ELECTRONIC EQUIPMENT (EEE) - CIRCABC - Welcome · - iii - Hazardous substances in electrical and electronic equipment (EEE) - Expanding the scope of the RoHS directive By: Emma Andersson

HAZARDOUS SUBSTANCES IN ELECTRICAL AND

ELECTRONIC EQUIPMENT (EEE)

- expanding the scope of the RoHS directive

Emma Andersson

Project report, April 2005

GÖTEBORG UNIVERSITY SWEDISH CHEMICALS INSPECTORATEDEPARTMENT OF APPLIED ENVIRONMENTAL SCIENCE DEPARTMENT OF RISK REDUCTION

UNIT STRATEGIES AND INCENTIVES

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Hazardous substances in electrical and electronic equipment (EEE) - Expanding the scope of the RoHS directive

By: Emma Andersson

This is a project report written as a part of a course at the Department of Applied Environmental Science at Göteborg University. The work was performed for the Swedish

Chemicals Inspectorate at the Department of Risk Reduction in Sundbyberg over a period of ten weeks during spring semester 2005. The author holds a M. Sc. in Environmental Science.

Supervisors

Swedish Chemicals Inspectorate (KemI):

Göran Gabrielsson Ulla Falk

Göteborg University:

Åke Larsson

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Summary The EC Directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment (the RoHS-directive) prohibits the use of lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls (PBB) and polybrominated biphenyl ethers (PBDE) in products put on the market after 1 July 2006. The directives will be reviewed every four years with the purpose to update its regulations based on new scientific evidence and the precautionary principle. The aim of this report is to provide the Swedish Chemicals Inspectorate with a review of substances used in electrical and electronic equipment (EEE) today which use entails a potential risk to human health and the environment throughout the life cycle of the products. The specified questions are as follows: What other substances, than the ones regulated through RoHS today, of very high concern (SVHC)1 are used in EEE?

• What is the purpose of their use in EEE? • What are the quantities of their use in EEE? • What share of the total use of the substance is used in EEE placed on the EU

market? • What are the intrinsic characteristics of these substances? • What are the routes of exposure of these substances to humans and the

environment? • What are the possibilities of substitution, through use of alternative substances or

alternative technical solutions? • What initiatives have been taken by the industry to phase-out these substances in

EEE and what is the outfall? • Have these substances been substituted in applications other than EEE?

The review shows that there are substances and materials that could be suitable candidates for inclusion in the RoHS directive due to their hazardous properties and the fact that there are alternatives available. Based on available research and contacts with the industry a few substances and materials were outlined. The following substances can be found in EEE and are classified as SVHC. (SVHC will be subject for authorisation within the upcoming new chemicals legislation – REACH.)

• Beryllium metal • Beryllium oxide • Three phthalates DEHP, BBP, DBP • Antimony trioxide (according to the classification proposed in the draft EU

risk assessment Risk assessment is underway for the phthalate DOP and for the brominated flame-retardant TBBP-A. There are also other substances that can be suitable for inclusion in the RoHS-directive for which there are no European risk assessments and which should therefore be investigated further in order to establish their effect to human health and the environment deriving from their use in EEE. 1 According to the definition of SVHC stated in the REACH proposal, i.e. CMRs (carcinogenic, mutagentic of toxic to reproduction) cat. 1 and 2, PBTs, vPvBs.

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Abbreviations

ABS = Acrylonitrile butadiene styrene – a polymer used in housings for consumer electronics

CMR = Carcinogen, Mutagen or Reprotoxic CRT = Cathode ray tube, a device that can produce an image on a screen with

electrical impulses. Cathode ray tubes are used in television sets, computers, automated teller machines (ATMs), oscilloscopes, and radar displays.

EAP = Environment Action Programme EEE = Electrical and electronic equipment ELV = End of Life Vehicle EPA = Environmental Protection Agency ISO = International Standardisation Organisation NIOSH = National Institute for Occupational Safety and Health OEM = Original Equipment Manufacturer PBT = Persistent, Bioaccumulative and Toxic PBB = Polybrominated biphenyls PBDE = Polybrominated biphenyl ethers PS = Polystyrene – a polymer used in computers, cabinets for display units,

equipment for refrigerators. PVC = Polyvinylchloride REACH = Registration, Evaluation and Authorisation of Chemicals – KOM proposal

for new EU legislation on chemical substances. RoHS = Restriction of Hazardous Substances in electrical and electronic equipment SVHC = Substances of Very High Concern UBA = Umweltbundesamt – The German Federal Environmental Agency vPvB = Very persistent and very bioaccumulative WEEE = Waste of electrical and electronic equipment

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SUMMARY IV

ABBREVIATIONS VI

TABLE OF CONTENTS VI

1 INTRODUCTION 1 1.1 BACKGROUND 1 1.2 AIM OF STUDY 1 1.3 SCOPE OF STUDY 2 1.4 METHODOLOGY 2 2 THE ISSUE 3

3 OUR OBJECTIVES 3 3.1 THE SIXTH EAP OF THE EC 3 3.2 THE REACH PROPOSAL 4 3.3 NON-TOXIC ENVIRONMENT (SWEDEN) 4 4 SOME RELEVANT INSTRUMENTS 6 4.1 LEGISLATION 6 4.2 ECO-LABELLING 7 4.3 OTHER DRIVERS 8 5 HAZARDOUS SUBSTANCES 9 5.1 ANTIMONY AND ITS COMPOUNDS 9 5.2 BERYLLIUM AND ITS COMPOUNDS 12 5.3 SELENIUM 15 5.4 TBBP-A 17 5.5 PVC 18 5.6 PHTHALATES 21 5.7 GALLIUM ARSENIDE 22 5.8 OTHER SUBSTANCES 23 6 DISCUSSION 26

7 FINAL ASSESSMENTS 27

8 REFERENCES 28

ANNEX

END USES AND SPECIFIC APPLICATIONS OF BERYLLIUM IN THE USA.

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Introduction Page 1

1 Introduction

1.1 Background In early 2003, the European Council adopted a directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment, also known as the RoHS-directive. The directive prohibits the use of lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls (PBB) and two polybrominated biphenyl ethers (penta- and octa-BDE) in products put on the market after 1 July 2006 (see also section 4.1.2). The substances have been selected due to their harmful properties to the environment and to human health. A review of the directive will be performed every four years with the purpose to update its regulations based on new scientific evidence and the precautionary principle. March 2005, the European Commission started the preparatory investigation for a review, where hazardous substances and materials, other than the ones included in the RoHS-directive at present, expectantly will be discussed for inclusion in the regulations. According to the directive, the Commission will investigate the effect they may have on human health and the environment and the potential for substitution to less hazardous alternative substances or techniques. Should the review reveal the need to increase the scope of the directive, the Commission will present a proposal to the Council and the Parliament.

1.2 Aim of study The aim of this report is to provide a review of substances used in electrical and electronic equipment (EEE) today which use entails a potential risk to human health and the environment throughout the life cycle of the products and the prospects of including them within the scope of the RoHS-directive. More specifically, the following questions are to be answered. What substances, other than the ones regulated through RoHS today, of very high concern2 are used in EEE?

Uses; • What is the purpose of their use in EEE? • What are the quantities of their use in EEE? • What share of the total use of the substance is used in EEE placed on the EC

market?

Characteristics; • What are the intrinsic characteristics of these substances? • What are the routes of exposure of these substances to humans and the

environment?

Substitution; • What are the possibilities of substitution, through use of alternative substances or

alternative technical solutions?

2 According to the definition of SVHC stated in the REACH proposal, i.e. CMRs cat. 1 and 2, PBTs, vPvBs.

Page 2 Introduction

• What initiatives have been taken by the industry to phase-out these substances in EEE and what is the outfall?

• Have these substances been substituted in applications other than EEE?

1.3 Scope of study The report is a review of some hazardous substances used in EEE and should not be regarded as a complete register. The presented information on the substances are dependent both on available knowledge and relevance with reference to the aim of study. Only product groups currently included in the RoHS-directive are considered.

1.4 Methodology Information on hazardous substances has been gathered through review of available research and reports on the subject. Particularly one report, written by Five Winds International for Environment Canada, has been a source of inspiration in the early stages of this project. In addition, reports from the Nordic Council of Ministers have played important parts in the choice of substances presented. Another vital source of information has been the industry itself. A number of companies’, e.g. Ericsson, Hewlett-Packard and BSH3, lists of restricted materials have been reviewed and some voluntary initiatives for substitution have been raised in the report. Other organisations have also been consulted such as ecolabelling organisations and electronic dismantlers.

3 BSH= Bosch und Siemens Hausgeräte GmbH

Our objectives Page 3

2 The issue There are estimated to be 30,000 man-made chemicals currently produced and used in volumes above one tonne in the EU. 4 For the vast majority, we have only very limited, if any, knowledge of the risks they present to human health and to the environment. The potential impacts on humans and the environment are many and can be very serious including cancer, birth defects, disruption of the body’s hormone system, damage to vital organs, allergies, asthma, etc. Yet chemicals bring numerous benefits to society including, for example, improved fire safety and products like high-speed computers and durable plastics. The electronic sector is evolving fast and electronics are taking important roles in an increasing number of areas in our everyday life. Some electrical products become outdated or unfashionable, at an unparallel rate in history. This result in a growing stream of waste of electrical and electronic equipment also referred to as WEEE. In estimation, 6.5-7.5 million tonnes of WEEE was generated in the EU in the late 1990’s, a volume increasing between 3-5% each year. WEEE is a priority waste stream of EU policy due to its complexity and high growth rate. Owning just 4 % of the total municipal waste stream, it is one of the largest known contributors of heavy metals and organic pollutants in municipal waste5.

