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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
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