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
