Subsitution of Hazardous chemicals in products and prozesses

SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES FINAL REPORT ANNEX I - V ANNEX I Legislation, policy and programs in the EU (standardised descriptions related to main report, section 2.2) ANNEX II Standardised short descriptions of guidance documents (related to main report, section 2.3) ANNEX III Standardised short descriptions of assessment tools (related to main report, section 2.4) ANNEX IV Technical case studies (related to main report, section 2.6) ANNEX V Summary report of the Conference on Substitution (Hamburg, 13-14 June 2002) 1 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT ANNEX I LEGISLATION, POLICY AND PROGRAMS IN THE EU STANDARDISED SHORT DESCRIPTIONS Annex I contains the standardised descriptions of legislation, policy and programs as they are presented and discussed in section 2.2 of the main report. Besides a selection of exemplary national documents relevant to the EU level is quoted. These documents were found to contribute interesting aspects in addition to the presently achieved level of European harmonisation. Besides relevant documents from the EU level, a selection of exemplary national documents is quoted where these were found to contribute interesting aspects in addition to the presently achieved level of European harmonisation. Their order of appearance is structured by the various types of general and specific approaches and their nature of being more or less legally binding. Abbreviations used for the various approaches are SP OSub ProSub SubOp LiSub LabSub SubVol IncSub Substitution principle Obligatory substitution Prohibited use of substances Substitution as an option for emission reduction List of (recommended or undesirable) substances Labelling of dangerous substances Substitution through voluntary agreements Incentive or economic instrument The standardised descriptions should be read in conjunction with the main report where a detailed analysis is given how these pieces of legislation, policy and programs are directly or indirectly addressing and promoting substitution. 2 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT SP 1 DE Name: GefahrstoffVO, TRGS 440 Addressee: Employer Item to protect: Health of workers Wording (relevant articles §§16 and 36): Legislation Ermittlungspflicht. (...)(2) Der Arbeitgeber muß prüfen, ob Stoffe, Zubereitungen oder Erzeugnisse mit einem geringeren gesundheitlichen Risiko als die von ihm in Aussicht genommenen erhältlich sind. Ist ihm die Verwendung dieser Stoffe (...) zumutbar und ist die Substitution zum Schutz von Leben und Gesundheit der Arbeitnehmer erforderlich, so darf er nur diese verwenden. (...), muß der Arbeitgeber prüfen, ob durch Änderung des Herstellungs- und Verwendungsverfahrens oder durch den Einsatz von emissionsarmen Verwendungsformen (...) verhindert oder vermindert werden kann. (...) die erforderliche Veränderung vornehmen. (...) Instrument type: Regulation with obligation to evaluate substitutes for substances hazardous to workers’ health. Criteria for substitution: Substitution of hazardous substances against less dangerous substances if measure justifiable and it is necessary for preventing harm to humans and their health. Substitution of processes in which hazardous substances are emitted against processes in which no or less hazardous substances are emitted if the measure is justifiable. SP 2 EU Legislation Name: Directive 98/8/EEC on placing biocidal products on the market Addressee: Users of biocides Item to protect: Environment, Public Health Wording: §10 (5) (i) An entry of an active substance in Annex I (positive list of allowed active substances) ..... may be refused or removed,... - if there is another active substance on Annex I for the same product type which, in the light of scientific or technical knowledge, presents significantly less risk to health or to the environment. When such a refusal or removal is considered, an assessment of an alternative active substance or substances shall take place to demonstrate that it can be used with similar effect on the target organism without significant economic and practical disadvantages for the user and without an increased risk for health or for the environment... (ii) The refusal or removal ........ shall be carried out under the following conditions: 1. the chemical diversity of the active substances should be adequate to minimise occurrence of resistance in the target organism; 2. it should be applied only to active substances which, when used under normal conditions in authorised biocidal products, present a significantly different level of risk; 3. it should be applied only to active substances used in products of the same product type; 4. it should be applied only after allowing the possibility, where necessary, of acquiring experience from use in practice, if it is not already available; 5. the complete data dossiers of the evaluation serving or having served for entry in Annex I, IA or IB shall be put at the disposal of the Committee referred to in Article 28(3). (iii) A decision to remove an Annex I entry shall not have immediate effect but shall be delayed for a period of up to a maximum of four years from the date of that decision. Instrument type: Regulative instrument in which an obligation for comparative assessment within the procedure of uptake of an active substance in the list of allowed active substances within the authorisation process is described. Criteria for substitution: The criteria for substitution are evaluated in a comparative assessment which is focused on the question, whether a less hazardous substance with the same function and which does not lead to economical and practical disadvantages exists. The aspects to be considered for evaluation are described under Article 5(II) (1-4). 3 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT OSub 1 EU Legislation Name: Directive 90/394/EEC on the protection of workers from the risk related to exposure to carcinogens at work, § 4 and 5, Directive 98/24/EC on the protection of the health and safety of workers from the risks related to chemical agents at work § 6(2) (6th and 14th individual Directives within the meaning of Article 16(1) of Directive 89/391/EEC on the introduction of measures to encourage improvements in the safety and health of workers at work) Addressee: Employers Item to protect: Workers Health Wording: Directive 90/394/EEC § 4 Reduction and replacement The employer shall reduce the use of a carcinogen at the place of work, in particular by replacing it, in so far as is technically possible, by a substance, preparation or process which, under its conditions of use, is not dangerous or is less dangerous to workers’ health or safety, as the case may be. § 5 Prevention and reduction of exposure Where it is not technically possible to replace the carcinogen by a substance or preparation or process which, under its conditions of use, is not dangerous or is less dangerous to health or safety, the employer shall ensure that the carcinogen is, in so far as is technically possible, manufactured and used in a closed system. Directive 98/24/EC, § 6 Specific protection and prevention measures The employer shall ensure that the risk from hazardous chemical agent to the safety and health of workers at work is eliminated or reduced to a minimum. In applying paragraph 1, substitution shall by preference be undertaken , whereby the employer shall avoid the use of hazardous chemical agent by replacing it with a chemical agent or process which, under its condition of use, is not hazardous or less hazardous to workers´ safety and health, as the case may be. Where the nature of the activity does not permit risk to be eliminated by substitution, having regard to the activity and risk assessment referred to in Article 4, the employer shall ensure that the risk is reduced to a minimum by application of protection and prevention measures, consistent with the assessment of the risk made pursuant to Article4. ...... Instrument type: Regulation of substances with carcinogenic effects. Criteria for substitution: From 90/394/EEC an obligation to substitute carcinogen substances if technically possible is outlined. OSub 2 AT Legislation Name: ArbeitnehmerInnenschutzgesetz AschG, Austria Addressee: Employer, Manufacturer Item to protect: Health of workers Wording: § 42 Abs. (1): Krebserzeugende,......dürfen nicht verwendet werden, wenn ein gleichwertiges Arbeitsergebnis erzielt werden kann..... mit Arbeitsstoffen, die weniger gefährliche Eigenschaften aufweisen. (2) Mit besonderen Gefahren verbundene Verfahren bei der Verwendung von in Abs. 1 genannten Arbeitsstoffen dürfen nicht angewendet werden, wenn durch Anwendung eines anderen Verfahrens, bei dem die Verwendung des Arbeitsstoffs ausgehende Gefahren verringert werden können, ein gleichwertiges Arbeitsergebnis erzielt werden kann. (3) ...gelten auch für die in Abs. 1 und 2 nicht genannten gefährlichen Arbeitsstoffe, sofern der damit verbundene Aufwand vertretbar ist. (4) Im Zweifelsfall entscheidet die zuständige Behörde......ob die Verwendung...zulässig ist, wobei der jeweilige Stand der Technik und die jeweils aktuellen wissenschaftlichen Erkenntnisse Instrument type: Legislation with obligation to substitute carcinogenic substances if the substitutes are less harmful. Criteria for substitution: CMR-substances must be substituted if an appropriate substitute that is less harmful is available Other hazardous substances have to be substituted if an appropriate substitute is available and the effort for the manufacturer appears justifiable. 