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BROMINATED FLAME RETARDANTS IN WASTE CONSUMER · PDF file BROMINATED FLAME RETARDANTS PBD Es - widely employed (worldwide 67,000 t in 2001) as flame retardants in applications such

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  • BROMINATED FLAME

    RETARDANTS IN

    WASTE CONSUMER

    ARTICLES

    Stuart Harrad

  • BACKGROUND � Chemicals are added to a wide range of products for a

    variety of reasons

    � One of these is to make them more fire resistant

    � Lots of consumer goods and materials represent excellent sources of fuel

    � Flame retardant chemicals are thus added to slow the burning process – e.g.

    – To plastic casing & internal components of electronics at 20-30%

    – To furniture (fabric covers and foam fillings) at 2-3%

    – To expanded and extruded polystyrene (e.g. building insulation foam)

  • WHERE ARE THE FRs?

    TV

    Router

    Phone

    Chair

    iPad

    YouView Box

    HDD

    Games console

    Remotes???

  • BROMINATED FLAME RETARDANTS � PBDEs - widely employed (worldwide 67,000 t in 2001) as flame

    retardants in applications such as carpet underlays, polyurethane foam-filled furniture, and electronic goods.

    � Interesting to compare with PCBs; temporal trends in concentrations of the 2 classes in Swedish human milk, indicate a decline in PCBs, but a dramatic rise in PBDEs (doubling every 5 years between 1972 and 1997). Similar findings recently reported for US foodstuffs

    � Penta- and Octa-BDE products listed under Stockholm Convention and manufacture and new use of Deca-BDE product restricted severely worldwide. Health concerns include impaired spermatogenesis, as well as developmental neuro- and immunotoxicity

    � HBCD also manufactured in high volumes (16,700 t worldwide in 2001) but concerns centring around liver and thyroid hormone disruption and reproductive disorders led to its listing under the Stockholm Convention

    � These actions should progressively reduce environmental contamination as BFR-containing products are discarded

  • THE BAD NEWS! � When we throw out our old products, the FRs in them don’t

    magically disappear

    � Best estimate is that globally around 20 million tonnes of electronic waste (e-waste) is generated every year

    � Globally, 200 million PCs discarded every year

    � Recent figures estimate nearly 1 million tonnes of soft furnishings are thrown out annually in the UK alone

  • (SLIGHTLY!) BETTER NEWS! � E-waste now legally required to be separated from other

    waste streams

    � A rich potential source of precious metals

    � In the developed world, resource recovery conducted under controlled conditions that protect workers

    � Despite this, HBCD concentrations in air around an e-waste treatment centre in the UK, are 400 X higher than on our campus

    0

    5

    10

    15

    20

    25

    Birmingham E-waste treatment plant

    H B

    C D

    C o

    n c e n

    tr a ti

    o n

    ( n

    g /m

    3 )

  • HUMAN EXPOSURE ARISING FROM TREATMENT OF E-WASTE

    � Substantial evidence shows that in less developed countries, e- waste treatment to recover resources often occurs in a rudimentary fashion

    � Such rudimentary e-waste treatment can not only expose workers (and their families) DIRECTLY, but contaminates the wider environment, including the food chain

    � We recently studied meat and eggs from animals reared around such e-waste treatment areas

  • LOCATION OF SAMPLING SITES, TAIZHOU CITY, EASTERN CHINA

  • CONCENTRATIONS OF PBDEs IN E-WASTE IMPACTED FOOD

    0

    1000

    2000

    3000

    4000

    Chicken meat Chickens' eggs Chicken liver Fish

    1160

    656 459

    4180

    2.3 7 3.3 71

    A v e ra

    g e C

    o n

    c e n

    tr a ti

    o n

    ( n

    g /g

    )

    E-waste impacted

    Non-e-waste impacted

  • EXPOSURE TO BDEs- 47 AND -99 VIA EATING

    FOOD PRODUCED NEAR RUDIMENTARY E-

    WASTE RECYCLING SITES

    0

    50

    100

    150

    200

    250

    300

    47-median 47-high 99-median 99-high

    Adult

    Child

    “Typical” High “Typical” High

    BDE-47 BDE-99

    E x p

    o s u

    re (

    n g

    /k g

    b w

    /d a y )

  • EXPOSURE TO BDEs- 47 AND -99 VIA EATING

    FOOD PRODUCED NEAR RUDIMENTARY E-

    WASTE RECYCLING SITES

    0

    50

    100

    150

    200

    250

    300

    47-median 47-high 99-median 99-high

    Adult

    Child

    US EPA Reference Dose (Rfd) for BDE-47 & BDE-99

    2.5x

    1.5x

    “Typical” High “Typical” High

    BDE-47 BDE-99

    E x p

    o s u

    re (

    n g

    /k g

    b w

    /d a y )