3 Our objectives Our objectives for the whole chemicals policy and our strategy for minimising risk derived from the use of chemicals naturally sets the frame for how we work with chemicals used in EEE.

3.1 The Sixth EAP of the EC In January 2001 the Commission adopted the Sixth Environment Action Programme (6th EAP) for the environment and health. It sets priorities for action on the environment for the subsequent ten years (2001 – 2010). The Sixth Environment Action Programme focuses on four major areas of action:

• Tackling climate change

• Nature and biodiversity

• Environment and health

• Sustainable use of natural resources and management of wastes Regarding chemicals the objective are as stated in the 6th EAP: “5.4. Chemicals: Aiming at a Non-Toxic Environment (…) To achieve an environment where the levels of man-made chemicals do not give rise to significant risk to, and impacts on, human health and the environment.”

4 COM (2001)88 5 Crowe, M et al, 2003

Page 4 Our objectives

It is the accordance of the chemicals policy in the 6th EAP that the Parliament and the Council shall decide on the prohibition and substitution of other hazardous substances in EEE than the ones listed in the RoHS directive at present.6

3.2 The REACH proposal The White Paper on the strategy for a future Chemicals Policy, adopted in early 2001, addresses the shortcomings of the current system for regulating marketing and use of dangerous chemicals in order to protect human health and the environment. The current system separates between “new” and “existing” chemicals. Existing chemicals (100.106 substances) are chemicals introduced on the EC market before 1981, risk assessments of these are very limited and public authorities hold the burden of proof. New chemicals are chemicals introduced to the market after 1981. For these substances, the control is instead very stringent resulting in a barrier to innovation. Evaluation of existing chemicals is governed by the Council Regulation 793/93/EEC. Council Directive 67/548/EEC on classification, packaging and labelling of dangerous substances stipulates the rules for "new" chemical substances. The Commissions White Paper was followed by a proposal from the Commission for the REACH system, a new EU regulatory framework for chemicals expected to be adopted in 2007. The REACH-system will replace over 40 existing regulations and directives. The core of REACH is the registration, evaluation and authorisation process, and a single fully integrated process that transfers the burden of proof on industry. Substances of very high concern (SVHC) will be subject to authorisation, i.e. substances with the following properties: carcinogenic, mutagenic or toxic to reproduction (CMR), persistent, bio accumulative and toxic (PBT) or very persistent and very bio-accumulative (vPvB) and other equivalent risk. Implementation of the REACH-system is hoped to increase knowledge about chemicals we use and reduce risk to the environment and to human health with minimum need for animal testing. It also hopes to promote innovation and to avoid unnecessary bureaucracy for producers and importers of small-scale chemicals and downstream users.7

3.3 Non-toxic environment (Sweden) "The environment must be free from man-made or extracted compounds and metals that represent a threat to human health or biological diversity."8 The Swedish government has stipulated 15 environmental quality objectives defining the aim of the environmental work of the country purposed to promote a sustainable development. A non-toxic environment is one of these quality objectives. Six interim targets states concrete measures needed for the fulfilment of the objective. Interim target 1 and 2 are purposed to increase knowledge about substances’ properties and spread the information. The following four interim targets aims to restrict exposure of hazardous substances. Interim target 3 is very relevant for the purpose of this report:

6 OJ L 037 13.2.2003 p. 19-12 7 OJ L 037 13.2.2003 p. 19-12 8 Webpage: The Swedish Chemicals Inspectorate - The environmental quality objective and the six interim targets

Our objectives Page 5

The implication of this interim target is that it is sufficient to know the inherent properties for the substance to be prohibited or for its use to be limited, if the properties are of very high concern of a substance. As a result, the pace of risk-limiting work can be greatly increased and it will be possible to take measures to deal with the most hazardous substances within a reasonable time.

INTERIM TARGET 3

Newly manufactured finished products will as far as possible be free from:

• carcinogenic, mutagenic and reprotoxic substances, by 2007, if the products are intended to be used in such a way that they will enter natural cycles;

• new organic substances that are persistent and bioaccumulating, as soon as possible, but not later than 2005;

• other organic substances that are very persistent and very bioaccumulative, by 2010;

• other organic substances that are persistent and bioaccumulative, by 2015; • mercury by 2003, and cadmium and lead by 2010.

Nor will these substances be used in production processes unless the company can prove that human health and the environment will not be harmed.

Already available finished products containing substances with the properties listed above, or mercury, cadmium or lead, will be handled in such a way that the substances in question are not released to the environment.

This interim target applies to substances that are man-made or extracted from the natural environment.

It also applies to substances giving rise to substances with the above properties, including those formed unintentionally.

Page 6 Some relevant instruments

4 Some relevant instruments

4.1 Legislation 4.1.1 The WEEE directive Directive 2002/96/EC of the European Parliament and of the Council of 27 January in 2003 on waste electrical and electronic equipment, also known as the WEEE-directive, was designed to tackle the growing stream of waste of electrical and electronic equipment. It aims to prevent WEEE arising and to encourage its reuse, recycling and recovery. Producers will have responsibility for financing the collection, recovery and recycling of separately collected WEEE. They will also be required to mark new equipment to enable distinction between WEEE and other household waste. This will work as an economic incentive to producers to regard end of life treatment already in the design phase of a product, making it more environmentally efficient. The following categories of electrical and electronic equipment are covered by and listed in Annex 1A of the WEEE Directive:

1. Large household appliances 2. Small household appliances 3. IT- and telecommunications equipment 4. Consumer equipment 5. Lighting equipment

6. Electrical and electronic tools. 7. Toys, leisure and sports equipment 8. Medical device 9. Monitoring and control instruments 10. Automatic dispensers

4.1.2 The RoHS directive Directive 2002/95/EC of the European Parliament and of the Council of 27 January 2003 on the restriction of the use of certain hazardous substances in electrical and electronic equipment, also known as the RoHS-directive, was designed to prevent the generation of hazardous waste. It complements the WEEE directive and covers the product categories 1-7 and 10 as listed in the WEEE-directive. In addition, the RoHS directive applies both to electric light bulbs and to household luminaries. It requires the substitution of the substances as listed below in new electrical and electronic equipment put on the market from 1 July 2006:

• Lead, • Mercury, • Cadmium • Hexavalent chromium • Polybrominated biphenyls (PBB) • Polybrominated biphenyl ethers.

Certain applications are exempt from the requirements of the Directive. The list of exemptions is to be reviewed every four years. The European Commission was supposed to review the scope of the directive to take into account, as necessary, new scientific evidence by 13 February 2005. This includes a review of whether categories 8 and 9 should be included in

Some relevant instruments Page 7

the scope and an adaptation of the list of substances based on scientific facts and considering the precautionary principle. 4.1.3 The ELV-directive The End of Life Vehicle (ELV) Directive (2000/53/EC) is the automotive industries equivalent to WEEE and RoHS. It restricts the use of lead, mercury, cadmium and hexavalent chromium in vehicles put on the market after 1 July 2003. It also sets targets for reuse and recycling of ELVs 9 Expectantly, the ELV-directive will help drive the phase out of potentially hazardous substances like brominated flame-retardants in plastics since their presence in the material make recovery more difficult and expensive.10 4.1.4 Hazardous Waste Directive (91/689/EEC)11 In 1991, the Hazardous Waste Directive was adopted to insure management, recovery and correct disposal of this type of waste. The Annexes of the directive lists waste considered as hazardous based on categories, constituents and properties. A number of heavy metals are listed and properties such as carcinogenic, mutagenic and ecotoxic render them hazardous. Having to treat wastes as hazardous involves an increased cost for the producer. This can work as an incentive to develop products that do not contain substances or materials that can render them hazardous waste during end-of-life treatment. 4.1.5 Council Directive 76/769/EEC12 – Directive on restrictions on the marketing and use of certain dangerous substances and preparations The so-called “Limitations Directive” is applicable for substances and preparations that can be considered dangerous enough to restrict their marketing and use. Substances falling under the Limitations Directive are listed in the Annex I to that Directive which also specifies the restrictions on marketing and use applying in each particular case. The future REACH system will replace the Limitations directive in the sense that it will be incorporated as an annex to the REACH-regulation. Penta- and octa-BDE are regulated as chemicals products and for use in goods from August 2004, through directive 2003/11/EC amending 76/769/EEC.

4.2 Eco-labelling The evolution of eco-labelling was an expression of the shift in environmental concern from process-oriented aspects to product-oriented aspects. The principal purpose of eco-labelling is to promote the progress to more environmentally preferable products and services and thereby reducing the impact caused by consumption. The International Standardisation Organisation (ISO) has developed a set of standards for environmental labelling, the ISO 14020 series. They describe three types of labelling.13 9 EUROPA - Research – Briefings – Recycling Vehicles 10 E-mail correspondence with Martin Påhlman, the Swedish Environmental Protection Agency, 2005-03-23 11 OJ L 377 of 31.12.1991 12 OJ L262, of 27.09.1976 p 201-203 13 Kuhre, W.L., ISO 14020s, Environmental Labelling-Marketing.