4 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT OSub 3 EU Legislation Name: Directive 99/13/EEC on the limitation of emissions of volatile organic compounds due to the use of organic solvents in certain activities and installations. Addressee: Users of VOC in products / processes Item to protect: Environment and workers health, Reduction of VOC emissions Wording: §5: Requirements, sub-para (6): Substances or preparations which, because of their content of VOCs classified as carcinogens, mutagens, or toxic to reproduction under Directive 67/548/EEC, are assigned or need to carry the risk phrases R45, R46, R49, R60, R61, shall be replaced, as far as possible and by taking into account the guidance as mentioned in Article 7(1), by less harmful substances or preparations within the shortest possible time. Instrument type: Legislative instrument with obligation to substitute substances with specified toxicological properties. Criteria for substitution: Solvents in preparations that exhibit the properties carcinogenic, mutagenic or toxic to reproduction according to 67/548/EC have to be substituted. ProSub 1 AT Legislation Name: Wasserrechtsgesetz (WRG) Addressee: Discharger of industrial waste waters Item to protect: Water environment Wording (§ 33b Abs. 2): ...darf die Einleitung gefährlicher Stoffe nur so weit bewilligt werden, als nach dem Stand der Technik die Vermeidung nicht möglich ist und die wasserwirtschaftlichen Verhältnisse, insbesonders bestehende Nutzungen und die bereits vorhandene Belastungen; dies zulassen. Bsp. für derartige Einleitungsverbote: halogenierte organische Verbindungen aus dem Einsatz von Chlorgas oder unterchloriger Säure und ihrer Salze bei der Zellstoffbleiche Schwer abbaubare organische Komplexbildner, Arsen und Quecksilber sowie deren Verbindungen, diverse schwermetallhaltige Farbpigmente und gewisse organische Lösungsmittel bei grafischen Prozessen EDTA - haltiges Abwasser aus Entfettungs-, Entmetallisierungs- oder Nickelbädern bei der Behandlung metallischer Oberflächen Schwer abbaubare Komplexbildner, anorganische Chromverbindungen, metallorganische Verbindungen, nichtoxidierende Mikrobizide etc. beim Betrieb von Kühlsystemen etc. Instrument type: Legislation which restricts discharge of certain hazardous substances. Certain substances from specific industrial sectors are prohibited. Criteria for substitution: In this context specific substances from processes are not allowed to be discharged. Criteria applied for this prohibitions are not specified but might be arisen from pollution problems within water treatment plants. 5 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT ProSub 2 EU Legislation Name: Directive 2000/53/EC on end-of life vehicles Addressee: Producers and importers of vehicles Item to protect: Prevention of waste from vehicles, environment, enabling recycling to avoid the dispose of hazardous substances. Wording (Article 4 2(b)): Member States shall ensure that materials and components of vehicles ...... do not contain lead, mercury, cadmium or hexavalent chromium other than in cases listed in Annex II under the conditions specified therein. .....The Commission shall on a regular basis, according to technical and scientific progress, amend Annex II, in order to.....(ii) exempt certain materials and components of vehicles from the provisions of subparagraph (a) if the use of these substances is unavoidable; (iii) delete materials and components of vehicles from Annex II if the use of these substances is avoidable;... Instrument type: Legislation which describes a prohibition of certain heavy metals in cars imported or produced in Europe. Criteria for substitution: The substances (elements) due to substitution are directly mentioned in the Directive. No criteria for other substances of concern are mentioned. The criteria are derived on the background of disturbance of shredder processes by these elements. ProSub 3 EU Legislation Name: Council Directive 75/442/EEC on waste Addressee: Member States i.e. manufacturer of products Item to protect: The waste stream must be protected from contamination caused during usage and disposal of products; producer responsibility Wording: a) Article 3 (1)a Member States shall take appropriate measures to encourage:.....the prevention or reduction of waste production and its harmfulness, in particular by:..... the technical development and marketing of products designed so as to make no contribution or to make the smallest possible contribution, by the nature of their manufacture, use or final disposal, to increasing the amount or harmfulness of waste and pollution hazards.... b) Article 15: In accordance with the ‘polluter pays’ principle, the cost of disposing of waste must be borne by: ... the producer of the product from which the waste came. Instrument type: Legislation Criteria for substitution: Restrictions for marketing of products are formulated, if release of hazardous substances can not be prevented during their disposal. Additionally, the Directive formulates the obligation for manufacturer to be responsible for their products also in the end-of life stage. Discussion of concept: The Directive might force indirectly the substitution of products i.e. ingredients in products, with which an environmentally sound disposal is not possible. 6 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT ProSub 4 DE Legislation Name: Kreislaufwirtschafts- und Abfallgesetz KrW/AbfG, Germany Addressee: Manufacturer of products Item to protect: The waste stream must be protected from contamination caused during usage and disposal of products; producer responsibility Wording: §22 Produktverantwortung. (1) Wer Erzeugnisse entwickelt, herstellt, (...) trägt (...) Produktverantwortung. (...) sind Erzeugnisse möglichst so zu gestalten, dass bei deren Herstellung und Gebrauch das Entstehen von Abfällen vermindert wird und die umweltverträgliche Verwertung und Beseitigung der nach deren Gebrauch entstandenen Abfälle sichergestellt ist. (...) §23 Verbote, Beschränkungen und Kennzeichnungen. (...) 2. Bestimmte Erzeugnisse überhaupt nicht in Verkehr gebracht werden dürfen, wenn bei ihrer Entsorgung die Freisetzung schädlicher Stoffe nicht (...) verhindert werden könnte (...) Instrument type: Legislation Criteria for substitution: The regulation formulates the obligation for manufacturer to design their products in a way that the amount of waste during production, usage and end of live is minimal. Additionally restrictions for marketing of products are formulated, if release of hazardous substances can not be prevented during their disposal. Discussion of concept: The regulation addresses indirectly the substitution of products i.e. ingredients in products, with which an environmentally sound disposal is not possible. SubOp1 AT Regulation Name: Verordnungen des Wasserrechtsgesetzes, Austria Addressee: Discharger of industrial waste waters Item to protect: Water environment Wording: ... können u.a. folgende die wasserwirtschaftlichen Verhältnisse von Betrieben oder Anlagen betreffende Maßnahmen ..... in Betracht gezogen werden (Stand der Vermeidungs-, Rückhalte- und Reinigungstechnik) u.a. a) Einsatz von Arbeits- und Hilfsstoffen, die einen geringen Gehalt an gefährlichen Inhaltsstoffen aufweisen und die zu möglichst geringen Beeinträchtigungen der Abwasserreinigungsverfahren führen b) Substitution gefährlicher Arbeits- oder Hilfsstoffe durch mindergefährliche bevorzugt biologisch gut abbaubare Stoffe vor. Instrument type: Regulation that describes options how to prevent discharge of hazardous substances. Substitution is one of them. Criteria for substitution: Criteria mentioned refer to the hazard and the biodegradability of the substitute. No obligation to substitute is mentioned. Discussion of concept: This regulations addresses substitution as one option for a technical measure the authority can refer to, if emission standards due to an applied or actual discharge will/are not kept to. 7 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT SubOp2 EU Legislation Name: Directive 96/61/EC concerning integrated pollution prevention and control (IPPC), ANNEX IV Addressee: Manufacturer, industrial plants Item to protect: Environment as a whole (emission into air, water, land) Wording: Annex IV