Bioaccumulation of PBDEs, their replacement products (TBB ... · -HBCD -HBCD -HBCD Br Br Br Br Br...

Bioaccumulation of PBDEs,

their replacement products

(TBB, TBPH, BTBPE) and

HBCD in freshwater mollusks

from the Yadkin River

(North Carolina, USA)

Mark J. La Guardia* and Robert C. Hale

Virginia Institute of Marine Science

College of William & Mary

Gloucester Point, Virginia

*markl@vims.edu

PBDEs, environment and human health

• Polybrominated diphenyl ethers (PBDEs)

• additive brominated flame-retardants (BFRs)

• formulations: Penta-, Octa-, Deca-BDEs

• uses: polyurethane foam, electronics (e.g. casings, wires) and textiles

• ubiquitous, persistent and bioaccumulative

• endocrine disrupters

• Penta- & Octa-BDEs

• 2004, production ended US, ban by EU

• 2009, listed POP Stockholm Convention

• Deca-BDE

• phased-out in Europe, 2008

• to be phased-out in US, 2013

BrBr

O

BrBr

O

Br

Br Br

Br

Br

Br

Br

Br Br

Br

Penta- and Octa-BDE replacement products

O

Br

Br

Br

O Br

Br

Br

BTBPE• TBB, TBPH and BTBPE

• additive brominated flame-retardants (BFRs)

• TBB, TBPH: detected in sewage sludge1, household dust2 and marine mammals3 (DNA damage exposed laboratory minnows4)

• BTBPE: detected in sewage sludge1, dust2, air5, sediment5, 6, aquatic species6 and bird eggs7

O

Br

Br

Br

Br

O

O

CH3

CH3

OCH3

CH3

Br

Br

Br

Br

O

O

CH3

CH3

TBB

TBPH

1La Guardia et al., ES&T 2010 2Stapleton et al., ES&T 2009 3Lam et al., ES&T 2009 4Bearr et al., Environ.. Tox. Chem 2010 5Hoh et al., ES&T 2005 6Wu et al., ES&T 2010 7Gauthier et al., ES&T 2009

• Penta- replacement

• Firemaster 550 and BZ-54 (Chemtura Corp. CT. USA)

• TBB (2-ethylhexyl 2,3,4,5-tetrabromobenozate)

• TBPH (di (2-ethylhexyl)-2,3,4,5-tetrabromophthalate)

• Octa- replacement

• FF-680 (Chemtura Corp. CT. USA)

• BTBPE (1,2-bis (2,4,6-tribromophenoxy) ethane)

• additive brominated flame-retardant (BFR)

• polystyrene foam, electronics, textiles

• 2001: 16,700 MT global demand

• Technical product: α-, β-HBCD (~20%), γ-HBCD (~80%)

• environmental exposure

• ubiquitous contaminant

• detected in sewage sludge1, house dust2, marine mammals3 and birds4,5

• human: breast milk6 and blood7

• considered an endocrine disruptor

• mimic thyroid hormone

• developmental neurotoxin8

• usage/review

• EU, phased-out by 2015

• US, EPA action plan 2010

• finalized by the end of 2011

-HBCD

-HBCD

-HBCD

Br

Br

Br

BrBr

Br

Br

Br

Br

BrBr

Br

Br

Br

Br

BrBr

Br

Hexabromocyclododecane (HBCD)

1La Guardia et al., ES&T 2010 2Stapleton et al., ES&T 2009 3Lam et al., ES&T 2009 4He et al., ES&T 20105Fernie et al., ES&T 2010 6Shi et al., ES&T 2009 7Meijer et al., ES&T 2008 8van der Ven et al., Tox Letters 2009

Yadkin River – outfall - samples

• Yadkin-Pee Dee River

• 690 km/430 miles, Blue Ridge Mountains North Carolina, South Carolina to the Atlantic Ocean

• Elkin, NC (textile outfall)

• 4MGD, wastewater treatment facility serves textile mills

• US EPA’s Toxics Release Inventory (TRI) 2001-2004 5350 kg/ 11,800 lbs deca-BDE released to surface water

• Sample Sites (collected 2009)

• sediments and mollusks

• 4-sites, Elkin (outfall) to Pilot Mountain State Park, NC

• 45 km/28 river miles

North Carolina

South Carolina

Atlantic Ocean

Boone, NC

Gastropod: Elimia proxima

Native range: North America (Virginia to Georgia)

Life span: several years

Feeding: grazer, algae (attached) and detritus

Reproduction: egg layers, mate yearly

Movement: <20m yr-1

Predators: fish, crayfish, birds…

Bivalve: Corbicula fluminea (Asian clam)

