Bat Bep 2

Guidelines on Best Available
Techniques and Guidance on

Best Environmental Practice for
Recycling and Disposal of c-
c-
PentaBDE and c-
c-OctaBDE
Containing Articles
Relevant to Annex A Part IV and V of
the Stockholm Convention
Version 1
9. December 2011
Table of Contents
1 Introduction .......................................................................................................................................... 7
1.1 POP-BDE in the Stockholm Convention................................................................................................7
1.2 Purpose of this document ....................................................................................................................8
1.3 Structure of this document and using guidelines and guidance ..........................................................9
1.4 Polybrominated diphenylethers listed in Annex A Part IV and Part V .............................................. 11
1.4.1 What are the POP-BDEs listed in Annex A Part IV and Part V? ................................... 11
1.4.2 Production volume ...................................................................................................... 12
1.4.3 Characteristics ............................................................................................................. 12
1.4.4 Uses ............................................................................................................................. 12
1.4.5 Risks............................................................................................................................. 13
2 POP-BDE Material Flows & POP-BDE Alternatives............................................................................... 13
2.1 POP-BDE containing material flows and recycling activities............................................................. 13
2.1.1 Polymers containing c-OctaBDE .................................................................................. 14
2.1.2 Polyurethane (PUR) foam containing c-PentaBDE ...................................................... 14
2.1.3 Printed circuit/wiring boards containing c-PentaBDE................................................. 15
2.1.4 Textiles and rubber containing c-PentaBDE................................................................ 15
2.2 Alternatives to POP-BDEs .................................................................................................................. 16
2.2.1 Introduction................................................................................................................. 16
2.2.2 Role of flammability standards ................................................................................... 16
2.2.3 Suggested ecological priorities for use of flame retardants ....................................... 16
2.2.4 Alternative flame retardants to c-PentaBDE and c-OctaBDE...................................... 17
2.2.5 BAT/BEP approach for the assessment of flame retardants....................................... 20
3 General BAT/BEP considerations for POP-BDE containing material flow and recycling....................... 21
3.1 Waste management hierarchy .......................................................................................................... 21
3.2 Recommendation and reason to separate BFR containing materials............................................... 22
3.3 Life Cycle Management Considerations for POP-BDE containing materials ..................................... 24
3.3.1 LC considerations for the polymer fraction from vehicles.......................................... 25
3.3.2 LC considerations for WEEE ........................................................................................ 26
3.3.3 LC considerations for the management of PUR foam................................................. 27
3.3.4 LC considerations for bromine recovery ..................................................................... 27
3.4 Overview on treatment options of POP-BDE containing materials considering key criteria............ 29
3.5 General BAT/BEP considerations ...................................................................................................... 30
3.5.1 Environmental management systems (EMS) .............................................................. 30
3.5.2 Material/Waste management in facilities and processes........................................... 31
3.5.3 Crusing, shredding, sieving and washing operations .................................................. 35
3.5.4 General BAT/BEP considerations in respect to air and water releases ...................... 35
3.5.5 Prevention of soil contamination................................................................................ 37
4 Specific BAT/BEP on monitoring of POP-BDE/BFR in articles............................................................... 38
4.1 Determination of POP-BDEs in articles.............................................................................................. 38
4.1.1 Identification of POP-BDEs by standard PBDE analysis............................................... 38
4.1.2 Rapid analysis techniques for POP-BDEs..................................................................... 38
4.2 In situ measurement of bromine in articles ...................................................................................... 39
4.2.1 Sliding spark spectroscopy .......................................................................................... 40
4.2.2 X-ray fluorescence (XRF) ............................................................................................. 40
4.2.3 X-ray transmission (XRT) ............................................................................................. 41
5 Specific BAT/BEP: POP-BDE/BFR containing polymer in WEEE ............................................................ 41
5.1 Recovery of materials from WEEE..................................................................................................... 41
5.2 Reuse of EEE ...................................................................................................................................... 42
5.3 Polymer recovery & separation of BFR containing materials from WEEE ........................................ 42
5.4 Technologies to separate PBDE/BFR-containing polymers............................................................... 44
5.4.1 Instrumental techniques to separate polymers.......................................................... 47
5.4.2 Instrumental separation of polymers in developing countries................................... 48
5.4.3 Separation of POP-BDE/BFR-containing polymer by manual pre-sorting................... 49
5.4.4 Separation of polymers by Sink and float technologies (S/F) .................................. 50
5.4.5 Combination of techniques for producing marketable products ............................... 51
5.4.6 Comparison of technology combinations to separate polymer streams.................... 52
5.4.7 Full scale plants to separate WEEE and POP-BDE/BFR containing polymers.............. 54
5.5 Material recycling of polymer containing POP-BDEs ........................................................................ 55
5.5.1 Labelling of POP-BDE containing polymer fraction and articles ................................. 55
5.5.2 Processing technologies for polymers ........................................................................ 56
5.5.3 Articles produced from POP-BDE containing recycled polymer (labelling) ................ 57
5.6 Energy recovery and end-of-life management of POP-BDE polymers .............................................. 57
6 Specific BAT/BEP: POP-BDE/BFR materials in the transport sector ..................................................... 58
6.1 Reuse of vehicles containing POP-BDEs ............................................................................................ 58
6.2 Transport sector and end-of-life management................................................................................. 58
6.3 POP-BDE/other POPs and contaminants in ELVs and waste management ...................................... 59
6.4 Recycling of end-of-life vehicles........................................................................................................ 60
6.4.1 Dismantling and de-pollution of the vehicle ............................................................... 60
6.4.2 Shredder plants (UNEP 2007)...................................................................................... 62
6.5 Recycling of ASR and other ELVs residues......................................................................................... 63
6.5.1 Recycling by improved de-pollution and post shredding techniques ......................... 63
6.5.2 Developing country considerations............................................................................. 65
6.5.3 Energy recovery and deposition of ASR and other ELV residues ................................ 65
7 Specific BAT/BEP: POP-BDE/BFR containing PUR foam ....................................................................... 66
7.1 Reuse of furniture and mattresses possibly impacted by POP-BDEs ................................................ 67
7.2 General Management and recycling of PUR foam ............................................................................ 67
7.3 Assessment of POP-BDEs/BFRs impact of PUR foam in a country/region ........................................ 68
7.4 Separation strategy of c-PentaBDE impacted PUR foam .................................................................. 68
7.4.1 Separation/exclusion of PUR foam categories from recycling.................................... 68
7.4.2 Separation of POP-BDE/BFR containing PUR foam in recycling.................................. 69
7.5 Recycling areas and technologies for flexible PUR foam .................................................................. 69
7.5.1 Collection of the PUR foam and separation in the collection phase........................... 69
7.5.2 Rebond Recycling PUR foam with phase out of c-PentaBDE ................................... 69
7.5.3 Material recovery from mattresses ............................................................................ 71
7.5.4 Regrinding ................................................................................................................... 71
7.5.5 Chemical recovery (glycolysis) .................................................................................... 72
7.6 Labelling of POP-BDE containing PUR foams recycling ..................................................................... 72
7.7 Other materials possibly impacted by POP-BDEs.............................................................................. 72
7.8 Energy recovery from POP-BDE containing materials....................................................................... 72
8 Energy/material recovery from POP-BDE materials ............................................................................ 73
8.1 General remarks on thermal treatment POP-BDE containing materials .......................................... 73
8.1.1 Calorific value and halogen content of POP-BDE containing materials ...................... 73
8.1.2 Monitoring of PBDD/PBDF and PXDD/PXDF release................................................... 73
8.1.3 Considerations on corrosion caused by bromine/HBr ................................................ 74
8.1.4 Considerations for removal of HBr and bromine in flue gas treatments.................... 74
8.2 Energy recovery of POP-BDE containing materials in incinerators ................................................... 74
8.2.1 Co-incineration of polymers from WEEE..................................................................... 75
8.2.2 Co-incineration of ASR in Municipal Solid Waste Incinerators (MSWI) ...................... 76
8.2.3 Recovery of metals...................................................................................................... 76
8.3 Cement kilns ...................................................................................................................................... 77
8.4 Melting systems................................................................................................................................. 80
8.5 Pyrolysis and gasification of POP-BDE containing materials............................................................. 80
8.6 Metal industries................................................................................................................................. 80
8.6.1 Copper smelters and integrated smelters-refineries.................................................. 81
8.6.2 Material recovery and energy recovery in electric arc furnaces................................. 84
8.6.3 Feedstock recycling of POP-BDE polymer in primary steel industry........................... 85
8.6.4 POP-BDE materials in secondary aluminium industries.............................................. 85
8.6.5 Antimony smelters recycling WEEE polymers............................................................. 86
8.6.6 Developing/transition country considerations ........................................................... 86
9 Recovery of bromine from POP-BDE/BFR containing materials........................................................... 87
9.1 Thermal recovery of Bromine ........................................................................................................... 88
9.1.1 Recovery of bromine from waste incinerators ........................................................... 88
9.1.2 Recovery from bromine from pyrolysis....................................................................... 88
9.2 Technologies for separating POP-BDEs/BFRs from the polymer matrix ........................................... 88
9.2.1 Separation of BFR/bromine and polymer recovery .................................................... 89
9.2.2 Recovery of metals, energy and bromine from PWB.................................................. 89
10 Disposal of POP-BDE containing materials to landfills......................................................................... 91
10.1 General remark to landfilling POP-BDE containing materials: .......................................................... 91
10.2 Types of wastes containing POP-BDEs that are landfilled................................................................. 91
10.3 Categories of landfills to receive POP-BDE containing wastes.......................................................... 92
10.4 Delivery of wastes to landfills............................................................................................................ 94
10.5 Operation and maintenance of landfills containing POP-BDE .......................................................... 94
10.5.1 PBDE releases from landfills........................................................................................ 95
10.5.2 Release of POP-BDE and PBDD/PBDF from landfill fires............................................. 96
10.5.3 BAT to prevent short- and long-term release of POP-BDE from landfills ................... 96
10.6 BAT/BEP of landfill aftercare:............................................................................................................ 97
10.7 Landfill mining and impact of POP-BDE ............................................................................................ 97
10.8 Summary, conclusions and outlook about landfilling of POP-BDE with regard to BAT/BEP............. 98
11 References........................................................................................................................................... 98
12 Annex ................................................................................................................................................ 105
12.1 Recommendations from COP5 (Annex to decision POPRC-6/2) ..................................................... 105
Abbreviations
ABS Acrylonitrile-butadiene-styrene
ASR Auto Shredder Residue
BDP Bisphenol A-bis(diphenylphosphate
BFR Brominated Flame Retardant
BSEF Bromine Science and Environmental Forum
CKD Cement kiln dust
COP Conference Of Parties
CRT Catode Ray Tube
DecaBDE Decabromodiphenyl ether
DOPO Dihydrooxaphosphaphenantrene
EAF Electric Arc Furnace
EEE Electrical and Electronic Equipment
ELV End of Live Vehicle
EMS Environmental Management System
ESM Environmental Sound Management
FPF Flexible Polyurethane Foam
FR Flame Retardant
GDP Gross Domestic Product
HBB Hexabromobiphenyl
HBCDD Hexabromocyclododecane
HIPS High Impact Polystyrene
MSW Municipal Solid Waste
NIR Near Infrared
ODS Ozone Depleting Substances
OctaBDE Octabromodiphenyl ether
PBB Polybromodiphenyl
PBDE Polybrominated diphenyl ether
PBT Polybutylene Terephthalate
PC Polycarbonate
PCB Polychlorinated biphenyl
PentaBDE Pentabromodiphenylether
PET Polyethylene terephthalate
PFR Phosphorous based Flame Retardant
POPs Persistent Organic Pollutants
POPRC Persistent Organic Pollutants Review Committee
PP Polypropylene
PPE Polyphenyl ether
PPO Polyphenylenoxide
PS Polystyrene
PUR Polyurethane
PVC Polyvinylchloride
PWB Printed Wiring Board
RDP Resorcinol-bis(diphenylphosphate)
RoHS Restriction of the use of certain hazardous substances in electrical and
electronic equipment
S/F Sink and Float
WEEE Waste Electrical and Electronic Equipment
XRF X-ray fluorescence
XRT X-ray transmission
1 Introduction
1.1 POP-BDE in the Stockholm Convention
The Conference of the Parties of the Stockholm Convention decided at the fourth meeting to list in
Annex A of the Stockholm Convention1 certain congeners contained in commercial
pentabromodiphenyl ether2 (c-PentaBDE) and commercial octabromodiphenyl ethers3 (c-OctaBDE).
For the purposes of this document the PBDE which are listed in Annex A have been labelled POP-
BDEs.
The decisions to list these POP-BDEs include specific exemptions allowing for recycling and the
subsequent use in articles of recycled materials containing these substances.
Decision SC-4/18 and SC-4/14 included specific exemption for use in articles in accordance with the
following provisions:
1. A Party may allow recycling of articles that contain or may contain tetrabromodiphenyl ether,
pentabromodiphenyl ether, hexabromodiphenyl ether, heptabromodiphenyl ether and the use and
final disposal of articles manufactured from recycled materials that contain or may contain
tetrabromodiphenyl ether and pentabromodiphenyl ether, provided that:
(a) The recycling and final disposal is carried out in an environmentally sound manner and does not
lead to recovery of tetrabromodiphenyl ether and pentabromodiphenyl ether for the purpose of their
reuse;
(b) The Party does not allow this exemption to lead to the export of articles containing
levels/concentrations of tetrabromodiphenyl ether and pentabromodiphenyl ether that exceed those
permitted to be sold within the territory of the Party; and
(c) The Party has notified the Secretariat of its intention to make use of this exemption.
At its sixth ordinary meeting and at every second ordinary meeting thereafter the Conference of the
Parties shall evaluate the progress that Parties made towards achieving their ultimate objective of
elimination of tetrabromodiphenyl ether and pentabromodiphenyl ether contained in articles and
review the continued need for this specific exemption. This specific exemption shall in any case expire
at the latest in 2030.
The allowance of reuse and recycling of articles containing listed PBDEs (POP-BDEs) results in the
need to define Best Available Technology (BAT) and Best Environmental Practices (BEP) to carry out
the recycling and final disposal in an environmentally sound manner (ESM) considering the
recommendations made by COP5 (Annex 1) for the management of c-PentaBDE/c-OctaBDE
containing materials.
1
Decisions SC-4/14 on the listing of hexabromodiphenyl ether and heptabromodiphenyl ether and SC-4/18 on
the listing of tetrabromodiphenyl ether and pentabromodiphenyl ether.
2
The listing includes tetrabromodiphenyl ether and pentabromodiphenyl ether, meaning 2,2',4,4'-
tetrabromodiphenyl ether (BDE-47, CAS No: 40088-47-9) and 2,2',4,4',5-pentabromodiphenyl ether (BDE-99,
CAS No: 32534-81-9) and other tetrabromodiphenyl and pentabromodiphenyl ethers present in commercial
pentabromodiphenyl ether.
3
The listing includes hexabromodiphenyl ether and heptabromodiphenyl ether, meaning 2,2',4,4',5,5'-
hexabromodiphenyl ether (BDE-153, CAS No: 68631-49-2), 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE-154,
CAS No: 207122-15-4), 2,2',3,3',4,5',6 heptabromodiphenyl ether (BDE-175, CAS No: 446255-22-7),
2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE-183, CAS No: 207122-16-5) and other hexabromodiphenyl
and heptabromodiphenyl ethers present in commercial octabromodiphenyl ether.
Since POP-BDE containing materials are still in use and in stockpiles they are present in some
recycling flows and also in wastes streams. Technologies are evaluated and defined in this document
which can be considered as Best Available Techniques and Best Environmental Practice to manage
these material streams in an Environmentally Sound Manner (ESM). This includes monitoring
methodologies to screen for POP-BDEs containing materials possibly separate POP-BDE containing
articles from the recycling flows for risk reduction and to address appropriately the
recommendations given by the COP5 (Annex 1). The actual technologies which might be used for
recycling of POP-BDE containing materials are described and precautionary measures for
occupational safety highlighted. Also BAT/BEP for thermal recovery/destruction operations like
incinerators, cement industries or possibly secondary metal industries need to define the level of
BAT/BEP for facilities appropriate to process POP-BDE containing material streams. These
facilities/processes overlap to some extent with processes which can also be considered technologies
suitable for the destruction of POP-BDE containing materials (e.g. thermal recovery of POP-BDE
containing articles in incinerators or cement kilns). In this respect the guidance will be harmonised
and linked then to a future extension of the Basel Convention guideline on POPs destruction
technologies4.
1.2 Purpose of this document
This document serves as guidance on BAT/BEP for the management of POP-BDE containing materials
and should be referred to by governmental counterparts and consultants in reviewing and updating
the NIP in respect to manage POP-BDE containing materials and articles. Further the document
should be used as a support for developing action plans for new POP-BDE containing articles and to
prioritize areas for the management and treatment of these material flows. Also it aims to provide
information for industries recycling materials containing or possibly containing POP-BDEs.
The document provides technical outlines, advantage/disadvantage, priority sources to be
addressed, health safety issues, and socio-economic aspects of the BAT/BEP introduced in this
guidance. To keep the document as short as possible, for further details, reference is given to official
and peer-reviewed reports such as other Stockholm Convention BAT/BEP guidance sections and to
the Best Available Techniques REFerence Documents (BREFs) issued by the European Commission5.
The concept of best available techniques is not aimed at the prescription of any specific technique or
technology. BAT means the most effective and advanced techniques available in addition to the
practical suitability of particular techniques. BEP describes the application of the most appropriate
combination of environmental control measures and strategies (Article 5, f (v)).
The current BAT/BEP guidance has highlighted developing country considerations. However there is
currently too little information on BAT and in particular BEP for larger material flows like polymers
from Waste Electrical and Electronic Equipment (WEEE) or for foams and other polymers from
vehicles. New experiences and information should be included in an update of this guidance.
4
The Basel Convention is starting to address new listed POPs and the revision of fact sheets of POPs
destruction technologies to contain also new POPs containing materials have started.
5
Schoenberger, H.; Integrated Pollution Prevention and Control in Large Industrial Installations on the Basis of
Best Available Techniques The Sevilla Process, J. Cleaner Production 17 (2009) 1526-1529
1.3 Structure of this document and using guidelines and guidance
As mentioned above, the document provides technical outlines, advantage/disadvantage, and

priority sources to be addressed by BAT/BEP. In section 1 the purpose and structure of the document
is shortly outlined. General considerations on BAT/BEP are described in section 2 and 3 while specific
BAT/BEP considerations are outlined in section 4 to 10.
The structure of the BAT/BEP document follows mass flow thinking, starting from production to
application and finally to reuse, recycling and disposal of products. This approach is illustrated in
Figure 1 and key sections mentioned for a quick overview below.
Use (1) & Production
Production c-PentaBDE (stopped) Production c-OctaBDE (stopped) Alternatives to POP-BDE (2.2)

(1)
Minor uses: Textile, Flexible PUR Foam HIPS ABS Other Polymers Life Cycle
Reuse (5,6,7)
PWB, rubber, oil drilling Consideration

POP-BDE
containing
Mattresses Furniture Transport sector Electrical & Electronic Equipment materials (3.3)
General BAT/BEP (3)

Recovery Recycling
PBDE screening technologies (4)
Management PUR Foam (7) Management transport sector (6) Management of WEEE & Polymers (5)
Energy/material recovery (8)*

Incineration (8.1) Cement (8.2) Melting (8.3) Pyrolysis (8.4) Smelters (8.5)
Recovery of Bromine (9)*

Disposal
Landfill disposal (10)
*Bromine recovery is not operated in full scale yet.
Reuse of Articles (e.g. cars, electronics, furniture) .
Figure 1: Mass flow for the relevant production and application of c-PentaBDE and c-OctaBDE and
the reuse, recycling and disposal of products containing these substances (The numbers of
the sections addressing the respective issue are in brackets).
In the Figure 1 above, the numbers of the different sections are indicated. They are briefly described
as follows:
Background information on POP-BDEs is given in section 1.2. Here the major uses of c-
PentaBDE and c-OctaBDE are described in section 1.2.4 and production volumes of
commercial PBDE mixtures in 1.2.2.
In section 2.1 the POP-BDE contaminated articles for relevant recycling flows are shortly
listed as a base of further priority setting for BAT/BEP measures.
Alternatives to c-PentaBDE and c-OctaBDE are briefly described in section 2.2.4 and
ecological priorities for flame retardants (2.2.3). BAT/BEP to assess flame retardants are
mentioned in (2.2.5). In this section also the role of flammability standards are emphasized
(2.2.2).
General BAT/BEP considerations for POP-BDE containing material and recycling flows are
detailed in section 3. Recommendations and practical reasons to generally separate
Brominated Flame Retardants (BFR) containing materials are detailed in section 3.2. Life
Cycle management considerations for POP-BDE containing materials are described in section
3.3 and an overview on treatment technologies is given in 3.4... Section 3.5 describes the
general BAT/BEP measures including Environmental Management Techniques like
Environmental Management System (EMS) (3.5.1)
Technologies for screening of POP-BDE and bromine containing materials are described in
section 4. The screening of POP-BDE containing materials in use and stockpiles and the
separation6 of POP-BDE containing materials require monitoring technologies enabling to
detect POP-BDEs or bromine as tracer.
BAT/BEP for management of c-OctaBDE containing Electrical and Electronic Equipment (EEE)
and related wastes (WEEE) is detailed in section 5. (W)EEE can be considered as the main
stock and recycling flow containing c-OctaBDE. The section includes general material
recovery from WEEE (5.1) and considerations on reuse of electronics (5.2). Recovery of
polymers (5.3) and the technologies described in section 5.4 to 5.6. BAT/BEP considerations
for the further processing of POP-BDE containing polymers are elaborated in 5.7.
BAT/BEP for management of POP-BDE containing materials in the transport sector (cars,
busses, trucks, trains, ship, planes) is described in section 6. This sector was a major use area
of c-PentaBDE (in PUR foam) and some c-OctaBDE has been used in polymer parts. Due to
the relatively long life time of vehicles and due to the high reuse and export rate to
developing countries the transport sector can be considered as the largest stock and reuse
flow of articles containing c-PentaBDE with particular relevance for developing countries.
Considerations for reuse (6.1) end of life management (6.2 & 6.3) and recycling (6.4 & 6.5)
are given in the respective sections.
BAT/BEP for managing and processing POP-BDE containing polyurethane from furniture,
transport sector, mattresses and other uses are described in section 7. Considerations for
reuse (7.1), general management and recycling (7.2), separation strategies (7.4), recycling
(7.5) are given in the respective sections. In this section also BAT/BEP management of minor
uses of POP-BDEs are shortly mentioned (7.7).
Energy/material recovery from POP-BDE containing materials by thermal treatment is
elaborated in Section 8. This includes waste incineration (8.2), cement kilns (8.3), melting
systems (8.4) and pyrolysis technologies (8.5). Also BAT/BEP considerations on different
secondary metal industries processing POP-BDE containing materials (for metal or energy
recovery) are described in section 8.6).
The recovery of bromine from POP-BDE/BFR containing materials is discussed in section 9.
Since none of the technologies have been realized in full scale only technologies evaluated in
pilot tests or in laboratory scale are described as an emerging approach.
BAT/BEP considerations on the disposal of POP-BDE containing materials in landfills are
elaborated in section 10.
6
The separation of PBDE containing materials is recommended by COP5.
11
1.4 Polybrominated diphenylethers listed in Annex A Part IV and Part V
1.4.1 What are the POP-BDEs listed in Annex A Part IV and Part V?
Polybrominated diphenyl ethers (PBDEs; Figure 2) are a group of industrial aromatic organobromine
chemicals which have been used since the 1970s as additive flame retardants in a wide range of products
including mainly consumer products. PBDEs were produced with three different degrees of bromination, and
marketed as commercial PentaBDE, commercial OctaBDE and commercial DecaBDE (Alaee et al. 2003;
Prevedouros 2004a; SFT 2009). A typical homologue distribution of the commercial mixtures is shown in
table 1. Commercial DecaBDE7 has not been found to contain POP-BDEs but can form POP-BDEs by
debromination during its life cycle (UNEP 2010c).
Under the Stockholm Convention from commercial PentaBDE the homologues tetrabromodiphenyl ether
and pentabromodiphenyl ether where listed8. From the commercial OctaBDE, hexabromodiphenyl ether
and heptabromodiphenyl ether9 were listed.
Therefore TetraBDE, PentaBDE, HexaBDE and HeptaBDE are listed in Annex A of the Convention and
production and their use has to be eliminated by Parties subject to the exemptions allowed by the
Convention. These listed POPs are referred in this document as POP-BDEs.
Figure 2: Structure of polybrominated diphenyl ethers (PBDEs)

Table 1: Typical PBDE homologue distribution in commercial PBDE products (Sellstrom et al. 2005; La
Guardia et al. 2006).
Commercial Congener % by weight

product tetraBDEs pentaBDEs hexaBDEs heptaBDEs octaBDEs nonaBDEs decaBDEs
C-PentaBDE 24-38 50-60 4-8
C-OctaBDE 10-12 44 31-35 10-11 <1
C-DecaBDE <3 97-98
7
DecaBDE can degrade in thermal processes, environment processes and in biota to lower brominated PBDE including
POPs PBDEs (UNEP 2010c). Another key degradation product are polybrominated dibenzoforans and depending on
conditions also polybrominated dibenzodioxins (Weber and Kuch 2003, Ebert and Bahadir 2003)
8
With the main congeners 2,2', 4,4'- tetrabromodiphenyl ether (BDE-47 CAS No. 40088-47-9) and 2,2',4,4',5-
pentabromodiphenyl ether (BDE-99 CAS No. 32534-81-9) and other tetra- and pentabromodiphenyl ethers present in
commercial pentabromodiphenyl ether.
9
With the main congeners 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153, CAS No: 68631-49-2), 2,2',4,4',5,6'-
hexabromodiphenyl ether (BDE-154, CAS No: 207122-15-4), 2,2',3,3',4,5',6-heptabromodiphenyl ether (BDE-175, CAS
No: 446255-22-7), 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE-183, CAS No: 207122-16-5) and other hexa- and
heptabromodiphenyl ethers
12
1.4.2 Production volume
The compilation of the PBDE production data for the POPs Reviewing Committee of the Stockholm
Convention estimates the total production of all PBDE from 1970 to 2005 was between 1,300,000 and
1,500,000 tonnes (UNEP 2010a). The use volume of c-PentaBDE and c-OctaBDE produced were each
estimated to be around 100,000 tonnes. C-DecaBDE10, not listed as POPs, has a production volume of slightly
more than 1 million tonnes (Table 2). While the production of POPs c-PentaBDE and c-OctaBDE has stopped,
the production of the DecaBDE continues.
Table 2: Estimated total production of PBDE commercial mixtures from 1970s to 2005 (UNEP 2010a derived
from Schenker 2008 and Li 2010).
Commercial Mixture Tonnes
c-DecaBDE 1,100,000 to 1,250,000

c-OctaBDE 102,700 to 118,500
c-PentaBDE 91,000 to 105,000
1.4.3 Characteristics
Commercial mixture of PentaBDE is highly persistent in the environment, bioaccumulative and has a high
potential for long-range environmental transport. These chemicals have been detected in humans in all
regions. There is evidence of its potential for toxic effects in wildlife, including mammals.
1.4.4 Uses
Use of Commercial PentaBDE
It is considered that the largest use of c-PentaBDE (90-95%) was for the treatment of polyurethane (PUR)
foam. These foams were in turn mainly used for the production of automotive and upholstery applications.
Minor uses included e.g. textiles, printed circuit boards, insulation foam, cable sheets, conveyer belts,
lacquers and possibly drilling oils (UNEP 2007b). Their total amount of c-PentaBDE used for these minor uses
is estimated to account for 5% or less of the total usage (SFT 2009, UNEP 2010b).
About 90% of the market in the mid-1990s was in the USA with most of the rest being located in Europe and
with possible production and use in China. Alcock et al. (2003) estimated that overall 85,000 t of c-PentaBDE
was used in the US and the remaining 15,000 t in Europe.
An approximate distribution of c-PentaBDE use of 36% in transport, 60% in furniture with a 4% residual in
other articles is considered to be reasonable and is generally consistent with the (relatively scare) analytical
data for different waste streams (UNEP 2010b).
The average use rate of c-PentaBDE in PUR foam is estimated at around 3-5% for upholstery, cushions,
mattresses, and carpet padding (ENVIRON 2003) used in particular in countries with flammability standards
for these applications (e.g. US, UK). PUR foam in the transport sector might have used lower concentrations
for applications like seat or arm/head rest at 0.5 to 1% (Luedeka 2011)11. Considering the approx. 100,000
10
DecaBDE is degraded over time to the lower brominated PBDE including POPs PBDEs (UNEP 2010b,c)
11
Depending on whether raw foam materials or composite seating, headliners or floor coverings are tested, compliance
with MVSS 302 requires varying amounts of FR content. One major global seating supplier reports that between 0.5
1.0% flame retardant (FR) additives are required for moulded foam products as may be found in seating, arm and head
rests. FR concentrations of 2-5% could be found in moulded carpet padding, and, depending on the headliner fabric and
13
tons of c-PentaBDE and a use rate of 4% in PUR foam the historic production of c-PentaBDE treated foam
can be estimated to approx. 2.5 million tonnes. This number might have been considerable higher
considering that a major application (PUR foam in transport in the US) used c-PentaBDE in transport with the
mentioned lower concentrations. Furthermore the recycling of contaminated PUR foam mixed together with
non-impacted PUR foam lead to increased total quantities of POP-BDE contaminated PUR foam material.
Use of Commercial OctaBDE
The main historic use of c-OctaBDE was in Acrylonitrilebutadiene-styrene (ABS) polymers. This represents
around 95 % of c-OctaBDE supplied in the EU was used in ABS. The ABS in turn was mainly used for
housings/casings of Electrical and Electronic Equipment (EEE), particularly in Cathode Ray Tube (CRT)
housings and office equipment such as copying machines and business printers.12 Other minor uses were
High Impact Polystyrene (HIPS), Polybutylene Terephthalate (PBT), and Polyamide Polymers. These polymers
were also mainly used in electronics but also to some extent in the transport sector.
Other minor uses found in literature include nylon, low density polyethylene, polycarbonate,
phenolformaldehyde resins, unsaturated polyesters, adhesives and coatings (UNEP 2010a,b).
Typical use concentrations in the main use areas were between 12 to 18 %. With the historic total
production of c-OctaBDE being approximately 100000 tones and with a dosage rate of 15%, the primary
treated polymers can be estimated to approximately 800,000 tonnes. Considering the recycling of c-OctaBDE
in new plastic products (secondary contamination) the amount of total impacted polymers is likely to be
considerable more than this.
1.4.5 Risks
At its second meeting, the Persistent Organic Pollutants Review Committee (POPRC) adopted the risk profile
on commercial pentabromodiphenyl ether. At its third meeting, the POPRC adopted the risk management
evaluation on commercial pentabromodiphenyl ether. To view these documents for further information on
the risks pose by commercial pentabromodiphenyl ether visit the New POPs section at www.pops.int.
2 POP-BDE Material Flows & POP-BDE Alternatives