Considerations to be taken into account generally or in specific cases when determining best available techniques, as defined in Article 2(11), bearing in mind the likely costs and benefits of a measure and the principles of precaution and prevention: the use of low-waste technology; the use of less hazardous substances; ....... Instrument type: Recommendation in a legislation Criteria for substitution: No hard criteria for substitution are described. Substitution must be considered as one technical measure among others when laying down BATechnique. Discussion of concept: The IPPC Directive mostly refers to the emission control principle. Replacement of hazardous substances is mentioned among 12 other aspects to be considered when the Best Available Techniques (BAT) are determined. Thus substitution is not directly addressed. Therefore this regulation can be considered as a framework that allows underlying regulations (e.g. in BAT Reference Documents for the sector level) to identify substitution as being BAT in specific industrial sectors. SupOp 3a DE Legislation Name: Bundesimmissionsschutzgesetz (BImSchG), Germany Addressee: Operating Company Item to protect: In order to protect the compartment air from emission of air pollutants. Wording: §54 Aufgaben. (1) Der Immissionsschutzbeauftragte berät den Betreiber (...). Er ist berechtigt und verpflichtet, 1. Auf die Entwicklung und Einführung a) umweltfreundlicher Verfahren (...) b) umweltfreundlicher Erzeugnisse (...) hinzuwirken. Instrument type: Legislation Criteria for substitution: The criteria for a change of the process / product is that the new product / process should be more “environmentally friendly”. Discussion of concept: The regulation is a general request that the plant inspector should urge the producer that he introduces environmental friendly processes and products. Substitution can here be seen in the choice for a more environmentally friendly product / process rather than a choice between different ingredients / substances. 8 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT SubOp 3b DE Legislation Name: Technische Anleitung zur Reinhaltung der Luft (TA-Luft), Germany Addressee: Operating Company Item to protect: In order to protect the compartment air from emission of lead containing substances. Wording: 2.2.1.4 Vorsorge (...) Sonstige Maßnahmen (z. B. Einsatz emissionsarmer Brenn- und Arbeitsstoffe, Betriebseinschränkungen, Einhaltung von Abständen) sollen insbesondere getroffen werden, (...) 3.1.2 Grundsätzliche Anforderungen Wenn Stoffe nach 2.3, 3.1.4 Klasse I oder II oder Blei und seine Verbindungen, (...) emittiert werden können, sollen die Einsatzstoffe (Roh- oder Hilfsstoffe) möglichst so gewählt werden, dass geringe Emissionen entstehen. (...) Instrument type: Regulation Criteria for substitution: When choosing raw material for incineration the raw material should be chosen, which results in lower emission of lead. Discussion of concept: The law is intended to force the use of raw materials which do not contain lead or smaller amounts of lead. It has not a binding character, as the wording is „if possible“. The wording addresses the lead emission (result / effect of the contamination) rather than the lead content in the raw material. Substitution can here be seen as the active choice for a less contaminated raw material rather than choice for a less harmful ingredient. LiSub 1 S Program Name: Observation List by the National Chemicals Inspectorate (KEMI) / National Board of Occupational Safety and Health / EPA (www.kemi.se/publikationer/obs_swe/OBSlistan.pdf). Addressee: Companies and others handling chemicals in their work to examine and analyse the use of substances. Item to protect: Human health and / or the environment Description: The list presents substances dangerous to human health which are derived from the Classification List of the Swedish Classification and Labelling of Chemical Products Regulation. Substances dangerous for the environment are derived from the International and Uniform Chemicals Information Database (IUCLID). The list includes approximately 250 substances. For each substance contained in the list it is indicated Based on which criteria (including trigger values) the substance has been selected, In which types of preparations it is contained, To which extent it is contained in chemical products for public use, In which regulations or agreements objectives or restrictions for this substance are established. KEMI regularly updates the Observation List and understands the list as a recommendation and not as a list of banned substances. The Observation list is compiled based on the Swedish Production Register identifying substances with > 1 t per year in Sweden. Instrument type: Information Criteria for substitution: Selection criteria are individually specified from categories (a) Very high acute toxicity, (b) Sensitising properties, (c) High chronic toxicity, (d) Properties impairing reproduction, (e) Carcinogenic properties, (f) Mutagenic properties, (g) High potential for bioaccumulation and / or low degradability, (h) Very high toxicity to aquatic organisms, (i) Dangerous for the ozone layer. 9 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT LiSub 2 DK Policy (Negative List) Name: List av unøskede stoffer (List of undesirable substances), Second, revised edition 2000. Danish Environmental Protection Agency (Miljøstyrelsen). Addressee: Public, authority, enterprises. “...the List can be used by the product developers in companies, by professional purchasers when making environmentally-aware purchases and by others who are interested in how chemical substances are used in products.” Item to protect: Waste, environment, health and safety of workers Description: The List contains certain substances which the Danish EPA claims to be of concern and gives a short information on each substances with the categories product groups, reason for selection, classification, present regulation, activities in past and future. The observation list includes all substances of the Danish “list of effects 2000” (1404 substances) which consumption in Denmark exceeds 100 t per year. The list includes approximately 80 substances and substance classes. Instrument type: Information Criteria for substitution: There are various selection criteria for the substances which are mentioned individually in the section “reason for selection” Policy (Positive List, official recommendation) Name: List of recommendable new colorants Evaluation of the notifications in accordance with the Chemicals Act, published by the Federal Institute for Safety and Health http://www.baua.de/english/prax/chem/index.htm Addressee: Enterprises using textile, paper plastic or leather dyes or producing pigments for paints lacquers, inks etc. . The list should be used by enterprises using such colorants to be in accordance with the substitution principle of Hazardous Substances Ordinance § 16 Section 2, which requires the user of chemicals to employ substitutes for hazardous chemicals and preparations wherever possible and appropriate. Item to protect: Health and safety of workers, environment, Description: The List contains more than 60 substances, which have been notified in Accordance with the Chemicals Act for colouring purposes until 1998. Due to the fact that for the same purpose more or less dangerous substances were developed, the FIOH feels responsible, to publish the products with the least dangerous properties. The reason is given: LiSub 3 DE The preventive aim of the Chemicals Act is vigorously supported in the Hazardous Substances Ordinance. For example, the rule contained in § 16 Section 2 requires the user of chemicals to employ substitutes for hazardous chemicals and preparations wherever possible and appropriate. In this as well as in further publications the Federal Institute will therefore at this point inform users about new substances for which no dangerous properties requiring classification and labelling have been identified in the notification procedure and for which no grounds for suspecting toxic effects that might give cause for concern have been determined. The positive list is also follow-up activity a result of the prohibition list (banning) of potentially carcinogenic azo-dyes issued by FIOH in 1996 Instrument type: Information, potentially enforced by local health and safety executives according to the general substitution obligation Criteria for substitution: No dangerous properties according to the data given by the companies for notification of a new substance” 10 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT LabSub1 EU Legislation Name: Directive 67/548/EEC Council Directive of 27 June 1967 on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances, and Directive 99/45/EC for dangerous preparations. Addressee: Producers and importers of chemicals in the European Union. Item to protect: Environment, consumers, health and safety