PBDE)

Flame Retardants in San

Francisco Bay

Daniel R. Oros, Ph.D.

San Francisco Estuary Institute

PBDEs are HOT contaminants!

PBDEs are HOT contaminants!

•Persistent: long lived in the environment

PBDEs are HOT contaminants!

•Persistent: long lived in the environment

•Bioaccumulative: transport through food

webs

PBDEs are HOT contaminants!

•Persistent: long lived in the environment

•Bioaccumulative: transport through food

webs

•Dispersed: world-wide contamination in

humans, animals, our food sources and

environment

PBDEs are HOT contaminants!

•Persistent: long lived in the environment

•Bioaccumulative: transport through food

webs

•Dispersed: world-wide contamination in

humans, animals, our food sources and

environment

•Endocrine disruptors: target the thyroid

O

Br

Br

Br

Br O

Br

Br

Br

Br

Br

O

Br

Br

Br

Br

Br

O

BrBr

Br

Br

Br

Br

Br

PBDE Commercial Mixtures and Major Congeners

BDE-47 BDE-99

BDE-209

BDE-100

BDE-183

O

Br

Br

Br

Br

Br

Br

BDE-154

O

Br

Br

Br

Br

Br

Br

BDE-153

O

BrBr

Br

Br Br

Br Br

Br

BrBr

Penta

Octa Deca

PBDEs Banned in California

•Ban on Penta and Octa mixtures, but not Deca, will be in effect on June 1, 2006

•The ban might not be very effective at decreasing environmental PBDE concentrations

North America use of PBDEs: Deca (75%),

Penta (21%) and Octa (4%) of total mass

Deca degrades to lower molecular weight PBDE congeners

Distribution of PBDEs in SF Bay Water 2002

PBDEs range 3-513 pg/L

Source: RMP

PBDEs range 0.2-212 ng/g dry wt

Distribution of PBDEs in SF Bay Sediments 2002

Source: RMP

PBDEs range (dry wt)Mussels 13-47 ng/gOysters 9-64 ng/gClams 85-106 ng/g

Distributions of PBDEs in SF Bay Bivalves 2002

Source: RMP

Distributions of PBDEs in SF Bay Bivalves 2001-2003

0

30

60

90

120

Clams Oysters Mussels

Bivalve

Mea

n T

ota

l PB

DE

s (n

g/g

dry

wt)

2001

2002

2003

Source: RMP

0

500

1000

1500

2000

2500

Jacksmelt LeopardShark

WhiteCroaker

Surfperch StripedBass

Halibut

Mea

n To

tal P

BD

Es

(ng/

g lip

id)

1997

2002

Distributions of PBDEs in SF Bay Fish 1997 and 2002

Source: EWG, 2003

Distributions of PBDEs in SF Bay Tern Eggs. Forester’s tern eggs showed the highest ever reported PBDE levels in wildlife = 63 ppm

Source: She et al., 2004

0

2000

4000

6000

8000

10000

LeastTern

CaspianTern

Forster'sTern

Mea

n T

ota

l PB

DE

s (n

g/g

lip

id)

Least Tern

Caspian Tern

Forster's Tern

Current work in the Bay

PBDE Conceptual Model and Impairment Assessment funded by RMP and CEP

•Identify PBDE Sources

•Estimate PBDE Loading

•Assess Extent of Bay Impairment from

PBDEs

Major Sources of PBDEs to the Environment

• Wastewater effluents

• Sludge disposal

• Volatilization from commercial

products

• Burning of disposed commercial

products

Other Suspected Sources

• Atmospheric deposition (e.g., autofluff

piles)

• Tributary inflow (stormwater runoff)

Like PCBs, the PBDEs in Guadalupe River are strongly associated with suspended sediments

Source: RMP

0

5

10

15

20

25

30

35

40

45

0 60 120 180 240 300 360 420

Time (min)

To

tal

Nu

mb

er o

f C

on

gen

ers

Sunlight degrades BDE-209 to lower molecular weight congeners (Source: Bezares-

Cruz et al., 2004).

10 Br Atoms (BDE-209)

0

5

10

15

20

25

30

35

40

45

0 60 120 180 240 300 360 420

Time (min)

To

tal

Nu

mb

er o

f C

on

gen

ers

Sunlight degrades BDE-209 to lower molecular weight congeners (Source: Bezares-

Cruz et al., 2004).

9-10 Br Atoms10 Br Atoms (BDE-209)

0

5

10

15

20

25

30

35

40

45

0 60 120 180 240 300 360 420

Time (min)

To

tal

Nu

mb

er o

f C

on

gen

ers

Sunlight degrades BDE-209 to lower molecular weight congeners (Source: Bezares-

Cruz et al., 2004).

9-10 Br Atoms10 Br Atoms (BDE-209)

7-10 Br Atoms

0

5

10

15

20

25

30

35

40

45

0 60 120 180 240 300 360 420

Time (min)

To

tal

Nu

mb

er o

f C

on

gen

ers

Sunlight degrades BDE-209 to lower molecular weight congeners (Source: Bezares-

Cruz et al., 2004).

BDE-209 is not detected at 30 min7-9 Br Atoms

9-10 Br Atoms10 Br Atoms (BDE-209)

7-10 Br Atoms

0

5

10

15

20

25

30

35

40

45

0 60 120 180 240 300 360 420

Time (min)

To

tal

Nu

mb

er o

f C

on

gen

ers

Sunlight degrades BDE-209 to lower molecular weight congeners (Source: Bezares-

Cruz et al., 2004).

BDE-209 is not detected at 30 min

5-8 Br Atoms

7-9 Br Atoms

9-10 Br Atoms10 Br Atoms (BDE-209)

7-10 Br Atoms

0

5

10

15

20

25

30

35

40

45

0 60 120 180 240 300 360 420

Time (min)

To

tal

Nu

mb

er o

f C

on

gen

ers

Sunlight degrades BDE-209 to lower molecular weight congeners (Source: Bezares-

Cruz et al., 2004).

BDE-209 is not detected at 30 min

4-7 Br Atoms

5-8 Br Atoms

7-9 Br Atoms

9-10 Br Atoms10 Br Atoms (BDE-209)

7-10 Br Atoms

0

5

10

15

20

25

30

35

40

45

0 60 120 180 240 300 360 420

Time (min)

To

tal

Nu

mb

er o

f C

on

gen

ers

Sunlight degrades BDE-209 to lower molecular weight congeners (Source: Bezares-

Cruz et al., 2004).

BDE-209 is not detected at 30 min

3-7 Br Atoms4-7 Br Atoms

5-8 Br Atoms

7-9 Br Atoms

9-10 Br Atoms10 Br Atoms (BDE-209)

7-10 Br Atoms

Closing

•The Bay Area appears to be a “Hot Spot” for PBDEs

•The CA ban on Penta and Octa, but not Deca, might not result in an immediate and significant decrease in environmental PBDE levels

•Water and sediment quality criteria have not yet been developed for PBDEs, but they are coming.

Acknowledgements

•RMP

•AXYS Analytical Services Ltd

•East Bay Municipal Utility District

•CA Dept of Fish and Game

•SFEI