2.1 POP-BDE containing material flows and recycling activities
The information on production and use areas and further considerations of average product lifetime and the
reuse and export potential of articles indicates that some areas are more relevant for this BAT/BEP guide
than others. Consequently, the focus is laid on them. In particular for the materials containing POP-BDE in
the recycling flows and in reuse which was the trigger for the COP4 decision for exemption of POP-BDE in
recycling and reuse need to be assessed in this respect.
It should be highlighted that the recommendations of COP5, POP-BDE containing materials in these areas
should be phased out where feasible (Annex 1). Details of technologies and considerations are then
described in the relevant sections of this guidance.
grade of foam substrate, up to 15% FR content could be found in foam for lamination to headliner fabric (Luedeka
2011).
12
In some regions CRT monitor housing and copying machines are generally already treated separately (e.g.
Europe and Japan)
14
2.1.1 Polymers containing c-OctaBDE
The material flow with the largest amount of c-OctaBDE content are polymers (in particular ABS, HIPS) used
in EEE. To a minor extent c-OctaBDE was used in polymers in the transport sector.
The last production of c-OctaBDE is assumed to have stopped in 2004 in the US. In other regions (e.g. Europe
or Japan) the use of these substances was stopped by the end of 1990s. Large amounts of EEE and WEEE
were and in some cases still are exported from industrial countries/regions (e.g. USA, Europe and Japan) to
developing countries. Furthermore some polymer resin from recycling of WEEE is partly sent to developing
countries (e.g. China or India) where it is recycled to produce new articles. Recent studies have shown that
recycled polymers containing POP-BDE have been used to produce articles for which no flame retardancy is
required including e.g. childrens toys, household goods or video tapes (Hirai & Sakai 2007, Chen et al. 2009,
Chen et al. 2010). This shows that the flow of polymers containing POP-BDE/BFR for recycling are not well
controlled and that polymer containing POP-BDE is being mixed with the non-flame retarded polymer
streams for recycling even for sensitive uses.
From a waste hierarchy and life cycle assessment perspective the mechanical recycling of polymer for
further use is strongly favoured. When polymers are contaminated with hazardous POPs, however,
particular care has to be given to how the waste hierarchy is followed. The Technical Review of the
Implications of Recycling Commercial Pentabromodiphenyl Ether and Commercial Octabromodiphenyl
Ether (UNEP 2010 a,b) highlighted that current exposures to POP-BDE are in some regions at levels where
serious health effects are being measured in epidemiological studies.
In these circumstances it is clearly not sensible to risk increased exposure by recycling materials containing
POP-BDE into uses where exposures cannot be effectively controlled. In some cases the use of recycled
polymer may be significantly more hazardous than in the original use (recycling from a printer housing into a
toy that may be chewed by a child, for example). One task of this BAT/BEP guide is to help to reduce total
exposures and to reduce future risks...
2.1.2 Polyurethane (PUR) foam containing c-PentaBDE
The main uses of PUR foam treated with c-PentaBDE were transport (cars, busses, train etc.) and furniture
with limited use in mattresses and some other uses. Therefore the reuse and recycling of these major
material flows need to be addressed by this BAT/BEP guidance.
For polyurethane foam larger recycling activities used for carpet padding are ongoing in the US and Canada
(Luedeka 2011). Relevant exposure of workers and carpet installers have been demonstrated in a first
studying the US (Stapleton et al.2008) with possible further exposure of consumers. Therefore BAT/BEP
measures are required to reduce of exposure by the separation of POP-BDE containing materials. The extent
of this recycling activity for other regions is unknown. Since the export of used PUR foam containing
furniture from US might be relatively small the impact of c-PentaBDE use in this sector in developing
countries might be expected relatively low but this need to be confirmed by measurements.
On the other hand c-PentaBDE in transport sector was and is regularly sent to developing countries via the
export of second hand cars, busses, trucks etc. from mainly industrial countries. Therefore the transport
sector needs specific BAT/BEP considerations for further management and control of c-PentaBDE in this
sector. The BAT/BEP treatment of these material flows are addressed in section 6.
PentaBDE was also used in rigid PUR foam in construction. In total this is considered a minor use. Further
recycling activities of rigid PUR foam are not known. Therefore this material is addressed by the end-of-life
treatment sections (8 and 10) of this guidance.
15
2.1.3 Printed circuit/wiring boards containing c-PentaBDE
While in western countries c-PentaBDE use in printed circuit board were phased out some time ago13, the
use of c-PentaBDE in South East Asia appears to continue at least until recently. PWBs are a part of WEEE
and contain valuable precious metals and are therefore recycled for material recovery all over the world. The
methods and technologies applied vary widely with a wide range of technologies. Considering the pollution
resulting from non-BAT treatment methods including simple smelters and small workshops of the informal
sector with related environmental pollution including POP-BDE and PBDD/PBDF (see e.g. Yu et al. 2007) a
need for definition of BAT and BEP is a matter of urgency. This material flow is addressed within the sections
5, 8 and 10.
PentaBDE have been used14 in limited quantities for the treatment of textiles (back-coating in transport;
curtains; functional textiles) (UNEP 2009). The extent of recycling of POP-BDE-containing textiles is unclear
but can be assumed to be small for composite materials such as those used in transport. There may be some
limited recycling also for other c-PentaBDE-containing textiles. It can however be assumed that low amount
of POP-BDE containing textiles are in use since the application has stopped about a decade ago. Considering
that the POP Reviewing Committee has decide to suggest Hexabromocyclododecane (HBCDD) to the
Conference of Parties and that the textile sector is a major application, the management of textiles treated
with brominated flame retardants (BFR) with POPs(-like) property can be expected to become a higher
relevance in near future.
PentaBDE has also been used in rubber for e.g. conveyor belts and other minor uses.
For these minor POP-BDE uses this BAT/BEP guide does not describe recycling technologies due to the limit
practical relevance but only refer here to end-of-life treatment (section 8 and 10)
2.1.4 Textiles and rubber containing c-PentaBDE
PentaBDE have been used15 in limited quantities for the treatment of textiles (back-coating in transport;
curtains; functional textiles) (UNEP 2009). The extent of recycling of POP-BDE-containing textiles is unclear
but can be assumed to be small for composite materials such as those used in transport. There may be some
limited recycling also for other c-PentaBDE-containing textiles. It can however be assumed that low amount
of POP-BDE containing textiles are in use since the application has stopped about a decade ago. Considering
that the POP Reviewing Committee has decide to suggest Hexabromocyclododecane (HBCDD) to the
Conference of Parties and that the textile sector is a major application, the management of textiles treated
with brominated flame retardants (BFR) with POPs(-like) property can be expected to become a higher
relevance in near future.
PentaBDE has also been used in rubber for e.g. conveyor belts and other minor uses.
For these minor POP-BDE uses this BAT/BEP guide does not describe recycling technologies due to the limit
practical relevance but only refer here to end-of-life treatment (section 8 and 10)
13
The main flame retardant use in PWB is Tetrabromobishenol A and derivatives
14
DecaBDE and HBCDD is still used in the impregnation of textiles.
15
DecaBDE and HBCDD are still used in the impregnation of textiles.
16
2.2 Alternatives to POP-BDEs
2.2.1 Introduction
C-PentaBDE and c-OctaBDE were phased out about a decade ago and therefore a number of replacements
have been introduced over past 20 or so years. An overview of the alternatives available for c-PentaBDE has
been compiled (UNEP 2009). The data illustrate that there are alternative chemical and non chemical flame
retardants commercially available which are less hazardous than c-PentaBDE. The same is true for c-
OctaBDE.
The goal is to replace harmful substances with safer options and to achieve this, the alternative flame
retardants need to be carefully evaluated. A case by case assessment is necessary to find the best alternative
suitable for specific uses. It is important to consider all the available health and environmental data to obtain
a comprehensive and robust understanding of toxicological, ecotoxicological effects and recycling
performance of the alternatives which may be used (see section 2.2.5 BAT/BEP approach for the assessment
of flame retardants). The options presented here represent a general overview and are not a definitive
review
2.2.2 Role of flammability standards
Policy makers also need to ensure that flammability standards are appropriate and that also consideration
has to be given to other policy measures to ensure fire safety. The difficulties associated with the recycling
PUR foam in the US, for example, arises from the particularly stringent Californian flammability standard
which requires the use of flame retardants in PUR foam in furniture. This and related flammability standards
have resulted in high exposure of the related population to PBDEs (Figure 2; Shaw et al 2010). These
standards have also resulted in associated recycling challenges of flame retarded materials (Luedeka 2011;
UNEP 2010a,b). In other regions in the world less stringent flammability requirements are applied for e.g. in
furniture. No obvious differences in the fire statistics between countries were found (Arcadis & EBRC 2011).
Figure 2: Levels of PBDE in human milk from the third WHO human milk survey (Malisch et al.2005).
2.2.3 Suggested ecological priorities for use of flame retardants
Substitution of flame retardants can take place at three levels:

17
A. Flame Retardant Substitution: This approach involves identifying a drop-in chemical substitute for the
BFR. It is the simplest approach because it typically does not require changes to the polymer material or to
the design of the product.
B. Resin/Material Substitution: This approach involves changing the resin system, while also changing the
flame retardant chemicals. This is a more complex approach than simple flame retardant substitution
because it has a greater effect on overall product cost and performance.
C. Product Redesign: This approach involves changes to the actual product design to minimise or eliminate
the need for flame retardant chemicals. Examples of product redesign include using fire barrier material,
increased separation or reduction of the source of heat from the product and/or the use of alternative
materials (such as metal casings instead of ABS).
The following ecological priorities for the use of flame retardants in products are suggested by the German
environmental agency (UBA 2008 with adjustment)16:
1. Design measures aimed at reducing the use of flame retardants
(E.g. use of flame resistant materials; integration of barrier layers; adjusting flame retardant use to device
voltage)
2. Inorganic flame retardants
(Aluminium hydroxide, magnesium hydroxide, micro-encapsulated red phosphorus and, ammonium
polyphosphate)
3. Reactively bonded, halogen-free organic nitrogen and phosphorus compounds
4a.*Additive halogen-free organic nitrogen and phosphorous compounds that are not persistent or
bioaccumulative and that are not toxic to humans or the environment in the long term.
4b.*Reactively bonded, halogenated flame retardants
4c.*Additive halogenated flame retardants that are not persistent or bioaccumulative and that are not toxic
to humans and the environment in the long term.
These ecological priorities are subject to the following conditions:

The relevant properties of all flame retardants used must have been adequately investigated.
Product manufacture and disposal should not give rise to environmental or health risks.
In specific cases, additional organisational and technical measures may allow alternative
prioritisation.
2.2.4 Alternative flame retardants to c-PentaBDE and c-OctaBDE
Some alternative flame retardants for the main applications of c-PentaBDE and c-OctaBDE are listed in Table
3. Methods and systems to flame retard materials are shown in Figure 3.
The approach to flame retardancy and the choice of the flame retardants should be based on effectiveness,
ecological priorities and consideration of health risks. An element which has largely been ignored in the past
16
In the UBA list the priorities were numbered 1 to 6. However, there have been no full life cycle
assessments (see section 10.4) of the individual FR additives and so prioritising of options 4 and 5 is difficult
given the challenges which may arise from recycling products containing some of the phosphorous based
flame retardants.
18
is the effect on the recyclability of the polymers and other flame retarded materials. The global assessment
of the challenges with the global recycling flow of materials containing c-PentaBDE and c-OctaBDE - which
are the key flame retarded material flows for POPs - (UNEP 2010a,b) demonstrates that significant
improvement in the management of these material flows is required. In future it is important to take into
account the whole life cycle (LCA) of the materials and articles which contain them (see section 2.2).
19
Table 3: Main use areas of c-PentaBDE and c-OctaBDE and alternative flame retardants
(derived from UBA 2008 with additions).
Main Use area of Alternative BFR or CFR Non-halogenated alternatives
POP-PBDEs
Casings of EEE DecaBDE, DBDPE (ABS, HIPS); Phosphorous based halogen-free flame
(c-OctaBDE) HBCDD (HIPS) Additive TBBPA retardants:
(ABS) RDP, BDP (PC, PC/ABS, PPE/HIPS)
FR 245 and S-8010 including
brominated polymers
Small components DecaBDE, DBDPE Microencapsulated red phosphorus,
in EEE (PBT, PET, PA) magnesium hydroxide, melamine, metal
(c-OctaBDE) Brominated polymers phosphinate (PA)
Metal phosphinate (PBT, PET)
Printed circuit Reactive TBBPA Phosphorus based halogen free flame
boards (epoxy resin) Additive TBBPA retardants:
(c-PentaBDE)) (phenol resin) DOPO/aluminium hydroxide (epoxy resin)
Metal phosphinate/DOPO/silica dioxide
(epoxy resin)
Polymer phosphonate (epoxy resin)
Flame resistant thermosets
Flame resistant thermoplastics (under
development)
Textile coatings DecaBDE Inherently flame resistant synthetic fibres
(c-PentaBDE) (various fibres) with integrated flame retardants (PP, PE);
HBCDD Flame resistant synthetic fibres
(various fibres) (polyaramide); glass fibres;
Halogenated PFRs Long term integration of phosphonium
compounds (cellulose);
Intumescent systems (various fibres)
Polyurethane Foam Firemaster 550 and 600 Various barrier technologies
(c-PentaBDE) Halogenated PFRs Substitution of PUR foam in certain
applications
ABS: acrylonitrile-butadiene-styrol PET: polyethylene terephthalate
BDP: bisphenol A-bis(diphenylphosphate PP: polypropylene
DOPO: dihydrooxaphosphaphenantrene PPE: polyphenyl ether
EPS: expanded polystyrene RDP: resorcinol-bis(diphenylphosphate)
HIPS: high impact polystyrene XPS: extruded polystyrene
PC: polycarbonate
20
Figure 3: Methods and systems to flame retard materials (Hull 2010)

2.2.5 BAT/BEP approach for the assessment of flame retardants
Best practice studies have been established for the assessment of flame retardant alternatives including life
cycle considerations and this could be considered to be BAT/BEP.
Assessment approach established by an EU research project (ENFIRO 2011)
ENFIRO (http://www.enfiro.eu/) is a European Commission-funded project which offers a prototypical case

study on substitution options for specific brominated flame retardants. The project aims to deliver a
comprehensive dataset on viability of production and application, environmental safety, and a life cycle
assessment of the alternative flame retardants.
Three FR/product combinations (e.g. metal-based FRs, phosphorous-based and nanoclay-based FRs in
printed circuit boards, paints and foam) are studied for:
Environmental and toxicological risks

Viability of industrial implementation, i.e. production of the FR
Fire safety
Application of the FR into products (electronic equipment, specific plastics, paints and textiles)
The information is used for a risk assessment of the alternative FRs. The outcome of that assessment
together with socio-economic information is used in a life cycle assessment. The project follows a pragmatic
approach, avoiding final recommendations on environment-compatible substitution options that would not
be viable for implementation by industry. The ENFIRO approach represents a practical approach to the
determination of BAT/BEP for the assessment of alternatives.
21
Assessment approach of EPA partnership program Design for the Environment
Under the EPA partnership program for the Design for the Environment17 a multi-stakeholder partnership
on flame retardants in printed circuit boards were formed
(http://www.epa.gov/dfe/pubs/projects/pcb/about.htm) with the goal of incorporating life-cycle thinking
for identifying and evaluating commercially available flame retardants and their human health, safety and
environmental aspects (including ultimate fate) in FR-4 printed circuit boards. The scope of the project
included aspects of the life cycle where public and occupational exposures could occur.
The analysis explored hazard data associated with potential exposure scenarios but did not intend to
conduct a full risk assessment. Therefore the project did not aim for a complete life-cycle analysis, which
inventories inputs and outputs from all (or most) processes throughout the life cycle and evaluates the
environmental impacts associated with those inputs and outputs.
The initial hazard assessment used EPAs criteria for the New Chemicals Program to evaluate hazard
concerns for each flame retardant formulation.
In addition to influencing design decisions, the generated information aimed to inform industry and other
stakeholders on environmentally preferable disposal or recycling scenarios.
The results were published in a report containing the summary of the environmental and human health
attributes of selected flame retardants used in printed circuit boards (USEPA 2008).
3 General BAT/BEP considerations for POP-BDE containing

material flow and recycling
3.1 Waste management hierarchy
Since the use of POP-BDE have largely stopped a decade ago, a large share of POP-BDE-containing materials
have already entered the waste management and recycling flow or might soon come to this stage and
considerations of waste management options play a crucial role in the overall assessment.
The Stockholm Convention guidelines on Best Available Techniques (BAT) and Best Environmental Practices
(BEP) provide a useful starting point for the assessment of waste management options. These guidelines
confirm that society can manage wastes in a number of ways, depending on their physical and chemical
nature, and on the economic, social, and environmental context in which they are produced. Specific
decisions will always be influenced by local circumstances such as the availability of waste treatment
facilities, alternative markets for materials, and the infrastructure available to safely collect, manage and
transport waste materials.
Section III C (ii) of the BAT-BEP Guidelines, shows a hierarchy of decision-making for waste management:
17
www.epa.gov/dfe
22
Figure 4: Waste management hierarchy (Stockholm Convention 2007)
Waste hierarchies (Figure 4) similar to this example have gained practically universal support as a starting
point for managing waste. They are typically used together with life cycle assessments (see section 3.3) and
similar techniques to ensure that the principles are applied soundly to any particular case. In the case of the
BAT-BEP Guidelines the hierarchy is recommended to be used along with a number of principles one of
which is that (in general) priority should be given to approaches that prevent the formation and release of
chemicals listed in Annex C of the Convention.
3.2 Recommendation and reason to separate BFR containing materials
The recommendation of the COP5 based on recommendations given from the POP Reviewing Committee
emphasize the importance to separate POP-BDEs containing materials (Annex 1). These recommendations
were based on an extensive Technical review of the implications of recycling commercial penta and
octabromodiphenyl ethers for the POPs Reviewing Committee (UNEP 2010 a,b).
Whilst separation of material containing any BFRs, including those which are not currently regulated as
POPs, from waste streams goes beyond the requirements arising from the decision of the Stockholm COP
there are good reasons to promote this approach.
These include:
A separation of BFR and non-BFR polymers will improve the recyclability of the polymer streams.
This is valid for all polymers as only single streams can be recycled if high quality needs to be
achieved. Therefore in developing BAT for BFR polymer recycling considerations need to be included
how separation of the individual type of polymers and additives might be achieved to make
mechanical recycling of polymer possible anyhow for EEE (currently e.g. in EU only 8 wt% of WEEE
polymers is recycled including the non flame retarded polymers).
23
For sensitive non-BFR applications made from recycled polymers (toys, kitchen articles, food
packaging, refrigerator interiors etc.) no brominated flame retardants or other critical chemicals
(heavy metals, critical softeners or critical phosphororganic flame retardants) should be present in
these materials.
The WEEE Directive requires the separation of plastics containing brominated flame retardants prior
to recycling, energy recovery or disposal. Also compliance with legislation on Restriction of
Hazardous (RoHS) limit on PBDE in Europe (where DecaBDE is included following the 2008
judgement of the European Court of Justice (ENDS 2008, European Court of Justice 2008)). China has
similar, and in some cases more stringent requirements in the Chinese RoHS. Similar RoHS-like laws
have been adopted in other countries. If properly enforced this is likely to require better separation
of BFR polymers to avoid potentially problematic contamination of polymer streams used in the
production of new EEE and sensitive polymer uses. Countries might define non-sensitive uses where
BFR containing polymer fraction might be used e.g. in construction.
For the recycling of polymers the fraction containing BFRs might be recovered in flame retarded
application if the POP-BDE level and RoHS substance levels are low.
To practically achieve the separation of POP-BDE containing materials in the frame of the convention
(due to legislative requirements)
Separation of BFR and organochlorine for halogen free/low materials for further energy recovery in
halogen sensitive facilities.
Separation of BFR containing polymers for bromine recovery (section 9)
DecaBDE, which is a major global BFR with a historic production of well over 1,000,000 tonnes, is a
precursor of POP-BDE in some environmentally relevant circumstances and technical processes
(UNEP 2010c; UNEP 2010b) and a PBDF precursor during lifespan of some applications and in some
end-of-life treatment scenarios (UNEP 2010b). It therefore needs careful control to avoid its entering
non-BAT processes such as feedstock recycling processes (e.g. fuel production) and other processes
where pyrolysis conditions are prevalent, to avoid the formation of POP-BDE during these processes
(Hall & Williams 2008) as well as the formation of PBDD/PBDF (Weber and Kuch 2003). DecaBDE will
ultimately be degraded with lower brominated PBDEs and PBDFs as significant degradation products
(UNEP 2010b,c). The question is essentially not whether DecaBDE will be degraded but how long
will it take to degrade and to which extent POP-BDEs and PBDFs are formed and what other
degradation products will occur.
In most developing/transition countries there is a limited capacity of the general waste management
streams to deal with any brominated wastes.
There is a current debate as to whether an updated RoHS regulation restriction should cover all BFRs
mainly driven by NGO and consumer demand. Only the development of a strict recycling scheme
with near complete separation of BFR and non-BFR-containing polymers and separation strategies
on polymer types will permit the production of polymer fractions suitable for such a market
demand. When recycling polymers BFR-retarded materials should only be reused in polymers which
require flame retardant properties and POP-BDE/BFR-retarded polymers should not enter non-flame
retarded polymer streams. All BFRs investigated have certain toxic properties and their unnecessary
incorporation into recycling streams is, in practical terms, the use of dilution to treat hazardous
wastes contrary to accepted good practice in waste management. Furthermore if risk assessments
had been undertaken for a BFR, the risk scenarios would only cover the original design usage. If the
BFR is subsequently used for another product then the risk assessment and exposure pathways can
be very different from the original use. This has been shown recently with assessments by Chen et
al. of the risks associated with recycled polymers containing BFRs being used for the production of
24
childrens toys which are vulnerable to exposure routes, such as mouthing, which were not
anticipated in the original use (Chen et al. 2009b, Chen et al. 2010a). Chen demonstrated that such
uses of contaminated recycled polymers carry unacceptable risks and uncertainties for human
health.
The control of the substance flow of BFRs can only realistically be achieved if the global recycling
industry separates the FR and non FR polymer streams.
Some global producers of electronics have phased out brominated flame retardants and aim to
recycle only BFR-free polymer fractions. They are faced with challenges to avoid cross contamination
which is more likely to occur if BFRs are diluted through the stock of polymers.
Many BFRs are aromatic compounds and therefore have varying capacity to form PBDD/PBDF during
the life cycle stages: from production, during use phase and in the end-of-life treatment (Shaw et
al.2010; UNEP 2010b). These chemicals therefore need to be carefully controlled when there is any
possibility that they could enter thermal processes which favour PBDD/DF formation such as
feedstock recycling to fuels; incomplete combustion processes, pyrolysis, gasification or thermal
stress in metal recycling (Weber & Kuch 2003). Separation can assure compliance with the German
Chemikalienverbotsverordnung (for brominated dibenzo-p-dioxins and dibenzofurans) (German
Federal Ministry of Justice 2003, Schlummer et al. 2006)
3.3 Life Cycle Management Considerations for POP-BDE containing materials
Life Cycle Assessment (LCA) is a comprehensive life cycle approach that quantifies ecological and human
health impacts of a product or system over its complete life cycle. The term products is used in a very
broad sense including physical goods as well as services. While the main applications of LCA include the
analysis of the origins of problems related to a particular product; the comparison of improvement variants
of a given product; the design of new products; and the choice between a number of existing comparable
products it can also be applied for comparing recycling and end-of-life scenarios. The use of LCA for the
assessment of management of material and recycling flow is considered BAT/BEP and therefore should be
applied where appropriate.
The basic application of this method includes:
Compiling the inventory of relevant inputs and outputs of a defined system;
Evaluating the environmental impacts associated with these inputs and outputs;
Interpreting of the results of the inventory analysis and the impact assessment.
LCA has been applied for recycling systems including a comprehensive assessment of the Swiss collection
and recovery systems for Waste Electrical and Electronic Equipment (WEEE) (Hischier et al., 2005; Wger et
al., 2011). In that case the following midpoint indicators18 according to the CML methodology (Guine, 2001)
were considered for the evaluation:
Acidification Potential, Global Warming Potential, Eutrophication Potential, Photochemical Oxidation
Potential, (Stratospheric) Ozone Depletion Potential, Abiotic Resource Depletion, Freshwater Aquatic
Ecotoxicity Potential, Human Toxicity Potential, and Terrestrial Ecotoxicity Potential.
18
Midpoints are considered to be points in the causeeffect chain (environmental mechanism) of a particular impact category somewhere between
stressor and endpoints.
25
According to the Eco-Indicator 99 methodology (Goedkoop and Spriensma, 2000) particular attention
should be given to the following endpoint indicators19:
Ecosystem quality,
Human health and
Resources
Life cycle assessments have been undertaken for electronics and transport - the main material flows
impacted by POP-BDE in end-of-life. While the polymer fractions are relevant in respect of POP-BDE
management the key economic drivers for the recycling are the metals. Their efficient recovery makes a
crucial contribution to securing access to many critical metals (mainly precious metals, rare earth elements
and a number of speciality metals). As well as reducing the energy/CO2 impact of metal production sound
recycling usually is much more energy efficient than mining (Hagelken and Meskers 2008).
Technically, recycling processes can be compared regarding their effectiveness and their efficiency. Assessing
the effectiveness makes use of the concept of mixing entropy. Metal concentrating effects (yields) and metal
dissipation (losses) can be evaluated in a comprehensive way by thermodynamically evaluating energy loss
or entropy production comparing the overall concentration of metals with the general resource
consumption (Gling-Reisemann et al. 2011 and Gling-Reisemann 2008a). Most recovered metals can be
processed in state-of-the-art metallurgical facilities to a physical and chemical quality that is identical with
those of primary origin. Thus down-cycling is not an issue for metals and in principle infinite cycles and
substitutability of primary metals can be achieved (Hagelken and Meskers 2008). The technical
performance of the recycling processes should also take into account the quality of resulting polymer
fraction in terms of its suitability to substitute for primary material. Any down-cycling approaches should
be critically reviewed to establish what real environmental or energy-savings are being achieved.
Since the life cycle assessments for Electronics and End-of-life Vehicles have so far only been performed in
industrial countries, it would be useful to perform such assessments in low and middle income countries
where recycling technologies and approaches are different and can be more labour intensive. This may lead
to better separation and sorting in the dismantling stage and hence higher value and more useful outputs.
In addition to LCA, economic considerations clearly need to be taken into account to ensure practical
applicability.
3.3.1 LC considerations for the polymer fraction from vehicles
The light fraction of auto shredder residue (containing most of the polymer fraction) is usually defined as the
1525% mass remaining after de-pollution, dismantling, shredding of the hulk, and removal of metals from
the shredded fraction from an end-of-life vehicle (Vermeulen et al 2011). These wastes tend to contain high
levels of heavy metals, flame retardants and POPs including PCBs and PCDD/PCDFs. The current disposal
practice for those wastes is mainly by landfilling. Also in developing countries having often no shredding
process the polymer materials are normally disposed to landfills/dumps.
Alternatives can be assessed and compared by using lifecycle assessment models and financial
considerations to quantify both the ecological and economical benefits of the technologies.
19
Endpoints are those elements of an environmental mechanism that are in themselves of value to societye.g. human health damage to plant or
animal species and depletion of natural resources such as fossil fuels and mineral ores.
26
To date only a few papers have addressed this topic (Vermeulen et al 2011). Depending on their basic
assumptions and system boundaries, general conclusions can slightly differ (Boughton and Horvath 2006,
Ciacci et al 2010; Duval et al (2007). There is common ground, however, that landfill should be the least
preferred option.
The life cycle assessment (LCA) approach of Boughton and Horvath (2006) considered hydrolysis to light fuel
oil (thermo-chemical treatment), co-combustion in a cement kiln and material recovery for recycling as
alternatives to landfill of ASR. They concluded that the co-combustion of ASR in a cement kiln is the most
advantageous and practical short term option, assuming that co-combustion of ASR would not affect the net
release of emissions, product quality or kiln operation. However, as mentioned in section 8.3 there are
environmental concern to be taken into consideration.
In another study five ASR management strategies were compared using the LCA approach to quantify their
environmental impact (Ciacci et al. 2010): (i) landfilling, (ii) increased metal recovery before landfilling, (iii)
increased metal recovery before thermal treatment with energy recovery, (iv) advanced material recovery
(by post shredder treatments) followed by energy recovery and (v) feedstock recycling. It was found that
scenario (iv) and (v) resulted in the highest environmental benefits compared to the present practice, with a
small advantage for feedstock recycling as the best solution because it achieved the highest recycling rate.
Both studies point out that environmental considerations should be matched with economical
considerations. In this respect one study revealed that market conditions still need to be improved in order
to facilitate profitable recycling of automotive plastics (Duval et al. 2007). These economic barriers or market
uncertainties often hamper the full-scale application of alternative ASR treatment methods (Vermeulen et al
2011). Considering that price for polymers is likely to increase with rising energy prices and decreasing oil
resources, such recycling can be expected to be more economically attractive in the future.
3.3.2 LC considerations for WEEE
Hischier et al. (Hischier et al. 2005) examined the question of whether WEEE recycling makes sense from an
environmental perspective by a detailed life cycle assessment approach focusing on the environmental
impacts of the Swiss take-back and recycling systems. The results of the LCA study demonstrated that for
waste electrical and electronic equipment a take-back and recycling system has clear environmental
advantages compared with the baseline scenario which assumed incineration of all WEEE. This was true
even if only the primary production of the raw materials was considered in the baseline scenario and
impacts of the disposal of the WEEE (i.e. its incineration) were ignored. The environmental impact from
recycling was assessed to be much smaller than that from the primary production.
The conclusion was that because recycling shows such clear environmental advantages over incineration a
recycling goal as high as possible should be aimed for (Hischier et al. 2005). The life cycle benefits are
particularly obvious for the recovery of metals. Printed Wire Boards (PWBs), for example, have an average
composition which includes 15-20% copper, 200-250 ppm gold, 1000 ppm Ag and 80-100 ppm palladium
(Hagelken 2006). This can be compared with gold ores which can be economically mined with
concentrations as low as 0.5 ppm20. Typical ore grades in open mines are 15 ppm and in hard rock mines
are usually at least 3 ppm. Most copper is mined as copper sulphide from deposits that contain 0.4 to 1.0%
copper. The recycling of precious metals including gold from PWBs is thus self-evidently attractive.
Moreover, PWBs also contain a wide range of other base and special metals, many of which can be co-
recovered in modern integrated smelter-refineries (Ni, Pb, Sn, Bi, Sb, ). Hagelken provides a detailed
description of such processes (Hagelken 2006)
20
http://en.wikipedia.org/wiki/Gold
27
Polymers are almost completely derived from petrochemicals produced from fossil oil and gas.21 Recycling
them from E-Waste makes sense from an environmental and economic perspective. Furthermore as the
manufacture of polymers also requires energy, their production consumes similar quantities of fossil fuels to
their raw materials (Hopewell et al. 2009). In spite of the fossil fuel intensity of polymers, and the low
thermal efficiency of most energy recovery processes (17-30% without combined heat and power for a
modern incinerator (European Commission 2006)) some countries burn most of their polymer waste
(Hopewell et al. 2009):
An assessment on the recycling potential of polymers from the European market have indicated significant
ecologic and economic benefits (Slijkhuis 2011): If 50% of the WEEE polymers from the European market
were recycled then emissions of CO2 could be reduced by nearly 2 million tons and over 10 million kilowatt
hours of energy would be saved in the energy required to convert petrochemicals into polymers. By
achieving this recycling level WEEE recyclers would become more economic because their single largest
waste stream would be turned into a resource. There would be significant environmental and social benefits
from such recycling if the necessary measures to prevent exposures of workers and the appropriate use of
the resulting polymers to protect consumers could be guaranteed. Furthermore additional jobs would be
created, as polymer recycling is more labour intensive than the production of virgin polymers (Slijkhuis
2011).
From an economic perspective the combination of separation technologies can lead to an economic process
for the polymer fraction from WEEE (Figure 7; section 5.4).
Japan has established a Japanese Industrial Standard (JIS) for optimising the recycling of polymers in electric
home appliances, marking for identification of plastic parts for electrical and electronic equipment (C9912).
This standard requires the marking of polymer parts such as flame retardants (FR), recycled polymers and
dismantling procedures. Thus, the information flow is linked with the mass flow. In particular, the marking
system includes polymers already recycled by closed-loop recycling (recycling from polymers of electric
home appliances to polymers of electric home appliances). Target recycling rates for different electronic
categories have also been set (Aizawa et al. 2010).
3.3.3 LC considerations for the management of PUR foam
PUR foam currently appears to be recycled to a major extent only in North America (to carpet padding). In
most countries PUR foam is sent to landfill or is incinerated. Therefore the current life cycle of polyurethane
cannot be considered sustainable in most countries. This has potential for improvement with increased
recycling. However one limitation is that currently PUR foam can only be brought back to the same use (by
grinding into new polymers or glycolysis) to a limited extent and most PUR foam is down-cycled to
applications like carpet rebond.
3.3.4 LC considerations for bromine recovery
Currently bromine is not recovered from the POP-BDE/BFR containing material flows and there is no
evidence of such closed cycle recycling in prospect22. While some promising technologies have been
21
Hopewell (Hopewell et al. 2009) suggested that around 4 per cent of annual petroleum production is
converted directly into polymers from petrochemical feedstock.
22
Also the recycling rate of BFR containing polymers is low (estimated for polymers from WEEE to 8% for the
EU; PlasticsEurope 2010) and only a part of these materials are recycled in flame retarded polymers.
Therefore the substance flow of BFRs in the overall material flow can currently not be considered
sustainable.
28
developed to recover bromine from POP-BDE/BFR containing material flows (section 9), no full scale facility
has been operated for this purpose. For a sustainable substance flow this gap should be closed. The
increased emphasis on separating POP-BDE/BFR containing materials likely to be triggered by Stockholm
Convention activities might offer options to collect bromine enriched material streams which could then be
used for bromine recovery.
Compliance with the Stockholm Convention obligations should also reduce the current non-sustainable
approaches of open burning and dumping of POP-BDE containing materials. The Convention should
therefore improve the end-of-life management of POP-BDE/BFR containing materials by encouraging the use
of more appropriate treatment and recycling technologies (Table 4). These are likely to have higher direct
costs than open burning and dumping (although they are actually cheaper when external costs on
environment and human health are included (see Table 4)). The recovery of bromine might offer a revenue
stream to contribute towards these costs in cases where the polymers can not be directly recycled. To
further encourage this option, the costs of thermal treatment and landfill or dumping need to better reflect
their true costs. For thermal facilities this might include environmental costs of emissions, corrosion of
facilities and the costs of appropriate disposal of the ashes. Such costs are currently only quantified in
hazardous waste incinerators which charge approximately 10 Euro per 0.1% of bromine (and chlorine) in
their waste streams (Fernwrme Wien GmbH 2011). In case of residue disposal (see section 10), costs need
to reflect the need for engineered landfills with long-term aftercare.
29
3.4 Overview on treatment options of POP-BDE containing materials considering key criteria
Table 4: Comparative emissions and impacts of the various recycling and recovery technologies (UNEP 2010a)
* The PBDE material is just introduced with the metal fraction; ** Economics includes external cost considerations
30
3.5 General BAT/BEP considerations
In this guidance a number of different techniques and processes carried out in specific
facilities/installations are described (Sections 5 10). However, for all these installations, applicable
general BAT/BEP have been developed which should be taken into account even though not all apply
to each installation. Consequently, this general BAT/BEP is supposed to be considered in individual
cases and may be adapted to them.
3.5.1 Environmental management systems (EMS)
These are techniques related to the continuous improvement of environmental performance. They
provide the framework for ensuring the identification, adoption and adherence to BAT options that
nevertheless remain important and can play a role in improving environmental performance at
facilities. Indeed, these good house housekeeping/management techniques/tools often prevent
emissions.
A number of environmental management techniques are determined as BAT. The scope and nature of
an Environmental Management System (EMS) will generally be related to the nature, scale and
complexity of the installation, and the range of environmental impacts it may have.
BAT/BEP in this respect include:
Implementing and adhering to an EMS that incorporates, as appropriate to individual circumstances,
the following features -
a. definition of an environmental policy for the installation by top management (commitment of
the top management is regarded as a precondition for a successful application of other features of
the EMS)
b. planning and establishing the necessary procedures
c. implementation of the procedures, paying particular attention to
structure and responsibility
training, awareness and competence
communication
employee involvement
documentation
efficient process control
maintenance programme
emergency preparedness and response
safeguarding compliance with environmental legislation.
d. checking performance and taking corrective action, paying particular attention to