of workers Description: The core of legislation for classification and labelling is the directive 67/548/EEC Council Directive of 27 June 1967 on classification, packaging and labelling of dangerous substances and the Directive 99/45/EC for dangerous preparations, including all amendments due to legal, scientific and technical progress. Based on the classification rules and the list of chemicals with hazardous properties all principles and details of labelling are regulated. Annexes contain lists with substances and their properties relevant for classification and labelling or criteria for the classification. Such properties can concern health aspects (carcinogenic, reprotoxic), safety aspects (e.g flammability) or environmental aspects (e.g. persistence, ecotoxicity). Instrument type: Legislation Criteria for substitution: Official classification of dangerous properties SubVol 1 EU Legislation Name: DIRECTIVE 2001/58/EC of 27 July 2001 amending for the second time Directive 91/155/EEC defining and laying down the detailed arrangements for the system of specific information relating to dangerous preparations in implementation of Article 14 of European Parliament and Council Directive 1999/45/EC and relating to dangerous substances in implementation of Article 27 of Council Directive 67/548/EEC (safety data sheets) Addressee: Manufacturers, importers or distributors of chemicals of substances or preparations Item to protect: Safety and health of workers; the environment Description: The SDS contain the basic hazard and safety information for the professional users of chemicals in Europe. It is meant to provide the employers with the basic information to determine whether hazardous agents are present at working places and which standard safety measures to take. The obligation to provide safety data sheet is constituted in Article 14 of Directive 1999/45/EC, Article 27 of Directive 67/548/EEC and Article 16(1) of Directive 89/391/EEC) (6). The current directive obliges the “persons responsible for placing on the market” to provide SDS for all their products containing dangerous substances. For dangerous preparations the SDS must be supplied with the product. Regular updates of the SDS have to be sent to the customer. For nondangerous preparation (not fulfilling the classification criteria of Directive 1999/45/EC) proportionate information has to be supplied on request if any single dangerous substance has a quantity exceeding more 1% of the product. The information required is given under 16 mandatory headings: 11 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT 1. IDENTIFICATION OF THE SUBSTANCE/PREPARATION AND OF THE COMPANY/UNDERTAKING (including intended or recommended use) 2. COMPOSITION/INFORMATION ON INGREDIENTS 3. HAZARDS IDENTIFICATION 4. FIRST AID MEASURES 5. FIRE-FIGHTING MEASURES 6. ACCIDENTAL RELEASE MEASURES 7. HANDLING AND STORAGE 8. EXPOSURE CONTROLS/PERSONAL PROTECTION 9. PHYSICAL AND CHEMICAL PROPERTIES 10. STABILITY AND REACTIVITY 11. TOXICOLOGICAL INFORMATION 12. ECOLOGICAL INFORMATION 13. DISPOSAL CONSIDERATIONS 14. TRANSPORT INFORMATION 15. REGULATORY INFORMATION 16. OTHER INFORMATION Safety data sheets could be one of the basic tools for qualitative comparison of hazards posed by chemicals. The R phrases allow the comparison of toxic hazards. The chemical-physical data could be used for a rough estimate of exposure potential. However, the Commission mentions in the Directive, that the current quality of SDS needs to be improved to become a better instrument for risk information and reduction. In particular, the new Directive requires a clear reasoning if information under a certain mandatory heading not filled in. It is not possible to carry out a comparative risk assessment between chemicals and assess substitutes based on SDS alone. The quantity and the conditions of use need to be considered as well. Additionally, most of the current SDSs provide a patchwork of valid information and data gaps, making it difficult to carry out systematic comparison among substances. Instrument type: Legislation Criteria for substitution: Standardised information tool on hazards (health, environment, chemical-physical) and safety measures related to chemical substances and preparations for all companies using chemicals. SubVol 2 DE, F, IT, UK Program Name: Joint BG/HSE/CNAMTS/ISPESL – Protocol on Improved Conditions of Use of UV-Technology in the Printing Industry in Germany, the United Kingdom, France, Italy And Other Interested Member States of the European Union, Version 9/2001, see at: www.bgdp.de, in February 2003 under: http://www.bgdp.de/pages/arbeitsicherheit/brancheninfo/UV-technologie.htm. Berufsgenossenschaft Druck und Papierverarbeitung (BG), Germany; Caisse Nationale de l’Assurance Maladie des Travailleurs Salariés (CNAMTS), France; Health and Safety Executive (HSE), UK; Istituto Superiore per la Prevenzione e la Sicurezza del Lavoro (ISPESL); Italia. Addressee: Printing companies, using the newly developed UV-curing inks. Item to protect: Health and safety of workers, environment Description: UV-Curing inks contain no or negligible amounts of VOC. However, this new technology bears new physical risks (exposure to ionisation, strong UV-light etc) and chemical risks. The acrylates necessary for the curing can cause serious skin diseases. To support the safe introduction of a generally favourable technology, Health and Safety Authorities from Germany (BG), the UK (HSE); France (CNAMTS) and Italy (ISPESL) agreed voluntarily on a “JOINT BG/HSE/CNAMTS/ISPESL – PROTOCOL ….” The selection of the least dangerous acrylates is 12 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT done by using a list of acrylates, prepared by CEFIC UV/EB group. Instrument type: Agreement on common information and enforcement measures Criteria for substitution: Dangerous properties according to EU directives 67/548/EEC and 88/379/EEC.” IncSub 1 NO Legislation Name: Regulations relating to pesticides issued by the Norwegian Ministry of Agriculture on 14.12.2000 (http://odin.dep.no/ld/norsk/publ/rapporter/020005-990284/index-hov005-b-n-a.html#5.9) Addressee: Users of pesticides in Norway Item to protect: (Ground) water Description: The Pesticide Regulation in Norway formulates three kinds of fees as there are a) Registration fee, b) Supervision fee, c) Environmental fee. The environmental fee is payable for individual preparations on the basis of the fee per standardised area dose (SAD) which is laid down by the Agricultural Inspection Service. The SAD presents the average amount of pesticide applied per square metre of ground necessary to observe the desired protection effect. This “basic fee” is multiplied by a factor that is derived from the “fee categories” the pesticide is assigned to. The fee categories are as follows: Fee category 0 (adhesive agents; factor: 0) Fee category I (staining agents, biological preparations and utility organisms; factor: 0.5) Fee category II (preparations with a low health and environmental risk; factor: 1) Fee category III (preparations with a low environmental and high health risk, or with a high environmental and low health risk: factor 4) Fee category IV (preparations with a high health and environmental risk; factor: 8) Fee category V (concentrated hobby preparations; factor: 50) Fee category VI (ready-to-use hobby preparations; factor: 150) The Agricultural Inspection Service issued more detailed provisions regarding the assessment of high and low environmental risk in the “Guidelines for classification of plant protection products in tax classes differentiated according to health and environmental factors.” Whether the health risk is low or high is evaluated on the basis of a combined assessment of the inherent substance properties and potential of exposure for the user. Inherent Properties are derived from R,S Codes and Labelling Categories of the Packaging and Labelling Directive Potential of exposure is based on the assessment of the two situations where the user may be exposed to the plant protection that is during diluting (product formula) and applying the product. For the time being, only the type of formula and the method of application is taken into consideration to obtain the exposure dimension with a higher weight on the mixing procedure because it implies handling of concentrated mixtures. The environmental hazard is assigned to categories low or high on the basis of specified k.o. criteria in the sections aquatic & terrestrial environment, bioaccumulation, persistence in soil and mobility. Instrument type: Levy system Criteria for substitution: For the use of pesticides with high health and/or environmental concern a higher levy has to be paid. 13 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX I: Legislation, policy and programs in the EU standardised short descriptions FINAL REPORT IncSub 2 DK Programme Developed by: Danish Ministry of Environment and Ministry of Taxation, 