bioaccumulation of pbdes, their replacement products (tbb ... · -hbcd -hbcd -hbcd br br br br br...
TRANSCRIPT
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
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