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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
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