1999 Name: Action Plan for reducing and phasing out phthalates in soft plastics, Ministry of Environment and Energy (June 1999) Addressee: Companies using phthalates in their products Item to protect: Health and Environment Description: Former legislation in the field of emission to air and water followed an emission control approach e.g. with limit values for air emission for DEHP of 0.005 mg/m3. The proposed taxation is one of the main instruments mentioned in the action plan. The tax shall apply to phthalates in a number of selected product groups for which the tax system was applicable. The tax system has a qualitative basis as the tax does not vary in relation to the exact phthalate content. On the one hand this helps to keep the tax more simple, but on the other hand will force manufacturers to choose alternative materials or plasticisers so that substitution ensures a complete elimination from the products. It is stated in the action plan that from a technical point of view the reduction of phthalates in the products is not a reasonable route anyway. It is proposed that the tax should be restricted to apply only to certain plastic goods where it is deemed possible that the tax will work, and where the products are homogenous so that a standardrate tax based on weight can be calculated on the basis of expected PVC and phthalate contents. The product groups under consideration for the tax are: Flexible pipes, tubes and hoses (garden hoses, water hoses, foodstuff hoses, and industrial hoses) Electrical wires with plastic coating Floor, wall, and ceiling coverings Certain office supplies (ring binders, magazine holders, and folders) Clothing (gloves, aprons, rainwear, and protective suits) Tarpaulins, roofing film, and membrane film Tape and self-adhesive film From a first proposal the tax might be approximately 1 € per kg phthalate. The taxes are reimbursed in connection with exports to keep competitiveness of Danish enterprises on the export markets. Instrument type: Taxation for specific substance as ingredient n products Reference to substitution: Taxes on phthalates in selected product groups which are being sold in the Danish market entail lower total sales due to price rises“. The scope of this downturn in sales for each of the relevant product categories depends on the price rise and its impact on demand (price elasticity). Therefore the tax might lead to an effective substitution enforced by economic incentives. Also substitutes with higher prices might be able to enter the market. Additionally, the qualitative nature of the tax model will make emission control measures unfavourable for companies. IncSub 3 PT Policy Developed by: INETI (Instituto Nacional de Engenharia e Tecnologia Industrial) 2001 for Portuguese Ministry of Environment and Spatial Planning Name: National Plan for the Prevention of Industrial Waste (Plano nacional de prevenção de resíduos industriais - PNAPRI), Lisboa, 2001, see at: http://www.inresiduos.pt/INDICE_PNAPRI.htm Addressee: Industry Item to protect: Environment (Soil and Water) Description: National Industrial Waste Prevention Plan includes a number of different measures to facilitate the reduction and recycling of industrial waste. As a financial incentive the companies collecting and treating waste can apply a reduced VAT of 5% (normal VAT). Instrument type: Taxation as general incentive for a better waste treatment Reference to substitution: A better treatment needs better knowledge about the hazardous properties of the waste and support indirectly substitution . 14 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX II: STANDARDISED SHORT DESCRIPTION OF GUIDANCE DOCUMENTS FINAL REPORT ANNEX II STANDARDISED SHORT DESCRIPTION OF GUIDANCE DOCUMENTS Annex II contains the standardised descriptions of guidance documents as they are presented and discussed in section 2.3 of the main report. Presented here are G1 G2 G3 G4 G5 G6 G7 G8 G9 (G10 Risk Reduction for Existing Substances (UK Gov. / Industry Working Group) Technical Guidance Document on Development of Risk Reduction Strategies (EU Commission) The Technical Rule for Hazardous Substances Nr. 440 (TRGS 440) The Column Model - a help tool for risk assessment of chemicals and options for substitutes (acc. to § 16 Dangerous Substances Act and TRGS 440 German BIA: Institute for occupational safety) Draft Guidance Document on Substitution of Hazardous Chemical Substances (GDS) COSHH ESSENTIALS: Easy steps to control chemicals GISBAU Information system for dangerous substances in the construction industry The complete idiot’s guide to CHIP (CHIP = Chemicals Hazard Information and Packaging for Supply) Guidance Manual for Formulators and Other Professional Users of Chemicals Environmental Labels as Guidance for Industry are contained in Annex III.) The standardised descriptions should be read in conjunction with the main report where the procedures and methods applied are presented with a detailed analysis of their effect on substitution. 15 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX II: STANDARDISED SHORT DESCRIPTION OF GUIDANCE DOCUMENTS FINAL REPORT Nr.: G 1 Name: Risk Reduction for Existing Substances Developed by: UK Government / Industry working group, 1995 Addressee: Rapporteurs of MS who work in Risk Management for the EU Commission Context of guide: Under Regulation 793/93/EEC on existing substances the rapporteur is advised to suggest a risk reduction strategy if the risk assessment resulted in a concern for this substance. In this guidance document a proposal is made how to proceed, starting from identification of potential risk reduction strategies, how to implement these in voluntary or regulatory measures and how to make the choice of selecting the most appropriate measure with the help of decision aid methods. The authors primarily propose to use the risk benefit analysis, which is described in detail in an additional report by the same group of authors. Purpose / aim: The aim of this report is to establish a guideline for rapporteurs in the risk management how to evaluate a risk reduction strategy under Reg. 793/93/EEC on existing substances. At the legislative level, this proposal aims at harmonising the procedure of evaluation of risk reduction strategies within the EU. This UK report can be seen as a first proposal for a EU guidance document on development of risk reduction strategies, which was actually published by the Commission in 1997. Methodology: Several steps are described in the guidance which are here shortly described: 1. Identify Risks: In the first step the possible risks from the emission of the substance of concern to human health and the environment are identified on a technical basis, i.e. make an exposure / emission analysis and assess the adjacent risks. Risk / exposure is analysed along the complete product life cycle from the substance during processing, distribution, use and disposal. 2. Identify sources: After this status analysis the most important sources for risk can be identified. 3. Work out risk reduction measures: Different options for risk reduction measures can be worked out from this and proposals are made in this report for all levels mentioned above. Options proposed are substitution, control of emission to air (threshold limits), limit of use etc. In the next step the guidance discusses the question, how to implement these measures into legislation / voluntary activities and the adjacent legislation are given (summary of possible political / legislational instruments). For an overview the procedure is illustrated in a table. 4. Choice making: For the last step, the choice making for the best option, criteria laid down on a rather general basis, e.g. measures should result in proportion to the risk and costs and all these measures should be compared and the minimum necessary burden should be imposed. For detailed analysis the reader is referred to literature on assessment tools. Reference to Substitution: Substitution is one of several practical options for risk reduction. On the implementation level substitution is not addressed directly. Examples: In an appendix, a general summary in form of a flow chart is given where the historical debate on TBT for anti-fouling, epichlorohydrin in electronic boards and vinyl chloride for PVC production is illustrated subdivided in RA and the adjacent risk management actions. 