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 severelyworldwide. 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-wastetreatment plant

HB

CD

Co

ncen

trati

on

(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 arudimentary fashion

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

� We recently studied meat and eggs from animals reared aroundsuch 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

656459

4180

2.3 7 3.3 71

Avera

ge C

on

cen

trati

on

(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

Exp

osu

re (

ng

/kg

bw

/day)

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

Exp

osu

re (

ng

/kg

bw

/day)

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)

Le

ac

hin

g R

ate

(%

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)

Le

ac

hin

g R

ate

(%

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 168Time (h)

TC

IPP

Co

nce

ntr

ati

on

(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 congeners

>the LPCL of 1,000 mg/kg

� Only 1 apparent LPCL exceedance for Octa-BDE (TV housing), but very high

Deca-BDE in this sample may suggest the Octa comes from the Deca-

formulation used

� Deca-BDE present frequently in plastics and WEEE. Also present in some PUF and fabric samples. Fair number of samples contain Deca-BDE > 1,000

mg/kg which may become relevant if and when a LPCL introduced for this

BFR.

� HBCDD detected at concentrations >proposed LPCL of 1,000 mg/kg in: (a)

ELV fabrics (n=2), (b) furniture foams (n=5) and fabrics (n=6), (c) 1 CD

player, and (d) C&D EPS samples (n=14; 35%).

� NO exceedances for: LHAs, fridges, curtains, mattress foams and fabrics and

only 1 sample of carpet & 2 SDAs >LPCL for Deca-BDE

How can LPCL compliance be checked more easily?� Given vast number and mass of POP-BFR containing waste articles, monitoring

compliance with these LPCLs constitutes a vast logistical challenge and presents

a potentially substantial barrier to the implementation of the circular economy

� One way to make LPCL compliance monitoring easier is to use hand-held XRF to

measure the Br rather than measuring BFRs via GC-MS or LC-MS/MS

� Main problem with using XRF is the possibility of false positives (when Br

detected is not due to a POP-BFR)

� The WAFER project thus also used hand-held XRF to measure Br in the same

items for which BFRs were measured conventionally

� Overall, false positives where an LPCL exceedance was reported by XRF but

was not due to a POP-BFR, were encouragingly quite low (few % of all samples)

� Most commonly detected BFR is TBBP-A (esp. in display items) which is the

principal cause of false positives, also identified DBDPE in 1 sample and

unconfirmed detection of EH-TBB in a few others

� Most promising for C&D EPS where in WAFER there were no such false

positives even though 35% of samples exceeded LPCL for Br (& HBCDD)

FUTURE RESEARCH DIRECTIONS� Investigate releases from end-of-life treatment of

flame-retarded waste

� Use findings to inform sustainable waste management

� INTERWASTE project

ACKNOWLEDGEMENTS

� The research leading to these results received funding from the European Union Seventh Framework Program (FP7/2007-2013) under grant agreement No 295138 (INTERFLAME project)

� We also acknowledge funding from the EPA of Ireland for the WAFER project

May 7-10 www.bfr2017.co.uk