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Type I labels are voluntary, multi-criteria-based and a third-party programme where the producer is authorized to place a certain label on its product, provided that it fulfils a list of criteria of environmental consideration. The Nordic Swan, the EU flower and the Blue Angel are three examples of ecolabelling schemes that have criteria for EEE e.g. personal computers. Type II and III labels are first party based and third party based materials declarations, respectively. The ITECO-declaration developed by the Association of the Swedish IT and Telecom Industry, is an example of type II. Environmental Product Declaration (EPD) developed by the Swedish Environmental Management Council is an example of a type III label. Materials declarations do not involve any list of criteria to fulfil but aim to drive the development towards more environmentally conscious design through transparency and disclosing comparable information on the contents of products to the consumer.

4.3 Other drivers There are several other drivers for companies to improve the environmental performance, for example reduced use of hazardous substances in electrical and electronic equipment. Here follows a list of examples.

• Upcoming legislation • Green customer demands • Green public procurement • Pressure from Non-Governmental Organisations (NGOs) • Prestige and brand image • Environment as competitive advantage • Top-management commitment

Hazardous substances Page 9

5 Hazardous substances This chapter is the central chapter in this review where some important, and potentially hazardous, substances used in EEE are listed and further described. The content of the list is based on what substances that have been brought to special attention by industry itself, NGOs and ecolabelling organisations. Each section starts with a summarising table followed by the substance's use, characteristics, alternatives and current regulations.

5.1 Antimony and its compounds

Table 1 Antimony and its compounds, main uses in EEE and hazard classification

Compound CAS No Use Hazard

Antimony (metallic) 7440-36-0 Solder alloy Toxic to aquatic organisms. May cause long-term adverse effects in the aquatic environment.

Antimony trioxide, Sb2O3

1309-64-4

Synergist flame-retardant, melting agent in glass manufacturing, pigment

Carcinogen. Cat. 3

Antimony pentaoxide, Sb2O5

1314-60-9 Synergist flame-retardant Harmful by inhalation, in contact with skin and if swallowed. Irritating to eyes.

Sodium antimonate (hexahydrate), SbNa(OH)6

33908-66-6 Used in glass manufacturing

Toxic to aquatic organisms. May cause long-term adverse effects in the aquatic environment.

Antimony trichloride, SbCl3

10025-91-9 Synergist flame-retardant Toxic to aquatic organisms. May cause long-term adverse effects in the aquatic environment.

Antimony pentachloride, SbCl5

7647-18-9 Synergist flame-retardant Toxic to aquatic organisms. May cause long-term adverse effects in the aquatic environment.

5.1.1 Use in EEE The basic element antimony (Sb) can be found in electrical and electronic equipment in many different forms.

• Flame retardant - The single largest use of antimony compounds is as flame-retardant synergist, primarily the compound antimony trioxide. Antimony trioxide has no significant flame retardant properties but it significantly increases the effectiveness of halogenated flame-retardants and is often used in PVC. Approximately 30% of the antimony utilised in flame-retardants was in 1995 used in the electrical and electronic industry. With the industry moving away from brominated flame-retardants it can be expected that the use of antimony will decrease.14 Tetrabromo bisphenol A, TBBP-A, is a common brominated flame retardant. When used as an additive flame retardant, it is generally used with antimony trioxide for maximum performance. (I.e. in ABS, PS, thermoplastic polyesters and phenolic resin)15 Antimony trioxide is generally not used in conjunction with TBBP-A in reactive flame retardant applications (where TBBP-A becomes covalently bound to epoxy or polycarbonate resins)16

14 Velzen D van, et al. (1998), 15 Danish EPA (1999) 16 RAR (2003) Draft

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• Sodium antimonate is used in CRT glass (cathode ray tubes) as a melting agent to help remove bubbles. The finished CRT contains 0,2% sodium antimony in the funnel and 0,24% in the panel.17 Antimony trioxide is used as a melting agent and as a decolourant in the manufacture of art, optical and fluorescent light bulb glass, and in glass for screens for television and computers etc. The final antimony-content in the glass is typically 0.8%, then in the form of antimony pentoxide.

• Solder alloy – Antimony can be used in alloys together with lead or in different

combinations with e.g. tin, silver and indium, in lead-free solders in low concentrations (0,5-10 %).18 Antimony trioxide is used as a lead free solder alternative together with tin, for instance in cabling. In these products, the antimony content represents less than 0.2% of the total weight.19

See Table 2 for volume and allotment of the use of antimony in the EU.

Table 2 Use of antimony trioxide in EU (2000) 20

Use Quantity (tonnes/year) %

Flame-retardant in plastics (except PVC) 12 800 51 Flame-retardant in PVC 9 000 36 Flame-retardant in textiles 1 800 7 Catalyst in PET production 650 3 Additive in glass manufacture 250 1 Pigments in paint and ceramics 500 2

Total: 25 000 100 5.1.2 Characteristics Exposure to higher levels of dust or fumes of antimony trioxide leads to irritation in the respiratory system and the eyes. Prolonged inhalation can cause liver damage and heart problems.21 Antimony trioxide is classified as category 3 carcinogen and listed in Annex 1 in directive 67/548/EEC. In the draft risk assessment for which Sweden is rapporteur, the proposed classification was category 2 carcinogen, category 3 mutagen and toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment.22 Antimony is not volatile and not readily soluble in water. No significant release can thus be expected during the use phase. Exposure to humans may occur during processing of antimony metal e.g. during recycling processes. Most products containing antimony is likely to be incinerated or used as landfill today. The WEEE directive and, to a lesser extent, directive on end-of life vehicles, will have an impact on the disposal of a large proportion of articles containing antimony trioxide. Following incineration of municipal solid waste containing antimony, the major part of is recovered and ends up in the fly ash and the bottom ash. However, antimony can leach from ashes and storing of ashes does not reduce the leaching, as 17 OECD (2000) 18 Andersson C., Liu J. (2001) 19 Five Winds International (2001) 20 RAR (2004) Draft 21 Prevent database “Chemical Substances 11.0” 22 RAR (2004) Draft


it normally does for metals. Instead the leaching increases and efforts to reduce it have failed. Presently, antimony is considered as the most problematic substance in ashes from municipal incinerators as regards possible reuse of bottom ashes.23 5.1.3 Alternative substances Since the use of antimony as flame retardant is to a large part connected with the use of halogenated flame-retardants and halogenated plastics, candidate alternatives are likely to be halogen free flame retardant systems. Sometimes phosphorous compounds (tricresyl phosphate, TCP), magnesium oxide, alumina trihydrate, molybdic oxide, zinc borate, or zinc oxide are used in combination or in place of antimony oxide to reduce costs, to increase char formation24, or to reduce smoke. However, the substitution greatly reduces the flame retardancy. Testing of the amounts of the halogen and antimony oxide in each formulation is necessary to optimize the flame retardancy and lower costs. Alumina trihydrate is not synergistic with halogenated flame-retardants. It functions as a flame retardant by the release of its water of hydration and cannot be used in high temperature processes.25 TDCPP, Tris (1,3-dichloro-2-propyl) phosphate, CAS No: 13674-87-8 is a chlorinated phosphate ester. One trade name is Fyrol FR-2. It is primarily used as additive flame retardant in flexible and rigid polyurethane foams (used in furniture upholstery). It has been reported to cause cancer and affect reproduction in rat.26 It has been assigned with the following risk phrases: limited evidence of carcinogenic effects (R40) and toxic to aquatic organisms; may cause long-term adverse effects in the aquatic environment (R51/53). 27 It can thus not be considered a suitable alternative from an environmental and health perspective. Combinations of calcium, copper, selenium, strontium, tin and sulphur can be used as substitutes for hardening of lead solder.28 5.1.4 Regulations, corporate initiatives etc Antimony is labelled as a “material of interest” with the American Electronics Industry Alliance (EIA) due to its carcinogenic properties. In a joint industry guide for material composition declaration antimony and its compounds are “Level B” listed implicating it’s determined relevant for disclosure in a material declaration, irrespective of lack of legislation. The threshold level is 0,1% by weight of the product. The C4E group (a collaboration of the European chemical, metal, electric and electronics industries organisations CEFIC, EECA, EICTA and EUROMETAUX) has prepared a guidance document for antimony, and other substances under special attention. The recommendations are to base policy decisions on the upcoming EU risk assessment and to take relevant safety measures as recommended by the industry technical data sheets. The OEL

23 RAR (2004) Draft 24 Char formation = The swelling of a fire- retardant coating when heated, resulting in the formation of low-density carbon layer which provides a degree of surface flame-spread resistance. 25 Webpage - United States Antimony Corporation 26 Prevent database “Chemical Substances 11.0” 27 AKZO Nobel MSDS for Fyrol FR-2 28 U.S. Geological survey (2005)


(Occupational Exposure Limit) is 0.5 mg Sb /m3 and different measures to minimise dust formation apply.29 Antimony and its compounds are classified as hazardous waste according to the EEC directive on hazardous waste (91/689/EEC). Wastes containing more than 1% of antimony trioxide are classified as hazardous.30 A number of OEMs and ecolabelling organisations have listed antimony and its compounds as banned or restricted substances.