16 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX II: STANDARDISED SHORT DESCRIPTION OF GUIDANCE DOCUMENTS FINAL REPORT Nr.: G 2 Technical Guidance Document on Development of Risk Reduction Strategies Developed by: EU Commission URL: http://europa.eu.int/comm/environment/pubs/risk.htm Addressee: Member States rapporteurs who develop a risk reduction strategy for certain substances for which the Risk Assessment resulted in a concern. Context of guide: If a substance came out to be of concern under regulation 793/93/EC on existing substances, Member States have to submit a proposal for a risk reduction strategy to the EU Commission. This guidance document describes how to develop such a strategy. If the outcome of the process is a recommendation for market restriction, a detailed analysis of disadvantages and advantages has to be submitted. Purpose / aim: This Technical Guidance Document aims at harmonising the procedure how to evaluate a risk reduction strategy in all Member States. Detailed description how to report the results of the procedure to the EU Commission (form of submission) are given to enable a harmonised report format. Methodology: The development of a risk reduction strategy is described in 5 steps: 1. Identify the use / production pattern of the substance of concern. Identify the options for a reduction measure (technical measures) 2. Identify the tools (legal or others) to implement the strategy 3. Select the most appropriate strategy – compare the different strategies in categories like economic, effectiveness etc. 4. If marketing restrictions are recommended, draw up an analysis of the advantages, drawbacks with respect to parameters like availability of alternatives 5. Submit the risk assessment and the risk reduction strategy to Commission In step 2 three general reduction measures are mentioned: information requirements, restrictions on marketing / use and control of emission. In this section a more detailed list of possible reduction strategies is given differentiated for the various stages of the product life cycle. Measures aiming at: i) manufacture, industrial and professional use, ii) packaging, distribution and storage, iii) domestic and consumer use, iv) waste management. In step 3 the different measures of the legal authority are described with their potential advantages and drawbacks as there are: Information programmes; unilateral action of industry (like responsible care programme); voluntary agreements; technical standards and authoritative guidance, which can be implemented on statutory, advisory or voluntary basis; economic instruments (i.e. emission charges, product charges, deposit schemes etc. which fall under categories taxes, subsidies and tradable permits); regulatory controls The main parameters under which the best options should be chosen are: effectiveness, practicability, economic impact and monitorability. If marketing restrictions are suggested, a detailed analysis of advantages and drawbacks has to be submitted as well as an analysis of the availability of the substitute. Reference to substitution: Substitution is one option among others for a risk reduction strategy. In the context of this document which is addressed to members of authorities, substitution is indirectly mentioned as a measure in form of market restrictions under Directive 76/769/EEC. The effectiveness and implementation of these measures in the enterprises as a part of their chemical management is only discussed on a general basis. Examples: A procedure is given with a fictive chemical to illustrate how to proceed. 17 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX II: STANDARDISED SHORT DESCRIPTION OF GUIDANCE DOCUMENTS FINAL REPORT The Technical Rule for Hazardous Substances Nr. 440 (TRGS 440) Determination and assessment of chemical risks at work places: determination of dangerous substances and methods for the assessment of substitutes Developed by: Committee of Hazardous Substances (AGS) (D) (latest version: March 2001) URL: : http://www.baua.de/prax Addressee: All stakeholders dealing with chemical management and substitution, mainly enterprises Context of guide: Public information, Technical Rule acc. to § 16 Dangerous Substances Act Purpose / aim: To give a general frame to administrations and enterprises for the selection and substitution process of chemicals Methodology: The AGS developed a legal frame to determine the risk of the work place chemicals, to register them and to look systematically for substitutes. Many practical hints are given how to determine dangerous substances or processes with probable emissions of such substances. The TRGS defines, that and how all dangerous substances have to be registered in a catalogue. The register includes data of the dangerous substances as: name, classified hazard, used amount, and work areas in which the substance is used. The TRGS gives also many hints, where and how to look systematically for substitutes. The assessment whether a substitute is really less dangerous than the currently used chemical, can be made with different methods. The “Column Model” (see G 4) is recommended. Further practical hints are given in the annexes. Annex 2 explains how to use the different assessment models, Annex 3 presents a model how to assess the overall reasonability of a substitution including detailed economic considerations. Reference to substitution: This document can be seen as a guide for all users of chemicals, which are legally obliged to check, whether a substitution is possible. Examples: Many examples given Nr.: G 3 18 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX II: STANDARDISED SHORT DESCRIPTION OF GUIDANCE DOCUMENTS FINAL REPORT The Column Model - a help tool for risk assessment of chemicals and options for substitutes (acc. to § 16 Dangerous Substances Act and to TRGS 440, see G4) Developed by: BIA (Institute for Occupational Safety) of the German Federation of Institutions for Statutory Accident Insurance and Prevention, published June 2001 (four pages folder and Internet) URL: http://www.hvbg.de/d/bia/pra/modell/spalte.htm Addressee: All stakeholders dealing with chemical management and substitution Context of guide: Public information, the methodology is one of the recommended models in the German legislation (TRGS 440) Purpose / aim: Give an easy support tool for the selection and substitution process of chemicals to administration and enterprises Methodology: The BIA developed a ranking scheme according to classification rules in Directives 1999/45/EC and 67/548/EEC. It is based on R-phrases. The user is requested to fill in the R-phrases resp. Information about the physicochemical properties and the applied technology. Depending on this information and the R-phrases, the user gets immediate advice. For each category an assessment in form of a priority it is given from “very high risk” to “negligible risk”. Columns Column 1 Column 2 Column 3 Column 4 Column 5 Column 6 Acute health Chronic EnvironFire and Liberation Risks by risk health risk mental risk explosion properties technology very high risk R 26, 27, 28, Carc. Cat. 1, R 2, 3,12, gas, liquids with open, N a vapour 32 K1, Carc. Cat. R 50, 51, 53, 17 skin contact, 2, K2; R 45, pressure > 250 large amounts 54, 55, 56, hPa, dust, 49; Mut. Cat. 57, 58, 59 1, M1, Mut. aerosol WGK 3 Cat. 2, R 46 R 11, 15, high risk R 23, 24, 25, Repr. Cat. 1, liquids with a Re1, Rf1, R 7, 8 , 9 35, 29, 31, vapour pressure R 43, Sh, Repr. Cat. 2, R 1, 4, 5, 6, 50...250 hPa 7, 14, 16, R4 2, Sa Re2, Rf2, R60, 61, Carc. Cat. 18, 19, 30, 44 3, K3, R 40 Mut. Cat. 3, M3, R 40 Medium risk R 20, 21, 22, Repr. Cat. 3, R 52, 53, 59 R 10 liquids with a closed with WGK 2 FP 21... vapour pressure possibilities of 64, R 34 (ph Re3, Rf3, 10...50 hPa dependant) R 62, 63 55°C exposure R 41 low risk R 36, 37, 38, WGK 1 FP 55 .. liquids with a 65, 66, 67 100°C vapour pressure 2.10 hPa completely Negligible risk NWG FP liquids with a (WGK 0) > 100°C vapour pressure close < 2 hPa A comparison may only be made column-wise never line-wise. The information should be taken from the MSDS. The meanings of these symbols are related to the nature of the special risks attaching to dangerous substances Reference to substitution: This document can be seen as a guide for all users of chemicals who have to check whether a substitution is possible. Examples: No examples given Nr.: G 4 19 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX II: STANDARDISED SHORT DESCRIPTION OF GUIDANCE DOCUMENTS FINAL REPORT Draft Guidance Document on Substitution of Hazardous Chemical Substances – Adapted to Industrial Users of Chemical Substances – Presented by Sweden. OSPAR Convention for the Protection of the Marine Environment of the North-East Atlantic, Meeting of the OSPAR Commission. Valencia: 25 - 29 June 2001 Document-Nr.: OSPAR 01/4/15-E. Developed by: Kemi (Sweden) Addressee: This guide is primarily written for industrial users and manufacturers of chemical substances / products. Context of guide: The proposal is a guidance for manufacturers / professional users of chemicals how to check their product / process ingredients for hazardous properties and how to implement hazard reduction strategies. Protection of workers health and environment are indirectly addressed. The document is a proposal of the Swedish government how they want to enforce the substitution in the OSPAR process. Purpose / aim: The aim of the process is to initiate a substitution or risk reduction at enterprise level. Substitution is addressed with priority when compared to exposure reduction. Methodology: General guidance how to proceed towards substitution which is based on the following main steps: 1) Starting situation: Realistic starting points for substitution efforts at the company are outlined, e.g. when new investments for production facilities are planned or the company wants to invest anyway in process or new product. 