Native range: Asia and Africa

Nonindigenous specie: North and South America and Europe

Life span: 1-4 years

Feeding: filter-feeder, phytoplankton

Reproduction: hermaphrodite, several yearly broods

Movement: relatively sessile

Predators: fish, birds, raccoons…

Mollusk samples - bivalves and gastropods

Size Exclusion ChromatographyEnvirosep-ABC, 350 x 21.1 mm

(Phenomenex)

Enhanced Solvent ExtractionASE 200 (Dionex)

Solid Phase ExtractionGlass column, 2 gm silica

Freeze-dry

exchange to hexane

Fraction #13.5mL (hexane)

reduce volumeGC/ECNI-SIM MS

PBDEs, TBB, TBPH, BTBPE

Samples

(sediment and mollusks)

Fraction #26.5mL (hexane/DCM, 60:40)

Fraction #38mL (DCM)

Fraction #45mL (DCM/Ace, 50:50)

BFR extraction and analysis

Solvent exchange

UPLC/ESI-NI MS/MS (-, -, -HBCD)

0

500

1,000

1,500

2,000

2,500

3,000

3,500

4,000

4,500

Outfall 17Km (11miles) 25Km (16miles) 45Km (28miles)

Penta- & Octa- BDEs

Deca-BDEs

TBB, TBPH, BTBPE

α-, β-, γ-HBCD

BFRs – river sediments

River flow

Conc.

ng/g

(ppb)

dry

wt.

BFRs – sediment and mollusks (outfall)

(TOC or lipid normalized)

Penta- & Octa-BDEs

0

2,000

4,000

6,000

8,000

10,000

12,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

BDE-47

BDE-100

BDE-99

BDE-85

BDE-154

BDE-153

BDE-183

Sediment Corbicula (clam) Elimia (snail)

Deca-BDEs

0

50,000

100,000

150,000

200,000

250,000

300,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

BDE-209

BDE-206

BDE-208

BDE-207

Sediment Corbicula (clam) Elimia (snail)

TBB, TBPH & BTBPE

0

2,500

5,000

7,500

10,000

12,500

15,000

17,500

20,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

TBB

TBPH

BTBPE

Sediment Corbicula (clam) Elimia (snail)

HBCD

0

50,000

100,000

150,000

200,000

250,000

300,000

350,000

Co

nc. n

g/g

(p

pb

), %

TO

C o

r %

lip

id

γ-HBCD

β-HBCD

α-HBCD

Sediment Corbicula (clam) Elimia (snail)

Penta- & Octa-BDEs

0%

20%

40%

60%

80%

100%

% C

on

trib

uti

on

BDE-183

BDE-153

BDE-154

BDE-85

BDE-99

BDE-100

BDE-47

Sediment Corbicula (clam) Elimia (snail)

BFRs – sediment and mollusks (outfall)

(TOC or lipid normalized)

Penta- & Octa-BDEs

0

2,000

4,000

6,000

8,000

10,000

12,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

BDE-47

BDE-100

BDE-99

BDE-85

BDE-154

BDE-153

BDE-183

Sediment Corbicula (clam) Elimia (snail)

Deca-BDEs

0

50,000

100,000

150,000

200,000

250,000

300,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

BDE-209

BDE-206

BDE-208

BDE-207

Sediment Corbicula (clam) Elimia (snail)

TBB, TBPH & BTBPE

0

2,500

5,000

7,500

10,000

12,500

15,000

17,500

20,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

TBB

TBPH

BTBPE

Sediment Corbicula (clam) Elimia (snail)

HBCD

0

50,000

100,000

150,000

200,000

250,000

300,000

350,000

Co

nc. n

g/g

(p

pb

), %

TO

C o

r %

lip

id

γ-HBCD

β-HBCD

α-HBCD

Sediment Corbicula (clam) Elimia (snail)

Deca-BDEs

0%

20%

40%

60%

80%

100%

% C

on

trib

uti

on

BDE-207

BDE-208

BDE-206

BDE-209

Sediment Corbicula (clam) Elimia (snail)

BFRs – sediment and mollusks (outfall)

(TOC or lipid normalized)

Penta- & Octa-BDEs

0

2,000

4,000

6,000

8,000

10,000

12,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

BDE-47

BDE-100

BDE-99

BDE-85

BDE-154

BDE-153

BDE-183

Sediment Corbicula (clam) Elimia (snail)