monitoring and measurement
corrective and preventive action
maintenance of records
independent (where practicable) internal auditing in order to determine whetheror not
the environmental management system conforms to plannedarrangements and has been
properly implemented and maintained.
e. a commitment to continuously increase the energy efficiency of the installation, by:
aa. developing an energy efficiency plan
31
bb. using techniques that reduce energy consumption and thereby reduce both direct (heat
and emissions from on-site generation) and indirect (emissions from a remotepower station)
emissions
cc. defining and calculating the specific energy consumption of the activity (or activities),
setting key performance indicators on an annual basis (e.g. MWh/tonne of material/waste
processed).
Within the EMS, have a noise and vibration management plan in place where needed.
Management of the process generated materials and residues BAT/BEP is to:
Have a residue management plan as part of the EMS including:
a. basic housekeeping techniques
b. internal benchmarking techniques
Consider any future decommissioning at the design stage. For existing installations and where
decommissioning problems are identified, put a programme to minimise these problems in place.
3.5.2 Material/Waste management in facilities and processes
Many processes described in this document are often related to products/materials after their
product lives are complete. In other words, they involve recycling, material/energy recovery or
disposal. Concerning material/waste management, the generic BAT/BET for material/waste
management systems described herein seek to increase the knowledge of incoming materials and
waste, and of how to properly store, handle, and dispose of wastes. as well as the improvement of
knowledge of material and waste leaving the facility (waste Out) are listed.
Material/Waste management system
BAT/BEP is to:
have a system in place to guarantee the traceability of materials and wastes treatment.
A good traceability system contains the following features:
a. A procedure to document the use and treatments of materials and wastes by flow charts and
mass balances
b. A procedure to carry out data traceability through several operational steps (e.g
preacceptance/acceptance/storage/treatment/dispatch). Records can be made and kept up-to-
date on an ongoing basis to reflect deliveries, on-site treatment and dispatches. Records are
typically held for a minimum of six months after the waste has been dispatched
c. A clear reference and recording system on waste characteristics and the source of the waste
stream that it is available at all times.
d. This may consist of a computer database or a series of databases, that are regularly backed up.
The tracking system for a material/waste inventory/stock control system should include:
date of arrival on-site, waste producer details, an unique identifier code, pre-acceptance and
acceptance analysis results, a description of package type and size, intended treatment/disposal
routes, an accurate record of the nature and quantity of materials/wastes held on-site including all
hazards details on where the material/waste is physically located in relation to a site plan, at which
point in the designated treatment route the material/waste is currently positioned.
e. Drums and other mobile containers should be moved between different locations (or loaded for
removal off site) only under instructions from the appropriate manager, ensuring that the waste
tracking system is amended to record these changes.
Have and apply mixing/blending rules oriented to restrict the types of wastes that can be
mixed/blended together in order to avoid increasing pollution emission of down-stream waste
treatments. These rules need to consider the type of materials/waste (e.g. hazardous, non hazardous),
32
waste treatment to be applied as well as the following steps that will be carried out to the waste OUT
(see below).
A segregation and compatibility procedure should be in place that includes:
a. Detailed and accurate records of the testing, including any reaction giving rise to safety
parameters (increase in temperature, generation of gases or pressure spikes); a record of the
operating parameters (viscosity changes and separation or precipitation of solids) and any other
relevant parameters, such as the generation of odours.
b. packing containers of chemicals into separate drums based on their hazard classification.
Chemicals which are incompatible (e.g. oxidisers and flammable liquids) should not be stored in
the same drum.
Have an approach for improving waste treatment efficiency. This typically includes the finding of
suitable indicators to report waste treatment efficiency and a monitoring programme.
Produce a structured accident management plan and have and properly use an incident diary.
Incoming materials and wastes
To improve the knowledge of the incoming material and waste, the BAT/BEP is to:
have a concrete knowledge of incoming material/wastes in respective facilities. Such knowledge needs
to take into account the outgoing material/waste, the treatment to be carried out, the type of
material/waste, the origin of the material/waste, the recommended procedures and the risks
involved.
Implement a pre-acceptance procedure containing at least the following items:
a. tests for the incoming material/waste with respect to the planned treatment
b. making sure that all necessary information is received on the nature of the process(es)
producing the material/waste, including the variability of the processes. The personnel having to
deal with a possible pre-acceptance procedure need to be able due to his profession and/or
experience to deal with all necessary questions relevant for the treatment of the materials/wastes
in the facility.
c. a system for providing and analysing a representative sample(s) of the material/waste from the
production process producing such material/waste from the current holder.
d. a system to carefully verify, if not dealing directly with the waste producer, the information
received at the pre-acceptance stage. This should include the contact details for the waste
producer and an appropriate description of the material/waste regarding its composition and
hazardousness.
e. making sure that the classification is according to the national legislation and is provided
f. identifying the appropriate treatment for each waste to be received at the installation by
identifying a suitable treatment method for each new material/waste enquiry and having a clear
methodology in place to assess the treatment of waste. This should considers the physico-
chemical properties of the individual material/waste and the specifications for the treated
material/waste.
Implement an acceptance procedure containing at least the following items:
a. a clear and specified system allowing the operator to accept material/wastes at the receiving
plant only if a defined treatment method and disposal/recovery route for the output of the
treatment is determined.
Regarding the planning for the acceptance, it needs to be guaranteed that the necessary storage
treatment capacity and dispatch conditions (e.g. acceptance criteria of the output by the other
installation) are also respected.
33
b. measures are in place to fully document and deal with acceptable material/wastes arriving at
the site, such as a pre-booking system, to ensure e.g. that sufficient capacity is available
c. clear and unambiguous criteria for the rejection of wastes and the reporting of all conformance
violations.
d. a system be in place to identifying the maximum capacity limit of material/waste that can be
stored at the facility
e. visually inspect the incoming material/waste to make sure it complies with the description
received during the pre-acceptance procedure..
Implement different sampling procedures for all different incoming material/wastes delivered in bulk
and/or containers. These sample procedures may contain the following items:
a. sampling procedures based on a risk approach. Some elements to consider are the type of
materials/waste (e.g. hazardous or non-hazardous) and the knowledge of the customer (e.g. waste
producer)
b. check on the relevant physico-chemical parameters. The relevant parameters are related to the
knowledge of the material/waste needed in each case to register of all waste/materials.
d. have appropriate sampling procedures. The procedure should contain a system for recording
the number of samples and degree of consolidation
e. sample prior to acceptance
f. a system for determining and recording:
a suitable location for the sampling points
the capacity of the vessel sampled
the number of samples and degree of consolidation
g. a system to ensure that the material/waste samples are analyzed if needed
Have a reception facility that meets at least the following criteria.
a. A laboratory to analyze the samples at the speed required by BAT. Typically this requires having
a robust quality assurance system, quality control methods and maintaining suitable records for
storing the analyses results. Particularly for hazardous wastes, this often means that the
laboratory needs to be on-site.
b. have a dedicated quarantine waste storage area as well as written procedures to manage
rejected waste. If the inspection or analysis indicates that the wastes fail to meet the acceptance
criteria (including, e.g. damaged, corroded or unlabeled drums) then the material/wastes can be
temporarily stored there safely. Such storage and procedures should be designed and managed to
promote the rapid management (typically a matter of days or less) to find a solution for that
material/waste
c. have a clear procedure dealing with wastes where inspection and/or analysis prove that they do
not fulfil the acceptance criteria of the plant or do not fit with the material/waste description
received during the pre-acceptance procedure. The procedure should include all measures as
required by the permit or national/international legislation to inform competent authorities, to
safely store the delivery for any transition period or to reject the material/waste and send it back
to the waste producer or to any other authorized destination
d. move material/waste to the storage area only after acceptance
e. mark the inspection, unloading and sampling areas on a site plan
f. have a sealed drainage system if needed
g. a system to ensure that the installation personnel who are involved in the sampling, checking
and analysis procedures are suitably qualified and adequately trained, and that the training is
updated on a regular basis.
34
h. the application of a waste tracking system unique identifier (label/code) to each container at
this stage. The identifier will contain at least the date of arrival on-site and the waste code
Storage and handling
In several areas of treating POP-BDE containing materials and wastes they have to be stored and
handled (e.g. electronic waste, shredder residues, PUR foams). Furthermore POP-BDE containing
materials might need storage until final disposal.
BAT/BEP is to:
Apply the following techniques related to storage:
a. locating storage areas away from water courses and sensitive perimeters, and in such a way so
as to eliminate or minimise the double handling of wastes within the installation
b. ensuring that the storage area drainage infrastructure can contain all possible contaminated
run-off and that drainage from incompatible wastes cannot come into contact with each other
c. using a dedicated area/store which is equipped with all necessary measures related to the
specific risk of the wastes for sorting and repackaging laboratory smalls or similar waste. These
wastes are sorted according to their hazard classification, with due consideration for any potential
incompatibility problems and repackaged if needed. After that, they are removed to the
appropriate storage area
g. equipping tanks and vessels with suitable abatement systems when volatile emissions may be
generated, together with level meters and alarms. These systems need to be sufficiently robust
(able to work if sludge and foam is present) andregularly maintained
h. storing organic waste liquid with a low flashpoint under a nitrogen atmosphere to keep it
inertised. Each storage tank is put in a waterproof retention area. Gas effluents are collected and
treated.
Apply the following techniques concerning tank and process pipework labelling:
a. clearly labelling all vessels with regard to their contents and capacity, and applying an unique
identifier. Tanks need to have an appropriately labelled system dependingon their use and
contents
b. ensuring that the label differentiates between waste water and process water, combustible
liquid and combustible vapour and the direction of flow (i.e. in- or outflow)
c. keeping records for all tanks, detailing the unique identifier; capacity; its construction, including
materials; maintenance schedules and inspection results; fittings; and the waste types which may
be stored/treated in the vessel, including flashpoint limits where necessary.
Apply the following techniques when handling waste.
a. having systems and procedures in place to ensure that wastes are transferred to the
appropriate storage safely
b. having in place a management system for the loading and unloading of materials/waste in the
installation, which also takes into consideration any risks that these activities may incur.
c. ensuring that a qualified person attends the waste holder site to check the old original waste,
waste from an unclear origin or undefined waste (especially if drummed), to classify the
substances accordingly and to package into specific containers. In some cases, the individual
packages may need to be protected from mechanical damage in the drum with fillers adapted to
the packaged waste properties.
The following techniques when containerised materials/wastes are handled:
a. storing of containerised wastes under cover. This can also be applied to any container that is
held in storage pending sampling and emptying. Some exceptions on the applicability of this
35
technique related to containers or waste not affected by ambient conditions (e.g. sunlight,
temperature, water) have been identified. Covered areas need to have adequate provision for
ventilation
b. maintaining the availability and access to storage areas for containers holding substances that
are known to be sensitive to heat, light and water, under cover and protected from heat and direct
sunlight.
Maximise the use of re-usable packaging (drums, containers, IBCs, palettes, etc.)
Outgoing materials and wastes
To improve the knowledge and management on the outgoing waste/material BAT/BEP is to:
analyse and guarantee the quality and composition of the material/waste OUT according to
the relevant parameters important for the receiving company/facility.
assess how and where wastes could be re-use in ESM as feedstock for another industry
assure that the materials and wastes are labeled according to the waste management
catalogue and other labeling criteria of the country.
assure that contaminated materials are only delivered to companies with appropriate
treatment capacity and management frames in place. For wastes the appropriateness of the
treatment technologies is to be assured (e.g. landfill category, co-incineration in BAT cement
kilns, BAT incinerators).
3.5.3 Crusing, shredding, sieving and washing operations
Within the management and treatment of POP-BDE containing materials crushing, shredding and
sieving operations are common.
BAT/BEP is to:
Perform crushing, shredding and sieving operations in areas fitted where needed with extractive vent
systems linked to abatement equipment when handling materials that can generate emission to air
(e.g. dust, VOCs, odours).
Perform washing processes considering:
a. identifying the washed components that may be present in the items to be washed (e.g.
solvents, oil, refrigerants)
b. transfering washings to appropriate storage and then treating them in the same way as the
waste from which they were derived
c. using treated waste water from the water treatment plant for washing instead of fresh water.
The resultant waste water can then be treated in the waste water treatment plant or re-used in
the installation.
3.5.4 General BAT/BEP considerations in respect to air and water releases
Air emission treatment
To prevent or control the emissions mainly of dust, VOC and odours and some inorganic compounds,
BAT is to:
restrict were needed the use of open topped tanks, vessels and pits by:
a. not allowing direct venting or discharges to air by linking all the vents to suitable abatement
systems when storing materials that can generate emissions to the air (e.g. VOCs, dust, odours).
b. where necessary keep the waste or materials under cover or in waterproof packaging.
36
Correctly operate and maintain the abatement equipment, including the handling and
treatment/disposal of spent scrubber media. Have a scrubber system in place for the major inorganic
gaseous releases from those unit operations which have a point discharge for process emissions.
Have leak detection and repair procedures in place in installations a) handling a large number of
piping components and storage and b) compounds that may leak easily and create an environmental
problem (e.g. fugitive emissions, soil contamination). This may be seen as an element of the EMS.
Air emissions should be reduced at least to the levels required by the respective national legislation.
Facilities are encouraged to use BAT technologies to achieve BAT emission level.
Appropriate monitoring schemes should be in place to supervise the performance and document
releases.
Waste water treatment
BAT/BEP is to:
reduce the water use and the contamination of water by:
a. applying where necessary site waterproofing and storage retention methods
b. carrying out regular checks of storages, bunkers, pits and tanks
c. where appropriate applying separated water drainage according to the pollution load (roof
water, road water, process water)
d. applying a security collection basin
e. performing regular water audits, with the aim of reducing water consumption and preventing
water contamination
f. segregating process water from rainwater
Have procedures in place to ensure that the effluent specification is suitable for the on-site effluent
treatment system or discharge
Avoid the effluent by-passing the treatment plant systems
Have in place and operate an enclosure system whereby rainwater falling on the processing areas is
collected along with tanker washings, occasional spillages, drum washings, etc. and returned to the
processing plant or collected in a combined interceptor
Segregate the water collecting systems for potentially more contaminated waters from less
contaminated water
Have a full concrete base in the critical area, that falls to internal site drainage systems which lead to
storage tanks or to interceptors that can collect rainwater and any spillage.
Collect the rainwater in a special basin for checking, treatment if contaminated and further use.
Maximise the re-use of treated waste waters and use of rainwater in the installation
Identify waste waters that may contain hazardous compounds. Segregate the previously identified
waste water streams on-site and specifically treat waste water on-site or off-site.
Select and carry out the appropriate treatment technique for each type of waste water.
Implement measures to increase the reliability with which the required control and abatement
performance can be carried out (for example, optimising the precipitation of metals)
Identify the main chemical constituents of the treated effluent (including the make-up of the COD)
and to then make an informed assessment of the fate of these chemicals in the environment
37
Only discharge the waste water from its storage after the conclusion of all the treatment measures
and a subsequent final inspection
Achieve the water emission values required by national legislation and/or competent authority before
discharge. Facilities are encouraged to use BAT technologies to achieve low releases of pollutants to
water.
3.5.5 Prevention of soil contamination
To prevent soil contamination, BAT is:

to provide and then maintain the surfaces of operational areas, including applying measures
to prevent or quickly clear away leaks and spillages, and ensuring that maintenance of
drainage systems and other subsurface structures is carried out
to utilise an impermeable base and internal site drainage
to reduce the installation site and minimise the use of underground vessels and pipe work
to avoid the releases of waste water discharge to soil
to assure that only non-contaminated sludges from waste water treatment are applied to soil
38
4 Specific BAT/BEP on monitoring of POP-BDE/BFR in

articles
The COP5 recommended separation of POP-BDE containing articles requires the screening and
detection of POP-BDEs or bromine containing materials. One challenge and prerequisite is a quick and
reliable detection of POP-BDE in articles which would allow the separation of POP-BDE containing
materials in recycling processes. These technologies are described and discussed shortly in this
section. Their applicability and potential use is then discussed in the sections describing BAT/BEP for
treating material and recycling streams.
4.1 Determination of POP-BDEs in articles
4.1.1 Identification of POP-BDEs by standard PBDE analysis
An International Standard IEC 62321 Ed.1 (International Electrotechnical Commission 2008) has been
developed for Electrotechnical products. The Determination of PBDEs (monoBDE to decaBDE) in
polymers by GC-MS is described in Annex A to IEC 62321 - including extraction, analysis and quality
assurance. So far the analytical method described in IEC 62321 is only informative and still not a
reliable method23 and is as edition 2 under evaluation.
The current state-of-the-art analytical GC/MS techniques for POP-BDE require appropriate
extraction and clean-up. Extraction is done by solid liquid extraction (soxhlet, pressurized liquid
extraction or ultrasonic assisted techniques) (Riess et al 2000) or by dissolution in appropriate solvent
(Schlummer et al 2005). Since the normally applied organic solvent co-extracts polymers, a cleanup is
necessary in order to provide an extract appropriate for a sensitive GC-MS analysis.
Sample extraction and clean-up take considerable time - normally days from delivering a sample to
receiving the results from the laboratory. If a large investment in equipment was to made then such
an analysis could be established in-house with automated preparation. In such cases the turn-
around time frame might be reduced to several hours. Even this would present practical difficulties
for routine use in the screening of the POP-BDE levels of recyclate at pre-treatment plant. Most
recycling operators would have to rely on commercial laboratory services for GC/MS analysis,
however, and the timescale of those services makes this type of screening entirely impractical.
Furthermore the relatively high price of GC/MS analysis will not allow a comprehensive screening of
POP-BDE containing equipment.
GC-MS analysis is therefore not practical to identify the presence of POP-BDEs in the recycling and the
waste stream for practical separation of materials.
4.1.2 Rapid analysis techniques for POP-BDEs
To achieve a practical screening method it is necessary to use faster extraction techniques and to omit
the clean-up steps. Phlein et al. (Phlein et al. 2008) developed a rapid screening method for BFR
including PBB and PBDE in polymer samples using ultra sonic extraction and GC-MS analysis. The time
of analysis is 9 min (GC/MS) or 15 min (GC/ECD) and this method was validated for suitability to
determine PBB, PBDE and other brominated flame retardants in styrenic industrial polymers from
WEEE.
An alternative method to screen brominated flame retardants including POP-BDEs in a selective mode
without extraction and clean-up has been established. Danzer et al. (Danzer et al. 1997) used online
pyrolysis of pulverised polymer and analysed with gas chromatography coupled to mass spectroscopic
detection (py-GC/MS). This thermo-desorption method for polymers was optimised for more than a
23
Sofar the inter-laboratory studies did not give very positive results
39
decade and was used by Rie in the rapid screening of approximately 100 TVs and 80 computers (Rie
et al. 2000).
The pyrolysis GC/MS method has since been developed to a commercially available application by
Shimadzu with a 48 sample auto-sampler (Shimadzu 2010).
A number of other rapid analysis systems for PBDE measurement have been presented at a meeting
for establishing the second edition of IEC 62321 standard for determining PBDE and PBB in electronic
equipment (Tange 2010).
The pyrolysis of matrices might also lead to degradation of PBDEs including the debromination
reactions which have been reported for GC/MS analysis.
An independent evaluation of the quality of results of such rapid screenings has not been performed.
This will be necessary since the approach of rapid extraction might lead to an underestimation of POP-
BDE concentrations.
Rapid analytical techniques with reduced (or no) clean-up steps will reduces the number of injections
between GC/MS (or other instrument) maintenance and shortens the lifetime of the relatively
expensive GC columns (even if pre-columns are used). Both possible drawbacks need to be assessed if
such rapid analysis might be used as options for POP-BDE screening. Such considerations are even
more important for developing countries where maintenance of sophisticated analytical instruments
is a particular challenge,
Such quick chromatographic methods optimized for time would still require at least 15 to 60 minutes
when the sampling, grinding, pyrolysis, minimum GC separation on short column, data acquisition and
data interpretation are included.
Even time requirements of 15-minutes for a sample would be still much too long for practical
application for separation in a WEEE or other recycling plant.
4.2 In situ measurement of bromine in articles
An alternative monitoring method can aim for the elimination of BFR-containing materials by
screening of Bromine using appropriate screening technologies. From a practical perspective a
separation of BFR materials from non-BFR-containing material is preferable to an attempt to sort POP-
BDE containing materials alone and there are a range of reasons to separate BFR containing polymer
(See section 3.2).
A range of technologies have been suggested or are used as screening tool in WEEE treatment plants
(FT-IR24, Sliding Spark Spectroscopy, XRT, XRF, LIBS25).
24
While the FT-IR can detect some IR active BFRs (e.g. TBBPA) it cannot detect PBDEs and therefore is not
applicable in this context. Near infrared technology (NIR) is performed with manual sensors (e.g. IOSYS) in
dismantling plants or in automatic sorting systems (e.g. TiTech, RTT). NIR light is directed to the waste plastic
and the reflected NIR spectrum is captured and analysed. Programmable operational databases allow the
identification of the different plastic types the machine has been taught. However, WEEE plastics normally
contain a high proportion dark coloured or black plastics and the reflected spectra from these are weak so that
they are often inadequate for accurate polymer identification. Furthermore whilst TBBPA and derivates can be
detected with NIR the technique is not capable of detecting and separating plastics containing PBB or PBDE.
These problems severely limit the operational utility of NIR for WEEE waste streams. While the FT-IR can detect
some IR active BFRs (e.g. TBBPA) it cannot detect PBDEs and therefore is not applicable in this context.
25
Michael Stepputat and Reinhard Noll, "On-Line Detection of Heavy Metals and Brominated Flame
Retardants in Technical Polymers with Laser-Induced Breakdown Spectrometry," Appl. Opt. 42, 6210-
6220 (2003)
40
From these methods three technologies have been approved BFR screening capability in long time
trials (WRAP 2006) and/or are used in full scale facilities and can be considered BAT/BEP for the
screening of bromine:
XRF
Sliding spark spectroscopy
XRT
4.2.1 Sliding spark spectroscopy
Sliding spark spectroscopy is a surface screening method capable to rapidly detect bromine, chlorine
and inorganic additives. With a comparatively simple system, sliding spark spectroscopy allows direct
in-situ analysis of handy, compact non-conductive material without prior sample preparation. The
basic principle of the method is the thermal vaporization, ionization and excitation of a small amount
of surface substrate using a train of high-current sliding sparks. The material components in the spark
plasma are activated to emit radiation. From the atomic spectrum, information on the composition
and the element concentration in the sample can be obtained.
As described by Seidel et al. (1993) intense optical emission is observed when positionally stable high-
current surface sparks (max. 800 Ampere/pulse) are sliding over compact non-conductive materials
such as polymers, glasses, quartz filters or powder pellets. Substrate vaporization, ionization and
excitation processes in the surface discharge plasma channel generate emission corresponding to
neutral and ionic states. The spectra are essentially composed of lines emitted by the electrode
material (e.g. copper, silver), from the substrate under investigation, radiation continuum as well as
structured background from the surrounding air atmosphere. Proper software treatment of the
detected spectra allows the rapid multi-element screening of the investigated material.
Thus, identification of chlorine containing polymers (PVC or chlorinated flame retardants), BFR
containing materials and inorganic additives (fillers, stabilizers, BFR synergists) is has been described
(Golloch and Seidel, 1994, Seidel et al, 1993, Schlummer and Murer 2006).
The instrument costs approximately $6,000 (Seidel, 2010).
4.2.2 X-ray fluorescence (XRF)
X-ray fluorescence (XRF) is the emission of characteristic "secondary" (or fluorescent) X-rays from a
material that has been excited by bombarding with high-energy X-rays or gamma rays. Whereas the
primary radiation in bench top systems is generated from x-ray sources, handhelds work with beta
emitters (Nickel-63). As the sample is exposed to a beam of X-ray quanta from a tube, a proportion of
these X-rays also reach the detector in the form of radiation background as a result of physical
scattering processes including Rayleigh and Compton scattering. While the scattered Bremsstrahlung
proportion generally produces a continuous background, the scattered characteristic radiation of the
anode material contributes towards the line spectrum. Besides the lines of elements from the sample,
the anode material's lines and the scattered Bremsspektrum usually appear as well as a background.
Background and characteristic scattering can be very effectively reduced by inserting a suitable
absorption material between tube and sample.
The Bremsspektrum and the characteristic radiation of the X-ray tube's anode material are used to
excite the characteristic radiation of the elements in the sample material. Therefore, it is necessary
provide incident X-ray quanta which are higher than the binding energy of the element's inner
electrons.
When measuring X-rays, use is made of their ability to ionize atoms and molecules, i.e. to displace
electrons from their bonds by energy transference. In suitable detector materials, pulses whose
strengths are proportional to the energy of the respective X-ray quanta are produced by the effect of
41
X-rays. The information about the X-ray quanta's energy is contained in the registration of the pulse
height. The number of X-ray quanta per unit of time, e.g. pulses per second (cps = counts per second,
kcps = kilocounts per second), is called their intensity and contains in a first approximation the
information about the concentration of the emitting elements in the sample.
The XRF technology can be used for detection and separation of PBDE/BFR-containing polymer with a
detection limit of 10 to 100 ppm. XRF analysis is limited to the detection of bromine in the material,
without any capacity to identify the type of BFR compound. Using handheld instruments the time
requirement for a measurement is less then a minute. Precision of XRF screening measurements is
limited and thus relative standard deviations of up to 30% may be obtained. However, this is only
critical when measuring levels very close to a given threshold. Therefore, the measuring threshold
should be at least 30% below the threshold defined for separation.
The cost of an instrument is approximately $30,000 to $50,000. Therefore the use in small size
enterprises may be limited.
Please note: Since handheld XRF are including radioactive Nickel-63 x-ray sources t should to be
considered and hint to the necessity to be operated by specially trained personnel and consider
national guidelines regulating the use and education of the operator. In addition it has to be stressed,
that the Nickel-63 containing XRFs require special waste management and treatment at the end of the
products lifetime.
4.2.3 X-ray transmission (XRT)
X-ray transmission technology uses an electric X-ray source which creates a broad-band radiation in
the energy range of 80 KeV to 160 KeV. This radiation penetrates the segregation material and, when
attenuated, hits an X-ray camera sensor using two independent sensor lines with different spectral
sensitivity. The absorption depends on both the solid density and the material thickness. The larger
the atomic mass and the thicker the material, the greater the absorption. In order to compensate for
this technical problem, the material to be sorted is illuminated from two different directions. The
resulting different transmission paths make it possible to ignore the material thickness, when applying
high speed X-ray processing.
The XRT monitors the atomic density of the materials. The atomic density, however, is increased if a
halogenated compound is present in the sample, and therefore XRT allows a separation of halogen
containing and halogen free materials. Anyway, absorption may be increased by other additives
(fillers), too, and in consequence, XRT separation may also separate some bromine and chlorine free
materials
In contrast to the handheld screening instrument (XRF and SSS) normally applied in dismantling plants
it is intended to sort scrap automatically.
5 Specific BAT/BEP: POP-BDE/BFR containing polymer in