5.2 Beryllium and its compounds

Table 3 Beryllium and its compounds, main uses in EEE and hazard classification


Beryllium metal 7440-41-7 In alloys EC category 2 carcinogenic, very toxic by inhalation and toxic by ingestion

Beryllium Oxide (Beryllia) BeO 1304-56-9 In ceramics as

cooling device EC category 2 carcinogenic, very toxic by inhalation and toxic by ingestion

5.2.1 Use in EEE Beryllium is used in high power components in motherboards and monitors and connectors.31 It is primarily used as beryllium oxide in ceramics and in its metallic form in alloys, e.g. beryllium-copper alloys.

• Beryllium alloys, e.g. beryllium-copper (containing about 0.5-2 % Be) are used in connectors in fiber-optic telecommunications systems, undersea cable network32, small movable sockets for joining integrated circuits to printed circuit boards. Beryllium-nickel alloys are mainly used in miniature electronic connector components that operate at high temperatures and in automotive passive restraint systems (airbags).33

Beryllium-aluminium alloys are becoming increasingly important in terms of beryllium consumption because of the amount of beryllium they contain - up to 65 % compared with the 0.5% and 2% typically present in beryllium-copper. U.S. producers such as Starmet and Brush Wellman have developed beryllium- aluminium alloys that have a wide range of applications ranging from aerospace (as castings) to computers. 34

• Beryllium oxide-containing ceramic represents a unique material due to its

ability to function as an effective electrical insulator and at the same time have a high thermal conductivity. Beryllium oxide is used in paste between components as cooling devices and heat shields. Ceramic bound beryllium is used in box-like shields over components due to their abilities to withstand

29 C4E Guidance Document, 2002 30 Hazardous waste directive 31 Five Winds International (2001) 32 Brush Wellman Engineered Materials (2004) 33 U.S. Geological survey (2005) 34 Roskill Information Services, Beryllium 2001


high temperatures. 35 It is corrosion resistant, lighter than aluminium oxide and has a good thermal shock resistance. However, it usually has a lower mechanical strength than alumina but this can be remedied through control of fabrication processes. The material has a wide array of applications in EEE particularly in high power devises or high-density electronics circuits for high-speed computers. Beryllium oxide is transparent to microwaves and x-rays and therefore used in windows, radomes36 and antennas in microwave communication systems, in microwave ovens and in x-ray windows, especially in severe operation conditions.37

Due to failed attempts in finding information on beryllium consumption in the EU, statistics from U.S. sources are presented, with the hope to provide a view of the proportional use in EEE (see Figure 1).

Figure 1 U.S. beryllium consumption, by end-use sector, from 1981 through 2000.38

In 2003, the total use of beryllium in the U.S. was around 190 tons where electronic and electrical components were estimated to represent 80%.39 Beryllium copper alloy (with a Be content of about 2 %) stands for about 70 % of the total U.S. consumption on a beryllium metal equivalent basis.40 In 2004, the U.S. sales of beryllium alloys increased due to high global demand in the automotive (particularly in Europe), industrial, telecommunication and computer industry. In the longer term, beryllium oxide consumption should continue to grow steadily, especially in computers where increasing operating speeds generate progressively larger amounts of heat.41

35 Personal communication Mats Moberg WÅAB Elektronik 36 Radome = a housing for a radar antenna 37 Brush Wellman Engineered Materials (2004) 38 U.S. Geological survey (2000) 39Ceramic Industry (2005) 40U.S. Geological survey (2000) 41 Roskill Information Services, Beryllium 2001


5.2.2 Characteristics Beryllium and beryllium compounds are very toxic by inhalation (R26) and they were recently classified as known to be a human carcinogen (EC category 2).42 It has not been classified as being toxic to the environment. Risk of use arise from airborne dust or fumes generated from the material. Generation of airborne particles of beryllium is likely to occur during grinding or welding operations. Occupational exposure represent the highest level of exposure to beryllium. Workplace regulations require suitable air extraction and filtration. Beryllium metal components have to be separated from equipment at end-of-life. When extracting the precious metals from the printed circuit boards, the boards are ground, causing the ceramic to break and form dust. This can entail a serious health hazard.43 Recyclers of EEE have difficulties identifying beryllium-containing components and information has to be sought out by the dismantler-companies themselves by asking the producers or through information found on the web such as in material-declarations of components.44 Chronic beryllium disease, or CBD, is an inflammation in the lungs that can occur when a person is exposed to respirable beryllium fumes, dusts or powder, and subsequently demonstrates an allergic reaction to beryllium. It can result in scarring and damage of lung tissue, causing shortness of breath, wheezing and/or coughing. Extreme cases of CBD can cause disability or death.45 5.2.3 Alternative substances Since the cost of beryllium metal is high, it is used only where its properties are crucial. Substitution usually results in substantial lowering of desired qualities. According to one of the major manufacturers of beryllium, there is no substitute for beryllium metal x-ray windows used in high-resolution medical radiography.46 Steel, titanium and graphite composites can work as substitutes for beryllium metal. Phosphor bronze may be substituted for copper-beryllium alloys, however with substantial loss of performance. One copper alloy, developed as an alternative to copper beryllium contains nickel, a substance regarded as a possible human carcinogen and known to be a dermal sensitizer. However, during grinding and welding nickel particles do not become airborne as beryllium. Beryllium-copper can show poorer performance, e.g. in hardness and cooling47. A U.S. research and development organization is developing magnesium graphite material to replace beryllium in military applications. The encapsulated powders of magnesium graphite (50 percent magnesium 50 percent graphite) can be made to offer the same attributes as Be such as light weight, high stiffness, and good thermal conductivity.48

42 NIEHS (2005) 43 C4E (2002) 44 Personal communication Mats Moberg WÅAB Elektronik 45 Brush Wellman 46 Brush Wellman 47 Baranek, Sherry L. (2002) 48 Powdermet, Inc (2003)


Aluminum nitride can substitute for beryllium oxide in some applications, e.g. in components,49. Another method of avoiding beryllium oxide is to change the design of the products thereby eliminating the need for cooling paste and heat shields. 5.2.4 Regulations, corporate initiatives etc Exaktafjädrar, a Swedish producer/supplier of springs, are actively avoiding beryllium alloys in their products. Instead, they recommend other solutions to their customers with less toxic alloys such as phosphorus bronze and copper bronze. For high performance applications such as medical devices and military equipment, the clients do not consider substitution possible. In those cases, the client has to turn to other suppliers.50 A number of OEMs has listed beryllium and beryllium compounds as banned or restricted substances. In the ITECO-declaration beryllium and its compounds was recently brought up as a voluntary declaration item, soon to be compulsory.51 Wastes containing more than 0,1% of this substance are classified as hazardous.52 Measures must be taken in order to protect workers from the risks related to exposure to carcinogens or mutagens at work.53 The Occupational Exposure Limit is 0,002 mgBe/m3 during one working day. The NIOSH Recommended Exposure Limit is 0,0005 mgBe/m3.54

5.3 Selenium

Table 4 Selenium, main uses in EEE and hazard classification


Selenium 7782-49-2Rectifiers and in detector instruments

R23/25, R33, R53 Toxic by inhalation and if swallowed. Danger of cumulative effects. May cause long-term adverse effects in the aquatic environment.

5.3.1 Use in EEE Selenium is a metalloid and a by-product of mining for gold, copper and nickel. In electrical and electronic equipment, selenium is used in plastics, photoelectrical coatings (e.g. in solar cells), diodes, rectifiers and in pigments.55 The annual global consumption of selenium in 2004 was estimated to have been about 2,700 tonnes. The use of selenium in electronics represents about 20% of the total use. Previously, its primary electronic use was as a photoreceptor on the drums of copiers, but now it is being replaced with low-cost organic photoreceptors. A new use for selenium was in amorphous selenium (aSe) detector technology. The Se detector enables the direct conversion of X-ray to

49 Anaren Microwave Inc. (2001) 50 Swedish Association of Environmental Managers – Best Practice 51 Webpage: It Eco Declaration 52 91/689/EEC annex III and 2000/532/EC article 2 53 2004/37/EC 54 NIEHS (2005) 55 U.S. Geological survey (2005)


digital information. The use of selenium as a substitute for lead in free machining56 brasses is increasing due to more stringent regulations on the use of lead.57 5.3.2 Characteristics Selenium is a somewhat unusual and interesting substance. Intake of small concentrations can have benefits; selenium is even an essential nutrient for animals and humans. However, in large concentrations, it can be very toxic and the range between too low and too high intake is narrow. 58 In Sweden and Finland there is a risk of selenium deficiency and some people take it as a nutritional supplement and it is added to food for animals.59 Selenium compounds are toxic by inhalation and intravenous routes. Selenium hydride is the most acute toxic selenium compound, resembling arsenic in its physiological actions. Some selenium compounds (selenium sulphide) are experimental carcinogens. Elemental selenium has low acute systemic toxicity, but dust or fumes can cause serious irritation of the respiratory tract. Inorganic selenium compounds can cause dermatitis. Pallor, nervousness, depression, digestive disturbances and death have been reported in cases of chronic exposure.60,61 Selenium compounds are released to the air and water in flue gas and fly ash during the combustion of coal and petroleum fuels (e.g. in coal-fired power stations), during the smelting and refining of metals such as copper, lead and zinc, from glass and ceramics manufacturing, and from refuse incinerators. Electronic and photographic waste, and photocopying accessories may be other contributors if improperly disposed of. 62 5.3.3 Alternative substances High-purity silicon has replaced selenium in high-voltage rectifiers. Silicon is also the major substitute for selenium in low- and medium-voltage rectifiers and solar photovoltaic cells. Amorphous silicon and organic photoreceptors are substitutes in xerographic document copiers. Bismuth, lead, and tellurium are substitutes in free-machining63 alloys; and bismuth and tellurium in lead-free brasses.64