  • FR EMISSIONS FROM LANDFILLED WASTE

    � While e-waste should no longer be landfilled in the EU it WAS in the past and no such prohibition exists with respect to landfilling waste soft furnishings, so we have examined transfer of HBCDs from treated fabrics under landfill conditions

    � Examined leaching under Japanese test protocols under lab-scale conditions

    � Examined effect of inter alia leachate temperature, pH, and duration of fabric:leachate contact

  • EFFECTS OF WASTE:LEACHATE CONTACT TIME ON

    HBCDD CONCENTRATIONS IN LEACHATE

    Concentrations (ng/L)

    Note high HBCDD concentrations & increase with contact time

  • Effects of Temperature on HBCD leaching rates (%/hr)

    0

    0.0000025

    0.000005

    0.0000075

    0.00001

    0.0000125

    0.000015

    0.0000175

    0.00002

    0.0000225

    0.000025

    20 50 80

    Temperature (°C)

    L e

    a c

    h in

    g R

    a te

    ( %

    h -1

    )

    α-HBCDD

    β-HBCDD

    γ-HBCDD

    0

    0.000005

    0.00001

    0.000015

    0.00002

    0.000025

    0.00003

    0.000035

    0.00004

    0.000045

    20 50 80

    Temperature (°C)

    L e

    a c

    h in

    g R

    a te

    ( %

    h -1

    )

    α-HBCDD

    β-HBCDD

    γ-HBCDD

    Textile A Textile B

    Higher temperatures enhance leaching

  • Leaching of TCIPP from PUF

    Elevated concentrations of TCIPP leached from PUF (containing 17,400 mg/kg TCIPP) under a periodic wetting and drying scenario where after leachate was removed after each time period and replaced with fresh room temp, deionised distilled water

    Likely due to the high surface area/porosity of PUF combined with the high water solubility of TCiPP (1.6 g/L).

    Almost all the TCIPP was leached from the PUF after 6 cycles. ~96%

    0

    10

    20

    30

    40

    50

    60

    70

    6 24 48 72 96 168 Time (h)

    T C

    IP P

    C o

    n ce

    n tr

    a ti

    o n

    ( m

    g L

    -1 ) Concentrations

  • SUMMARY

    � Leaching of HBCDs from waste fabrics relatively facile

    � That of TCIPP from furniture foam even more so

    � Suggests that as well as e-waste, we need to ensure sustainable end-of-life treatment of fabrics and soft furnishings

  • SO, DON’T LANDFILL?...

    � Even if waste plastics (such as electronic/TV/PC monitor casing) are not landfilled, there are potential problems…

    � Along with other groups, we are finding evidence of the presence of BFRs in items that do not require to be flame-retarded

    � Examples are black plastic kitchen utensils

    � Expanded polystyrene packaging

    � This suggests that BFR-containing waste plastics are being recycled and mixed with “virgin” plastics

    � To prevent this, the EU has introduced LPCLs for POP- BFRs of 1,000 mg/kg (0.1%) such that waste articles containing POP-BFRs at concentrations exceeding the LPCL cannot be recycled and must be subjected to “special” treatment

  • SO, DON’T LANDFILL?...

    � What’s the scale of the problem?

    � We are currently completing a project (WAFER) that has measured POP-BFRs in >550 articles of e-waste, vehicle waste and waste soft furnishings from Ireland

    � Results are overleaf

  • BFR Concentrations in Irish Waste

    Waste Classification No. Samples Analysed POP-BFR range

    Deca-BDE included (ppm) % LPCL exceedances (Deca-

    BDE included)

    Construction & Demolition (C&D) EPS 40 0-10000 35 % (due only to HBCDD)

    C&D XPS 22 0-94 0 %

    LHAs 59 0-200 0 %

    Display 43 0-60000 6.9 %

    Fridges 30 0-4 0 %

    SDAs 29 0-1600 6.9 % (due only to Deca-BDE)

    IT & Telecommunications 78 0-7600 6.4 % (1.3% due to HBCDD)

    ELV 135 0-31000 5.2 % (1.5 % due to HBCDD)

    Carpets 32 0-7000 3.1 % (due only to Deca-BDE)

    Furniture Foam 20 0-8000 40 % (25% due to HBCDD)

    Furniture Upholstery 22 0-73000 36 % (27% due to HBCDD)

    Curtains 15 0-56 0 %

    Mattress Foam 17 0-870 0 %

    Mattress Upholstery 17 0-49 0 %

    Total 559 0-73000 8.6 % (5.2% due to HBCDD)

  • Data Highlights � Other “headlines” from these data are:

    � Penta-BDEs rarely detected - no samples contain Penta-BDE congener