Bioaccumulation of PBDEs, their replacement products (TBB ... · PDF file -HBCD -HBCD -HBCD Br Br Br Br Br Br Br Br Br Br Br Br Br Br Br Br Br Br Hexabromocyclododecane (HBCD) 1La

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

*[email protected]

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

Br Br

Br

Br

Br

Br

Br Br

Br

Br

Br

Br

Br Br

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 2010 5Fernie 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:

Size Exclusion Chromatography Envirosep-ABC, 350 x 21.1 mm

(Phenomenex)

Enhanced Solvent Extraction ASE 200 (Dionex)

Solid Phase Extraction Glass column, 2 gm silica

Freeze-dry

exchange to hexane

Fraction #1 3.5mL (hexane)

reduce volumeGC/ECNI-SIM MS

PBDEs, TBB, TBPH, BTBPE

Samples

(sediment and mollusks)

Fraction #2 6.5mL (hexane/DCM, 60:40)

Fraction #3 8mL (DCM)

Fraction #4 5mL (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

C o n c .

n g /g

( p p b )

d ry

w t.

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

C o

n c .

n g

/g (

p p

b ),

% T

O C

o r

% l

ip id

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

C o

n c .

n g

/g (

p p

b ),

% T

O C

o r

% l

ip id

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

C o

n c .

n g

/g (

p p

b ),

% T

O C

o r

% l

ip id

TBB

TBPH

BTBPE

Sediment Corbicula (clam) Elimia (snail)

HBCD

0

50,000

100,000

150,000

200,000

250,000

300,000

350,000

C o

n c . n

g /g

( p

p b

), %

T O

C o

r %

l ip

id

γ-HBCD

β-HBCD

α-HBCD

Sediment Corbicula (clam) Elimia (snail)

Penta- & Octa-BDEs

0%

20%

40%

60%

80%

100%

% C

o n

tr ib

u ti

o n

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

C o

n c .

n g

/g (

p p

b ),

% T

O C

o r

% l

ip id

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

C o

n c .

n g

/g (

p p

b ),

% T

O C

o r

% l

ip id

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

C o

n c .

n g

/g (

p p

b ),

% T

O C

o r

% l

ip id

TBB

TBPH

BTBPE

Sediment Corbicula (clam) Elimia (snail)

HBCD

0

50,000

100,000

150,000

200,000

250,000

300,000

350,000

C o

n c . n

g /g

( p

p b

), %

T O

C o

r %

l ip

id

γ-HBCD

β-HBCD

α-HBCD

Sediment Corbicula (clam) Elimia (snail)

Deca-BDEs

0%

20%

40%

60%

80%

100%

% C

o n

tr ib

u ti

o n

BDE-207

BDE-208

BDE-206

BDE-209

Sediment Corbicula (clam) Elimia (snail)

BFRs – sediment and mollusks (outfall)

(TOC or lipid normalized)

Penta- & Oc