5.3.4 Regulations, corporate initiatives etc Selenium is listed as a priority pollutant by the USEPA. It is designated pursuant to the Clean Water Act and subject to limitation in drinking water due to its harmful properties to human health.65 Releases of selenium are controlled under the UK Pollution Prevention and Control Regulations, implementing the EC Directive on Integrated Pollution Prevention and Control (IPPC). Its release is also covered by at least two EC Directives: Directive 84/360/EEC on the 'Combating of air pollution from industrial plants' and Directive 91/689/EEC on 'Hazardous 56 Free machining = The property of materials that makes it easy to cut 57 U.S. Geological survey (2005) 58 Irwin Roy J. (1997) 59 Prevent database “Chemical Substances 11.0” 60 Lewis, Richard J., Sr. (1992) 61 National Pollutant Inventory – Selenium and compounds 62 National Pollutant Inventory – Selenium and compounds 63 Free machining = The property of materials that makes it easy to cut 64 U.S. Geological survey (2005) 65 U.S.EPA, Ground water and drinking water


Waste'. Selenium releases are covered by an international agreement called the 'Basel Convention on the Transboundary Movements of Hazardous Wastes and their Disposal'. It is also listed as a substance for priority action on its control under the Helsinki Convention.66 Some OEMs have listed selenium as a banned or restricted substance.

5.4 TBBP-A

Table 5 TBBP-A, main uses in EEE and hazard classification


Tetrabromo bisphenol A (TBBP-A) 79-94-7 Flame retardant

Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment

5.4.1 Use in EEE TBBP-A (tetrabromo bisphenol- A) is a brominated flame retardant used in EEE. The use is widespread; it is the brominated flame retardant produced in the largest volume. The primary use of TBBP-A is as a reactive flame retardant (90 %) in printed circuit boards. It is also used as an additive in polymeric material in housings and packaging. It is used in polymers such as ABS, epoxy and polycarbonate resins, high impact polystyrene (HIPS), phenolic resins, adhesives and others. 5.4.2 Characteristics TBBP-A has no official classification but studies indicate negative effects to the environment and to human health, e.g. it has been shown to have a potential for endocrine modulating effects (hormone disruptor) 67. It has been identified as very toxic to aquatic organisms and it may cause long-term adverse effects in the aquatic environment.68 A reactive flame retardant is chemically bound to and becomes a constituent of the base material. An additive flame retardant is dispersed in the polymer but not chemically bound. These are often used with thermoplastics69. When TBBP-A is used additively there is risk of leakage and exposure during the use phase and also release from landfills. During a products’ life cycle the risk of leakage for a reactive flame retardant is significantly less than for an additive. Workers at recycling plants have high risks of being exposed to flame retardants and high concentrations of various brominated compounds, including TBBP-A, have been detected in their blood and in the ambient air at recycling plants.70, 71 TBBP-A and its derivates have furthermore been detected in diverse samples of sediment and biota in Sweden and Japan. It is suspected to form dioxins and furans upon incineration.72 A risk assessment of TBBP-A is currently performed within the frame of the EU’s Existing Substances Regulations. 66 Webpage: Environment Agency 67 C4E (2002) 68 The Swedish Chemicals Inspectorate, report 4/03 69 Thermoplastic = materials that soften or melt when heated and harden when cooled, e.g. polyethylene, polystyrene, polyester, polyvinyl chloride. 70 Five Winds International (2001) 71 Sjodin, A., et al. (2001) 72 The Swedish Chemicals Inspectorate, report 4/03


5.4.3 Alternative substances In printed circuit boards, the use of reactively bound phosphoric and nitrogen compounds have been used. However, these alternatives do not always fulfil the fire safety standards. It also leads to processing difficulties and a cost increase. One limiting factor for substitution could be current fire safety standards that are considered inappropriate for some classes of products. A revision of these standards could enable a reduction of up to 50 % in TBBP-A usage. 73 For the electronics manufacturer NOTE, brominated flame retardant, and thus also TBBP-A, is the primary target outside the scope of RoHS. They are searching for a substitute but none has yet been found.74 In the reactive use of TBBP-A in laminates for printed circuit boards, no alternatives have been found in terms of cost and performance.75 In applications where TBBP-A is used additively, triphenyl phosphate or organic phosphorus compounds can work as alternatives.76 5.4.4 Regulations, corporate initiatives etc Numerous companies in the EEE sector have developed halogen free alternatives for TBBP-A in their products. However, the demand for such alternatives is still quite low. In an evaluation of flame-retardants performed by the UBA77, the phase out of additive TBBP-A was recommended and reduction of reactive TBBP-A was advised and substitution desired.78

5.5 PVC

Table 6 Polyvinyl chloride (PVC), main uses in EEE and hazard classification


PVC 9002-86-2 Cables and sleeve material

Hazard is to a large part dependent on the additives used.

5.5.1 Use in EEE PVC (polyvinyl chloride) has a vast array of applications in EEE for example in sleeve material of capacitators, as well as in cables, tubing, films, labels and gaskets.79,80 The European market for PVC was 5.5 million tonnes in 2000 and growing at around 2 % per year.81 According to data presented in the proposal for the WEEE-directive and the RoHS-directive, more than 4% of WEEE consists of PVC and the amount that is recycled is very

73 Environment Agency, (2003) 74 Phone conversation with Inga- Brita Mörch, NOTE 75 C4E (2002) 76 Danish EPA (1999) 77 Umweltbundesamt – The German Federal Environmental Agency 78 Webpage: Umweldtbundesamt 79 Webpage: Nichicon Corporation 80 Personal communication Carl Lindqvist, TetraPak 81 Webpage, Eurochlor


limited.82 Recycling of cables, which can be considered to represent the major PVC content in electronics, is the exception. Cables are recycled to a large part, driven by the economic value of the copper or aluminium conductor. However, this development may be restricted by the concerns of contents of PCB (polychlorinated biphenyls) previously used as additives in PVC cables and the uncontrolled transfer of lead (added as stabiliser) to products made by the recyclate.83 For allotment and average lifetime of the use of PVC in the EU, see Table 7

Table 7 Main use categories of PVC in Europe (1999)84

Use Percentage Average life-time

Building 57 10 to 50 Packaging 9 1 Furniture 1 17 Other household appliances 18 11 Electric/Electronic 7 21 Automotive 7 12 Others 1 2-10

5.5.2 Characteristics PVC is manufactured through polymerisation of vinyl chloride. It represents an important source of chlorine to the waste stream. The presence of chlorine atoms gives a number of technically desirable properties, but also results in the formation of toxic, persistent and frequently bio accumulative compounds (Persistent Organic Pollutants). Emissions of these substances occur both during production and during disposal of PVC. 85 However, sources say that, a discontinued manufacturing of PVC would result in a large surplus of chloral gas, difficult to manage.86 One of the main environmental aspects of PVC products is the additives primarily stabilizers and plasticizers that are used to give the products their required properties. The most common stabilizers in PVC are lead sulphide and lead phosphate. They are primarily used in pipes, cables and sections, in order to prevent degradation by heat and light. The lead stabilizers represent approximately 70% of total stabilizer use in Europe. In the past cadmium stabilizers were used in large quantities and are still used in some window frames. However, the European PVC industry has taken action towards the discontinued use of cadmium stabilizers. With the RoHS-directive, lead and cadmium will be banned in EEE. Organic tin compounds are used in some applications of stiff PVC. Among these compounds, dioctyl tin has been observed to have immunotoxic properties and can present an environmental risk locally in the aquatic environment. However, organotins are not used in applications commonly associated with EEE. Other less dangerous stabilizers in use include calcium zinc and barium zinc systems.87 82 COM(2000)347 final 83 AEA Technology (2000) 84 Prognos, (2000) 85 Bertin Technologies (2000) 86 Edshammar, L-E (2002) 87 COM(2000)469


Plasticizers are necessary to manufacture flexible PVC products. The without question most common plasticizers are phthalates. Five of these compounds have been banned in toys and childcare articles. See also section 5.9 for more information on phthalates. 5.5.3 Alternative materials SonyEricsson has replaced PVC with polyethylene materials in some internal wiring components and output cords on AC adapters88. In power cables, some of the PVC has been replaced by olefin material.89 Olefins are manufactured polypropylene and polyethylene fibres also known as polyolefins. It has been used almost exclusively in the home furnishings area and the high performance active wear market.90 SonyEricsson is just one example of companies who have taken measures towards reducing the use of PVC in cables, Electrolux is another example. One issue with replacing PVC at TetraPak has been that the alternatives are not approved by food regulations. Instead for listing substances or materials that are restricted, as in chemicals legislation, food regulations lists materials that are approved for use. According to TetraPak, this becomes a problem when attempting to introduce new technique and substituting materials.91 5.5.4 Regulations, corporate initiatives etc In the Commission’s Green Paper – environmental issues of PVC presented in 2000, the Commission focuses on additives and waste management. The Green paper lists a range of measures, mandatory as well as voluntary. The European PVC industry has signed a voluntary commitment on the sustainable development of PVC, which among others addresses the reduction of the use of certain heavy metal stabilisers, the mechanical recycling of certain post consumer wastes and the development of further recycling technologies. In an assessment made by the UBA92 a phase out of flexible PVC is recommended, for those applications where safer alternatives are available. This is based on the permanent loss of plasticizers, principally phthalates, into the environment. In SonyEricsson’s products, PVC is no longer used in vinyl ties93 and packaging. In some other applications, SonyEricsson has set dates for phase-outs, for example use in certain types of cords. Applications for where no alternatives exist, e.g. in curl cords and wires for high voltage, are exempted.94 The Nordic Swan criteria for personal computer prohibit all use of chlorine-based plastics (for example PVC) in housings and chassis.95