2) Identification of hazardous substances used in the company / identification of hazardous properties; advice for this procedure is given in Annex I of the document 3) Identify use pattern (exposure, emission) 4) Identify alternatives 5) Evaluate potential concern for substitutes 6) If substitution of the substance of concern is not possible, then exposure should be reduced 7) The final step of decision making is an assessment of economical versus environmental benefits; the analysis methodology proposed relies mainly on the concept of risk-benefit analysis, acknowledging parameters for benefit analysis like e.g. cost savings due to reduced waste discharge costs, less illness of staff etc. but also soft factors like the reputation of the enterprise in the public. Reference to substitution: The report is an attempt to implement substitution at the enterprise level. The guide suggests an evaluation of hazards and the possible measures for enterprises on a voluntary basis. Substitution is addressed directly. It should become part of their management controlling functions. The reason for this might come from the context of marine protection, because the Esbjerg / Sintra goal of zero concentration and emission in marine environment could hardly be reached by measures based on emission control alone. Examples: In ANNEX II of the document 3 examples for substitution at enterprises from Sweden are presented in short form: i) ABB, who produce machines for industrial demands. Introduction of solvent free paints and elimination of Cr VI from rinsing solutions in machinery production of ABB, ii) Exact Spring (produce metal springs) phased out solvents for cleaning by keeping the goods clean in the initial state. This could be done by using packaging paper containing copra acid (electric element instead of hazardous anti corrosion oil). iii) Bahco Group (produce metal saw blades) introduced a new hardening technique based on vacuum heat treating instead of using an metal-salt bath. The examples are illustrative. The special technical / legislative circumstances are not described in detail. The examples were collected by a questionaire in a written form. Nr.: G 5 20 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX II: STANDARDISED SHORT DESCRIPTION OF GUIDANCE DOCUMENTS FINAL REPORT COSHH ESSENTIALS Easy steps to control chemicals Developed by: Health and Safety Executive (HSE) (UK). A working group of the HSE, supported by the employers Federation (CBI) and the Trade Union (TUC) developed this guide (latest version: 2001) URL: : http://www.hse.gov.uk Addressee: Enterprises dealing with chemicals Context of guide: Public information according to COSHH (Control of substances Hazardous to Health Regulations) Purpose / aim: To guide enterprises to identify hazardous substances and find the best control measures. Methodology: The guide is made up as a user friendly loose-leaf binder. It consist of three major parts: - step by step guide to identify the hazards and the right controls - index of situations of possible chemical hazards - control guidance sheets. The guide is targeted to enterprises. It should help them, to meet the legal duties and to get an overview about possible risk reduction measures. The index of risk situations includes working processes with high risk of exposure to chemicals and hazardous substances. These situations are e.g. dust, extraction, transfer, mixing, sieving, coating, dipping, pelletising etc. The examples include three types of technical emission control measures: general ventilation (e.g. storage ventilation) engineering control (e.g. mixing liquids, sieving, spray painting) containment (e.g. pumping of a liquid instead of simple pouring). Substitution as a strategy to reduce hazards, is covered in the general guide (Step 5A “Assess other Chemicals and Tasks”), but not in the examples. Reference to substitution: This document is a very user-friendly guide for all users of chemicals, which are obliged to check and control chemical hazards. The focus is on practical measures for emission control. Examples: Circa 50 examples given in the form of “Control Guidance Sheets”. Nr.: G 6 21 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX II: STANDARDISED SHORT DESCRIPTION OF GUIDANCE DOCUMENTS FINAL REPORT Dangerous Substances Information System for the Construction Industry GISBAU - Gefahrstoff-Informationssystem der Berufsgenossenschaften der Bauwirtschaft (“Hazardous materials information system for the construction sector””), see at: http://www.gisbau.de/ Developed by: Federation of Institutions for Statutory Accident Insurance and Prevention in the Construction Industry, since 1989 continuously revised, available in German and English as database on CD Addressee: Construction industry, all types of representatives and workers Context of guide: Information to an area with a large number of SME’s and low enforcement possibilities Purpose / aim: Support of handling and management of chemicals for the SME in the construction industry. Methodology: GISBAU is an information system for employers, workers, workers representatives, physicians and safety representatives in the building sector. It is composed of leaflets about chemical products, typically used in the construction industry. It is delivered as a software, which allows to retrieve information according to the type of work, the type of employee, the product, the product group, the substance or the substance group. The software is able to build the obligatory hazardous materials register according to the German Dangerous Substance Ordinance. The information concerns: - the name of the products, - the toxicological class - limit values - the health effects - the precautions - substitutes etc. GISBAU is not a tool for environmental impact assessment, it is a guide how to protect workers against the effects of building chemicals. GISBAU covers 18 areas, from floor laying to painting and approximately 3.000 products. Reference to Substitution: GISBAU developed codes – GISCODES - to easily assess the risks connected with the use of a substance or preparation. Substitution is promoted by defining classes of risks. Examples: GISBAU recommends substituion via Product Codes. The product with the highest code should be replaced by products with lower codes. Product Codes for Concrete Release Agents BTM 10 Concrete Release Agents, not classified and labelled BTM 15 Concrete Release Agents, not classified and labelled, free of aromates BTM 20 Concrete Release Agents, highly liquid BTM 30 Concrete Release Agents, free of aromates BTM 40 Concrete Release Agents, low content of aromates BTM 50 Concrete Release Agents, flammable, free of aromates BTM 60 Concrete Release Agents, flammable, low content of aromates Nr.: G 7 22 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX II: STANDARDISED SHORT DESCRIPTION OF GUIDANCE DOCUMENTS FINAL REPORT The complete idiot’s guide to CHIP CHIP = Chemicals Hazard Information and Packaging for Supply) Developed by: UK Health and Safety Executive, INDG181(rev1) 1999 (published 1994, regularly renewed). In an adopted form published by the German BAUA as “Gefahrstoffe: Kennzeichnung - kein Problem”, last version printed in May 2000 Addressee: Suppliers of chemicals Context of guide: Information material from a national authority Purpose / aim: The aim is to enhance compliance and awareness (Step 2 of the guidance) Methodology: This guide is made as easy as possible, to help suppliers of chemicals to comply with the existing chemicals regulation. The basic rules of trading chemicals are explained (providing of hazard information, MSDS, labelling etc.). Reference to Substitution: This document contributes indirectly to substitution because it shows to suppliers of chemicals that business risks and the legal requirements are much higher if dangerous chemicals are used. Examples: Formal procedure and labelling examples Nr.: G 8 23 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX II: STANDARDISED SHORT DESCRIPTION OF GUIDANCE DOCUMENTS FINAL REPORT Name: Guidance Manual for Formulators and Other Professional Users of Chemicals Developed by: German UBA (Ökopol GmbH), UBA-Texte 89/99 (ISSN 0722-186X) Addressee: Formulators (professional users of chemicals) Context of guide: Based on a substitution approach the guide was commissioned by the UBA in the context of protection of the marine environment under the “generation goal” of the INK (Esbjerg) and OSPAR Statement (Sintra) and as a continuos follow up of activities concerning discharges