WEEE
As described above (section 1.4.4) the main use of c-OctaBDE was in polymer parts of Electrical and
Electronic Equipment (EEE) which can be considered the largest stock and recycling flow containing c-
OctaBDE. Therefore the management of this material flow and related EEE waste (WEEE) is of
particular relevance for this BAT/BEP guidance.
5.1 Recovery of materials from WEEE
The management of POP-BDE containing polymers needs to be assessed and addressed in the larger
frame of BAT/BEP for the management and treatment of EEE and WEEE. To describe BAT/BEP for the
recycling of WEEE is beyond the scope of this document. However BAT/BEP for management of
(selected) WEEE is currently established e.g. in the frame of the Basel Convention and on national
42
level (e.g. in Germany VDI 2343 (2007)). The first international guidance in this respect has been
established for ICT equipment under the Partnership for Action on Computing Equipment PACE (Basel
Convention and UNEP 2011).
Following guidance documents might be consulted for the management of EEE and WEEE
e-Waste Assessment Methodology Manual developed (based on the methodology of the e-
Waste Africa project of the Secretariat of the Basel Convention)) (PACE project group 2010)
Sustainable Innovation and Technology Transfer Industrial Sector Studies: Recycling from E-
waste to resources (UNEP and StEP 2009)
Technical review of the implications of recycling commercial penta and octabromodiphenyl
ethers and Annexes. (UNEP 2010 a,b)
Guideline on environmentally sound material recovery/recycling of End-of-Life computing
equipment (Basel Convention and UNEP 2011)
5.2 Reuse of EEE
According to the waste management hierarchy, repair and reuse of used EEE is the preferred option
for end-of-life management. Reuse extends the life span of products, hence safes energy for the
manufacturing of new equipment and lowers the environmental impacts of mining for raw materials.
However also re-used equipment will turn to waste at a certain point and requires appropriate
treatment options.
Since the use of c-OctaBDE has ended for most regions before 2000 currently not many EEE now and
in future considered for reuse are expected to contain POP-BDE. Therefore the reuse sector for many
EEE is likely not impacted significantly by POP-BDE. Exceptions are CRT monitors and TVs, which still
appear in significant volumes on the reuse market, especially in developing countries. Some special
attention also has to be given to EEE with origin from the US market, where c-OctaBDE has been used
until 2004.
5.3 Polymer recovery & separation of BFR containing materials from
WEEE
Currently mainly the recovery of metals is the key driving force in WEEE recycling. Therefore current
WEEE recycling activities and facilities are normally not optimized for the separation of PBDE/BFR
containing polymer. The metal recyclers have to look then for a downstream outlet for the WEEE
polymers which is an increasing market in recent years.
In most facilities WEEE shredded is resulting in a mixed polymer fraction. Since the recycling industry
collects different categories (TV/monitors, PCs, white goods, small electronics, lamps, etc. eventually,
others) and uses different plant designs to recover metals and other recyclable materials, the final
polymer rich fraction is a complex mixture of polymer types with some contaminants (POP-BDE, other
BFRs, heavy metals). Example of an average composition of WEEE polymer fraction is shown in the
graphs below (Figure 5 and 6). Currently most WEEE recycling facilities do not separate these mixed
polymer fractions and pass the polymer rich fraction to other specialised operators.
43
Figure 5: Composition of the polymers rich mixture after metal recovery from E-Waste shredding
(source MBA polymers 2007)
Some aim for the recovery of residual metals in these polymer-rich fractions, others recycle parts of
the polymer fraction, a third group recovers energy and a large proportion of WEEE polymers are sold
as mixed polymer for export - mainly to China or India (UNEP 2010b). In many parts of the world the
polymer fraction, particularly in shredder residues, is sent to landfill or incinerated, often in non-
BAT/BEP facilities.
The four main reasons for the limited number of approaches for recycling mixed polymers from WEEE
are:
a) Industry using secondary polymer materials has tight specifications in relation to polymer quality,
both chemically (RoHS compliance) and with respect to material properties.
b) WEEE polymer fractions often contain 15 and more different polymer types (Figure 6; Dimitrakakis
et al. 2009). Whilst three polymers (ABS, PS, PP26) account for between 70% and 85% of total the
efficient sorting of the mixtures presents difficult technical challenges and a degree of cross-
contamination is inevitable in practice.
c) WEEE polymers contain RoHS/SC listed BFRs (c-OctaBDE and c-DecaBDE but normally no/low c-
PentaBDE or PBB)27 along with other BFRs which may be more heavily regulated in the future.
Potential customers are therefore risk adverse to contaminated recyclate. Only a limited number of
companies can separate polymers with BFR.
d) Production of larger volumes with identical properties and performance, as required by many major
manufacturers, is difficult, whereas one main challenge is to overcome inhomogeneity in different
input streams.
26
Without BFR
27
But normally no PBB which is also listed in RoHS and the Stockholm Convention
44
Figure 6: Polymer types identified in small WEEE polymer samples (%, w/w) (Dimitrakakis et al. 2009).
Some types of polymers used in WEEE equipment are high value engineered thermopolymers, types
which can be repeatedly softened by heat and hardened by cooling, and so are valuable to recycle. If
these engineered thermoplastics can be recovered in a consistent, steady stream of raw material, they
can be sold for a profit.
TV and computer monitors provide two of the richest sources of polymers: the polymer content in
these two product groups varies between 10 and 40 weight percent. The major polymer part of a
monitor is the rear part of the housing and this is separated for recycling and to gain access to the
cathode ray tube. These polymer parts are normally removed by hand in the facilities and result
therefore in a clean polymer fraction consisting mainly of ABS and HIPS which can then be recycled.
To maximize resale value, polymers must then be sorted by polymer type (e.g., HIPS, ABS
thermoplastic), and by colour (e.g., white, black). After polymer has been cleaned and sorted into a
specific type, it will need to be reduced in size to make it manageable for storage, transportation, or
further processing. This can be done by hand tools such as scissors, shears, etc., or by baling,
shredding and size grading. Some mechanized operations combine heating, rapid cooling and cutting
into grain. These smaller pieces are then typically heated and forced (extruded) through a die to form
strings and pellets for final sale as polymer raw materials. It must be mentioned that this polymer
fraction is most heavily traded at prices which do only allow a limited number treatment steps,
especially when cost for incineration of PBDE/BFR containing polymers has to be covered. Therefore
the cost of such treatment needs to be covered by the revenue of WEEE recycling (e.g. noble metals)
or by legal implementation of the extended producer responsibility (e.g. European WEEE or Chinese
WEEE regulation). Alternatively to incineration, BFR containing polymers may serve as source for
recovery of bromine (see section 9) or might be treated by the CreaSolv process extracting ABS and
PS from polymer mixtures to recover and sell BFR free polymers (processes not yet as full scale; see
section 8).
While initial collection and handling of unbroken polymer parts and cases should not involve relevant
exposure to hazardous substances, all subsequent processing that involves breakage of recovered
polymers may cause concerns. Polymer particles, additives and brominated flame retardants may be
released, causing exposures to workers. Size reduction and granulation can also generate heat and, if
not properly managed, open smoke and fire. After granulation, the polymer will be moulded into a
desired shape under elevated pressure and temperature, and there may again be exposure to
substances contained in the polymer and new substances such as halogenated dioxins and furans.
Even when BFRs are not present, workers should be protected with ventilation and personal
protective equipment from inhalation of hydrocarbons and additive stabilizers.
5.4 Technologies to separate PBDE/BFR-containing polymers
Technologies to separate PBDE/BFR-containing polymer intend to pick PBDE/BFR free polymers out of
WEEE polymers and aim at transferring these into valuable and marketable products. The overall cost
45
for these technologies (or a set of technologies, including treatment of by-products without an
economical value) need to be covered by revenues from the marketable products. Thus, development
and running and combining these technologies is driven mainly by economy of the overall process
chain. That means that separation of PBDE/BFR is only a part of the overall strategy to produce
valuable products with a reasonable high yield and a quality accepted by producers of new products
(See Figure 7).
Polymers in waste of electric and electronic equipment may be transformed into valuable recycled by
a chain of optimised processes. These processes may be performed by more than one company. Only
if the cumulative cost of processing is lower than the revenues for the recycled product, the process
chain is economic feasible (See Figure 7).
Therefore, separation of PBDE/BFR-containing polymer needs to be effectively integrated with the
technologies used for shredding of WEEE and separation of polymers for polymer material recycling
and for metal recycling as these are the main driving force of a recycling plant.
The following techniques are used in full-scale plants for recycling polymers and may be used in a
plant recycling polymers from WEEE belong to one of the following groups:
a) Sorting technologies optimised for bulk polymer shred, capable to detect BFRs
b) Manual sorting approaches, capable to detect BFRs partly supported by handheld screening
instruments intended for large polymer parts as complete casing parts
c) Polymer separation technologies aiming at the sorting of pure and defined polymer fractions
46
Figure 7: Polymers in waste of electric and electronic equipment and their transformation into
valuable recycled by a chain of optimised processes28. A list of possible processes is given,
but it does not claim to be complete. Only if the cumulative cost of processing are lower
than the revenues for the recycled product, the process chain is economic feasible.
None of the single techniques, however, has the ability to separate mixed polymers from WEEE; to
ensure that the polymer is separated into marketable polymer fractions; and that at the same time
POP-BDE/BFR-containing polymers are separated. Therefore, combinations of the above mentioned
28
There is no stringent rule for the choice of processes; however, in the sense of this guidance at least one
principle of BFR removal should be applied. Further, the processes may be performed by more than one
company.
47
techniques are applied (see section 5.4). In addition it has to be stressed, that no technique achieves a
100% separation, leading to residual BFR levels in the intended bromine-free fraction. In case of
handheld sorting this is due to personal mistakes of the personnel. In case of automated systems, it
has been shown that sorting efficiency with blowing bars has its limits and the purity of sorted
fractions is normally below 95%.
Another general drawback is that there are polymer parts in WEEE which origin from recycling from
POP-BDE/BFR containing polymers. These may contain mixtures of different BFR, including c-OctaBDE,
but exhibit bromine levels in the range of 100-1000 ppm. Only XRF is sensitive enough to trace these
materials.
It need to be mentioned for recycling companies handling CRT monitors often managed the polymers
in a separate way as they are aware of the specific type of polymers and type of flame retardant. By
pre knowledge they keep these streams separate and collect the polymers. Because the main stream
is grey coloured more techniques can be used.
The following sections shortly describe technologies capable to separate BFR containing polymers. A
following section (5.4.5) will describe how these techniques can be combined with other treatment
processes for waste polymers in order to recover valuable and marketable recycled polymers.
5.4.1 Instrumental techniques to separate polymers
XRF technology
The XRF technology has been described in section 4. It can be used for detection and separation of
POP-BDE/BFR-containing polymer with a detection limit of 10 to 100 ppm. XRF analysis is limited to
the detection of bromine in the material, without any capacity to identify the type of BFR compound.
Applying handheld items the time requirement for a measurement is less then a minute. With the cost
of approximately $40,000 to $50,000 the use in small size enterprises may be limited. However, the
handheld XRF instrument needs a direct contact to the material surface and it is therefore not
applicable for use in automated sorting systems but is used in the dismantling stage. Coated materials
need to be specifically addressed by scratching the coating.
Sliding spark spectroscopy
The lowest detection limit for bromine with this technology is 0.1%. For practical reasons the system is
normally set at 1% bromine by the recyclers in order to screen out POP-BDE/BFR containing polymers
which normally contain between 3 and 20% POP-BDE/BFR.
Sliding spark spectroscopy using hand-held instruments is used in WEEE dismantling plants and other
fields for screening halogens in polymer. It allows operators to distinguish between BFR-containing
(halogen containing) and almost BFR (halogen) free components. The scanning time is quick and takes
only a few seconds. As discussed for handheld XRF, the SSS instrument needs a direct contact to the
material surface and coated materials need to be specifically addressed by scratching the coating.
With dual-function equipment including NIR this method can also distinguish different polymer types.
Instruments with this integrated function therefore have the potential for practical separation not
only of PBDE/BFR and non-PBDE/BFR polymer but also for separation of polymer types at e-waste
dismantling and recycling facilities at the dismantling stage. As mentioned above, NIR has difficulties
with recognizing black polymer.
XRT technology
The X-ray transmission has been described above (section 4). It (e.g. X-Tract, TiTEch) has been
developed to separate materials with different optical densities. In contrast to the handheld screening
instrument (XRF and SSS) normally applied in dismantling plants it is intended to sort scrap
automatically. Applying fast-running belts and blow out bars, which eject particles from the waste
stream, if the measured optical density increases an adjustable threshold value, industrial machines
sort up to 1 tonne of scrap per hour.
48
The technology is successfully used to separate PBDE/BFR-containing polymers from BFR-free types at
RUAG company (Switzerland). It may, therefore play an important role in WEEE polymer recycling
plants particularly if combined with NIR.
According to TiTech their system is able to clean and separate alumina fractions, CRT glass fraction (Pb
vs non-Pb), RDF fractions from metals, glass and PVC and to remove halogen-containing materials.
However, there is only limited information on the separation success with mixed WEEE polymer scrap,
the waste fraction containing the majority of WEEE polymers. And, XRT is not a stand-alone technique
as the produced bromine reduced fractions require further treatment with respect to produce
marketable recycled polymer.
Sorting machines based on X-ray transmission are available at an industrial scale. They cost several
hundred thousand Euros (the system from TiTEch, for example costs approximately 400,000) and
consequently may be too expensive for small to medium recycling and WEEE dismantling operations.
5.4.2 Instrumental separation of polymers in developing countries
Screening technologies to determine polymers containing POP-BDE/BFR for developing countries need
to be straightforward to use, reliable and economical. The XRF and Sliding Spark Technology are
established, relatively simple and robust methods and therefore appear appropriate for use in
developing countries in WEEE recycling and similar facilities. Both methods are labour intensive and
this is a disadvantage in industrial countries where they are relatively expensive to use because of the
associated operational costs. The lower wages in developing/transition countries and the need to
provide employment means that these handheld screening technologies might be seen as an
advantage for these countries.
The cost of the XRF equipment is in the range of $40,000 to 50,000 and therefore might be costly for
(small and medium size) WEEE recycling companies in developing countries.
The sliding spark technology for the detection of halogens (IoSys 2010) is cheaper and costs around
US$ 6,000. A German producer of sliding spark technology has confirmed that equipment has been
supplied to China and South Africa (Seidel 2010) thus indicating that the technology is already used in
developing/transition countries29. Such handheld sliding spark equipment is available with additional
detectors (NIR) for determination of the polymer type and can be used for producing clean polymer
fractions with associated higher market values (cost approximately US$ 33000). The manual
determination of polymer type to produce clean polymer fractions might be an attractive option for
recovery of high quality polymer from developing and transition countries and this could be combined
with the separation of POP-BDE/BFR-containing polymer.
The use of these technologies needs to be further assessed for their practicability30. Alternatively to
screening for separation purpose of polymer such equipment might be used for confirmation of other
separation techniques (sink & float or manual separation based on experience).
The automated XRT method is a relatively expensive technology which can be used for automated
screening. Its potential usefulness for developing countries should be evaluated with experiences
gained in industrial countries.
29
It is not documented for what tasks the equipment is used in South Africa and China.
30
International projects on WEEE recycling in developing/transition countries could determine whether such
equipment is already used for selection of the polymer types and if there is already any experience on
determining bromine content in practical operations.
49
5.4.3 Separation of POP-BDE/BFR-containing polymer by manual pre-sorting
BEP Approach applied in Sweden
The principal method currently used in the Swedish recycling industry for the assessment and
separation of polymers from TVs and computer monitors containing BFRs from those without is
manual pre-separation (Retegan et al. 2010). This approach is used only for TVs and Monitors and not
for other WEEE. However it is not clear how many of the non-marked polymer do contain POP-
BDE/BFRs. Operators use written instructions and guidelines listing various WEEE polymer
components which are most likely to contain BFRs. The listed items are removed manually from the
waste stream (Retegan et al. 2010).
More experienced staff and those with formal training and experience of manually sorting WEEE
polymers and parts containing BFR can effectively sort polymers and remove those components which
their experience has shown to contain BFRs (Retegan et al. 2010).
Even experienced manual sorting operatives cannot ascertain which type of BFR is incorporated in the
polymers.
The use of manual sorting relies on the expertise of experienced and motivated personal. According to
the Swedish report the accuracy of such sorting should be supervised by spot-checks using XRF
measurements (Retegan et al. 2010).
The Swedish report did not include information about the effectiveness of this approach. It claimed,
however, that for waste TV and PC monitors the accuracy of these sorting methods are satisfactory for
complying with the European directives/legislation (Retegan et al. 2010). The compliance with
legislation is not surprising as the numbers of residual articles still containing c-PentaBDE or c-
OctaBDE has now dropped to low levels in Europe (Wger et al.2010) (i.e. the lifespan of the articles in
which POP-BDE were used is short and there has very little use of POP-BDE for the past decade in
Europe).
Applicability of manual separation for other regions
The effectiveness of manual separation need to be evaluated in other countries or regions where the
composition of BFR in the different WEEE categories is likely to be different before a BEP
recommendation can be given.
The separation of a larger share of potentially c-PentaBDE and c-OctaBDE-containing equipment might
be possible in particular for regions where c-PentaBDE and c-OctaBDE were phased out in the 1990s
(e.g. Japan or Europe). Here mainly older TVs, monitors, and other electronics produced in the 1990s
and earlier, would need separation and could be separated.
For regions where c-OctaBDE (and c-PentaBDE) was used until 2004, and particularly in the US where
volumes were very high, even relatively new equipment can contain c-OctaBDE (and c-PentaBDE) and
manual separation of POP-BDE-containing equipment is likely to be less effective.
Manual separation of POP-BDE/BFR-containing polymer in developing
countries
Manual separation of POP-BDE-containing materials without instrumental help might be an option to

some extent if the flow largely stem from the period where c-OctaBDE have not been used anymore in
the region and only a few older equipment have to be sorted out. In developing countries often large
stocks of WEEE from the 1990s and early 2000 exists with high percentage of BFR containing TV
casings and computer monitors (Sindiku et al.2011). Therefore for stocks in developing countries (at
least the African region) such pure manual pre-sorting without a bromine screening seems currently
not a feasible approach to remove POP-BDE. However practical tests are missing.
50
Also considering the complexity of the thousands of different electronics (different types, different
producers and different series from same type and same producer) and the uncertainty of producers
having used a BFR type, manual separation seems challenging.
Whilst there are obvious attractions in the simplicity of this approach a more detailed analysis of the
correlation between the visual assessments and XRF screening would be necessary before such an
approach could be recommended as BAT/BEP.
5.4.4 Separation of polymers by Sink and float technologies (S/F)
Polymer types exhibit different specific weights and therefore liquid media with appropriate densities
allow for separation of different thermoplastics into density groups. The salinity, and hence the
density, of the liquid media can be changed by adding different salts. If water is being used, for
example, the density can be raised to 1.15 by the addition of magnesium sulphate.
Brominated flame retardants additives increase the density of the ABS and HIPS materials
significantly, when added at typical concentrations (> 3%). If treated in an appropriate liquid medium,
bromine-free polystyrene will float while bromine-containing polystyrene will sink, thus separating the
polymers containing bromine from other polymers.
Schlummer et al. propose a simple two stage separation, which has recently been tested successfully
in a German collaborative project (SpectroDense). At first the mixture is treated in a liquid with a
density around 1100 kg/m. The float fraction will mainly consist of PP, PE and BFR-free PS, ABS,
whereas BFR containing styrenics, but also PPO/PS and PC/ABS (both flame retarded with phoshphate
based FR) and highly filled PP items will sink. The float fraction is further treated with water (density
1000 kg/m) in order to separate HIPS and ABS from PP and PE.31 Valuable polymers as PC/ABS and
PPO/PS (normally free of POP-BDE) might be separated from the heavy fraction by downstream NIR
techniques, as these materials are grey in many cases.
For selected input fractions the sink and float technology produces very clean and qualitatively good
products in respect to separation of BFR-containing materials. TV-cases contain mainly HIPS and in
Europe about 30%32 of the casings contain BFR. Here S/F is a good way to separate them, whereas the
high yields of BFR free materials suggest a good economy of the process.
With respect to BFRs, and especially POP-BDE, S/F has been reported to effectively separate BFR-
containing from non-BFR types of ABS and/or HIPS. For Sweden, S/F has been reported separation of
BFR rich fractions of TV/PC from low BFR fraction intended for recycling purposes. One challenge of
the sink and float technology is that the fractions of HIPS/PPO (1150 kg/m3) and PC/ABS (1180 kg/m3)
are present containing phosphorus flame retardants and must be considered in the overall separation
strategy (see below).
With respect to polymers from small electronic equipments and mixed WEEE polymer from recycling
of mixed WEEE, S/F can produce almost bromine-free polymer fractions, which consist of largely of
ABS, PS (incl. HIPS) and polyolefins. However, due to a large share of black polymers in these low-
bromine fractions, which inhibit a downstream NIR separation, it is challenging to produce high quality
polymers with a good market price as useful output. Currently, the yield of these techniques does not
normally allow economic recovery of polymers. Unless the bromine free fraction can be converted
into valuable recyclate then S/F is unlikely to be widely used as operators are (understandably)
31
These two binary mixtures could further be separated by NIR or electrostatic separation.
32
The content of BFR will depend on the region and the legislation for flammability standards - in the US/Canada
most of the casings contain flame retardants.
51
unwilling to use a separation technique to produce what might be, in effect, two new waste streams
without adding value to the output.
5.4.5 Combination of techniques for producing marketable products
None of the single techniques described above has the ability to separate mixed polymer from WEEE;
to ensure that the polymer is separated into marketable polymer fractions; and that at the same time
POP-BDE/BFR-containing polymers are separated. Therefore, combinations of the above mentioned
techniques need to be in a practical way.
In this section theoretically suitable process chains are described, which include steps for a separation
of POP-BDE/BFR followed by technologies focussing on polymer separation and upgrade of fractions
(whereas section 5.4.7 list existing plants). The process combination base only on technical
considerations and do not state economic feasibility. However, the latter may differ significantly in
different countries and need to be calculated for the respective combination of technologies and
country frames.
Dismantling NIR sink and float ( Electrostatic separation)
Dismantling sites usually recover CRT glass from computer monitors. As these products contain rather
large polymer housings, which are in most cases built by PS, ABS or blends of these polymers with
polycarbonate (PC/ABS) or polyphenylene oxide (PPO/PS), dismantling personal can easily produce a
polymer fraction from these items upon the established glass recycling process.
After a coarse crashing process, the material waste polymers can be separated into the following
polymer fractions by online NIR: light PS, light ABS, light PC/ABS, light PP, light PPO/PS and dark
materials which cannot be identified with NIR.
The light PS and light ABS as well as the dark fraction are most likely containing higher amounts of BFR
which can be separated by the sink & float technology when performing two separation runs in
density media of 1000 and around 1100 kg/m. The sink & float technology bases on the fact, that BFR
rich ABS and PS exhibit significantly higher densities compared to non-BFR ABS and PS.
As the dark density fraction 1000-1100 kg/m is intended to contain both, ABS and PS, a subsequent
separation of both materials is preferred and can be performed by electrostatic separation (e.g.
Hamos GmbH, Penzberg). The latter technique is available on industrial scale and works best for
binary and well dried polymer mixtures. In this process, the plastic mixture is fed via a vibrating
conveyor into a so-called tribo-electric charging unit. Different plastics are charged here selectively
and specifically according to the material, taking on a positive or negative charge. This effect is
brought about by the passing of electrons from one particle to another. After charging has taken
place, the plastic mixture reaches a high tension field where the components are separated
electrostatically into pure sorted fractions according to their different charges. Positive particles are
attracted by a negative electrode, while negative particles are rejected and vice versa.
Dismantling -> Sink and float ( Electrostatic separation)
Dismantling sites usually recover CRT glass from TV-sets. As TV-sets contain rather large polymer
housings, which are predominately composed of by PS and only in minor cases by ABS or PP,
dismantling personal can easily produce a polymer fraction from these items upon the established
glass recycling process. In a recent research project it has been shown, that it is possible to reduce the
amount of non BFR-ABS in this fraction to a minimum by training of personnel. This is important, since
the main colour of TV-sets is dark and thus not available to NIR sorting.
After a material grinding process, the PS rich fraction is separated in a BFR rich and almost BFR free
fraction by sink&float. Again, the sink&float technology bases on the fact, that BFR rich PS exhibit
significantly higher densities compared to non-BFR ABS and PS.
52
As the dark density fraction 1000-1100 kg/m is intended to contain both, ABS and PS, a subsequent
separation of both materials is preferred and can be performed by electrostatic separation. The latter
technique is available on industrial scale and works best for binary and well dried polymer mixtures.
Dismantling -> manual sorting ( sink and float)
The most elaborative approach is the manual sorting, preferably assisted by handheld NIR and a
handheld bromine identification tool (SSS or XRF). In addition to these tools, sorting personnel would
be able to check casing for materials stamps indicating the type of material. By these techniques
trained personnel may be able to collect a high share of (almost) BFR free materials by sorting
bromine negative items from dismantled polymer streams. Subsequently NIR technologies will enable
to produce fractions of defined polymer types for further processing.
A disadvantage of this approach may be that large items like housing of printers, monitors and TV-sets
have a comparable high share of highly BFR containing materials, which are side products requiring a
sound waste treatment. In contrast, polymers parts from non BFR or low BFR equipment are normally
smaller are most often not dismantled and treated by shredder techniques instead.
Shredder sink&float Electrostatic separation
Shredded polymers from mixed WEEE (especially small WEEE appliances) have to pass removal steps
for FE and non Fe metals and dust before they may be treated by a two-step sink and float process in
density media of around 1100 kg/m and 1000 kg/m. The fraction smaller than 1000 kg/m is
intended to be rich of PP and minor amounts of PE. The intermediate density fraction is considered to
contain BFR free ABS and PS as well filled PP types. These three fractions may be subsequently
separated by electrostatic separation.
Shredder XRT spectroscopy
From mixed WEEE fraction pa polymer fraction is recovered in state of the art WEEE treatment plants
by a set of smashing, grinding and mechanical separation processes. Since this fraction has a typical
particle size below 20 mm, automated online rather than manual separation processes are required
for further upgrading this fraction for polymer recovery.
Bromine and chlorine may be removed by online XRT technology producing a low-bromine fraction of
mixed polymers composed of up to 16 polymer types. The main polymer types (PS, ABS, and PP) may
be recovered subsequent online NIR, however, this technique is limited to the fraction of light
materials, which is unfortunately not the major fraction of WEE polymers.
In a current pilot test, Fraunhofer IVV (Freising, Germany) and the company Unisensor (Karlsruhe,
Germany) test and optimise a new automated sorting technique basing on laser spectroscopy. Results
obtained so far clearly indicate that this technique is able to separate several polymer types out of a
mixed input stream of shredded polymers automatically with high throughput rates (~1 ton per hour).
Laser spectroscopy (in contrast to NIR) can identify black and dark polymers and might therefore
become a key technology to transform BFR free polymer shred from WEEE into marketable sorted
polymer type fractions. Further investigations are focusing on the identification of BFRs with laser
spectroscopy applying comparable high throughput rates.
5.4.6 Comparison of technology combinations to separate polymer streams
Some practical combinations of technologies used for separation of polymers for different input
materials are listed in Table 5. Also the possible product output, the status of development and the
economy or available commercial systems are mentioned
Table 5: Combinations of separation techniques, input materials, products, status of development and
remarks on related economy
53
Combination Suitable BFR free Technical Economy Reference