88 AC adapter = Electrical power adapter that converts AC power and converts it to DC power. This type of power adapter is frequently used on a laptop computer when it is not running off of its internal battery 89 Webpage: Sony 90 Webpage: Fibersource 91 Conv. With TetraPak 92 Umweltbundesamt (1999) 93 Vinyl ties are used to hold bundles of wiring cables together 94 Webpage:Sony 95 Webpage: The Nordic Swan


5.6 Phthalates

Table 8 Phthalates, main uses in EEE and hazard classification


diethylhexylphthalate (DEHP), 117-81-7 In PVC in cables EC category 1 toxic to reproduction

butylbenzylphthalate (BBP), 85-68-7 -‘’- EC category 2 toxic to reproduction

dibutylphthalate (DBP) 84-74-2 -‘’- EC category 1 toxic to reproduction

di-''isononyl'' phthalate (DINP) 28553-12-0 -‘’- No classification

5.6.1 Use in EEE Phthalates is a large group of diesters of orthophthalic acid. The primary application is as plasticizer in plastics and rubber in general and in PVC in particular. The most common phthalates are diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) and di (2-ethylhexyl) phthalate (DEHP). The loading can range from 20% up to 55% of the weight of the final product.96 The estimated consumption of phthalates in Western Europe was 894,000 tonnes 1990-1995. Based on industry data the annual use of DEHP was 476,000 tonnes/year in 1999. The use of DEHP has decreased significantly during the past four years in favour of DINP and DIDP.97 5.6.2 Characteristics Phthalates are widespread and can be found in numerous biological and geochemical samples. Phthalates are not chemically bound to the material but dispersed in the matrix, which means that they are likely to be released to the environment.98 Leaching out from certain applications and transportation in the air seems to be the major route of entering the environment. The exposure appears to be continuous through our lifetimes via products we surround us with. DEHP and DBP has been classified as category 1 reprotoxic, BBP is classified as category 2 reprotoxic. Some phthalates have a potential for bioaccumulation and are not readily biodegraded.99 5.6.3 Alternative substances Other plasticizers used in PVC are adipic acids, sebacates. They are more effective, but expensive and volatile.100 Other plasticizers are trimelllitates, organophosphates and epoxidised soybean oil. These substances represent only a small fraction of plasticizers used and their environmental impact is not well studied.101

96 The Swedish Chemicals Inspectorate report 12/94 97 RAR (2001) 98 The Swedish Chemicals Inspectorate report 12/94 99 The Swedish Chemicals Inspectorate report 12/94 100 Edshammar, L-E (2002) 101 COM(2000)347 final


5.6.4 Regulations, corporate initiatives etc Five phthalates: DINP, DEHP, DIDP, DNOP, DBP and BBP are banned in toys and articles intended to be placed in the mouth by children under the age of 3 through the directive 1999/815/EC. Some Member States have drawn up risk management strategies to reduce the use of phthalates. The Swedish Government has presented a bill on “Swedish environmental quality objectives” which aims at reducing the use of the main phthalate DEHP (and other plasticizers with harmful effects) through voluntary basis for outdoor use of PVC in coated woven fabrics and coated plate and for corrosion protection in cars by 2001. Other uses of DEHP as a plasticizer in PVC, with the exception of medical products and drugs, should be phased out on a voluntary basis by 2001. The Danish government has adopted an action plan to reduce the use of phthalates by 50% over the next 10 years. The German Umweltbundesamt recommends a phase-out of flexible PVC, for those applications where safer alternatives are available, due to the permanent loss of softeners, in particular phthalates, into the environment.

5.7 Gallium arsenide

Table 9 Gallium arsenide, main uses in EEE and hazard classification


Gallium arsenide 1303-00-0 Used in power amplifiers and in semiconductors

Human carcinogen (WHO on arsenic compounds)

5.7.1 Use in EEE Gallium arsenide (GaAs) is a compound of gallium and arsenic. It is used to build radio frequency power amplifiers in mobile phones. Expensive GaAs is used since silicon technology does not meet the performance requirements at 900 to 1900MHz.102 It is also an important semiconductor, and is used to make devices such as microwave frequency integrated circuits (i.e., MMICs), infrared light-emitting diodes and laser diodes. 5.7.2 Characteristics Studies have shown developmental toxicity and carcinogenicity103 Arsenic and its compounds is classified as a human carcinogen by the WHO104 GaAs has been assigned with the following risk phrases105: toxic by inhalation and if swallowed, very toxic to aquatic organisms and may cause long-term adverse effects in the aquatic environment. No studies of exposure of gallium arsenide to man and the environment have been encountered. It is not likely that there is significant exposure during the use phase. Instead, exposure is suspected to occur during manufacturing and during waste treatment. 102 Webpage: EETimes UK (2002) 103 Tanaka A (2004) 104 IARC (1987) 105 Prevent database “Chemical Substances 11.0”


5.7.3 Alternative substances The electronic properties of GaAs are superior to silicon's. It has a higher saturated electron velocity and higher electron mobility, allowing it to function at frequencies in excess of 250 GHz. In addition, GaAs devices generate less noise than silicon devices. These properties have made GaAs circuitry common in mobile phones, satellite communications, microwave point-to-point links, and some radar systems. GaAs circuitry requires less power than silicon, an important consideration for low-power or high-density applications. This is another reason GaAs is popular in cell phone applications. 106 However, silicon has two major advantages over GaAs. First, silicon is cheap. This is for several reasons: silicon's large wafer size, high strength allowing for easier processing, and of course the scale of the economy. The second major advantage is the existence of silicon dioxide—one of the best-known insulators of any kind. Silicon dioxide can easily be incorporated into silicon circuits wherever a good insulator is required. GaAs circuits must use either the intrinsic semiconductor itself or silicon nitride; neither comes close to the extremely good properties of silicon dioxide.107 The use of silicon bipolar technology together with a new radio frequency design methodology has been suggested to outcompete the expensive GaAs technology. However, a more current analysis forecast a growth in the GaAs market for integrated circuits that reaches 3.7 billion US dollar in 2008. The development is mainly driven by the mobile phone handset market and wireless technology.108 5.7.4 Regulations, corporate initiatives etc Gallium arsenide is not listed in a priority list under the evaluation of existing substances.

5.8 Other substances Other substances that have been brought to special attention are indium, molybdenum, cobalt, and the use of liquid crystals. Liquid crystals can be composed of more than 2000 substances of which many are toxic and hazardous. The economic interests are large and the formulations often proprietary.109 5.8.1 Silver Silver and silver compounds are primarily used in photographic materials, electroplating, electrical conductors, dental alloys, solder and brazing alloys, paints, jewellery, coins, and mirror production. Solder alloys containing silver has been suggested as an alternative to lead solders in board assemblies. The phasing out of lead in applications in EEE with the RoHS directive could result in a significant increase of the amount of silver in WEEE. However, if substituted, silver containing alloys are to be preferred as these metals can be easily recycled in today’s recovery processes. More importantly, silver will, due to its monetary value, increase the economic incentives to recycle PCBs.110 The use of silver-ion in antibacterial coatings, 106 Webpage: Wikipedia 107 Ibid. 108 Webpage: EETimes UK (2004) 109 The Nordic Council of Ministers (1995) 110 Kindesjö U. (2002) IIIEE Master’s Theses