Deca-BDEs

0

50,000

100,000

150,000

200,000

250,000

300,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

BDE-209

BDE-206

BDE-208

BDE-207

Sediment Corbicula (clam) Elimia (snail)

TBB, TBPH & BTBPE

0

2,500

5,000

7,500

10,000

12,500

15,000

17,500

20,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

TBB

TBPH

BTBPE

Sediment Corbicula (clam) Elimia (snail)

HBCD

0

50,000

100,000

150,000

200,000

250,000

300,000

350,000

Co

nc. n

g/g

(p

pb

), %

TO

C o

r %

lip

id

γ-HBCD

β-HBCD

α-HBCD

Sediment Corbicula (clam) Elimia (snail)

TBB, TBPH & BTBPE

0%

20%

40%

60%

80%

100%

% C

on

trib

uti

on

BTBPE

TBPH

TBB

Sediment Corbicula (clam) Elimia (snail)

BFRs – sediment and mollusks (outfall)

(TOC or lipid normalized)

Penta- & Octa-BDEs

0

2,000

4,000

6,000

8,000

10,000

12,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

BDE-47

BDE-100

BDE-99

BDE-85

BDE-154

BDE-153

BDE-183

Sediment Corbicula (clam) Elimia (snail)

Deca-BDEs

0

50,000

100,000

150,000

200,000

250,000

300,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

BDE-209

BDE-206

BDE-208

BDE-207

Sediment Corbicula (clam) Elimia (snail)

TBB, TBPH & BTBPE

0

2,500

5,000

7,500

10,000

12,500

15,000

17,500

20,000

Co

nc.

ng

/g (

pp

b),

%T

OC

or

% l

ipid

TBB

TBPH

BTBPE

Sediment Corbicula (clam) Elimia (snail)

HBCD

0

50,000

100,000

150,000

200,000

250,000

300,000

350,000

Co

nc. n

g/g

(p

pb

), %

TO

C o

r %

lip

id

γ-HBCD

β-HBCD

α-HBCD

Sediment Corbicula (clam) Elimia (snail)

HBCD

0%

20%

40%

60%

80%

100%

% C

on

trib

uti

on

α-HBCD

β-HBCD

γ-HBCD

Sediment Corbicula (clam) Elimia (snail)

0.0

0.5

1.0

1.5

2.0

2 4 6 8 10 12

Biota Sediment Accumulation Factors (BSAFs)

(Cs/foc)

(Ct/fl)BSAF =

log Kow

(Bioaccumulation at BSAF >1, BSAF = lipid normalized tissue conc./organic carbon normalized sediment conc.)

0

1

2

3

4

5

6

7

5 6 7 8 9 10 11 12

log Kow

BS

AF

Corbicula (clam)

Elimia (snail)

BFRs BSAFs – Corbicula and Elimia

(Cs/foc)

(Ct/fl)BSAF =

BDE-154

octa-, nona-BDEs

BDE-47

α-, β-HBCD

γ-HBCD

BDE-100

BDE-209, TBB

BTBPE TBPH

BDE-99

BDE-153, -154

-HBCD

-HBCD

-HBCD

Br

Br

Br

BrBr

Br

Br

Br

Br

BrBr

Br

Br

Br

Br

BrBr

Br

0

0.5

1

1.5

2

2.5

3

3.5

BS

AF

α-HBCD, log Kow 5.07

β-HBCD, log Kow 5.12

γ-HBCD, log Kow 5.47

Bioaccumulation or bioisomerization*

(*Law et al., Environ. Tox. Chem. 2006)

Corbicula (clam) Elimia (snail)

• PBDEs, TBB, TBPH, BTBPE and HBCD

• enter the aquatic environment (via treated effluent)

• persistent, all detected 45Km (28 miles) downstream from outfall

• bioavailable, detected in Corbicula and Elimia

• BSAFs: TBB, TBPH and BTBPE (Penta- & Octa-replacement products)

• < Penta- & Octa-BDEs

• BDE-209 TBB, TBPH, BTBPE

• HBCD

• α-, β-HBCD BSAFs Penta-BDEs

• α-, β-HBCD BSAFs 3 to 6-times γ-HBCD

• indicates bioisomerization in low tropic organisms

• Transformation products

• methoxy and hydroxy-BDEs

• debrominate

• deca-BDE to more toxic lower brominated PBDEs

• TBB and TBPH

• TBPH to DEHP (di(2-ethylhexyl) phthalate)

• isomerization of γ-HBCD

Conclusions

OO

O

CH3

CH3

OCH3

CH3

DEHP

O

Br

Br

Br

Br

O

O

CH3

CH3

OCH3

CH3

TBPH