Input Products status of
development
Dismantling NIR Polymers ABS, PS Approved Economy Schlummer
sink and float ( from depends on (2011)
Electrostatic separation) dismantled the yield of
WEEE items BFR free
products
Dismantling Sink and TV casings HIPS Approved Approved Schlummer
float ( Electrostatic (2011)
separation)
Dismantling manual Polymers ABS, PS, Approved Not approved
sorting ( sink and from PC-ABS in developed
float) dismantled countries
WEEE items
Shredder Sink and Mixed WEEE ABS, PS, Approved System runs HAMOS33,
float ( Electrostatic (small PP successfully at Wersag34
separation) appliances) wersag AG
(Groschirma,
Germany)
Shredder XRT Mixed WEEE BFR and Approved No information Schlummer
spectroscopy PVC (2011)
free
polymer
mix
33
www.hamos.com/products/newsletter/newsletter-archive/2011-recycling_of_plastics_from_electronic_waste,378,eng,455
34
www.wersag.de/index.php?page=about&lang=de
54
5.4.7 Full scale plants to separate WEEE and POP-BDE/BFR containing

polymers
In table 4 full scale WEEE treatment plants or plants treating WEEE polymers and their potential to
separate POP-BDE-containing polymers.
Table 4: Full scale WEEE/WEEE-polymer treatment plants and their potential to separate POP-BDEs-
containing polymers.
PBDE/BFR
Quality of Elimination Development
Separation Polymers
WEEE input separated (RoHS Reference
techniques Separated Stage*
polymers compliant
products)
Yes
Mixed A) Low-BFR
A) Good
polymer types of
Not (Custome BFR rich
Industrial
MBA
from WEEE ABS, HIPS fraction Polymer
disclosed r specify) scale
(Austria, and PP incinerated Patent
China)
Small
electronic BFR and
Industrial (Gerig
equipment, Includes XRT PVC free Good Yes
scale 2010)
White goods polymers
(Switzerland)
Low-BFR
WEEE
types of Industrial (Morton
polymers Undisclosed Good Yes
ABS and scale 2007)
(UK)
HIPS
Low-BFR
WEEE Undisclosed
types of Industrial (wersag
polymers (incl. S/F and Good Yes
PP, ABS scale 2011)
(Germany) Electrostatic)
and HIPS
TV and Low-BFR
computer Manual, not types of Industrial (Retegan
casings Good Yes
disclosed ABS and scale 2010)
(Sweden) HIPS
Mixed
Successive BFR and Not
polymer Industrial (Adamec
Grinding and PVC free approved Yes
from WEEE scale 2010)
XRT polymers yet
(Germany)
55
5.5 Material recycling of polymer containing POP-BDEs
The recycling of POP-BDE containing material is discouraged by the recommendations of COP5 (Annex
1) and the reasons detailed in the reports from the POPs Reviewing Committee (UNEP 2010a,b) and
other studies (Wger et al.2010). Additionally for Europe the RoHS Directive35 regulates the End-of-
Waste status of recycled polymers also restricting DecaBDE into EEE36. Similar regulations have been
established in other countries.
However the exemptions listed in the Convention allow the recycling of POP-BDE containing materials
if a country has registered for this exemption.
For such recycling of POP-BDE containing polymers important considerations needs to define the
BAT/BEP in respect to:
the labelling of WEEE polymer fractions containing POP-BDE for further processing and the
labelling of articles produced from such recyclates
minimization of occupational exposure in the processing stage
the type of articles produced from such WEEE polymer fractions
the end-of-life treatment of materials and articles containing POP-BDE from recycling.
5.5.1 Labelling of POP-BDE containing polymer fraction and articles
Polymer fraction containing POP-BDE (and other polymer fractions from WEEE recycling37) should not
be recycled into sensitive uses (see Table 6). To avoid such uses, polymer fractions from WEEE
recycling should be labelled or otherwise marked that its origin is known when it is exported/imported
and used by industries for new articles.
Table 6: Examples of sensitive use areas* where POP-BDE containing recycled polymers must not be
used**
Sensitive uses
Toys
Food packaging; food containers
Kitchen equipment
Refrigerator interior***; Freezer interior***
Water tanks (in particular tanks used for drinking water)
Water pipes (in particular drinking water pipes)
Silos, storage and piping for food and animal feed
Polymer parts with direct contact
(Furniture, handles of tools, doors, etc.)
* In such applications generally recycled polymer fractions containing heavy metals, or critical
softeners, brominated flame retardant, phosphororganic flame retardant or other critical chemical
should not be used.
** The list are just key examples of sensitive uses and is not considered comprehensive
35
And the REACH Regulation
36
c-DecaBDE can still be recycled into applications different than EEE.
37
These polymers can contain other hazardous substances like heavy metals (including antimony,
cadmium), other BFRs, PFRs or softeners.
56
*** The recycling of polymers from WEEE polymers containing no critical chemicals is encouraged
following cradle to cradle principle e.g. polymers from refrigerators/fridges to
refrigerators/fridges.
5.5.2 Processing technologies for polymers
A range of processing technologies are used to convert raw polymers and recyclates into the required
shape of the final product. The processing step itself is mainly a physical transformation step using
different technologies such as (European Commission 2011a):
extrusion (for pipes, profiles, sheets and cable insulation)
injection moulding (for products of different, often very complex shapes like machine parts,
electrical plugs and medical equipment such as syringes; thermoplastics and thermosets)
pultrusion for rods, tubes, etc.
blown film for thermoplastics
cast film for thermoplastics
coating (for thin layers on different substrates)
pressing (for resins)
spinning (for fibres)
transfer moulding for thermosets
compression moulding for thermosets
blending (generally applicable technique)
Usually, chemical reactions do not occur during these processes except during specific special
processing steps which are described in literature [14, Winnacker-Kuechler, 1982].
Techniques to prevent/reduce VOC emissions related to processes and facility
design (European Commission 2011a)
Environmental and health concerns of the processing polymer recyclates are emissions of
volatile/semivolatile organic compounds, in some cases waste waters with the potential for high loads
of organic compounds, spent solvents and non-recyclable waste.
General BAT/BEP considerations are described in section 3.5 should be taken into account for the
facilities. Techniques to reduce emissions can be considered during the process design and the plant
design,
Process design
Process design conditions (e.g. temperature, pressure, vapour pressure of materials/chemicals) can
influence the levels of (VOC) emissions.
Techniques to reduce (VOC) emissions resulting from process design include
To optimise the reactor design and physical parameters to minimize (VOC) releases
(homogeneous recyclate, optimum temperature, appropriate suction systems)
Minimize the use of volatile compounds and use of materials with low vapour pressure
To treat waste water streams which contains VOCs by stripping, rectification or extraction in
order to remove solvents which could contribute to VOC emissions in further treatment
operations
To carry out solid-liquid separation in a way to minimize VOC emission (e.g. using centrifuges,
keeping the system closed)
57
Plant design
The selection of plant components and the way they are configured can greatly influence the extent of
fugitive emissions.
A) Limiting the number of potential emission points
To design piping layout appropriately by minimizing pipe length and reducing the number of
connectors and valves. Also welded fittings and pipe can help to reduce emissions.
To minimize the use of pumps and to use pressure transfer
B) Maximize inherent process containment features
To enclose effluent drainage systems and tanks used for effluent storage/treatment
C) Select high quality equipment
Appropriate valves
Fitting high-integrity gaskets for critical applications
Pumps, compressors and agitators fitted with mechanical seals
D) Selecting appropriate material for equipment
The select equipment appropriate for the process
To avoid corrosion by selection of appropriate material
To prevent corrosion by lining or coating equipment
E) Facilitating monitoring ad maintenance activities by good access to critical components
F) Collecting and treating emissions
Economic considerations
While the reduction of emissions might need some investment cost they also provides opportunities
for saving raw materials.
5.5.3 Articles produced from POP-BDE containing recycled polymer (labelling)
Although not recommended by COP5 (Annex 1), polymer fractions containing POP-BDE might be
down-cycled to materials with non-sensitive use such as lumber or pallets. Such products made from
POP-BDE containing materials should be labelled (see SC guidance document labelling) to guarantee
their appropriate end-of-life management of such products required by the Stockholm Convention
(see Convention text Annex A part IV and V),
Furthermore it needs to be ensured that the recycling and final disposal is carried out in an
environmentally sound manner.
5.6 Energy recovery and end-of-life management of POP-BDE polymers
For POP-BDE/BFR containing polymer fractions energy recovery in appropriate BAT/BEP

incinerators or possibly other thermal BAT/BEP facilities offer energy/material recovery38 options.
The treatment technologies and requirements are described in section 8. BAT/BEP considerations
for deposition of POP-BDE containing materials are described in section 10 (this option is least
38
Material recovery is considered here for metals in WEEE including co-processing of a share of the
polymer fraction
58
preferred considering the life cycle considerations (see section 2.3) and that POPs are not
destroyed but stored for the next generation).
6 Specific BAT/BEP: POP-BDE/BFR materials in the transport

sector
As described above a main use of c-PentaBDE was in PUR foam in the transport sector (cars, busses,
trucks, trains, ship, air planes). C-PentaBDE has been used in upholstery of seats, headrest and ceiling
and application in textile back-coating. Furthermore some c-OctaBDE has been used in polymer parts
(e.g. dashboard, steering wheel). Due to the relative long life time of vehicles (in particular in
developing countries) and due to the high reuse and export rate, the transport sector can be
considered as the largest stock and reuse/recycling flow of articles containing c-PentaBDE. Therefore
this sector is of particular relevance for the implementation of the Stockholm Convention in respect to
POP-BDEs and this guidance
6.1 Reuse of vehicles containing POP-BDEs
The reuse and repair & reuse of used vehicles are the preferred end-of-life management when
considering the waste management hierarchy. Reuse safe energy of new manufacturing and avoid the
environmental impact of the generation of new raw materials which is in particular important for this
resource intensive material flow.
Since the use of c-OctaBDE has ended for most regions before 2000 currently not many electronics
now and in future considered for reuse are expected to contain POPs BDE. Therefore the reuse sector
for electronics is likely not impacted significantly by POPs BDE. Some special care has to be taken for
cars and other transport from the US where c-PentaBDE and c-OctaBDE has been used until 2004.
Vehicles from other regions can be expected to have considerably lower overall c-PentaBDE (and
possibly c-OctaBDE) use considering the much lower use volumes in other regions in the world39 (see
section 1). However also in Asia and Europe some c-PentaBDE and c-OctaBDE have been used for this
application.
The human exposure to POP-BDE from POP-BDE containing vehicles might be relevant in particular for
aged vehicles with bridal PUR foam. This might be of importance in particular in developing countries
where some cars are used for decades and many cars from the 70s, 80s and 90s are operated there).
In particular taxi driver or other professional drivers might be specifically exposed.
For the use, reuse of POP-BDE containing cars and other vehicles, a country needs to register for
exemptions (Annex Y Reiner Arndt*)
6.2 Transport sector and end-of-life management
The transport sector (cars, busses, trucks, trains, ships, air planes) is one of the large material flows of
goods and finally also a large waste flow to be managed. Cars and other vehicles (trucks and busses)
make the largest share of the transport sector. However also ships have become an important part of
end-of-life wastes addressed as a priority by the Basel Convention
(http://www.basel.int/ships/index.html).
Overall the management of POP-BDEs in the transport sector need to be integrated within the reuse
of vehicles and the overall management of end-of-life vehicles (ELV). Normally the materials
containing POP-BDE (PUR foam, textile back-coating, dashboard) end up in the automotive shredded
residue (ASR) fraction when processing ELVs (Figure 8). The ASR is normally further separated in a
39
Some uncertainty exists for the production and use of c-PentaBDE in China.
59
light ASR and a heavy ASR where the PUR foam is contained in the light ASR fraction and make up
4 to 20% of this fraction (Figure 8)
The POP-BDE containing polymers and other materials from ships and air planes need to be managed
according to the BAT/BEP principles described in this section.
Figure 8: Schematic of the processing of an End-of-Life Vehicle (Vermeulen et al. 2011; J. Hazard.
Mater. Elsevier)
6.3 POP-BDE/other POPs and contaminants in ELVs and waste

management
POP-BDEs are only one of the contaminants in ELVs. Other POPs contaminants are PCBs40 and
PCDD/PCDF41 (Stockholm Convention BAT/BEP Guide, Vermeulen et al.2011).
Other hazardous substances are heavy metals, such as copper, cadmium, lead, nickel and zinc. These
co-contaminants need to be considered for proper assessment of final waste management.
40
The data available indicate that polychlorinated biphenyls released from shredder plants are from
industrial/intentional polychlorinated biphenyl production and have been introduced with the oils and dielectric
fluids, etc., contained in the vehicles or more probably in consumer goods which are shredded in particular
white goods (BAT/BEP guidance Stockholm Convention)
41
Van Caneghem et al. [40], reported a PCDD/F-fingerprint of ASR dominated by higher chlorinated
PCDD congeners: approximately 90% of the total PCDD/F content of the ASR was accounted for by
hepta- and octa-CDD while the PCDFs represented only ca. 3%, with hepta-CDF and octa-CDF being
most abundant. This indicate that the main contribution stem from PCP treated materials. ASR can
contain up to 40% of textiles and leather, suggesting that this fraction might be a contamination
source of PCDD/Fs in ASR (Vermeulen et al. 2011).
60
Total (heavy) metal concentrations in ASR were reported up to 22% (Lanoir et al.1997, Vermeulen et
al.2011). The metals with the highest concentrations are Al (0.7-8.6 %), Fe (1-18 %), Cr (0.037-11
mg/g), Cu (4-60 mg/g), Zn (0-30 mg/g) and Pb (1.4-11 mg/g) (Vermeulen et al.2011).
The fine ASR fraction generally contains the highest heavy metal concentrations (Granata et al.2009,
Morselli et al.2010). For some heavy metals, such as Cu, Cd, Pb, Ni, Zn, concentrations may exceed the
limit values of applicable landfill regulations and pose a threat for the environment as these metals
can leach from deposited ASR (Gonzalez Fernandez et 2008). Disposal of ASR is therefore problematic
and is regulated e.g. for the European Union where ASR is classified as hazardous waste according to
the list of hazardous wastes 2000-532-EEC42.
Furthermore ASR contains significant levels of chlorine. The chlorine content of ASR ranges normally
from 1 to 4 wt% and is mainly due to the presence of chlorinated polymer components such as PVC or
halobutyl rubber (Boughton 2007, Vermeulen et al.2011). This high chlorine content together with the
presence of brominated flame retardants makes the waste a challenge for incineration. In Switzerland
(co-incinerating all ASR) the maximum co-incineration rate is therefore 5%.
Therefore ASR requires BAT waste incinerators for proper treatment. Non-BAT incineration or
treatment by pyrolysis lead to the formation of PCDD/PCDF and other unintentionally POPs (Sakai et
al.2007, Weber and Sakurai 2002).
Furthermore end-of-life vehicles contain waste oil, and ozone depleting substances (ODS) like CFC
refrigerants and climate active refrigerants like HFC which need specific pre-treatment before the
shredding step.
All these co-contaminants need to be considered when managing ASR. Due to these contaminants,
some countries have classified ASR as hazardous waste and have established legislative controls.
Developing countries rather recently started with BEP measures to manage Vehicles and ELV. One
suggested BEP approach is the concept of environmentally friendly mechanic village addressing the
repair and the waste management of vehicles and end o life vehicles (Nwachukwu et al.2011).
6.4 Recycling of end-of-life vehicles
End-of-life vehicles contain valuable materials (in particular metals) and therefore the recycling rate of
ELVs has always been high (about 70%) due to recycling of the metal fraction.
The environmental impact of the non-recycled fraction of an ELV should nevertheless not be
overlooked, as it often exhibits hazardous characteristics due to the presence of spent oils and
lubricants, heavy metals, persistent organic pollutants (POPs), (Vermeulen 2011). Furthermore many
ELVs today have air conditioner containing ODS and/or climate change gases. Therefore the
dismantling and de-pollution step (section 6.4.1) is of crucial importance for an environmental sound
management of ELVs.
The polymer containing fraction is often not recycled but disposed to landfills (see below). One reason
is the complex mix after a shredding step. Only more recently some facilities aim on recycling of the
polymer fractions (section 6.5).
6.4.1 Dismantling and de-pollution of the vehicle
Before dismantling, the potentially hazardous and toxic parts need to be removed from the ELV. This
is described in the Stockholm Convention BAT/BEP Guideline (UNEP 2007) as primary measures:
Fluids, like brake fluid, petrol, steering fluid, motor oil, coolants and transmission fluid should
generally be removed from the ELVs or other devices before shredding. This is especially applicable in
42
Section 1910, an annex of the European Directive 91-689-EEC on hazardous waste
61
the case of PCBs, which should be identified and removed from any device to be shredded. Specific
attention should be given to transformers and condensers. Measures should include (UNEP 2007):
The removal of batteries and liquefied gas tanks;
The removal or neutralization of potential explosive components, (e.g., air bags);
The removal and separate collection and storage of fuel, motor oil and oil from other
components
The removal of catalysts;
The removal of tyres and large polymer components (such as bumpers, dashboards, fluid
containers, etc.), if these materials are not segregated in the shredding process in such a way
that they can be effectively recycled as materials.
The removal of ODS and climate change gases from the air conditioning system
This de-pollution step offers the option to remove possible POP-BDE containing materials for further
treatment. These materials could be separated utilizing bromine screening technologies (see section
4) in case the non impacted materials are further considered for material recycling.
In the next step, during dismantling, reusable and recyclable components are removed, with special
emphasis on components with a sufficient market value (e.g. aluminium rims) or containing valuable
materials (e.g. catalytic converters). Table 7 lists parts of an ELV that can easily be recycled, indicating
also possible end-products.
In general, 535% of an ELVs mass can be removed for reuse or recycling, depending on the age of
the ELV, on the market value of the removed parts, and on the labour costs to remove these parts
(Vermeulen et al. 2011). A large difference exists between for instance European countries, where
only about 510% of an ELVs mass is removed during dismantling, and e.g. South Korea, where up to
35% of an ELVs mass is removed during this stage (Ferrao et al.2006, Joung et al.2007, Forton et
al.2006). This demonstrates the large potential of the separation step as BEP measure.
62
Table 7: Parts that can be recycled from ELVs (Zameri & Saman 2006, Vermeulen et al.2011: J. Hazard.
Mater. Elsevier)
6.4.2 Shredder plants (UNEP 2007)
Shredder plants for the treatment of end-of-life vehicles are listed in Annex C of the Convention as a
source that has the potential to form and release unintentional produced persistent organic pollutants
and are therefore described in the Stockholm Convention BAT/BEP guidelines (Part III Source category
(k): Shredder plants for the treatment of end-of-life vehicles. End-of-life-vehicles are often processed
through shredders. The practice is to shred them along with other end-of-life metal products43 (white
goods such as household devices; bicycles, office furniture, vending machines). In the plant, a high-
performance-hammer mill produces sized pieces of ferrous scrap of a high physical and chemical
purity. The ferrous scrap is sought after by steel makers and other secondary metal producers. An
overview of the process is shown in figure 9.
Figure 9: Overview of the shredder process (Source Stockholm Convention BAT/BEP guidance (UNEP
2008))
Many components of vehicles and other electrical devices are made of non-ferrous materials, such as
copper, aluminium and zinc. In the shredding process, magnetic separation is used to remove the
43
These other good often make more than 70% of input materials.
63
magnetic ferrous fraction from other materials. The non-ferrous metals, such as copper and
aluminium, are normally sorted out at a later stage by manual or optical separation. The remainder is
the automotive shredder residue (ASR) and is estimated at between 15% and 30% of the weight of
ELVs (UNEP 2007, Vermeulen et al.2011). ASR consists of glass, fibre, rubber, automobile liquids,
polymers, PUR foam and dirt (Figure 10) and is normally further separated in the light fraction
(containing PUR foam, most of the textile and polymer) and a heavy fraction (Figure 9). One
challenge with shredders (including BAT shredders) is that the light shredder fraction is difficult to
recycle.
Figure 10: Composition of shredder waste (Source: Environment Australia, Department of the
Environment and Heritage (2002); SC BAT/BEP guide (UNEP 2007)
6.5 Recycling of ASR and other ELVs residues
In industrial countries the light shredder residues from ELVs is normally not recycle but either subject
to thermal destruction/energy recovery (see section 8) or dispose of in landfills (see section 10).
In the view of the necessity to progress to circular economies, some industrial countries have
introduced legislation requiring recycling quota for end-of-life vehicles (and other materials). E.g. the
Japanese Government introduced the Law on Recycling of ELVs (ELV Recycling Law) in 2002 which
requires manufacturers to retrieve chlorofluorocarbons (CFCs), airbags, and ASR from ELVs and to
properly recycle the remaining materials. Also Europe has introduced ELV Directive requiring a
recycling quota of 95% from 2015 on (European Commission 2000/2011). Another driving force for a
high recovery/recycling rate is that the residues are increasingly difficult and expensive to dispose of.
6.5.1 Recycling by improved de-pollution and post shredding techniques
As mentioned above in the section on de-pollution of ELVs (section 6.4.1) a significant share of
materials can be recycled. The possible POP-BDE containing materials (PUR foam and polymer/textiles
from the interior) are normally not listed as materials being recycled (see table 7). However due to the
increased pressure on material recycling a higher share of the polymer fraction will need to be
recycled in future. According to Ferra et al. (2006), increasing the recycling of the polymers from ASR
is the key issue to achieve e.g. the European reuse and recycling target of 95% by 2015. Since
polymers are increasingly used in cars this fraction will become even more relevance in future.
Therefore several facilities to process ASR have been established in Europe (Table 8).
64
The PUR foam (considered to contain the main POP-BDE fraction44) is approximately 5% and up to 15%
of the ASR fraction (in average approximately 16 kg PUR foam/car), it amounts however to over 30%
of its volume (Hoffman 2008). The US industry says that the viability of foam recovered from shredder
residue for the foam-rebond market depends on two key factors: Development of an economical
process for recovering foam from shredder residue, and confirmation that the recovered foam meets
quality requirements (Hoffman 2008). The POP-BDE content can become one of the quality
requirements.
Argonne National Laboratory has developed a polymers separation system based on froth flotation. A
series of six tanks is used, each with a specific function, depending on the polymer being recovered.
The chemical solutions in each tank are chosen for the particular application. It has been used for
recovering selected polymers from automobile shredder residue, disassembled car parts, industrial
scrap polymers, and consumer electronics (Selke 2006). Argonne finds the highest-quality foam comes
from dismantling and then washing the foam from seats. But they claim that manual separation of the
foam is not economical for industrial countries (Hoffman 2008). Argonnes mechanical-separation
plants unit operations can operate in different sequences. It typically starts with the manual removal
of large metallic, PUR foam objects and rubble. In full-scale shredders these larger pieces are screened
by a trommel and/or a de-stoner and then separated to recover the metals and polyurethane foam
(Hoffman 2008). The process is designed to efficiently separate polymers of equivalent densities by a
process called froth flotation. This was originally developed to separate ABS from high-impact
polystyrene (HIPS).
In 2004 NV Salyp of Ypres, Belgium, commissioned the Salyp ELV Centre which operated the Argonne
technology under license to recover polyurethane foam and other polymers from shredder residue. It
is reported to have an operational process capacity of 6 tonnes of ASR per hour. The plant also used
technology licensed from a German firm, KUTEC, for separating different types of thermoplastics from
the Argonne technology reject stream. The Argonne technology separates the fluff into three streams:
fines, foam, and a thermoplastic-rich stream. The foam stream is cleaned and sold for markets such as
rebond foam in carpet underlay and for padding in automobiles (UNEP 2010b).
Other facilities take polymer enriched fractions from the shredding process of vehicles. One
precondition is also here pre-processing step to 70 to 80% polymers that the transport to a polymer
recycling facility becomes economically viable.
44
In the US c-PentaBDE containing main PUR-foam applications in transport (seat, arm/head rest) was
treated with approximately 1% PUR foam to meet MVSS 302 (Luedeka 2011; see section 6).
65
Table 8: Overview of post shredder technologies (Vermeulen et al.2011: J. Hazard. Mater. Elsevier) 45
6.5.2 Developing country considerations
For developing countries the details of recycling activities of POP-BDE containing materials in ELVs are
unclear. In the first preliminary new POPs country assessment (Nigeria) no specific recycling activities
of POP-BDE containing materials from the transport sector were found.
6.5.3 Energy recovery and deposition of ASR and other ELV residues
Energy recovery
ASR has a favourable calorific value (1430 MJ/kg), but the high ash content and the elevated chlorine
and heavy metal concentrations limit its use as fuel substitute (Vermeulen et al.2011). The aim of
advanced secondary recovery techniques is to segregate ASR and to isolate the combustible materials
with low ash content and with low halogen and contaminant concentrations. The finest fraction of
ASR generally has the highest ash and mineral oil content, combined with the lowest calorific value.
Screens, shaker tables, rotary drums or float/sink separation techniques can be applied to remove this
fine sized fraction and thus improve the fuel characteristics of the ASR (Morselli et al.2010, Boughton
& Horvath 2006, Hjelmar et al.2009). Halogenated polymer components such as PVC, PBDE/BFR
containing materials or (halobutyl) rubber are the main sources of the high halogen (mainly chlorine)
concentrations often found in ASR. PVC removal from ASR is a simple way of lowering the overall
chlorine concentration. Several studies pointed out that density separation, using a bath density of
11001200 kg/m3, can remove the majority (up to 68 %) of chlorinated and PBDE/BFR containing
polymers (density of about 1400 kg/m3 or more) from the combustible materials of ASR (Hwang et
al.2008, Boughton 2007). In some cases heavy metals must be removed from ASR before recycling or
energy recovery46 in order to meet the regulatory limits of the final application.
45
Other operating facilities recovering polymers from vehicles are TBS in Enns (Austria) und SRW in Espenhain
(Germany).
46
According Vermeulen et al.(2011), certain heavy metals can easily be removed by mechanical separation
(Granata et al.2009, Kurose et al.2006) Granataetal. (2009)) found that the ASR fraction smaller than 0.5 mm
contained the highest Cr, Ni, Pb and Zn concentrations: removing this fraction can reduce the overall
concentration of these elements in the ASR by more than 77%. Kurose et al. (2006) demonstrated that Cr, Cd
and Pb concentrations in ASR could be reduced by at least 83% by eddy current separation of non-ferrous
66
The thermal treatment technologies and requirements are described in section 8.

The removed fractions (halogen rich and heavy metal rich) need further treatment and waste
management considerations which can be challenging.
Deposition of ASR
Even industrial countries currently mainly deposit ASR in landfills (see section 10). BAT/BEP
considerations for deposition of POP-BDE containing materials are described in section 10 (this option
is least preferred considering the 3R concept and it has the drawback that POPs are not destroyed but
stored for the next generation by this approach).
Another recycling approach for ASR is the direct incorporation of the fine sized ASR fraction into
materials such as composites, concrete or asphalt which might be considered a temporary storage.
7 Specific BAT/BEP: POP-BDE/BFR containing PUR foam

Flexible polyurethane foam (FPF) is a manufactured article with a multitude of end uses. Main uses of
FPF products are:
in residential and commercial upholstered furniture (coach, chairs);
in residential and institutional mattresses and top-of-bed products including pillows and
mattress pads;
in vehicles (cars, trucks, train, ship, plane; see also section 5) as interiors for seating,
upholstered trim and acoustic panels; further in military defence to help prevent fuel-related
flash fires in vehicles, vessels and aircraft.
minor use volumes are in protective packaging applications; in healthcare for restraining,
support, pressure-relief, fluid absorption and wound care applications; in air and fluid
filtration; in laboratories and testing instruments as absorption medium; for apparel padding
and insulation;
furthermore; and particularly in the United States as a cushion underlayment for residential
carpet installation.
Rigid polyurethane foam was and is used in construction as filler and insulation material.
While FPF may appear to be a generic commodity product, it is, in fact, often a technical article with
specific performance attributes created through proprietary formulations and fabrication processes.
Many FPF manufacturers produce more than 150 different FPF products, each having unique
characteristics appropriate for specific end uses (Luedeka 2011).
The FPF industry uses two basic production methods: slabstock (outside the US, referred to as block
foam) and moulding. Each production method requires unique product formulations using a number
of raw materials including, but not limited to a polyol, diisocyanate, surfactant, catalyst, auxiliary
blowing agent and numerous optional specialty additives including, in some instances, fire retardant
products (Luedeka 2011).
Formulations for slabstock and moulded products may require adjustment prior to or during
production to respond to ambient production conditions including humidity, temperature and
barometric pressure. Such formulation adjustments may include variations in concentration and/or
metals. Further heavy metal removal can be obtained by washing ASR with an acid extraction agent (Granata et
al.2009, Kurose et al.2006)
67
changes in the selection of various raw materials including additives such as optional fire retardants
(Luedeka 2011).
The use of flame retardants are in particular triggered by flammability standards often specific for
countries. E.g. due to specific flammability standard in California for furniture since 1975 (CA TB117))
and other flammability standards in the US (certain flammability standards in transport47) by far the
largest part of c-PentaBDE have been used in PUR foam in this region (estimated to 90% of total c-
PentaBDE use (UNEP 2010a,b)) with minor use in Europe (with the exemption of UK48) and Asia.
The regional use of POP-BDE is in particularly relevant for considerations of recycling of PUR foam
for regions possibly impacted from those markets by (second hand) car or furniture export/imports.
It is also important to know for all regions which are not considerably affected by c-PentaBDE
retarded PUR foam for the selecting management options.
7.1 Reuse of furniture and mattresses possibly impacted by POP-BDEs
The reuse of furniture49, mattresses and textiles is the preferred end-of-life management when
considering the waste management hierarchy. Reuse safe energy of new manufacturing and avoid the
environmental impact of the generation of new raw materials.
Markets with flammability standards for furniture at the time of production of c-PentaBDE (before
2005) are the US and the UK. Mattresses for private consumers were not significantly impacted by c-
PentaBDE use but only those from public/governmental institutions like prisons, military or hospitals
(Luedeka 2011).
For most other countries no specific flammability standards have been established in the past for
furniture and therefore these countries/regions are not or only to a minor extent impacted by c-
PentaBDE in PUR foam applications depending on the import of such articles from countries with
specific flammability standards (US and UK). Therefore the reuse sector for furniture and mattresses is
likely not (significantly) impacted by POP-BDE in most countries/regions. However if an aged couch
contain c-PentaBDE then human exposure to POP-BDE might be relevant in particular due to dust
particles from the bridal PUR foam.
Therefore the assumption that most regions are not impacted by POP-BDE in these use areas require
some confirmation before the unrestricted reuse of these material streams can be considered BEP.
For the use and reuse of POP-BDE containing products in a country register for exemptions are
required (Annex Exemptions Reiner Arndt*).
7.2 General Management and recycling of PUR foam
For management and recycling considerations in particular the large use areas (furniture, vehicles,
mattresses, and construction) need management considerations. The other minor uses of mainly
47
Federal Motor Vehicle Safety Standard No. 302 (MVSS 302).
48
The United Kingdom established Furniture and Furnishings (Fire) (Safety) Regulations in 1988 setting levels of
fire resistance for domestic upholstered furniture, furnishings and other products containing upholstery fillings.
British Standard 5852 (BS 5852) contains flammability testing criteria and performance standards for furniture
and other filled products intended for residential use including upholstered furniture, children's furniture, head-
boards of beds, sofabeds, futons and other convertibles, nursery furniture, garden furniture which is suitable for
use in a residence, loose cushions, seat pads and pillows, and mattresses made of a single filling material, such
as solid foam core mattress. (A different UK standard, BS 7177, is applied to mattresses having 2 or more filling
components.)
49
PUR foam containing furniture is e.g. sofa, couch, armchairs, chairs.
68
smaller PUR foam with shorter half-life are not or less relevant considering their volume and that
possible PUR foam treated have already been deposited.
In all facilities dealing with recycling or with end-of-life of PUR foam treating also the general BAT/BEP
considerations from section 3.5 should be taken into account.
7.3 Assessment of POP-BDEs/BFRs impact of PUR foam in a
country/region
As mentioned above the use of flame retardants and the type of flame retardants used highly depends
on the region and country. It is assumed that more then 90% of c-PentaBDE in PUR foam and also
most HBB has been produced/used in the US and is largely either already deposited in landfills, in use
or recycled in carpet rebond (UNEP 2010a,b). Therefore it can be assumed that most other regions
and countries have a low content of c-PentaBDE and HBB in their current PUR foam. The most critical
use areas considered should however be assessed for the recycling activities of PUR foam in a
country/region.
The compilation of data in the country and
Such assessment might include
- literature data of POP-BDE in PUR foam the region/country
- generation of monitoring data of POP-BDE in PUR foam (screening of bromine and/or
confirmation data)
- assessment of workers working in PUR foam recycling facilities50
7.4 Separation strategy of c-PentaBDE impacted PUR foam
7.4.1 Separation/exclusion of PUR foam categories from recycling
Countries/regions with low impacted flexible PUR foams
In most regions in the world the recycling quota of PUR foam are very low and the largest part end up
in landfills or is incinerated. Further in most areas key PUR foam categories (furniture and mattresses)
are probably not impacted by c-PentaBDE (to be confirmed from the above mentioned screening
assessment). Categories which are possibly impacted are PUR foam in transport or furniture (in
particular imports from US/UK) and possibly mattresses from public/specific institutions (prison,
hospitals, and military). In all regions with low recycling quota the PUR foam from these possible
impacted uses could be excluded from PUR foam recycling until these applications have been assessed
for the overall presence of POP-BDE by a monitoring program (Bromine screening) for a general
conclusion on further use or exclusion. This approach avoids then the continuous screening for
bromine in recycling facilities.
Countries/regions with high or possibly high POP-BDE impacted PUR foam
As mentioned above, PUR foam in key applications (e.g. furniture, transport) from the US and possibly
from the UK is considerably impacted by c-PentaBDE and other flame retardants due to flammability
standard requirements. The US Foam Association state that for the US (not party to the Convention)
having high recycling quota such a separation approach is currently not applied. The recycling industry
is blending/diluting c-PentaBDE containing PUR foam into carpet rebond in a way that the standard of
0.1% c-PentaBDE developed in some states is met According to the PUR Foam Association at the
current high contamination level, separation of POP-BDE containing foam is not feasible in the US
50
High levels of PBDE have been found in workers at recycling facilities of PUF in the US (Stapleton et
al.ES&T)
69
since exclusion of major use area would at the same time possibly stop recycling. Furthermore the
high impact from c-PentaBDE would need to test all incoming PUR foam by physical contact.
Furthermore for the US also other brominated aromatic flame retardants are currently used. If all
bromine content was to be separated, a large volume would have to be excluded from bonded
cushion manufacturing in this region (Luedeka 2011).
Neighbouring countries in the North American region might be impacted to some extent by sharing
the same market or imports/exports. For such countries basically the same approach of excluding the
highly impacted categories from recycling or the separation at recycling facilities by bromine screening
might be applicable considering that these countries probably have lower contamination levels then
the US.
7.4.2 Separation of POP-BDE/BFR containing PUR foam in recycling
If flexible PUR foam categories known to partly contain POP-BDE impacted material such material
could be screened with bromine (see section 4) to separate POP-BDE containing materials.
Such separation can either be at the state of collection or in the facility recycling PUR foam.
While the separation of POP-BDE/BFR polymer by separation of BFR-containing fractions has been
developed to full scale for WEEE polymers (see section 5), there is no dedicated information on such
separation for other POP-BDE/BFR containing materials. For larger polyurethane foam items like
mattresses or furniture the same screening methods used for WEEE polymers items might be applied
with handheld XRF or sliding spark spectroscopy. A screening program supported from government
might reveal if such an approach is needed.
7.5 Recycling areas and technologies for flexible PUR foam
7.5.1 Collection of the PUR foam and separation in the collection phase
Before recycling of PUR foam the materials must be collected from waste. The foams to be recycled
can arise from a number of sources. The principal ones being:
Furniture
Cars and other transport (see section 6)
Mattresses
Carpet padding (mainly US, Canada and Australia)
Packaging
For the consistent bulk supplies needed for recycling emphasis is placed on mattresses - together with
scrapped cars.
Recycling of vehicles is normally a process involving the de-polluting of the vehicle (section 6 above),
increasingly combined with the manual stripping of components which can be re-used or recycled.
Only at the stage of de-polluting of the vehicle an effectively sorting of residues contaminated with
POP-BDE along with other hazardous components could be implemented if the foam is gathered for
recycling.
7.5.2 Rebond Recycling PUR foam with phase out of c-PentaBDE
Rebonding is the process whereby scrap PUR foam is shredded into small pieces and then
reconstituted with a polyurethane prepolyol binder to produce an aggregated polyurethane foam
product (USEPA 1996a). The main use is in the production of carpet cushions (Eaves 2004) as shown in
Figure 11 below.
The North American bonded foam carpet cushion industry represents a major end-use for flexible
polyurethane foam manufacturing trim scrap generated throughout the world, but particularly in
North America. To a lesser degree, the North American bonded carpet cushion industry also consumes
70
significant amounts of US post-consumer polyurethane foam scrap, mainly obtained by take-up of