previously primarily found medical instruments, is becoming standard in home appliances e.g. refrigerators and washing machines. This will also result in an increase of silver in WEEE. Silver is bioaccumulative in some organisms and extremely toxic to aquatic organisms in its ionic form. In humans, exposure of silver through dermal absorption, inhalation or ingestion can cause argyria (gray or blue-gray discoloration of the skin). 5.8.2 Nanotechnology Nanotechnology is a fast emerging science where device, thin films, fine particles, advanced microlithography are being built in nanometer scale, i.e. on a molecular and atomic level. At this level, many materials begin displaying a set of unique characteristics based on quantum mechanical forces that are exhibited. Due to these quantum mechanical effects, materials may become more conducting, be able to transfer heat better, or have modified mechanical properties. Development of nanotechnology is revolutionary and is has potential of making great changes in most scientific areas. Attention has been brought to the short- and long-term effect nanotechnology might have on the environment and human health. Materials considered safe in bulk may a have unpredictable properties in nanoscale, such as enhanced reactivity and greater ability to penetrate tissue and membranes. In early 2004, the European Commission published a preliminary risk analysis. One outcome was that it is important to differentiate between free and fixed nanoparticles (NPs), the latter being much less likely to raise concerns because of their immobilisation. It also gave recommendations of developing new nomenclature, new CAS- registry number to engineered NPs and new analysis methods and regulations.111 5.8.3 Synthetic Vitreous Fibres Synthetic vitreous fibres are a group of fibrous, inorganic materials that contain aluminum or calcium silicates. They are widely used for thermal and sound insulating purposes and to reinforce other building materials. There are three categories of synthetic vitreous fibres: glass fibres (fibreglass), mineral wool and refractory ceramic fibres.112 Refractory ceramic fibres (RCFs) are a primary replacement to asbestos and used in furnace and kiln linings.113 About 20% of a total 8000 tonnes (total use in the UK in are used in domestic appliances 114 Respirable RCFs can be classified as probable human carcinogen according to the US EPA based on chronic inhalation studies on rodents where RCFs caused lung cancer.115 5.8.4 Tellurium Tellurium is a by-product of copper refining and the supply is largely dependent on the copper production. The major use of tellurium is as an alloying additive in steel to improve machining characteristics. In electronics (representing 8% of the total use worldwide), it is used in photoreceptors and thermoelectric devises. The total world production was estimated to 95 tonnes (excluding U.S. production) in 2004. In the U.S., a small amount of tellurium is also used in cadmium telluride solar cells, in thermal elements and in alloys with germanium 111Webpage: EUROPA - EU preliminary risk analysis Nanotechnologies, 112 ATSDR (2004) 113 Webpage: U.S. EPA 114 AEA Technologies (2004) 115 Webpage: U.S. EPA


and antimony in DVDs (digital video disks). A new development in bismuth coupling materials, which consists of bismuth, germanium and tellurium enables DVDs to be rewritable at high and low speed.116 Tellurium has shown to have mutagenic properties and have an effect on reproduction.117

116 U.S. Geological Survey (2005) 117 Lewis R.J. (1992)

Page 26 Final Assessments

6 Discussion According to manufacturers of EEE the industry continue to develop products of reduced size with fewer and less harmful chemicals. However, increasing growth might offset the positive environmental aspects of this development. The ambition and knowledge with the OEMs is high. But on the customer demand side, environmental aspects of the products are not at the top of the agenda. There are drivers far more important such as cost, design properties and so on. Here, legislation has an important role to play. In addition, it is important that the set of conditions are the same for all actors on the market. For many of the substances covered in this report EU risk assessments are not planned or are not finished. This factor that makes it difficult to outline the substances most important to include in the RoHS-directive. However, based on the facts presented in this report it can be concluded that there are substances that should be examined further for inclusion in the RoHS directive. The use of phthalates in EEE should be minimised based on the probable release during use phase and the documented harmful effects these substances may have on humans. The discontinued use of PVC, that in some cases requires phthalates and many other additives, would not only remove a major part of the contents of these substance in EEE but would also eliminate a substantial source of chlorine to the waste stream of EEE. The use of antimony as flame retardant is expected to decrease with a declining use of brominated flame-retardants. However, this should not be considered a guarantee that the use of antimony and its compounds in EEE does not or will not entail significant risk to health and the environment. New applications can be developed, resulting in increased use. Antimony trioxide it is a viable candidate for inclusion in the RoHS-directive, considering the proposed classification as a carcinogen and the availability of alternatives. The difficulties in identifying beryllium oxide during end of life treatment present a risk to the workers and measures should be taken towards the implementation of unanimous standard for marking these types of components, if such a standard does not already exist. It is not certain what amounts of beryllium are used in EU at present. The previous use of beryllium oxide in resistors has declined. However, it can not, from the information retrieved in this review, be fully established that the use has seized completely. Use of beryllium and its compounds are steadily finding new applications, at least in the U.S. Considering the category 2 carcinogen classification, the hazards disassembly workers are exposed to during recycling and the presence of alternative materials and techniques, beryllium is a viable candidate for inclusion in the RoHS-directive.

Discussion Page 27

7 Final Assessments Even though the present RoHS-directive might confine the substances of highest concern in electrical and electronic products, it can be concluded from this review that there is still substances and materials used that are hazardous and may constitute health and environmental risks.

Based on intrinsic properties, use and exposure during the lifecycle the use of above listed phthalates and antimony trioxide are outlined as substances which use should be restricted in EEE. Based on intrinsic properties, the same is true for beryllium compounds, TBBP-A, selenium and gallium arsenide. Exposure to these substances, derived from their use in EEE, should be investigated further.

SVHC (CMRs cat. 1 and 2, PBTs, vPvBs) according to current or suggested classification:

Compound CAS No Main use in EEE Hazard

Beryllium metal 7440-41-7 In alloys EC category 2 carcinogen

Beryllium Oxide (Beryllia) BeO 1304-56-9 In ceramics as

cooling device EC category 2 carcinogen

Diethylhexylphthalate (DEHP), 117-81-7 In PVC in

cables EC category 1 toxic to reproduction

Butylbenzylphthalate (BBP), 85-68-7 -‘’- EC category 2 toxic to reproduction

Dibutylphthalate (DBP) 84-74-2 -‘’- EC category 1 toxic to reproduction

Antimony trioxide, Sb2O3 1309-64-4 Synergist flame-retardant EC category 2 carcinogen (suggested).

European risk assessment underway:


Dioctylphthalate (DOP). 117-84-0 In PVC in cables

Very toxic to aquatic organisms.May cause long-term adverse effects in the aquatic environment

Tetrabromo bisphenol A (TBBP-A) 79-94-7 Flame retardant

Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment

No European risk assessment is planned:


Gallium arsenide 1303-00-0 Used in power amplifiers and semiconductors

Human carcinogen (arsenic compounds according to WHO)

Selenium 7782-49-2 Rectifiers and in detector instruments

Toxic, Danger of cumulative effects. May cause long-term adverse effects in the aquatic environment.

Page 28 References

8 References Written sources: AEA Technology (2000) “Economic evaluation of PVC waste management”, Oxfordshire, UK, Final Report. Accessible on http://europa.eu.int/comm/environment/waste/studies/pvc/economic_eval.pdf AEA Technology (2004) WEEE and Hazardous Waste - A report for DERFA, Oxfordshire, UK, Accessible on http://www.defra.gov.uk/environment/waste/topics/electrical/pdf/weee-hazwaste.pdf AKZO Nobel MSDS for Fyrol FR-2, http://www.phosphoruschemicals.com/pdf/fyrol%20fr-2%20msds.pdf Anaren Microwave Inc. (2001) Anaren Microwave Inc introduces new RF power aluminum nitride resistors and terminations, Syracuse, New York, February 12. Accessible on: http://www.anaren.com/press/press_release.cfm?id=38 Andersson C., Liu J. (2001) “Litteraturstudie om blyfria lodlegeringar”, Chalmers University of Technology, PTI 01:01. ATSDR, Agency for Toxic Substances and Disease Registry (2004). Toxicological Profile for Synthetic Vitreous Fibers. Atlanta, GA: U.S. Department of Health and Human Services, Public Health Service. Accessible on http://iier1.isciii.es/tfacts161.html Baranek Sherry L. (2002) “Copper Beryllium Vs. Beryllium-Free Copper”, Communications Technologies. Accessible on http://www.performancealloys.net/misc/copper.pdf Bertin Technologies (2000) The influence of PVC on the quantity and hazardousness of flue gas residues from incineration Brush Wellman Engineered Materials (2004) MB 009 Benefits Beryllium Brochure, Patrick Carpenter. Accessible on http://www.berylliumproducts.com/web/bpdweb.nsf C4E (CEFIC - EECA - EICTA – EUROMETAUX) Guidance Document on the Appliance of Substances under Special Attention in Electric & Electronic Products, Version 2.2, November 25, 2002 Ceramic Industry (2005) “Raw and Manufactured Materials: 2005 Review and Forecast” By Christine L. Grahl. Accessible on: http://www.ceramicindustry.com/CDA/ArticleInformation/coverstory/BNPCoverStoryItem/0,2708,140963,00.html COM(2000)347 final, Proposal for WEEE and RoHS. Accessible on http://europa.eu.int/eur-lex/en/com/pdf/2000/en_500PC0347_02.pdf COM (2001)88, The White Paper on the strategy for a future Chemicals Policy COM (2000)469, Greenbook: Environmental issues relating to PVC Crowe, M et al, 2003, ‘Waste from Electrical and Electronic Equipment (WEEE)- quantities, dangerous substances and treatment methods’, European Topic Centre on Waste, European Environment Agency Danish EPA (1999) Brominated flame retardants – Substances flow analysis and assessment of alternatives, report No.494 Edshammar, L-E (2002) Plasthandboken – en materialguide för industrin, Industrilitteratur, Uppsala Environment Agency, P R Fisk, A E Girling and R J Wildey, (2003) Prioritisation of flame retardants for environmental risk assessment, Peter Fisk Associates

