Click here to load reader

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

  • View
    10

  • Download
    0

Embed Size (px)

Text of Bioaccumulation of PBDEs, their replacement products (TBB ... · PDF file -HBCD -HBCD -HBCD 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

    *[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