used polyurethane foam carpet cushion at end-of-life during installation of replacement carpet
cushion. In 2010, it was estimated that about 700 million pounds of bonded carpet cushion were
produced in the United States, Canada and Mexico.3 (Luedeka 2010). Bonded polyurethane pads are
also manufactured in China primarily for export as carpet cushion and for reported vehicle and
mattress padding applications.
In the US, bonded foam carpet cushion represents close to 90% of all carpet cushion products sold.
There is very little use of bonded foam products in vehicle and mattress padding applications. In 2010,
industry estimates indicate that the following recovered foam materials were used in bonded
polyurethane pad production: (Luedeka 2011)
Imported scrap (primarily furniture manufacturing trim with some post-consumer content)
196 million pounds.
Domestic manufacturing scrap (primarily from furniture trim) 50 million pounds
Domestic post-consumer take-up scrap 265 million pounds4
The vast majority of carpet, and therefore carpet cushion, are used in English speaking countries,
specifically the US, UK and Australia. Up to now little carpet cushion is used in the rest of the world
(Luedeka 2011).
Figure 11: Simplified materials flow of foam and recycling routes (marked in red) to carpet cushions
(adapted from (USEPA 2005)).
Prior to 2005 in the US (and UK), c-PentaBDE could have been present both in the furniture
manufacturing trim scrap and post-consumer take-up scrap foam used to make new bonded carpet
cushion in particular in countries with flammability standards. The amount of c-PentaBDE used in
furniture manufacturing varied by density. Higher density foam products typically required less c-
PentaBDE FR content to meet CA TB 117 test requirements (Luedeka 2011). Compliance with MVSS
302 standard required much less use of c-PentaBDE FR than compliance with CA TB 117 for furniture
filling materials. The manufacturing scrap recovered from these industries was part of the raw
materials mixture used in the production of bonded carpet cushion (largely in the US).
71
Eight US states including California, Hawaii, Illinois, Maine, Maryland, Michigan, Minnesota, New York,
Oregon, Rhode Island, and Washington have enacted laws prohibiting manufacture or sale of products
containing c-PentaBDE content of more than 0.1% by weight. This permit was given in the US to allow
continued diversion from landfill and sale of recycled materials. Other countries with low recycling
quota and low c-PentaBDE content in the flow can aim to avoid recycling of c-PentaBDE containing
foams.
Polyurethane recycling, other than rebond has been quite limited in the United States (Selke 2006).
Media reports indicate that other recycling uses for foams which are not re-used in the refurbishment
of mattresses or for rebond include pet bedding, stuffed animals and insulation (Rowe 2010). It is
assumed that this is a very low volume outlets for foams.
Other uses of rebond include school bus seats (USEPA 1996b) and floor mats for gymnasia (Zia et al.
2007).
Whilst the use of carpet cushion may be almost unique to North America it is noted that the European
Isocyanates Producers Association says that up to 50,000 tonnes of rebonded foam are processed
each year in Western Europe and new applications are constantly being developed (ISOPA 2001). It is
assumed that this rebonded foam is less likely to contain c-PentaBDE given the much smaller levels of
initial use in Europe than foam in the US.
7.5.3 Material recovery from mattresses
As mentioned above, only mattresses in specific institutions (prison, hospital, military) are flame
retarded even in countries with specific flammability standards. Such specific sources should be
excluded from recycling or at least monitored for an overview of presence of BFRs with XRF screening
if these areas also are included in the recycling.
A review of mattress recycling by the International Sleep Products Association summarises some of
the key issues with materials recovery for mattresses (International Sleep Products Association 2004):
The economics of recycling are finely balanced and the value of the recovered mattress materials
alone cannot sustain a mattress disposal operation. Finding a sustainable income source to
supplement the scrap revenue is therefore key to a successful operation (fees from consumers,
retailers, manufacturers or municipalities equal to the tipping fee that a landfill would otherwise
have charged had the mattress instead been dumped at the landfill).
Facility location and security are critical as it is important to minimise the cost of moving product to
the facility and when selling the recovered materials to potential customers.
Preparing recovered scrap in saleable form can be challenging particularly for the steel scrap which
is by far the most valuable and easily recovered mattress material.
Consistent product volume is necessary to maintain an efficient dismantling operation.
Low-tech manual dismantling appears to be more efficient than more automated alternatives,
although new technologies are under development a manual approach using relatively low-skilled
manual labourers equipped with box-cutters is the preferred approach at present. Capital
expenditures are still needed, however, to shred product that cannot be quickly dismantled by hand.
These include magnetic separators, bailers, forklifts to handle the product and the scrap, etc. A
sustainable supplemental income source is necessary on top of the value of the recovered steel scrap
(International Sleep Products Association 2004).
7.5.4 Regrinding
Eaves (2004) notes that the declining use of scrap foam in North American carpet cushion has spurred
the uptake of innovative processes allowing manufacturers to non-cryogenically grind foam scrap
72
from the manufacturing process. The ultrafine powder can then used to displace approximately 10%
of the virgin chemicals in the manufacture of new foam.
With minor formulation adjustment, the resulting foam is said to have properties equal to the original
foam. The economics are driven largely by the difference between the value of scrap and the price of
chemical raw materials (Eaves 2004). However, currently regrinding has not a significant use in the
PUR foams (Luedeka 2011).
7.5.5 Chemical recovery (glycolysis)
The chemical recycling of polyurethane foam is still in an early stage. A few companies have
developed the reprocessing of polyurethane#. The largest facility on thermal glycolysis of PUR foam is
in Germany (http://www.rampf-ecosystems.de/en/home/).
7.6 Labelling of POP-BDE containing PUR foams recycling
Consideration should also be given to possibilities for labelling of suitability for export of articles after
screening and sorting and whether it is appropriate to issue certification that sorted articles are POP-
BDE free.
7.7 Other materials possibly impacted by POP-BDEs
Some minor other uses of POP-BDE has been applied in the past. These are
textiles (e.g. back-coated textiles in vehicles)
rubber (e.g. for conveyer belts)
Coatings/lacquers.
Due to the minor amount of POP-BDEs used in these applications no specific BAT/BEP section is
developed for addressing these uses. However basically the same approach as described for PUR foam
might be considered:
1) Country/region survey on the presence of POP-BDE in these sectors
2) Assessment of recycling activities of these materials
3) Exclusion of specific impacted streams from recycling
4) Screening and separation by bromine screening approaches in the recycling.
7.8 Energy recovery from POP-BDE containing materials
For POP-BDE/BFR containing PUR foam, rubber and textiles, energy recovery in appropriate BAT/BEP
incinerators or possibly other thermal BAT/BEP facilities offer energy recovery options. The treatment
technologies and requirements are described in section 8
BAT/BEP considerations for deposition of POP-BDE containing materials are described in section 10
(this option is least preferred considering the 3R concept and that POPs are not destroyed but stored
for the next generation).
73
8 Energy/material recovery from POP-BDE materials

General comment: This Guideline on BAT/BEP for the management and treatment of c-PentaBDE/c-
OctaBDE containing materials can not describe the BAT/BEP for the single thermal treatment
technologies since meaningful BAT/BEP descriptions of each of the processes would require several
100 pages. However such descriptions have been compiled in the Best Available Techniques
REFerence Documents (BREFs) developed for respective industrial processes
(http://eippcb.jrc.es/reference/) and also have to some extent be described in the Stockholm
Convention BAT/BEP Guideline document with emphasis on UPOPs reduction (UNEP 2007).
Therefore the current guideline simply highlights the specific features of POP-BDE containing material
in respect to the treatment/recovery technologies. For more detailed information this document
refer in the respective sections to the related section in the Stockholm Convention BAT/BEP guideline
document (UNEP 2007) and, since the Stockholm BAT/BEP focuses on reduction of UPOPs, additionally
refer to the related BREFs in which BAT are described in detail for those technologies.
Additionally, in the respective sections considerations for developing countries which often lack the
capacity to establish facilities according to BAT requirements are noted. It is expected that further
information on BEP and possibly BAT from developing countries will evolve during this process and
will be considered in an update of this guidance.
The general considerations for BAT are described in section 3.5 and need to be considered for all the
facilities and treatment technologies.
8.1 General remarks on thermal treatment POP-BDE containing
materials
8.1.1 Calorific value and halogen content of POP-BDE containing materials
POP-BDEs/BFRs are mainly used in materials with high calorific values (polymers, polyurethane foam,
polystyrene foam, textiles). One option for the recovery of such materials is to utilize the energy
present in the material and the metals attached to the POP-BDE-containing polymers. The potential
energy value of polymers is nearly 40 MJ/kg which corresponds to 80/mton (at 2/GJ) (Tange &
Drohmann 2005).
The Technical guidelines for the identification and environmentally sound management of plastic
wastes and for their disposal (Basel Convention, 2002) recommends feedstock recycling and thermal
energy recovery for POP-BDE-containing polymers. The Basel Convention document states:
Plastic wastes which contain polybrominated diphenyl ethers (PBDE) should be excluded from
material recycling because of the possibility of emitting dioxins and furans. Instead such plastic wastes
should be treated in feedstock recycling facilities or in controlled incinerators recovering energy.
The thermal treatment of POP-BDE containing wastes (Auto Shredder Residues or polymers from
WEEE recycling) is due to its high halogen content a challenge for thermal facilities. For such wastes
with a halogen content above 1% normally a hazardous waste incinerator is required in countries with
a respective law. When using other facilities for recovery of energy or treatment special care needs to
be taken to avoid the release of UPOPs.
8.1.2 Monitoring of PBDD/PBDF and PXDD/PXDF release
Since POP-BDE containing materials are flame retarded their flammability is reduced and this can
result in increased formation of products of incomplete combustion in facilities which are not
equipped with optimally efficient combustion chambers as specified in the BAT/BEP (Weber & Kuch
2003). Furthermore, since materials containing PBDE are excellent precursors of PBDF, the formation
of the more toxic PBDF is a crucial parameter to be considered and evaluated during thermal recovery
74
and destruction operations (Sakai et al. 2001; Weber & Kuch 2003; WHO 1998; Vehlow et al. 2002,
UNEP 2010b). Since normally chlorine is present at relevant levels in PBDE containing materials (WEEE
polymer, ASR, PUR foam) also the formation of mixed brominated-chlorinated PXDD/PXDF can
comprise the highest share of dioxin-like compounds (Hunsinger et al.2002, Zennegg et al.2009).
Therefore the measurement of only PCDD/PCDF in such operations is not sufficient and rather
misleading51. The instrumental analysis of >5000 PXDD/PXDF congeners with several hundred 2,3,7,8-
substituted congeners is however complex and can currently not give a TEQ. To overcome this
dilemma of instrumental analysis of the mixed halogenated PXDD/PXDF it is recommended to support
such monitoring by using accredited bio-assays measuring total dioxin-like toxicity like CALUX,
DRCALUX or EROD (see also Stockholm Convention BAT/BEP (UNEP 2007)). Their ability to assess such
complex dioxin-like mixtures has been demonstrated e.g. with the assessment of e-waste recycling
sites (Yu et al. 2008).
8.1.3 Considerations on corrosion caused by bromine/HBr
Bromine/HBr has a high potential to cause corrosion in particular to metal parts. Therefore the effect
of corrosion needs to be taken into account when larger amounts of bromine containing waste are
thermally treated in facilities. The process should be closely observed and the economic benefits and
drawbacks assessed, including the cost of maintenance and repairs. In particular the boiler section is
of concern from an economic perspective. Since all halogens enhance corrosion, operators of facilities
with boilers are reluctant to burn large amounts of bromine-containing waste (Rademakers et al.
2002).
8.1.4 Considerations for removal of HBr and bromine in flue gas treatments
For all thermal treatment technologies the behaviour of bromine within the facility and the flue gas
line need to be considered. Due to the similar redox potential of bromine and oxygen (table 9)
bromine is present in the flue gas partly as HBr and partly as elemental bromine. The ratio is
influenced e.g. by the level of sulphur present.
HBr (together with HCl and other acid gases) can be removed by the usual removal technologies
(dry/semi dry scrubbing with basic adsorbens, scrubbing with a NaOH solution, etc.). The technique to
remove elementary bromine (and iodine) from the flue gas is a reductive wet scrubber stage with the
addition of sulphite or bisulphite.
Table 9: Redox potential of halogens and boiling/melting point52 of potassium and sodium halogenides
Fluorine Chlorine Bromine Iodine
Boiling Point Potassium halogenides (C) 1505 1500 1380 1330
Boiling Point Sodium halogenides (C) 1704 1465 1393 1304
Melting point Potassium halogenides (C) 858 790 732 686
Melting point Sodium halogenides (C) 995 801 755 662
Redox potential +2.87 +1.36 +1.09 +0.54
The standard electrode potential of Oxygen is +1.23
8.2 Energy recovery of POP-BDE containing materials in incinerators
In this section, specific features regarding the treatment of POP-BDE containing materials in
incinerators are described. Basic BAT/BEP for waste incineration is specified in Section V for Source
51
The addition of bromine can result in reduced levels of PCDD/PCDF by partly bromination of the
chlorinated aromatics.
52
GESTIS-Substance datenbase of IFA
75
category A of the Stockholm Convention BAT/BEP guidelines (UNEP 2007). Further details are
described in the EU BREF document on waste incineration (European Commission 200653).
In general, shredder waste from the transport or electronic sectors is not suited for mono-incineration
(Moakly et al.2010). Co-incineration of such high shredder waste can be conducted in various types of
incinerators, such as grate furnaces, fluidized bed incinerators and rotary kilns.54 Considerations need
to be given to material with a halogen content exceeding 1%. Such wastes are best disposed of in
hazardous waste incinerators55 . BAT/BEP municipal solid waste incinerators (MSWI) or cement kilns
(see below) might be used for the treatment of this waste material if it has been demonstrated
through pilot tests that emission parameters are not increased compared to normal operation.
As mentioned above, the corrosion of boilers must be taken into consideration when incinerating
POP-BDE/BFR-containing waste. If bromine is considerably lower compared to the chlorine input, the
corrosion is mainly caused by chlorine (Rademakers et al. 2002).
8.2.1 Co-incineration of polymers from WEEE
BAT waste incinerators operated according Best Environmental Practices (BEP) can co-incinerate POP-
BDE containing waste material without significant releases of POP-BDE or unintentionally formed
brominated or chlorinated dioxins (Sakai et al. 2001; Vehlow et al. 2002; Weber & Kuch 2003).
However, it must be highlighted that extremely high levels of PCDD/PCDF were formed intermediately
during solid fuel burnout when incinerating fractions from waste electrical and electronic equipment
(WEEE) with a mixture of municipal waste (Hunsinger et al. 2002). The formation of mixed
brominated-chlorinated PXDD/DF in relation to PCDD/PCDF depends strongly on Cl/Br ratio of the
waste mixture. When co-combusting WEEE at very high share (Cl/Br approx. 3-4 of the fuel mixture)
PXDD/DF were formed in some orders of magnitude higher than PCDD/PCDF56 (Hunsinger 2010).
These PCDD/PCDF and PXDD/DF were efficiently destroyed during controlled flue gas burnout in the
secondary combustion zone, finally resulting in moderate PCDD/PCDF and PXDD/DF levels in the raw
gas and low levels in the clean gas (Nordic Council of Ministers 2005, Tange & Drohmann 2005,
Vehlow et al. 2002). These tests demonstrate that BAT incineration can cope with addition of POP-
BDE/BFR-containing polymers and the resulting high levels of unintentionally formed chlorinated,
brominated and brominated-chlorinated dioxins formed and released from the fuel bed can be
destroyed in the secondary combustion zone operated according to BAT (sufficient residence time (2
seconds), temperature (>850C) and turbulence (Stockholm Convention 2007, European Commission
2006). But the test also highlights the associated risk of incinerating POP-BDE/BFR-containing WEEE in
incinerators with lower combustion quality.
53
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54
Mark (1998 [65]) compared different alternatives (co-incineration with MSW, co-incineration in a
cement kiln and co-incineration with hazardous waste) and concluded that co-incineration of ASR with
MSW was most appropriate.
55
The EU Waste Incineration Directive, for example, requires that if hazardous wastes with a content of more
than 1% of halogenated organic substances, expressed as chlorine, are co-incinerated, the temperature has to be
raised from 850 C to 1,100 C (European Commission 2000).
56
In another experimental series in this incinerator an addition of 0.06% bromine to the fuel feed
(containing approximately 0.6% chlorine) resulted in the formation of high levels of PXDD/DF (mainly
mono bromo- and dibromo-polychloroDD/DFs) in the first combustion zone at levels higher then the
PCDD/PCDF. This demonstrates that despite the high Cl/Br ratio of >10 in the fuel input, considerable
PXDD/DF can be formed) (Hunsinger et al. 2001).
76
8.2.2 Co-incineration of ASR in Municipal Solid Waste Incinerators (MSWI)
Extensive co-incineration tests were carried out in municipal solid waste incinerators. In Switzerland
up to 10% of shredder residue was co-incinerated (Jody et al.2006, Keller 1999, Diesler and Keller
1997) and in a Swedish test up to 20% (Aea Redin et al.2001) to assess the technical feasibility and
environmental impact. The co-incineration was reported to meet the regulatory environmental limits.
In Switzerland currently all ASR (55000 t/year) is treated in MSW incinerator (at a cost of 150 EURO/t).
It was shown that flue gas emissions did not change significantly compared to the incineration of
MSW.
During a co-incineration test in Sweden, PCBs appeared as critical organic pollutants: their
concentration increased by a factor of 35 in the flue gases and by a factor of 5 in the bottom ashes,
but all regulatory limits were still met (Vermeulen et al.2011). Pilot-scale incineration plant testing in
Japan has revealed a high formation of unintentional POPs during the primary combustion stage of
ASR (Sakai et al.2002). This is similar to the above mentioned high release of PCDD/PCDF and
PXDD/PXDF formation in primary combustion zone of a mixture of municipal/WEEE waste (Hunsinger
et al.2002, Hunsinger 2010)57. In the studies on Japanese and German state-of-the-art incineration
facilities, most UPOPs formed in the first combustion chamber were destroyed in the secondary
combustion zone (Sakai et al.2002, Hunsinger et al.2002). This however highlights the risk of non-BAT
incineration.
In another study involving the co-incineration of ASR (31%), the concentrations of Zn, Pb, Sn, Sb, Cu
and Co in the fly and boiler ashes increased significantly: the respective concentrations of Pb and Zn
were even up to 18 and 16 times higher than the average baseline level (Mark et al.1998). In
Switzerland some incinerators leach the ashes by acidic washing to remove the heavy metals.
While the co-incineration with MSW in the above mentioned test of ASR were conducted in grate
furnaces, ASR might also be co-incinerated in kinds of furnaces such as fluidized bed incinerators
(Vandecasteele 2011).
In many countries, bottom ashes from MSW incinerators are used as a secondary raw material in
construction (Arickx et al. 2007, Vandecasteele et al.2007). Therefore, it is important to monitor toxic
components (heavy metals, POPs) in the bottom ashes when ASR is co-incinerated (Vermeulen et al.
2011) and avoid environmental contamination in further use and deposition. In this way, legal
concentration limits for toxic elements in bottom ashes are needed and limit the amount of ASR that
can effectively be co-incinerated (Moakly et al. 2010).
8.2.3 Recovery of metals
The shredder fractions of ASR and WEEE still contain considerable amount of heavy metals. BAT/BEP is
to recover the metals in the heavy ASR fraction in metal smelters (see below) while the light ASR
fraction needs to be incinerated or deposited in secured landfills (section 8 and 10) if appropriate
thermal treatments are not available. In almost all incinerators, the heavy metals other than some
bulk metal parts are not recovered from the ashes. Promising pilot tests to comprehensively recover
metals from bottom ashes are currently conducted in Switzerland (ZAR 2011). Since metal resources
will become more scarce and precious in the future, the pressure to recover such materials will
57
It must be highlighted that extremely high levels of PCDD/PCDF were formed intermediately during solid fuel
burnout when incinerating fractions from waste electrical and electronic scrap (WEEE) with a mixture of
municipal waste (Hunsinger et al. 2002). The formation of mixed brominated-chlorinated PXDD/DF in relation to
PCDD/PCDF depends strongly on Cl/Br ratio of the waste mixture. When co-combusting WEEE at very high share
(Cl/Br 3-4 of the fuel mixture) PXDD/PCDF were formed some orders of magnitude higher than PCDD/PCDF64
(Hunsinger 2010 personal communication).
77
increase and technologies likely evolve. The high price of metals can serve here as economic base and
incentive to develop such technologies further...
Only BAT incinerators should be used to treat POP-BDE-containing materials, considering the high
dioxin/UPOPs formation potential of WEEE and ASR. However there are hardly any BAT incinerators
available in developing countries. The construction of BAT incinerators in developing/transition
countries is questionable, considering the high final cost of waste treatment (normally above $100)
(Brunner & Fellner 2007; World Bank 2005). Therefore waste incinerators are unlikely (at least
currently) to be a feasible option for treatment of POP-BDE-containing waste in developing countries.
8.3 Cement kilns
Some key BAT/BEP considerations for cement kilns are described in Section V for Source category 2B
of the Stockholm Convention BAT/BEP guidelines (UNEP 2007). Further details are described in the EU
BREF document on waste incineration (European Commission 201058).
In this section specific considerations in respect to treatment of POP-BDE containing materials are
described.
Cement kilns are increasingly used in waste management schemes in industrial and in developing
countries (Holcim & GTZ 2006; Reijnders 2007). Also major POP-BDE containing material like polymers
from electronic waste, ASR and potentially other POP-BDE and BFR containing materials are partly
treated.
The Stockholm Convention Guidelines on Best Available Techniques (UNEP 2007) includes Electronic
Waste on the negative list of waste not recommended for co-processing in cement plants. The
guidelines expand upon this by saying:
Electronic waste is composed of computer and accessories, entertainment electronics, communication
electronics, toys and also white goods such as kitchen devices or medical apparatus. The average
composition shows that electronic waste contains, on the one hand, substances potentially harmful to
health and the environment such as Cl, Br, P, Cd, Ni, Hg, PCB and brominated flame retardants in
certain concentrations, often higher than threshold limit values. On the other hand, electronic waste
contains such a high scarce precious metal content that all efforts have to be undertaken to recycle it.
Co-processing of the plastic parts of electronic waste would be an interesting option, but requires
disassembling and segregation first (after Holcim & GTZ 2006).
This reflects the interest by the industry in cement kilns as a possible energy recovery option for
polymer waste containing POP-BDEs from electrical and electronic equipment (Tange & Drohmann
2005).
Also ASR (and other PBDE/BFR containing wastes) are a potential alternative fuel and mineral
feedstock for cement production as about 50wt% of ASR consists of combustible matter such as
polymers or rubber, and another 40 wt% is made up of silicates, calcium, aluminium and iron
(Boughton 2007, Vermeulen 2011). When the fuel of the cement kiln contained 50% of ASR, instead of
the regular fossil fuel mix, strong negative effects on the quality of the clinker have been noted.
(Gendebien et al. 2003). In this case the concentrations of Cl, Pb, Cd, Cu and Zn in the clinker increased
by one order of magnitude or more (Gendebien et al. 2003). In this case, the Swiss product
specification for clinker was not met for Cl, Cd, Cu, Pb and Zn. Other problems related to co-
incineration of ASR in cement kilns include increased ash formation, clogging of the fuel injection
58
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78
zone, volatilization of mercury, and increased concentrations of hazardous elements in the cement
kiln dust (Reijnders 2007, Fink et al.1999). In general, upgrading and purification of ASR is required
before its use as fuel substitute in high percentages in a cement kilns (Vermeulen 2011).
Unfortunately no study has yet been published on monitoring releases of POP-BDE and PBDD/PBDF
when PBDE/BFR containing waste materials are co-incinerated. It is therefore not possible to be
confident about the effectiveness of cement kilns for wastes containing POP-BDEs, particularly since
the feeding point is in the colder kiln inlet area:
The destruction efficiency of POP-BDEs in the waste will depend to a significant extent on the feeding
point in the kiln. Stable molecules (and dioxin precursors) like PCB or POPs pesticides need to be fed at
the hot end of the kiln into the burner flame with temperature up to 2000C and residence time of
more then 2 seconds is required above 1100 C to guarantee a high destruction efficiency. This also
assures the destruction of POP-BDE in secondary fuels and suppression of PBDD/DF formation at this
feeding point. However POP-BDE-containing waste (e.g. WEEE polymer, automotive/transport
shredder, polyurethane foam from furniture, insulation or mattresses) are solid waste fractions that
are challenging to feed at the hot end. Such solid waste fractions are normally fed at the colder kiln
inlet where temperatures between 700 and 1000C exist and the residence time depends strongly on
the plant configuration of the respective cement kiln.
Therefore the current situation of accepting and treating POP-BDE/BFR-containing waste in cement
kilns requires a detailed and site-specific assessment including feeding points, temperature, residence
time, POP-BDE destruction efficiencies (in particular if fuel is fed at the kiln inlet) and related
emissions. A properly configured test-burn, together with the establishment of the destruction
efficiency which incorporates an analysis of all emissions from the process including from products
and the bypass stack, should always be carried out before any POPs waste is considered for routine
disposal.
A second important consideration in treating POP-BDE/BFR-containing waste in cement kilns is the
sensitivity to halogen input, particularly with BAT cement kilns types with preheaters to halogen input.
For pre-heater kilns (with or without a pre-calciner) the main kiln type considered from the
Stockholm Convention BAT/BEP guidelines as an option for waste treatment (Stockholm Convention
2007) - the average total chlorine input from the combination of raw material, fuel and other
materials (including waste) should stay below 0.03% (of total input recalculated to the clinker) to
avoid clogging (Waltisberg 2010). Here, chloride entering the cement kilns builds up within the kiln
(around kiln inlet zone) resulting in hot meal (meal at kiln inlet) levels of up to 2% chlorine within this
area. This circulates within the system with possible negative impact on the operation by clogging at
the colder areas at kiln inlet and lower cyclone stages (Waltisberg 2010).
Furthermore, although cement kilns with pre-heaters normally have PCDD/PCDF emission levels well
below 0.1 ng TEQ/Nm3 (Karstensen et al. 2006) but with high chlorine levels wet and (long) dry kilns
can reach emission levels well above 1 ng TEQ/Nm3. Levels as high as 136 ng TEQ/Nm3 have been
reported (Stockholm Convention 2007, Karstensen 2008).
The behaviour of bromine in cement kilns and associated releases of unintentionally produced
POPs/by-products or elemental bromine has not been investigated or described (UNEP 2010b). As
bromine has similar physico-chemical properties to chlorine, e.g. boiling point of the potassium salt
(see Table 9) for KBr/KCl) crucial for the adsorption/desorption and therefore accumulation behaviour
of a halogen in a cement kiln, bromine will probably act in a similar way as chlorine within a cement
kiln.
Therefore with increased input of bromine via POP-BDE and other BFRs containing waste fractions,
the risk of increased clogging in preheater kilns and a possible formation of brominated &
brominated-chlorinated PXDD/DF and other brominated organics for all kiln types (but in particular for
wet and long dry kilns) needs to be considered and assessed.
79
Therefore the options and limitations for the destruction of wastes containing POP-BDE (such as
polymers from WEEE, automotive/transport shredder, polyurethane foam from furniture insulation or
mattresses) in cement kiln need an detailed evaluation of the individual kiln to decide the options and
limits of recovery energy from POP-BDE/BFR-containing materials in such kilns. Such assessment
should include a comprehensive monitoring of the release of POP-BDEs and other unintentionally
produced brominated and brominated-chlorinated toxic substances including PBDD/DF and PXDD/DF.
Considering that the built-up of chloride within a cement kiln can take weeks, an assessment of the
fate of POP-BDE/BFR-containing materials on associated POPs releases can best be performed through
long term monitoring (Reinmann et al.2010) over an extended time frame of weeks and months. In
this respect also the releases from bypass operations should be assessed including the contamination
levels of cement kiln dust (CKD) and the necessity of environmentally sound management of such
solid residue.
One option to increase the halogen input in a cement kiln is to install a chlorine bypass system
between the feed end of the rotary kiln and the pre-heater tower. The bypass enables a removal
option of chlorine from the kiln and might work similarly for bromine. In this case high
chlorine/bromine-containing cement kiln dust (CKD) can be generated in the system and be phased
out. The chlorine (and bromine) content of such CKD presents challenges for disposal and specific
management considerations are needed if it cannot be added to the final cement formulation (which
is often practised).
Cement kilns are increasingly used in waste management schemes also in developing /transition
countries for energy and material recovery (Holcim and GTZ 2006)59. The facilities have been and are
used for destruction of PCB contaminated oil. In some pilot tests they have also been used to destroy
pesticide stockpiles in developing countries (Karstensen et al. 2006). Since no carefully monitored
studies have yet been published (POP-BDE and PBDD/PBDF) on how effective cement kilns are in
destroying POP-BDE/BFR-containing wastes even in industrial countries, no final recommendation can
currently be given even for dry BAT kilns. Appropriate monitoring tests are needed.
With long dry kilns without pre-heaters and pre-calciners as well as wet kilns the PCDD/PCDF
formation and release potential is known, particularly when chlorine-rich (alternative) fuel/feed is
brought into such kilns. Therefore these two types of kilns can not be considered BAT and they are not
recommended for use in destroying/thermal recovery POP-BDE-containing materials.
Only BAT/BEP cement kilns with multi-stage preheater/pre-calciners which are already operating in
compliance within their authorized parameters/permits should be considered for such waste
management (Holcim and GTZ 200660).
A properly configured test-burn, including the assessment of the destruction efficiency of the kiln
which incorporates an analysis of emissions (including a sampling for POP-BDE and PXDD/PXDF) from
the process and the bypass stack together with the concentrations in clinker and cement kiln dust,
should always be carried out before POP-BDE waste is considered for routine disposal. The routine
disposal of POP-BDE containing materials can be supervised by long term monitoring of
unintentionally POPs and PBDD/PBDF or POP-BDE in stack emissions (Reinmann et al.2010).
59
http://www.coprocem.com/
60
http://www.coprocem.com/
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8.4 Melting systems
In Japan a study of a direct melting system (shaft-type gasification and melting technology) has be
found to be appropriate for ASR treatment, indicating the effective decomposition of brominated
flame retardants and polybrominated dioxins (Sakai et al.2002).
However the long term operation needs to be documented before this technology might be
considered as BAT/BEP for energy recovery of POP-BDE-containing materials.
8.5 Pyrolysis and gasification of POP-BDE containing materials
In its simplest definition pyrolysis is the degradation of polymers at moderate to high temperatures
under non-oxidative conditions to yield marketable products (e.g. fuels, oils or activated carbon).
Pyrolysis is capable of converting plastic waste into fuels, monomers, or other valuable materials by
thermal and catalytic cracking processes (Tange & Drohmann 2005, Scheirs & Kaminsky 2006). This
method can be applied to transform both thermoplastics and thermosets in high-quality fuels and
chemicals. Moreover it allows the treatment of mixed, unwashed plastic wastes (Scheirs & Kaminsky
2006). Considering the results from laboratory thermolysis, however, elevated concentrations of
PBDD/DF can be expected from pyrolysis processes when POP-BDE is present in the waste (Ebert &
Bahadir 2003, Weber & Kuch 2003). Therefore for the feedstock recycling via pyrolysis/gasification of
POP-BDE and BFR-containing waste, the formation of PBDD/PBDF maybe problematic. Also depending
on the chlorine content also the possible formation of brominated-chlorinated PXDD/PXDF needs to
be considered (Weber & Kuch 2003). Furthermore since pyrolysis and gasification are thermal
processes in reducing atmospheres, debromination and dechlorination processes take place. This
might lead, for example, for pyrolysis of chlorine-rich automotive shredder waste to high PCDD/PCDF
releases (Weber & Sakurai 2001). During pyrolysis/gasification significant debromination of DecaBDE
to lower-brominated PBDEs (including POP-BDEs) takes place (Hall & Williams 2008). Therefore in all
pyrolysis and gasification processes the fate of debromination of DecaBDE to POP-BDEs needs to be
considered and assessed for feedstock recycling of PBDE containing materials (c-PentaBDE, c-OctaBDE
and c-DecaBDE). Furthermore the conversion to PBDF during thermal degradation of c-PentaBDE, c-
OctaBDE and DecaBDE-containing materials in feedstock recycling needs to be taken into
consideration and evaluated.
Another issue to consider is the halogen content of the resulting oil.. Only if the pyrolysis oil has below
50 ppm (Cl or Br) it can be possibly used as a fuel with an acceptable impact on corrosion.
Currently pyrolysis and gasification can not be considered BAT/BEP for treatment of POP-BDE
containing materials until long term full scale applications have shown to result in products and
product flows which can be considered environmentally sound.
Another option for possibly utilizing pyrolysis is for the treatment of POP-BDE/BFR containing
materials in the recovery of bromine (see section 9).
No recommendation can currently be given for using pyrolysis or gasification technologies for the
treatment of POP-BDE-containing materials for developing/transition countries due to the lack of
reported long term full scale operation of such technologies even from industrial countries.
8.6 Metal industries
Some POP-BDE/BFR-containing materials are treated or end up in integrated metal smelters/copper