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European Environment Agency (EEA), Waste from electrical and electronic equipment (WEEE)- quantities, dangerous substances and treatment methods, Copenhagen, 2002 accessed on waste.eionet.eu.int/publications/WEEE Five Winds International (2001) Toxic and hazardous materials in electronics, Final Report, Ottawa, Canada IARC. (1987) Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Man. Geneva: World Health Organization, International Agency for Research on Cancer. p. S7 57 Irwin Roy J. (1997) Environmentals contaminants encyclopedia – Selenium entry, Fort Collins, Colorado, USA Accessible on: http://www.nature.nps.gov/hazardssafety/toxic/selenium.pdf Kindesjö, U. (2002) Phasing out lead in solders: An assessment of possible impacts of material substitution in electronic solders on the recycling of printed circuit boards, IIIEE Master´s Theses 2002:20, Lund Kuhre, W.L. ISO 14020s, Environmental Labelling-Marketing. Prentice Hall PTR, Upper Saddle River, NJ, USA, 1997. Lewis, Richard J., Sr. (1992) Sax’s Dangerous Properties of Industrial Materials, eighth ed., New York, Van Nostrand Reinhold. National Pollutant Inventory, Australian Government, Department of Environment and Heritage, Substance profile – Selenium and compounds (1999). Accessible on http://www.npi.gov.au/database/substance-info/profiles/75.html NIEHS (National Institute of Environmental Health Sciences), 11th ed., Report on Carcinogens, Beryllium and beryllium compounds, 31.1.2005 OECD (2000) The evolution of materials used in personal computers. Presented at a workshop by Amanda Monchamp, Electronic Industries Alliance, 28-29 Sept., Vienna, Austria. Accessible on http://www.oecd.org/dataoecd/44/46/2741576.pdf Powdermet, Inc (2003). Light Weight High-Stiffness Materials for Beryllium Replacement, Euclid, Ohio. Accessible on http://www.mdatechnology.net/techsearch.asp?articleid=594 Prevent database “Chemical Substances 11.0” Prognos, Mechanical recycling of PVC wastes, Study for DG XI, January 2000 RAR (2001) Risk assessment of bis (2-ethylhexyl) phtalates (DEHP) CAS-No. 117-81-7, R042_0109_env_hh_0-3, Sept 2001. RAR (2003) Draft risk assessment report Tetrabromo bisphenol A, Rapporteur country UK, Dec 2003 version. RAR (2004) Draft risk assessment report Diantimony trioxide, Rapporteur country Sweden, Sept 2004 version Roskill Information Services (2001), The Economics of Beryllium, http://www.roskill.com/reports/beryllium?currencySymbol=USD Sjodin, A., Carlsson, H., Thuresson, K., Sjolin, S., Bergman, A. & Ostman, C. (2001) Flame retardants in indoor air at an electronics recycling plant and at other work environments. Environmental Science and Technology 35(3): 448-454 Swedish Association of Environmental Managers – Best Practice, Exaktafjädrar AB posted on 2004-01-14, http://www.godaexempel.nu Tanaka A (2004) Toxicity of indium arsenide, gallium arsenide, and aluminium gallium arsenide Toxicol Appl Pharmacol.198(3):405-11 The Nordic Council of Ministers 1995:554, Waste from electrical and electronic products, Copenhagen

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The Swedish Chemicals Inspectorate (KemI) report 4/03: Brominated flame-retardants, Stockholm The Swedish Chemicals Inspectorate (KemI) report 12/94, Phthalic acid ester used as plastic additives, Stockholm, Lundberg Göran, Nilsson Charlotte Umweltbundesamt, (1999) Handlungsfelder und Kriterien für eine vorsorgende nachhaltige Stoffpolitik am Beispiel PVC, Pressrelease accessible on http://www.umweltbundesamt.de/uba-info-daten/daten/pvc.htm U.S. EPA Ground Water and Drinking Water, Consumer fact sheet on Selenium (2005). Accessible on http://www.epa.gov/safewater/dwh/c-ioc/selenium.html U.S. Geological survey (2000), Beryllium recycling in the United States in 2000 By Larry D. Cunningham Reston, VA, Open-File Report 03-282 U.S. Geological survey, Mineral Commodity Summaries, Januari 2005, http://minerals.usgs.gov/minerals/pubs/commodity/ Velzen D van, Langenkamp H., Herb G. (1998), Antimony, its sources, applications and flow paths into the urban and industrial waste: a review, Waste management and research, 16:1, pp. 32-40 Webpages: EETimes UK (2002) Cheap silicon replacement for gallium arsenide in mobiles http://www.eetuk.com/showArticle.jhtml?articleID=19202968, accessed on 2005-02-21 (2004) Gallium arsenide IC market “worth 2.9 billion in 2004” http://www.eetuk.com/showArticle.jhtml?articleID=47204335, accessed on 2005-02-21 Environment Agency http://environment-agency.gov.uk/ EuroChlor http://www.eurochlor.org/pdf/pvc%5Ffs.pdf, accessed on 2005-03-31 EUROPA- Environment - Chemicals http://europa.eu.int/comm/environment/chemicals/index.htm, Accessed on 2005-04-18 Research – Briefings – Recycling Vehicles http://europa.eu.int/comm/research/leaflets/recycling/sv Accessed on 2005-04-18 Controlled management of hazardous waste http://europa.eu.int/scadplus/leg/en/lvb/l21199.htm EU preliminary risk analysis Nanotechnologies, http://europa.eu.int/comm/health/ph_risk/documents/ev_20040301_en.pdf Fibersource http://www.fibersource.com/f-tutor/olefin.htm accessed on 2005-04-18 IT Eco Declaration http://www.itecodeclaration.org/, Accessed on 2005-03-02 Nichicon Corporation http://www.nichicon-us.com/english/eco/eco02.html Accessed on 2005-02-21 The Nordic Swan http://www.svanen.nu

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SONY http://www.sony.net, Accessed on 2005-03-01 The Swedish Chemicals Inspectorate (KemI): The environmental quality objective and the six interim targets http://www.kemi.se/templates/Page____2392.aspx Accessed on 2005-04-06 United States Antimony Corporation www.usantimony.com Accessed on 2005-04-18 U.S. EPA Integrated Risk Information Services – Refractory Ceramic Fibres http://www.epa.gov/iris/subst/0647.htm accessed on 2005-04-18 Umweltbundesamt Environmentally hazardous and health damaging flame-retardants: Reduce use and replace http://www.umweltbundesamt.de/uba-info-presse-e/presse-informationen-e/p5601-e.htm Wikipedia http://en.wikipedia.org/wiki/Gallium_arsenide, Accessed on 2005-04-18 Personal communication Mats Moberg WÅAB Elektronik Inga- Brita Mörch, NOTE Carl Lindqvist, TetraPak Martin Påhlman, Swedish EPA

Annex 1

End uses and specific applications of beryllium in the USA. Defense • Fasteners, equipment supports and structural components including rudders and wing leading edges • Infrared sensors for fighter jet optical targeting, radar and navigation/guidance systems including the F-15 Strike Eagle, F-16 Fighting Falcon, F-18 Superhornet and the F-22 Raptor • Optical sensors for unmanned aerial vehicles • AH-1Z SuperCobra, AH-64 Apache and OH58D Kiowa Warrior helicopters • Infrared and optical sensors for the Ground Based Interceptor and launch detection satellites • Optical systems on various air-launched missiles • Submarine-launched intercontinental missiles and other ballistic missile systems • Structures, mechanisms, electronic housings, heat sinks and sensory equipment in military communications satellites • M60 and M1A2 Abrams main battle tanks Transportation • Engines, braking systems, integrated traction control systems and transmissions • Electric motors and connectors for windows, seats, mirrors, door/window locks, fuel pumps • Electrical terminals used in “drive by wire” power steering, braking and throttle systems • Instrument and radar connectors • Ground wiring connections to all electrical equipment on aircraft • Brake bushings • Landing gear bushings and bearings • Door and hatch components • Engine attachment assemblies • Wing sliding track assemblies • Altimeters and barometers, and altitude fuel mixture instruments Medicine applications • Mammography x-ray and other medical imaging equipment • Ultrasound diagnostic monitoring devices • Argon-ion lasers for eye surgery • Laser-based scientific and medical test equipment • Electron microscopes

Safety equipment • Automotive air bag collision detection sensors and switches • Braking system terminal connections • Electrical relays in car and truck hazard lights • Water release valve springs used in automatic fire sprinklers • Safety tools including hammers, wrenches and scrapers • Pressure sensing bellows in emergency breathing tanks • Weather forecasting satellites Discovery • Space shuttle window frames and door systems • Mars Rover • Gravity Probe B Satellite • Cassini Orbiter • Spitzer Space Telescope, Hubble Space Telescope and its planned successor, the James Webb Space Telescope • Joint European Torus test reactor • International Thermonuclear Experimental Reactor • CERN LHC and Brookhaven RHIC colliders Energy generation • Directional drilling tools and oil and gas well completion/production equipment • Down hole geological x-ray sensors • Non-sparking tools Communication • Network, data processing and storage area servers, workstations, notebooks, sub-notebooks, and PDAs • Cell phone battery contacts and electrical connectors • Micro-magnetic radiation shielding in cell phones • Wireless base stations • Fiber optic communications equipment • Hubs, routers and other Internet infrastructure equipment; local area networks that support the Internet • Repeater housings for undersea fiber optic telecommunication systems • NAVSTAR Global Positioning System

Source: Brush-Wellman Engineered Materials http://www.berylliumproducts.com/web/bpdweb.nsf/AllDocsByID/25DA80109665873C85256F170057D39E/$File/mb-009+Benefits+Beryllium+Brochure.pdf

Documents

ELECTRONIC EQUIPMENT (EEE) - CIRCABC - Welcome · - iii - Hazardous substances in electrical and electronic equipment (EEE) - Expanding the scope of the RoHS directive By: Emma Andersson