smelters and other metal industries. These are used to recover metals from Printed Circuit Boards,
cables and other polymer materials from WEEE which are firmly combined with the metals to be
recovered. In most cases such material is mixed with other primary (ore concentrates, anode slimes
etc.) or secondary materials (e.g. catalysts, industrial residues). Releases of POP-BDEs have also been
81
reported from electric arc furnaces, sinter plants and aluminium smelters revealing that also POP-BDE
and BFR-containing materials which are processed in these facilities (UNEP 2010b). The main sources
of such releases is probably the recovery of materials from End-of-life Vehicles or electronic wastes
(UNEP 2010b).
As for PCB containing materials, thermal treatment options need to be assessed for their destruction
efficiency for POP-BDEs containing materials. In this regard the formation and release of chlorinated,
brominated and mixed halogenated dioxins and furans need to be taken into account (Weber et
al.2003 and 2007; UNEP 2010b;).
Recent studies have reported here on the release of POP-BDE61, polybrominated dioxins and furans
(PBDD/PBDF) and brominated-chlorinated dioxins and furans (PXDD/PXDF) from these metal
industries revealing that also POP-BDE and BFR-containing materials are processed in these facilities
(Du et al. 2010a,b, Odabasi et al. 2009, Wang et al. 2010). Whilst the type of feeding materials was not
specifically measured62 or documented in these studies these emissions indicate that POP-BDE- or BFR
containing waste has been processed in these facilities and this has resulted in such emissions.
Therefore only limited conclusions can currently be made about the effectiveness and environmental
impact of these processes for recovering energy and materials from articles containing POP-BDE.
These processes need further assessment before final conclusions on BAT/BEP for treatment of POP-
BDE containing materials in such facilities can be made.
8.6.1 Copper smelters and integrated smelters-refineries
Category 2D Thermal processes in the metallurgical industry in Section V of the Stockholm

Convention BAT/BEP Guidelines (UNEP 2007) describes some key BAT/BEP issues regarding secondary
copper production. In particular, BAT/BEP of reducing UPOPs emissions in that document should be
considered. BAT/BEP details on the technologies are described in the EU BREF document on non
ferrous metal industries (European Commission 200163) as well as the updated draft of the document
(European Commission 200964)
Smelters treat a wide range of mixed waste streams such as shredder residues (which can contain high
concentrations of PBDE, other BFRs, PVC, and catalytic metals such as copper (Hwang et al. 2008).
Other flame retarded materials, notably printed circuit/wiring boards (PWB)65, are often processed in
secondary copper smelters for recovery of the copper and other precious metals including WEEE
polymers. Since the scale of these feedstock recycling operations as practiced for printed circuit
boards involves tens of thousands of tonnes/year (see Table 10) and is recommended by the industry
for BFR-containing polymers from electronics (Mark and Lehner 2000; Hagelken 2006; Brusselaers et
al. 2006) the releases of POP-BDEs and PBDD/PBDF and PXDD/PXDF could be substantial depending
on destruction efficiency of the respective facilities. Also the European Draft Reference Document on
Best Available Techniques for the Non-Ferrous Metals Industries mention that If major amounts of
61
Since thermal processes can lead to debromination of DecaBDE to lower-brominated PBDE the emission
pattern of PBDE in these studies only allow limited conclusions on the actual input of c-PentaBDE and c-OctaBDE
into these processes. Nor, without specific details of the concentration levels of brominated compounds in the
inputs can the destruction efficiency or appropriateness of treatment for PBDE-containing waste be assessed
(UNEP 2010b).
62
Although the Du study does provide some limited information on feedstock in the supporting information (Du
et al. 2010)
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65
PWB is used as an acronym instead of PCB to avoid confusion with Polychlorinated biphenyls)
82
electronic scrap with brominated flame-retardants are used as feedstocks, this may result in the
formation of mixed halogenated dioxins (European Commission 2009).
The polymers/resin content serves a dual function as a reducing agent and as a source of energy for
the smelting process. Further antimony can be recovered in integrated smelters. While the
temperature in the molten metal bath is high (above 1100C) and appropriate for the destruction of
POP-BDE, the temperature from the charging point to the surface of the bath ranges through a full
temperature gradient from ambient conditions to the bath temperature. Smelters can be described as
thermal processes with incomplete combustion occurring at the charging of the material. While coke
is mainly oxidized in the melting bath, the more flammable resins of printed circuit boards and
polymers from WEEE charged to the smelter are ignited and burns/pyrolyse to some extent on top of
the melting operation. Experience with waste incinerators demonstrates the concentration of
PCDD/PCDF and the brominated and brominated-chlorinated PXDD/DF in the off gas of the first
combustion zone is high (up to one thousand ng TEQ/Nm3) when adding a high proportion of WEEE.
These where destroyed in the secondary combustion zone (Hunsinger et al. 2002, Hunsinger 2010).
From this evidence together with a basic consideration of dioxin formation, high levels of brominated
PBDD/PCDF and brominated-chlorinated PXDD/PCDF can be formed and released from smelter
furnaces treating POP-BDE and other BFR-containing polymer. Therefore effective afterburners are
required as BAT/BEP. Moreover information from the industry (UMICORE) suggests that afterburner
are needed for the treatment of exhaust gases from smelting processes in which. printed circuit
boards are treated (Kegels 2010).
The use of a BAT afterburner (850 C; 2 seconds residence time; sufficient turbulence) in smelters
could possibly substitute for a secondary combustion chamber. PCDD/PCDF emissions of up to 5
ng/m3 are reported in the updated EU Draft BREF (European Commission 2008a) even with
afterburners. Two larger pilot studies at full scale plants on BFR WEEE polymer recovery in smelters as
substitute for coke/oil as reduction agent have been documented in Europe (Mark & Lehner 2000;
Hagelken 2006; Brusselaers et al. 2006). One in an integrated smelter in at Sweden (Boliden66) and
the second at in an integrated smelter in Antwerp/Belgium (Umicore67). However levels on POP-BDEs
and brominated-chlorinated PXDD/PXDF were not measured or were at least not reported. In the two
larger pilot projects utilizing brominated flame retarded material in smelters PBDEs and brominated-
chlorinated PXDD/PXDF have not been measured or were not reported (Mark and Lehner 2000,
Hagelken 2006; Brusselaers et al. 2006), PCDD/PCDF values were mentioned for both case studies.68
Therefore no adequate study has yet been performed (or at least published) to assess the release of
POP-BDE and the formation and releases of PBDD/DF and PXDD/DF from the feedstock recycling of
PBDE/BFR-containing materials in smelters. This type of feedstock recycling is used for tens of
thousands of tonnes of printed circuit boards every year and has been recommended for PBDE/BFR-
containing polymer from electronics (Mark & Lehner 2000, Hagelken 2006, Brusselaers et al. 2006).
For the individual smelters which want to process PWB and possibly utilize POP-BDE/BFR containing
polymer as reducing agent, assessment of POP-BDEs and halogenated Dioxins (PCDD/PCDF,
PBDD/PBDF and PXDD/PXDF) release need to be performed to decide on the appropriateness of the
smelter setting and the effectiveness of the afterburners and flue gas treatment.
66
http://www.boliden.com/
67
http://www.umicore.com/en/
68
The value in the fuming plant during recycling of PC scrap in the Swedish study was found to be 0.08-0.12 ng
TEQ/m3, (around the limit of stack emissions for waste incinerators) (Mark & Lehner 2000) and therefore above
the German workplace level of 0.05 ng TEQ/Nm3 (TRGS 557 2000) even without considering the PBDD/DF or
PXDD/DF. Also in the pilot test at the smelter in Belgium only PCDD/PCDF were measured and only at the stack
after flue gas treatment (Hagelken 2006; Brusselaers et al. 2006).
83
State-of-the-art integrated smelters require investments of well above US$ 1 billion. Currently, only 5-
10 plants feature the technological performance necessary for the described operations. These
include e.g. the plants run by UMICORE (Belgium) the Aurubis AG (former Norddeutsche Affinerie AG)
(Germany), Boliden (Sweden/Finland), Johnson Noranda (Canada) and DOWA (Japan).
Using BAT/BEP metallurgical facilities as mentioned above has significant benefits beyond their good
environmental performance, since a much wider range of metals can be recovered with higher yields
and less energy requirements than in less sophisticated installations (Hagelken 2006; Hagelken and
Meskers 2008). Final waste streams are usually small, since the depleted, inert slags from the smelting
operations can possibly be used as construction material (considering their leaching properties)
and/or additive for the cement industry.
Table 10: European Smelter Capacity according BSEF69
Plants Existing Recycling capacity (per year)
Boliden, Sweden 35,000 tons of E&E scrap (25% polymer)

Umicore, Belgium Can treat >10,000 tons per year (mainly circuit board)
Norddeutsche Affinerie AG, Treats 10,000 tons of circuit boards plus an other >15,000 tons
Germany (now Aurubis AG) of E&E polymers
Specific BAT/BEP considerations for reduction and avoidance of POP-BDE and PXDD/PXDF release
from copper smelters are:
1) BAT post combustion afterburners
Already the Stockholm Convention BAT/BEP guide mention post combustion afterburners as BAT for
minimization of PCDD/PCDF formation and releases for secondary metal installations (UNEP 2007).
The efficiency of the post combustion needs to be assessed to decide on the appropriateness to safely
process POP-BDE/BFR-containing material input.
2) Off gas treatment

BAT/BEP also include as primary measures the adequate off-gas handling and appropriate off-gas
conditioning to prevent conditions leading to de novo synthesis formation of PCDD/PCDF. The same
measures reduce the formation of PCDD/PXDF unless they are emitted from the furnace.
Key secondary measures for reduction of UPOPs
Adsorbent injection (for example, activated carbon)
High-level de-dusting with fabric filters (to <10 mg dust/Nm3)
As mentioned above, details can be found in the Stockholm Convention BAT/BEP guidance and the
respective EU BREFs.
69
BSEF http://www.bsef.com/science/brominated-flame-retardants-and-recycling/technical-recycling-
and-wastesolutions/
84
8.6.2 Material recovery and energy recovery in electric arc furnaces
Some key BAT/BEP considerations for electric arc furnaces in particular addressing UPOPs release
reduction are described in Section VI Part III Source category (b) Thermal processes in the
metallurgical industry not mentioned in Annex C, Part II of the Stockholm Convention BAT/BEP
guidelines (UNEP 2007) and should be considered. Details on the technologies are described in the EU
BREF for the Iron and Steel Industry (European Commission 201170)
Electric arc furnaces (EAFs) have not been widely considered to be facilities for recovery of POP-
BDE/BFR containing waste. It has been established for a number of years that electric arc furnaces
processing scrap metals can generate high levels of PCDD/PCDF in solid wastes and dust from flue gas
cleaning (ENDS 1997). More recently, emissions of PBDE and PBDD/DF from EAFs have been reported
for China, Taiwan and Turkey (Du et al. 2010a,b, Odabasi et al. 2009, Wang et al. 2010). The levels
from metallurgical processes were higher than combustion processes (Du et al.2010a,b). This
demonstrates that feedstock wastes containing PBDE is entering EAFs and need to be addressed in the
Stockholm Convention implementation. Since EAFs recover metal, such cases might fall into the
category of recycling and recovery of materials containing POP-BDE.
Specific BAT/BEP considerations for reduction and avoidance of POP-BDE and PXDD/PXDF release
from Electric Arc Furnaces are:
1) Separation of POP-BDE containing materials from scrap. The separation step is in particular
important if the Electric Arc Furnace dies is not BAT/BEP
As materials recovered/recycled in EAF possibly containing POP-BDEs following categories need to be
considered:
Car scrap and components of other transport vehicles (busses, trains, aeroplanes) containing
POP-BDE in polyurethane foam from seats and roof, polymer from interior or cables
White goods and other WEEE containing POP-BDE in polymer part.
2) BAT post combustion afterburners

Already the Stockholm Convention BAT/BEP guide (UNEP 2007) mention post combustion
afterburners as BAT for minimization of PCDD/PCDF formation and releases for EAF. As for the
smelters the efficiency of afterburner it needs to be assessed to which extent EAFs using BAT with
afterburners are able to safely process POP-BDE/BFR-containing material input. It is recommended
that also for BAT/BEP EAFs the input material containing POP-BDE might need an additional
separation step before recovering the metals in the furnace.
3) Off gas treatment

BAT/BEP also include as primary measures the adequate off-gas handling and appropriate off-gas
conditioning to prevent conditions leading to de novo synthesis formation of PCDD/PCDF. This may
include post-combustion afterburners, followed by rapid quench of off-gases.
The key secondary measures for reduction of UPOPs
Adsorbent injection (for example, activated carbon)
and high-level de-dusting with fabric filters (to <5 mg dust/Nm3)
70
ftp://ftp.jrc.es/pub/eippcb/doc/IS_11_17-06-2011.pdf
85
As mentioned above, details can be found in the Stockholm Convention BAT/BEP guidance and the
respective EU BREFs.
8.6.3 Feedstock recycling of POP-BDE polymer in primary steel industry
BAT of blast furnace operation is not described in the Stockholm BAT/BEP since it is not considered a
relevant UPOPs source. However it is covered by the EU iron and steel BAT reference document
(European Commission 2001 and 2011).
Polymers are used in the primary steel industry either directly in the blast furnace to substitute coke
or in the coking plant as a substitute for coal in the production of coke (Japan National Institute for
Environmental Studies 2010, European Commission 2011). In a life-cycle assessment for POP-BDE-
containing TV casings, Hirai et al. (Hirai et al. 2007) assessed four scenarios: material recycling,
feedstock recycling, incineration and landfilling. They concluded that feedstock recycling of POP-BDE
containing material in the primary steel industry would be preferable compared to material recycling
or incineration for energy recovery.
The European BAT reference document for Iron and steel mentions shredder residue as a used
feedstock in primary steel production (EC 2011). No published data from operations of a blast furnace
with explicit co-treatment and measurement of POP-BDE containing materials are available. However
the BAT/BEP document emphasize that for an assessment of the options and limitations of the
feedstock use of such polymer rich fractions (from mixed electronics and or car shredder) the heavy
metal content, particularly mercury but also Cobalt, Chromium, Arsen, Lead, Nickel, Cadmium and Zinc
in polymer feedstock is crucial for the evaluation of options and limitation for their use71 (European
Commission 2011). In the study of Hirai bromine/halogen content was one factor limiting the extent
of use in the primary steel industry72. The Japanese steel industry accepts a halogen content of up to
0.5% (bromine or chlorine). While in Europe the accepted halogen content seems high73
The conditions in a blast furnace are likely to destroy POP-BDEs and other halogenated organics in the
furnace with high efficiency. The utilization of POP-BDE/BFR-containing materials in the primary steel
industry and the related emissions of POP-BDE and PBDD/PBDF need a detailed assessment in the
frame of Stockholm Convention implementation.
The direct injection of polymers as reducing agent is applicable at new and existing blast furnaces. The
investment for the polymer injection plant at Voest Alpine Stahl GmbH (Austria) was about $US 27
million for an injection capacity of 220000 tonnes per year (EC 2011).
8.6.4 POP-BDE materials in secondary aluminium industries
Some key BAT/BEP considerations for secondary aluminium production in particular addressing UPOPs
release reduction are described in Section V for Source category 2D Thermal processes in the
metallurgical industry of the Stockholm Convention BAT/BEP guidelines (UNEP 2007) and should be
71
The European Steel BREF mention limits for Cobalt, Chromium, Arsen, Lead, Nickel, Mercury, Cadmium and
Zinc in plastic feedstock recycling in a blast furnace (European Commission 2009).
72
The bromine content of waste TV casings generated in Japan each year is 705 tons or nearly twice the 400
tonnes of total halogen which could be accepted/managed by plastic feedstock recycling in the Japanese
primary steel industry. Consequently a maximum of about 50% of the TV plastics could theoretically be
recovered via this route for Japan (Hirai et al. 2007).
73
In Europe the Chlorine content of up to 1.5% (Bremen/Germany) (Tukker 2002) and 2% (Linz/Austria)
(European Commission 2009) is reported to be accepted from steel industry.
86
considered. Details on the technologies are described in the EU BREF documents on non ferrous metal
industries (European Commission 200174)
PBDD/DF and PXDD/DF have been detected in stack gas from secondary Aluminium smelters (Du et al.
2010 a,b). PBDE have also been found in the waste input of an aluminium recycling plant. Samples
were taken from waste from handling of electric and electronic polymers, filter dust from electronic
crusher, cyclone dust from electronic crusher and light residues from a car shredder. In the screening
analyses, PBDE were identified in all samples in amounts of 24567,450 ng/g. The highest levels were
found in the polymers from electronics. Other brominated flame retardants were also observed in all
samples. The major PBDE congeners found were PentaBDE (150 ng/g), HexBDE (20 ng/g) and DecaBDE
(10 ng/g) (Sinkkonen et al. 2004).
Therefore, secondary aluminium plants should further be assessed for POP-BDE-containing material
input and for the release of POP-BDEs, PBDD/PBDF and PXDD/PXDF to air and solid residue.
8.6.5 Antimony smelters recycling WEEE polymers75
Some flame retarded WEEE polymer is recovered in antimony smelters where Sb2O3 (used as flame
retardant synergist with halogenated flame retardants) is recovered and the polymer serves a function
as a reducing agent. No data on volumes treated, destruction efficiency for POP-BDEs, or POP-BDE and
PBDD/PBDF release are available for these processes. Also no published reports on monitoring of
PBDE and PBDD/PBDF during Antimony recovery of WEEE polymer.
As for integrated/copper smelters, also antimony smelters processing POP-BDE/BFR containing
polymers can be considered to require afterburners for flue gas treatment to be considered BAT/BEP.
In all cases actual measurements are required to decide on the appropriateness to use an antimony
smelter to process POP-BDE containing polymers.
8.6.6 Developing/transition country considerations
As mentioned above, recent studies in China, Taiwan and Turkey have reported releases of PBDE and
PBDD/PBDF from metal industries (copper smelters, electric arc furnaces, sinter plants, secondary
aluminium industry) revealing that also PBDE/BFR-containing materials are entering these facilities
(Du et al. 2010; Odabasi et al. 2009; Wang et al. 2010). Many developing/transition countries have
some of these industries and therefore possible releases from these facilities. On the other hand such
facilities might be able to recover metals and energy from these material/waste streams with
associated benefits for resource conservation and energy efficiency.
However often the technology level and applied abatement technology of metal industries in
developing countries is low. Therefore it is currently not clear whether metal industries in developing
countries are appropriate to treat materials containing POP-BDE
Since there are still considerable knowledge gaps for the different metal industries in industrial
countries (copper smelters, electric arc furnaces, secondary aluminium, and antimony smelters)
currently no recommendation can be given for such practices for developing and transition countries.
74
75
The following knowledge gaps exist (UNEP 2010a,b):
Extent of WEEE plastic use for Antimony recovery?
What are the PBDE destruction rates and the levels of PBDE and PBDD/DF releases in Antimony smelters when
WEEE plastic is recycled?
What level of technology is necessary Antimony smelters?
87
As mentioned for industrial countries, monitoring of releases from facilities treating POP-BDE/BFR
containing material are a first necessary step.
9 Recovery of bromine from POP-BDE/BFR containing

materials
There are a number of promising technologies in development or pilot stage capable of recovering
bromine from the polymers and thus possibly allowing the safe recycling or recovery of feedstock. The
recovery of bromine include techniques for recovering materials for recycling, for recycling feedstock -
as either fuel or for manufacturing use, the pyrolysis of polymers with bromine recovery, recovery of
bromine in incinerators, and separation of PBDE/BFR from polymer for recovery of bromine in
industrial use (Figure 12). However, the lack of any real market incentive to remove POP-BDE/BFRs
from end-of-life articles is possibly one reason that these technologies appear to remain at the
laboratory/pilot stage. No information was available on any full-scale operation approximately 10
years after industry announced this approach as an aim (BSEF 2000).
Since the option of recovering bromine is increasing with full scale facilities separating
brominated/halogenated polymer, the status of these technologies although not available in full scale
are shortly described here for further consideration
These technologies will, however, need further assessment before any firm recommendation can be
given in respect to BAT/BEP status of these technologies. Any assessment should also address the
issue of the practical level of separation of BFR/Bromine from materials containing BFR and consider
the current high price of Bromine (approx. $USD 2,500/tonne in 2010 and $USD 4000 in 2011)
together with the future markets for such bromine and the contribution relied upon from this in
relation to the economics of the process
Figure 12: Potential options for the bromine recovery process and closing the bromine cycle (Tange
and Drohmann 2002).
88
9.1 Thermal recovery of Bromine
9.1.1 Recovery of bromine from waste incinerators
For BAT incinerators treating relatively high levels of POP-BDE/BFR-containing wastes Vehlow
suggested that bromine recovery might be possible (Vehlow et al. 2002). It was suggested that a
typical MSW combustion line treats 20 tonnes of MSW per hour and that normally, to achieve suitable
economies of scale, several lines operate alongside each other. On the basis that 3% of WEEE
polymers containing 2.5 wt% bromine was added to three lines, (1800 kg/h WEEE polymers), this
would represent 45 kg/h of bromine in the feed. At a typical scrubber efficiency of >97% and a
bromine recycling yield of >90%, such a unit could in theory recycle 310 tonnes of bromine per year. It
is possible to distil HBr as a 48% solution, in which case the recycling level would be around 660
tonnes of 48% HBr per year. This, Kennedy and Donkin had calculated, could contribute 7% to the
income of a municipal waste incinerator (PB Kennedy & Donkin 1999).
9.1.2 Recovery from bromine from pyrolysis
Two thermal processes utilising pyrolysis have been developed to pilot scale where the recovery of
bromine from electronic waste and waste polymer was one project feature.
A main issue is to get a clear separation between the gas/liquid fuel and the HBr. If a too high
concentration of halogens is left in the fuel (>50 ppm Cl or Br) it can not be further used due to a
higher potential for corrosion.
The Haloclean process
The Haloclean process is a low temperature pyrolysis developed as a thermal-chemical process for the
treatment of waste electrical and electronic equipment (Hornung and Seiffert 2006, Koch 2007). The
Haloclean reactor was developed with a gas-tight rotary kiln. The process tries to divide shredded
electronic scrap into a valuable material stream and an energy flow. In a two-stage pyrolysis the
polymer components are converted into oil and gas. A further chemical process step (called
Polypropylene Reactor) aims to strip and recover bromine and other halogens out of these
products. From the remaining pyroylsis residue precious metals and other metals can be separated
(Hornung and Seiffert 2006, Koch 2007). To date only a demonstration plant has been developed. The
process is currently used for biomass pyrolysis.
Recovery of bromine by two stage pyrolysis-gasification
In a pilot trial carried out for the bromine industry (EBFRIP) at Energy Research Centre (ECN)
(Boerrigter 2001, Tange and Drohmann 2005) in Holland it was shown that it is possible to recover
bromine via thermal processes. The process (Pyromaat) consisted of a staged gasification,
comprising pyrolysis (550 C) and a high temperature gasification (>1230 C). In pilot test runs, the
HBr was recovered by wet alkaline scrubbing of the syngas from treating polymer fraction of WEEE
(Boerrigter 2001, Tange and Drohmann 2005):
9.2 Technologies for separating POP-BDEs/BFRs from the polymer
matrix
Technologies of separating BFRs (including POP-BDE) from polymer matrix have only been established
in pilot scale for:
a) POP-BDE/BFR-containing polymer; and
b) Printed circuit boards.
These two POP-BDE/BFR-containing material categories have commercial market value and this has
been the main driving force for the development of improved recycling technologies. Neither of the
89
separation technologies is currently operating at an industrial scale. For POP-BDE/BFR separation from
polymer the technology now seems ready for industrial application. For printed circuit board, the POP-
BDE/BFR separation technology is still only developed and operating at a laboratory scale (see below).
9.2.1 Separation of BFR/bromine and polymer recovery
The common sorting approaches are based on cherry picking the most valuable components of the
electronics/polymers from the input. Yields are generally fairly low and are normally in the range of
20% to 60% depending on input, the plant design and technologies used. The POP-BDE/BFR and
bromine load however is enriched in the residual waste fraction. Some technologies
The CreaSolv process extracts PBDE/BFRs from target polymers from polymer-rich fraction and is
able to remove non-dissolved (e.g. non-target polymers and other interfering materials) and dissolved
contamination (e.g. POP-BDE, PBB or other brominated flame retardants) from the target polymers
(Schlummer et al. 2006). BFR from flame retarded polymers is extracted using a proprietary CreaSolv
solvent formulation and produces a by-product with high levels of BFR. The market price of Bromine is
approximately 2500$/t (Hofland 2010a) so this by-product might be used for bromine recovery by the
bromine industry. Alternatively it could be chemically treated or incinerated. It has been developed
and optimised to certain WEEE polymer fractions and is able to produce RoHS compliant polymers
even from BFR-rich fractions (Schlummer et al. 2006). The extracted recycled polymers are of high
quality and intended for applications such as EEE production.
An assessment of practical and commercial applicability of the technology has been performed in the
UK (WRAP 2006a). The study shows that the Creasolv process for extraction of brominated flame
retardants from WEEE polymers has potential to be commercially viable in the UK context at a
throughput of 10,000 tonnes/year.
According to Fraunhofer-Institute IVV, where the process was developed, the process could be
developed commercially with plant capacities of 2000 t/year and greater (Schlummer 2010).
The process should be able to compete with incineration ($100+ per tonne gate fee) or landfill76
disposal (cost of landfill gate fee depends strongly on region and country policy) or as treatment
methods for segregated polymer streams (WRAP 2006a). Creasolv will compete for BFR removal
processes using spectroscopic sorting techniques, since it reaches higher yields due to the fact, that
also most of PBDE/BFR-containing polymers are converted to RoHS compatible and marketable
polymer products (WRAP 2006a).
The assessment concluded that the process could compete with export of mixed WEEE polymer
outside the EU (current sales value around $100/tonne) if the finished high grade compounded
recyclate can be sold at about 80% of the virgin compound price (WRAP 2006a).
9.2.2 Recovery of metals, energy and bromine from PWB
The mechanical recycling of printed wiring/circuit boards (PWG) which also separates the BFRs from
other materials in the recovery process has been developed at a laboratory scale (Kolbe 2010a; Kolbe
2010b).
Within the complete material recovery strategy also the bromine is planed to be recovered (Kolbe
2010a). The main parts of metals are mechanically removed from PWB in a first step. In a second step
76
According to the convention POPs waste need to be destroyed or irreversibly transformed. Landfilling should
be avoided if possible as it is not, in most circumstances, an approach which can guarantees long-term security.
POPs Studies from different regions are documenting that PBDE are released from landfills and contaminate
ground and surface water, the surrounding soil and for developing and transition countries contamination of
humans working on or living around the landfill sites has been documented as discussed in the section on final
disposal.
90
the PWB resin is dissolved and the remaining metals and the glass-fibre are recovered. The metals are
further recovered in metal smelters. The dissolved resin is debrominated and the bromine recovered
(as NaBr). The resulting debrominated oil is planned for use in a power plant (Kolbe 2010a). The glass-
fibre is pressed, washed and dried and can be reused as filler material.
The company also plans to recycle the residues and dust from the production of printed circuit boards
(Kolbe 2010b).
91
10 Disposal of POP-BDE containing materials to landfills

10.1 General remark to landfilling POP-BDE containing materials:
The goals of waste management are threefold and comprise first the protection of men and the
environment, second resource conservation, and third after care free treatment and disposal of
wastes (no transfer of waste related problems to the next generation or sustainability). Thus, for
goal oriented waste management, landfilling of wastes containing POPs is the least preferred option
and must generally be avoided. This is in agreement with the results of several life cycle analysis of
PBDE disposal (Vermeulen et al 2011; Boughton and Horvath 2006; Ciacci et al 2010; Duval et al 2007).
It is also in agreement with the Stockholm Convention BAT-BEP guidance (UNEP 2007) which
recommends e.g. that car shredder residues which always contain POP-BDEs, other POPs and
hazardous substances must be disposed of in proper incinerators equipped with sophisticated air
pollution control devices. Hence, the following guidelines for landfilling assume: All possibilities to
establish clean material cycles or to mineralize POP-BDE&PFOS by modern incineration with
advanced air pollution control have been exploited.
Both, clean recycling and sophisticated incineration, are expensive means of waste management. They
are practiced mainly in affluent countries because financial resources for waste management are
limited elsewhere. A survey about waste management costs in different regions demonstrates that
expenditures for waste management amount to between 0,2 % and 0,4 % of Gross Domestic Product
(GDP) of a country (Brunner and Fellner, 2007). Since GDP ranges globally from 200 US & to 100000
US$ per capita (The World Bank, 2011), the financial resources available for waste management
covers a range of factor 500. It becomes evident, that waste management practice must differ
considerably from region to region. Many countries cannot afford yet a waste management system
comprising incineration and other sophisticated means of waste transformation and recycling. For this
reason, in emerging economies the fraction of wastes that is disposed in landfills and dump sites is
much larger than in affluent economies. Hence, these guidelines must focus in the first place on
landfilling in developing countries and countries with economies in transition. This is of particular
importance because these countries often adhere to open dumping, with severe consequences for the
adjacent environment. Nevertheless the guidelines will also include affluent countries since landfilling
of wastes containing POPs is still practiced there, too.
10.2 Types of wastes containing POP-BDEs that are landfilled
Wastes containing POPs can be categorized as follows: A) wastes consisting mainly or exclusively of
POPs, B) mixed wastes containing POPs as additives, C) and wastes polluted with traces of POPs. In
landfill practice, information is available that allows landfill operators to identify type A wastes. If type
B wastes derive from a single and known process such as a car shredder, the presence of POP-BDEs
can be assessed according to the Stockholm Convention Inventory Guidelines for POP-BDEs and HBB
(sections 4, 5, and 6). In fact, according to the Stockholm Convention, car shredder residues always
contain some POP-BDEs. However, it is beyond landfill practice to recognize type C wastes, or type B
and C wastes when mixed with other wastes. It must also be taken into account that wastes of type B
and C are likely to comprise additional hazardous substances, such as other POPs and heavy metals.
Thus, decisions on the management and landfilling of POP-BDE containing wastes cannot be taken on
the grounds of POP-BDE content alone.
In the following, those wastes that are the most important carriers of POP-BDEs are summarized:
The four major application areas for POP-BDE are (see also section 5, 6 and 7 of this guidance):
electrical and electronic equipment (computers, telephone sets, office appliances, cables etc.),
the transport sector (plastics, textiles and upholstery etc. in end-of-life vehicles),
furniture, mattresses and others (including carpets, textiles, and the like),
92
the construction sector (insulation, foils, and other polymer materials)
Hence, the main waste flows originate from these four areas, too. There are two ways to determine
mass flows and concentrations of POP-BDE containing wastes: Either by direct analysis as described in
the document Inventory Guidance for PentaBDE, OctaBDE and HBB (Draft v10, Nov. 17, 2011), or by
an MFA approach as applied e.g. by (Morf et al, 2008). Numeric examples of common waste flows and
corresponding POP-BDE concentrations are presented in section 4 and 5 of the Stockholm Convention
Inventory Guidance for POP-BDE and HBB.
In general, the physical characteristics of PBDE containing wastes are the same as for other wastes
that are landfilled: If not pre-treated, particle sizes cover a wide range from 10-6 to 1 m, and densities
vary between 0,02 and 2 g/cm3. Thus, sampling, sample preparation and analysis of PBDE containing
wastes is a difficult task and expensive. There are no standard procedures yet to sample and analyse
such wastes for POP-BDEs at a given, predefined standard deviation. Support for waste sampling and
characterization is given in CEN/TR 15310-1 Characterization of waste Sampling of waste materials
Part 1: Guidance on selecting a basic statistical approach to sampling, as applied under a variety of
scenarios.
10.3 Categories of landfills to receive POP-BDE containing wastes
The four types of landfills given on the left hand side of Table 9.1 are common in countries with
advanced landfill management (see for instance Austrian Landfill Ordinance, (Deponieverordnung,
2011)). In addition, so called hazardous waste landfills have been designated in some countries. While
most advanced nations refrain from operating hazardous landfills, others are using underground
repositories that are completely cut off from the hydrological cycle for very long time frames such as
salt mines or equivalent geological formations. Since space is rare and rather expensive in such
caverns, only materials that are toxic and comparatively highly concentrated are allowed to be stored
in such underground storages. Specific regulations apply according to the site specification;
underground depositions of wastes that are highly concentrated in POP-BDE are a special issue that is
not treated in this section.
93
Table 9.1: Types of landfills, and corresponding constraints for disposing of wastes containing POP-BDEs. The table serves as an example, and may be different for
different countries.
A. B. C. D. E.
Landfill for Landfill for Landfill for Landfill for MSW and Underground storage for
construction wastes hazardous wastes
excavated soil inert material residual wastes
General waste content Excavated soil from Track ballast and similar Wastes from construction and Pretreated MSW with organic Hazardous wastes,
construction sites demolition, such as masonry, content < 50g/kg; organic
concrete, mortar, brick, fraction from construction
asphalt, inorganic insulation wastes, residual fractions from
material, recycling.
Content with regard to None Residues of POP-BDE in badly Contains some WEEE, wastes Concentrated wastes of POP-
POP-BDE wastes separated insulation and from ELV, furniture and BDE from production or
plastic material if construction household articles, and POP- manufacturing
waste is not appropriately BDE containing residues from
separated the construction sector
(insulation, foils, and other
plastic materials)
Barriers appropriate to No No In part Yes, but for limited time Yes, if POP-BDE is safely
retain POP-BDEs frames only contained and stored in stable
geological formation
Leachate collection
Gas collection and No No yes

treatment
Regulations regarding No, but limits for eluate: No, but limits for eluate: No, but limits for eluate: No, but limits for wastes:
1)
POP-BDEs in wastes, and EOX< 0,3 mg/kg EOX< 0,3 mg/kg EOX< 3 mg/kg POX (as Cl) < 1000 mg/kg
(as Cl) (as Cl) (as Cl) (dm)
in eluates derived from for eluate:
wastes EOX< 30 mg/kg
(as Cl)
Regulations regarding Plastics < 0.5% Metal and plastics < 10% by TOC< 10%
wastes that potentially by weight (dm) volume
may contain POP-BDEs
1) Purge-able organic halogen compounds
94
The landfill categories given in Tab. 9.1 do not apply to emerging economies. In such countries, either one or
two categories of landfills are met: a type of landfill that is not yet corresponding to a sanitary landfill
comprising liners and collection systems for leachates and gases, and a type of landfill that is engineered to
contain more challenging materials such as hazardous wastes and hospital wastes. It has to be kept in mind
that in countries with a low GDP, the main task of waste management is complete collection of wastes,
which is cardinal for sanitation. This usually consumes 80 to 90 % of the waste management budget. Hence,
the remaining fraction does not allow sophisticated incoming control of wastes and leachate and gas
collection and treatment as in the case of affluent countries.
10.4 Delivery of wastes to landfills
Wastes must be characterized and controlled before landfilling. Characterization includes the history of the
waste (process of waste generation), type, properties and composition of the waste. Waste composition is
determined according to existing landfill regulations by sampling, sample pre-treatment and analysis. Mixing
of wastes in order to lower amounts of critical parameters is prohibited and must be prevented.
Up to now, modern regulations restrict individual inorganic substances and some organic sum parameters in
waste inputs, but do not focus on individual organic substances. In emerging economies input control on the
substance level is for financial reasons - impossible for both inorganic as well as organic parameters.
Investigations of PBDEs in wastes are not required by modern landfill regulation. This can be justified on the
grounds that wastes to be landfilled are composed of a great number of substances, many belonging to the
family of POPs and other hazardous compounds. Hence, the analytical expenditure to determine all these
substances is too large. It is more effective to regulate sum parameters (Tab. 1), and to use the results of the
analysis of these sum parameters for decision making. If landfill specifications are not met, wastes must be
either pretreated, or disposed of in another landfill class.
In emerging countries, characterization and control of incoming wastes must be based on a heuristic
concept, relying on local experience and good governance practice. Incoming wastes must be visually
screened for those categories that are enriched with POP-BDEs such as residues from shredding End-of-Live-
Vehicles (ELV), plastics and boards from dismantling of electronic wastes, insulation materials from
constructions, or wastes from removing insulations from cables. Wastes that contain POP-BDEs should be
mixed with other wastes, thus reducing the risk of producing large amounts of volatile and toxic halogenated
compounds in case of landfill fires (see below 9.5.2).
10.5 Operation and maintenance of landfills containing POP-BDE
Of all man made constructions, sanitary landfills are those with the longest lifetime. Materials buried in
landfills are expected to stay there forever. Considering geological processes of erosion and weathering,
forever presumably means ten thousands of years; after this period, most landfills will be removed by
geogenic processes.
Because PBDEs are very slowly degrading only, the residence time of these substances will be long, too.
Danon-Schaffer recently modelled the debromination of DecaBDE to lower PBDE (including POP-BDEs) in
landfills (Danon-Schaffer & Mahecha-Botero 2010). Depending on the selected degradation rates, significant
debromination occurs within 70 to several hundred years.
Ultimately containments of sanitary landfills will degrade allowing landfilled substances to dissipate over
time. USEPA expressed concerns that the large amounts of PCBs contained in land disposal sites present a
severe hazard for the future (USEPA 1979). The risks presented by POP-BDE are similar. Since the lifetime of
landfill containments is limited to decades to centuries - actual experience does not allow yet to draw more
precise conclusions (Buss et al. 1995, Allen 2001, Simon & Muller 2004) - it must be expected that POP-
BDEs and other substances contained in landfills are emitted over a long time period (centuries) (Weber et al
2011). Thus, the behaviour of landfill constituents as well as of the corresponding containment must be
known in order to predict emission levels to the environment over the whole life time of the landfill. Up to
now, there are many studies available assessing the first decades of open dumps as well as of sanitary
95
landfills. Studies investigating or modelling the full life cycle of PBDEs in landfills over long time periods are
still scarce.
Landfills in emerging economies may contain the widest range of compounds because it is not possible to
completely control waste collection and delivery to landfills. In affluent economies, this situation has been
mitigated by waste pre-treatment and by strict input regulation. However, even under these firm control
measures, it is still possible that some amounts of wastes that are not appropriate for a certain landfill class
are disposed of in landfills. It is thus indispensable that landfills are constructed with liners controlling inputs
and outputs. The expenditure for such a containment depends on the content and thus on the class of
landfill. With increasing reactivity and leachability of the waste categories from landfill type A to E, the liners
must fulfil more stringent requirements. Under the conditions of emerging economies with mixed waste
landfills prevailing, liners should fulfil the same conditions as for landfill type D. However, this requires
financial means that are often not available in emerging economies.
In order to understand and control landfill behaviour and relating emissions, reactions taking place in
landfills must be understood. A landfill is basically an anaerobic biochemical reactor driven by the nutrients
carbon and nitrogen and controlled by the flow of water. In simplified terms, the end products of such a
reactor are methane, carbon dioxide and water. Due to the many inorganic and organic constituents, some
of them refractory, the products of landfilling contain a large amount of gaseous and liquid harmless as well
as hazardous compounds. Thus, it is of prime importance to collect leachates and landfill gas in order to
reach the goals of waste management.
10.5.1 PBDE releases from landfills
In general, trace organic substances such as PBDEs are of little importance for the functioning of the landfill
reactor. This may be different in the special case when wastes with high PBDE load are landfilled which may
be found in emerging countries where incineration facilities are lacking. However, the landfill reactor is of
significance for the release of trace substances. In addition to the intrinsic properties of the trace substances
(Kow, Henry coefficient, vapour pressure, solubility, and persistence), landfill parameters such as
temperature, pressure, ionic strength, pH and redox conditions determine the fate of individual waste
constituents.
When evaluating information about emissions of PBDEs from landfills, it is important to distinguish between
state of the art landfills on one hand, and other disposal practices which include landfilling without top and
bottom liners, open dumping, or illegal dumping on the other hand. The first practice results in very low
flows of PBDE to the environment, the latter may result in significant environmental pollution. Several
authors acknowledge that semivolatile compounds like PBDE and PCB are leaching together with heavy
metals and other substances from inappropriate landfills into soil and hydrosphere (Osako et al. 2004,
Odusanya et al. 2009, Danon-Schaffer 2010, Danon-Schaffer & Mahecha-Botero 2010, Weber et al 2011).
Leachate concentrations of PBDEs in the range of 30 to 250 ng/L have been found in a study of five different
landfills in North America by Oliaei et al (Oliaei et al. 2002). PBDEs have also been detected in soils adjacent
to landfills in various regions of Canada (Danon-Schaffer 2010), indicating atmospheric PBDE release from
landfills and subsequent deposition. Higher values have been recorded in leachates from illegally dumped
shredder residues from ELV and electronic wastes that are well known sources of landfill emissions of POPs,
requiring costly remediation actions (Takeda et al 2007).
On the other hand, if state of the art landfilling with liners, collection of leachate and gas, and subsequent
treatment of leachate and gas is applied, pollution by POP-BDEs can be kept at low and environmentally safe
levels. This has been documented in several reviews: An assessment of management options for c-OctaBDE
commissioned by the European Commission concluded that c-OctaBDE are not expected to be leached
significantly from polymers, unless the polymer is degraded (BiPRO 2007). The authors consider that releases
after proper disposal are negligible, a conclusion that seems applicable to the whole UNECE region (BiPRO
2007). A similar conclusion was reached in a report prepared for the New Zealand Department of the
96
Environment for the POPRC process (Keet et al 2010). By reference to three investigated landfills, the
authors claim that the disposal of waste plastics containing PBDEs in controlled landfills is a well developed
and safe activity resulting in very low levels of PBDEs in leachates. Compared to the quantities of PBDEs
stored, the quantity of these products leaving the landfill was infinitesimal in this study. However, the
authors recommend to validate their findings more widely. This seems justified in particular for larger time
scales requiring a modelling approach.
Based on these findings, the key environmental problem besides landfill fires (see below) - consists of the
inappropriate landfilling resulting in contamination of the hydrosphere as it is most often observed in
emerging economies and transition countries. This may even result in the exposure of humans in the vicinity
of landfills, as reported for breast milk from women living near a landfill site in India (Someya et al 2010) and
for juvenile scavengers living and working on a landfill in Nicaragua (Athanasiadou et al. 2008). For affluent
economies with modern BAT landfilling, it must be observed in the future which of the two processes
debromination/degradation of PBDEs or degradation of containment systems is more rapid.
For long term considerations, climate change and extreme weather events have to be considered (Laner et al
2009; Weber et al 2011). However, these causes are generic impacts, and not of specific importance for POP-
BDEs. Thus, BAT landfill practice will take these impacts, which are likely to include more rapid degradation
of liners, enhanced leachate production, mobilization of a larger waste fractions, and higher volatilisation
rates into account. The situation may be of concern for coastal areas where flooding and interaction with
seawater poses a threat to environment and human health by bioaccumulation (Bebb & Kersey 2003).
10.5.2 Release of POP-BDE and PBDD/PBDF from landfill fires
Particularly in emerging economies, landfill fires are inevitable and are often observed. In fact, landfills are
sometimes deliberately set on fire in order to save landfill space, and to improve hygienic conditions
(rodents, birds). Even in industrial countries with modern landfilling practice, it may seldom occur that a
landfill catches fire for unknown reasons. A survey in Finland finds annually 0.6 fires per landfill site, with 25
% of fires at a depth of more than 2 m where thermal conditions are favourable to produce brominated
dioxins and furans (PBDD/PBDF) (Ettala et al 1996).
Landfill fires are always difficult to extinguish, and release considerable amounts of hazardous volatile and
pyrogenic substances into the air. They are a relevant source of PCDD/PCDF in particular for developing and
transition countries (UNEP 2005). The best practice to reduce the risk of landfill fires is a strict entrance
control for highly inflammable waste constituents, paired with a daily cover of the freshly deposited waste
by inert materials such as inorganic construction waste.
The main concern with regards to landfill fires and POP-BDEs relates to the potential formation and release
of PBDDs and PBDFs (WHO & IPCS 1994, UNEP 2010b). PBDE and PBDD/DF have been measured in
intentional fires of open dumps in Mexico for the purpose of a scientific study on emission factors of open
burning in dump sites (Gullett et al. 2009). These studies demonstrate that PBDE originate most likely from
commercial brominated flame retardants and are not formed by thermal processes. Emissions of
PBDD/PBDF were similar in magnitude to their chlorinated counterparts (PCDD/PCDF). Smouldering
combustion yields larger emissions than flaming combustion. For a better understanding of PBDD/PBDF
formation, the thermal debromination process needs to be investigated at varying oxygen concentrations
and temperatures, in particular the thermal conversion of DecaBDE to lower POP-BDEs which might
significantly contribute to the formation of POP-BDEs and PBDD/PBDF in thermal processes (UNEP 2010b).
10.5.3 BAT to prevent short- and long-term release of POP-BDE from landfills
To follow, focussing on:
Landfilling practice
97
Collection and treatment of leachates
Collection and treatment of landfill gas
Monitoring of landfill
10.6 BAT/BEP of landfill aftercare:
To follow, focussing on:
Goals of after care
Means for after care

10.7 Landfill mining and impact of POP-BDE
The objectives of landfill mining are threefold:

A Recovery of land
B Recovery of materials
C Environmental protection
From an economic point of view, A recovery of land is most attractive, and often the driving force of
landfill mining. This is especially the case in regions of rapid development, where former landfills become
neighbours of residential or office environments, and land increases highly in value. Recovery of valuable
materials from landfills as well as landfill mining for environmental protection has not proven yet to be
economically feasible. However, to pursue the three objectives in combination may be an attractive solution
for three real challenges.
From the point of view of PBDEs, only objective C Environmental protection is a driving force. Excavation
of landfill bodies allows to physically separated and thermally mineralized waste constituents that carry
hazardous organic substances into carbon dioxide, water and halogen salts. However, the separation
efficiency for POP-BDEs containing wastes is rather low since chemical properties do not go along with
physical characteristics. It thus is advisable to choose a different strategy, namely to separate the relatively
small amount of valuable materials (metals) and to incinerate the rest. Care must be taken to prevent POP-
BDEs from leaching and volatilization during excavation. Depending on the wastes landfilled, it may be
necessary to cover the site in order to prevent release of POPs and other toxic substances (for an extensive
example, see SMDK 2011).
Besides products of complete mineralization, landfill mining may generate other outputs such as soil
fractions, metals and plastics. So far, these fractions contained substantial levels of contamination that may
impact their marketability. In any case, it will be difficult to effectively separate POP-BDEs mechanically from
such fractions (soil and plastics!), resulting in POP-BDE contaminations of many products of separation. Thus,
in view of goal oriented waste management, landfill mining practice should produce a fraction that contains
most of the POPs including POP-BDEs. This fraction must be mineralized in a modern incinerator with BAT air
pollution control.
98
10.8 Summary, conclusions and outlook about landfilling of POP-BDE with

regard to BAT/BEP
POP-BDE emissions from landfills are a specific but - when compared to other issues such as hygiene and
sanitation secondary problem for landfilling in emerging economies. In affluent countries with state of the
art landfills, PBDE emissions are small and generally of no environmental significance. Exceptions are landfill
fires, and possibly long term leaching of POP-BDE and metabolites when landfill containments fail their
functions due to deterioration of engineered liners. On a global scale, state of the art landfills are still a
minority; hence, contaminations with PBDEs have been observed in the vicinity of landfills worldwide in both
emerging and affluent countries.
If BAT is applied, PBDE emissions prove to be small. BAT includes allocation of PBDE containing wastes to
appropriate landfill types, strict entrance control, operation of landfilling with daily covers, state of the art
bottom liners and final covers, collection and treatment of leachate and gas, and after care with monitoring
for long time periods (centuries). When discussing BAT, it must be kept in mind that landfill regulation does
not include individual organic substances such as POPs or others. Thus, there is no individual governance of
POP-BDEs in landfilling, but POP-BDEs are treated and regulated like other pollutants.
For emerging economies with limited financial resources, prevention of landfill fires and collection and
treatment of leachates are the most effective means to protect human health. Since financial means for
waste management are coupled with GDP between 0.2 to 0.4 % of GDP are spent for waste management
the most effective means to improve landfill management is to increase GDP. This will allow a change from
waste disposal to incineration and recycling, decreasing on a large scale the amount of PBDE that today is
being landfilled.
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12 Annex
12.1 Recommendations from COP5 (Annex to decision POPRC-6/2)
Recommendations on the elimination of brominated diphenyl ethers from the waste stream and on risk
reduction for perfluorooctane sulfonic acid (PFOS) and its salts and perfluorooctane sulfonyl fluoride
(PFOSF)
I) Recommendation on the elimination of brominated diphenyl ethers from the waste stream
1. The Committee reviewed the information provided by parties and observers on newly listed
persistent organic pollutants and in the draft technical paper. On the basis of this information, the
Committee identified potential gaps in the information and developed recommendations on the
elimination of brominated diphenyl ethers from the waste stream, including on how to fill the
information gaps identified.
A. Overall recommendation
2. The objective is to eliminate brominated diphenyl ethers from the recycling streams as swiftly as
possible. To meet this objective, the principal recommendation is to separate articles containing
brominated diphenyl ethers as soon as possible before recycling. Failure to do so will inevitably result in
wider human and environmental contamination and the dispersal of brominated diphenyl ethers into
matrices from which recovery is not technically or economically feasible and in the loss of the long-term
credibility of recycling. Initially, the main focus should be on developed countries handling primary
77
flame-retarded articles containing higher concentrations of brominated diphenyl ethers and attention
should be paid to identification and treatment of brominated diphenyl ethers in articles for both
domestic use and for export.
3. Time is short because articles containing brominated diphenyl ethers are already present in many
existing waste streams as a result of the time frame of former production of these articles. Brominated
diphenyl ethers should not be diluted since this would not reduce the overall quantity in the
environment. In some cases, it is likely that the quantities in waste have reduced significantly from their
peak concentration levels.
4. To prevent similar difficulties with other substances, parties should step up efforts to regulate
chemicals with the aim of preventing the production and use of chemicals that exhibit the
characteristics of persistent organic pollutants in compliance with paragraphs 3 and 4 of Article 3 of the
Stockholm Convention.
B. Recommendations for short-term activities

5. The key recommendation for the short-term in countries in a position to do so, especially developed
countries, is to establish and apply screening techniques and to separate materials containing
brominated diphenyl ethers in order to stop these materials from being recycled. In detail, the
recommendations are:
To begin establishing national control schemes for recycling of waste potentially containing
brominated diphenyl ethers and to implement effective screening and separation
techniques for material containing brominated diphenyl ethers.
Following the implementation of effective screening and separation techniques, to stop the
recycling of articles containing brominated diphenyl ethers.
77
That is articles for which the flame retardant content was added for the purposes of flame retardancy
rather than articles which contain some flame retardant as a consequence of contaminants in recyclate.
106
To store in a safe manner materials and articles containing brominated diphenyl ethers when
screening and separation techniques are not readily available.
To stop the export of waste materials containing brominated diphenyl ethers except for the
purpose of environmentally sound disposal in the importing country as set forth in
paragraph 1 (d) of Article 6 of the Stockholm Convention.
To alert, equip and train the relevant authorities (for example, Customs and border control
authorities) to allow them to control, identify and, where necessary, intercept shipments of
wastes containing brominated diphenyl ethers.
To generate and collect information on releases of brominated diphenyl ethers and
unintentionally produced brominated organic compounds such as polybrominated
dibenzodioxins and polybrominated dibenzofurans (PBDD/PBDF) in emissions to air and
in the solid residues from thermal processes used in treating materials contaminated with
brominated diphenyl ethers.
To identify disposal options that would comply with the Stockholm Convention guidelines to
be developed for the destruction of wastes containing brominated diphenyl ethers. These
may include best available technique incinerators with effective primary and secondary
combustion zones that operate under best environmental practice conditions with
continuous monitoring and sampling to ensure that brominated diphenyl ethers and/or
PBDD/PBDF are not released.
To collect information relevant to the establishment of best available techniques and best
environmental practices for treatment and disposal techniques for materials containing
brominated diphenyl ethers.
To assess occupational exposures of staff working in facilities where articles and wastes
potentially containing brominated diphenyl ethers are stored, sorted, treated, recycled,
recovered or disposed of. Appropriate precautions should be taken to minimize any
occupational exposure.78
6. Additional short-term goals could include:
To endeavour to promote the commercialization of separation techniques, which have already
been evaluated in trial plants or which have yet to be developed, for removing brominated
diphenyl ethers from plastic matrices to permit continued recycling.
To develop a system or mechanism to prevent the entry of substances that exhibit
characteristics of persistent organic pollutants into the recycling stream as soon as they are
identified.
To promote and facilitate public awareness-raising on the potential harm of materials
containing polybrominated diphenyl ethers currently in use (e.g., furniture, mattresses or
carpet with recycled back-coating containing polybrominated diphenyl ethers).
7. Since the presence of brominated diphenyl ethers is less well characterized in developing countries
and countries with economies in transition it is further recommended:
To exchange information on and experiences of successful environmentally sound handling,
management and disposal of articles and wastes containing brominated diphenyl ethers.
To encourage developed countries to promote the transfer to developing countries of screening
and separation techniques.
78
International Labour Organization Convention concerning Safety in the use of Chemicals at Work,
No. C170, 1990 and ILO Recommendation Concerning Safety in the Use of Chemicals at Work, No. R177,
1990.
107
To undertake a more detailed survey in representative countries in each region to determine

the extent of brominated diphenyl ethers in recycling and waste streams. This should be
supported by capacity-building efforts and measures to raise the awareness of all
stakeholders.
C. Recommendations for medium-term activities

To promote and implement analytical techniques and technologies specific to brominated
diphenyl ethers.
To improve and extend as necessary disposal options to ensure compliance with Stockholm
Convention obligations and guidelines, taking into account the relevant decisions of the
Persistent Organic Pollutants Review Committee on the updating of the Basel Convention
technical guidelines on the environmentally sound management of persistent organic
pollutants.
To evaluate surveys conducted in developing countries and countries with economies in
transition and apply their conclusions, where appropriate, to other countries with similar
waste streams. If the survey indicates a significant presence of materials containing
brominated diphenyl ethers, screening techniques should be implemented.
To undertake further assessment and produce best available technique and best environmental
practice guidance. These tasks should be undertaken by the Stockholm Conventions
expert bodies and include consideration of polybrominated diphenyl ethers and
PBDD/PBDF releases from smelters and other thermal recovery technologies, including
secondary metal industries, cement kilns and feedstock recycling technologies.
8. The main recommendations in respect of deposition of and deposited polybrominated diphenyl
ethers in landfills are:
To assess further the long-term chemistry of polybrominated diphenyl ethers in landfill sites
and the fate and risk of polybrominated diphenyl ether release from landfills into the
environment.
To reduce releases of polybrominated diphenyl ethers from landfills by avoiding the
landfilling of materials containing them. Significant reductions can be made by restricting
the landfill disposal of waste streams with high concentrations of brominated diphenyl
ethers. This does not, however, need to apply to the landfill sites in which proper
management is applied to isolate the landfill contents from the environment.
To assess and determine any necessary remediation measures in landfills. In some cases (such
as sites vulnerable to erosion, those which are below the water table or vulnerable to
flooding) this may even require the removal of materials containing polybrominated
diphenyl ethers from landfills for further destruction.
D. Recommendations for long-term activities

To prioritize for remediation activities landfills, sediments and production, manufacturing and
treatment sites that present significant risks to human health and/or the environment.
To evaluate surveys conducted in developing countries and countries with economies in
transition and apply their conclusions, where appropriate, to other countries with similar
waste streams. If the survey indicates a significant presence of materials containing
brominated diphenyl ethers, provisions for technology transfer should be implemented.

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Guidelines on Best Available

Techniques and Guidance on

As mentioned above, the document provides technical outlines, advantage/disadvantage, and

Production c-PentaBDE (stopped) Production c-OctaBDE (stopped) Alternatives to POP-BDE (2.2)

PWB, rubber, oil drilling Consideration

General BAT/BEP (3)

PBDE screening technologies (4)

Energy/material recovery (8)*

Recovery of Bromine (9)*

Landfill disposal (10)

*Bromine recovery is not operated in full scale yet.

Reuse of Articles (e.g. cars, electronics, furniture) .

1.4 Polybrominated diphenylethers listed in Annex A Part IV and Part V

Figure 2: Structure of polybrominated diphenyl ethers (PBDEs)

Commercial Congener % by weight

1.4.2 Production volume

c-DecaBDE 1,100,000 to 1,250,000

Use of Commercial PentaBDE

2 POP-BDE Material Flows & POP-BDE Alternatives

2.1.1 Polymers containing c-OctaBDE

2.1.3 Printed circuit/wiring boards containing c-PentaBDE

2.1.4 Textiles and rubber containing c-PentaBDE

2.2 Alternatives to POP-BDEs

Substitution of flame retardants can take place at three levels:

These ecological priorities are subject to the following conditions:

Figure 3: Methods and systems to flame retard materials (Hull 2010)

ENFIRO (http://www.enfiro.eu/) is a European Commission-funded project which offers a prototypical case

Environmental and toxicological risks

Assessment approach of EPA partnership program Design for the Environment

3 General BAT/BEP considerations for POP-BDE containing

Figure 4: Waste management hierarchy (Stockholm Convention 2007)

3.3.4 LC considerations for bromine recovery

3.5 General BAT/BEP considerations

d. checking performance and taking corrective action, paying particular attention to

3.5.3 Crusing, shredding, sieving and washing operations

3.5.4 General BAT/BEP considerations in respect to air and water releases

Air emission treatment

To prevent soil contamination, BAT is:

4 Specific BAT/BEP on monitoring of POP-BDE/BFR in

4.1.1 Identification of POP-BDEs by standard PBDE analysis

4.1.2 Rapid analysis techniques for POP-BDEs

4.2.1 Sliding spark spectroscopy

5 Specific BAT/BEP: POP-BDE/BFR containing polymer in

5.4.2 Instrumental separation of polymers in developing countries

5.4.3 Separation of POP-BDE/BFR-containing polymer by manual pre-sorting

BEP Approach applied in Sweden

Manual separation of POP-BDE-containing materials without instrumental help might be an option to

5.4.4 Separation of polymers by Sink and float technologies (S/F)

Combination Suitable BFR free Technical Economy Reference

5.4.7 Full scale plants to separate WEEE and POP-BDE/BFR containing

5.5 Material recycling of polymer containing POP-BDEs

5.5.1 Labelling of POP-BDE containing polymer fraction and articles

For POP-BDE/BFR containing polymer fractions energy recovery in appropriate BAT/BEP

6 Specific BAT/BEP: POP-BDE/BFR materials in the transport

6.3 POP-BDE/other POPs and contaminants in ELVs and waste

6.4.2 Shredder plants (UNEP 2007)

6.5.2 Developing country considerations

The thermal treatment technologies and requirements are described in section 8.

7 Specific BAT/BEP: POP-BDE/BFR containing PUR foam

7.4 Separation strategy of c-PentaBDE impacted PUR foam

7.4.1 Separation/exclusion of PUR foam categories from recycling

Countries/regions with low impacted flexible PUR foams

significant amounts of US post-consumer polyurethane foam scrap, mainly obtained by take-up of