into water under the EU Water Framework Directive. Purpose / Aim: The aim of this report is to provide formulators with information how to proceed for checking their raw products for substances which are hazardous to the marine environment. The scope of the guidance goes beyond present legislation and suggests to implement the precautionary principle by taking into account also prioritisation lists of voluntary initiatives and lists of other countries (i.e. instruments which are not legally binding at present). Methodology: The first chapters contain a status analysis of national and international instruments and legislation and their concepts regarding chemicals in the marine and occupational environment. Based on this status a guidance is proposed how to assess the identified chemicals used during production. The main steps proposed are: Collection of substance data: Information on intrinsic substance properties is suggested to be collected by also referring to international substance lists and lists of voluntary initiatives and classifications according to chemicals legislation. For each criteria a level of risk is assigned on a scale from I to IV according to specific threshold limit values (e. g. bioconcentration factor> 1000 IV) Exposure analysis: Additional to the characterisation of properties of substances also their exposure is estimated and assessed according to qualitative parameters (Characterisation of Potential Releases in own company, during use and upon disposal (e.g. open to environment, closed system etc). The qualitative parameters are assigned to levels on a scale from I to IV (e.g. exposure criteria: open to environment IV). Risk Assessment: All information is aggregated in one scheme to enable a straight forward illustration of the multi criteria problem. At the end of the process a prioritisation is envisaged, e.g. a certain combination of risk parameters results in „substance is of concern“, as for example low degradability and use open to environment. Reference to Substitution: This method serves as a guidance for enterprises how to assess their hazardous substances with respect to protection of the marine environment. The concrete measure to be undertaken when a substance is of concern is not outlined. Substitution is seen here as an integrated instrument of the enterprise´s management system. As a result the enterprise will obtain a status analysis of the substances and their harm to the environment and decide about measures for risk reductions if necessary. Examples: Fictive examples are given to illustrate the last step of substance prioritising. Nr.: G 9 24 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT ANNEX III STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS Annex III contains the standardised descriptions of assessment tools as they are presented and discussed in section 2.4 of the main report. For a theoretical background, the first four assessment tools presented (A1 – A4) describe some principal options of how decisions can be taken in multi-criteria problems in general. The subsequent tools A5 – A10 give examples from both government authorities and private enterprises how these principles can be applied in the assessment of substitution options and other risk reduction measures. Three examples are given for Eco-Labels (E1 – E3) whose criteria can have a dual function of guiding market actors (see tool G10 in section 2.3), while often they are actually used by companies as an internal assessment tool of their products’ environmental performance. The standardised descriptions should be read in conjunction with the main report where the procedures and methods applied are presented with a more detailed analysis of their effect on substitution. 25 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT Name: Dominance Analysis Tema Nord, Miljö Institute, Council of Nordic Ministers (1997) Purpose / Aim: Decision aid method for multi-criteria problems Methodology: An alternative is dominated if there is another alternative which excels it in one or more criteria and equals it in the remaining criteria. The first alternative is compared with the second and if one is dominated by the other, the dominated is discarded. The a follow up comparison with the third follows. At the end, the analyst obtains a set of non-dominated alternatives. Applicability for substitution: This tool can be used as a first step after determining the criteria. The analyst has to justify his choice for the criteria to make this process a transparent one. Dominance analysis can be applied to reduce the number of alternatives. Advantages: The method is simple and easy to use. The methodology does not require any assumptions or transformations of criteria values. The terminology used is easily understood. Disadvantages: Some dominated alternatives, which get discarded, may actually be overall more suitable than some of the non-dominated alternatives. Nr.: A 2 Name: Positional Analysis Tema Nord, Miljö Institute, Council of Nordic Ministers (1997) Purpose / Aim: Decision aid method for multi-criteria problems Methodology: With positional analysis for each criterion a direction is defined (minimisation or maximisation). The values for each criterion are therefore subject to an assessment and the full set of criteria is presented. From this criteria considered the most important is identified and the decision made upon this single criteria. Applicability for substitution: This tool should be used always as a first step after determining the criteria. The analyst has to justify his choice for the criteria to make this process a transparent one. Advantages: The method is simple and easy to use. The methodology does not require any assumptions or transformations of criteria values. The terminology used is easily understood. Disadvantages: The procedure is not compensatory, as all criteria not assigned as important are neglected for the final decision. The decision is therefore only based on a small subset of all collected data. Nr.: A 3 Name: Elimination by aspects (EBA) Procedure Tema Nord, Miljö Institute, Council of Nordic Ministers (1997) Purpose / Aim: Decision aid method for multi-criteria problems Methodology: In the Elimination by aspects (EBA) procedure the decision maker is assumed to have minimum/maximum cut-off levels for each criterion. A criterion is selected, and all alternatives not meeting the cut-off values are eliminated. This procedure is continued for other criteria until all but one single alternative are eliminated. The sequence of applying the different criteria is a crucial point as it has a major influence on the result (TemaNord 97) Applicability for substitution: For a transparent decision the ranking order of the criteria have to be explicitly shown. This method is suitable, if some criteria are dominating. In case of substitution it might be a suitable method in a first step but discrimination of specific parameters is high. Advantages: The method is simple and easy to use. It enables a presentation of the decision process and does not need any computational help. Disadvantages: The procedure is not compensatory, as some alternatives might be eliminated in an early step although these might be the most appropriate one. Nr.: A 1 26 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT Name: Risk Benefit analysis Tema Nord, Miljö Institute, Council of Nordic Ministers (1997) Methodology: Risk benefit analysis is based on monetary values. It can be started from a qualitative risk-benefit analysis where risks and benefits are described but not quantified and valued. This may be followed by a quantitative analysis of the benefit, which means that the risk can be assigned to a monetary benefit value. It has to be decided hereafter if the risk is significant enough to justify this monetary value. If also the risk can be expressed in monetary terms, e.g. by valuing risks like death or illness in prices, the method is a real cost benefit analysis which is an aggregative method. Valuing the risk is a difficult task as it relies on statistics or on the willingness-to-pay method, i.e. how much would you pay to fly with a safer air-line? The economic impact with respect to product and production costs, which are more easily to obtain, can be compared with this value and conclusions can be drawn. Applicability for substitution: Risk benefit analysis can be applied on different levels, e.g. in the evaluation of risk reduction strategies within the EU. Risk is here seen as the general statistical risk for the public or individuals caused by the hazardous substance. Risk benefit analysis was proposed by the UK for the evaluation of risk reduction for existing substances in 1995 and the report is discussed in detail below and is referred to in the Technical Guidance Document for Risk Reduction Strategies as one (among others) appropriate assessment tool for choice making. For enterprises, the benefit evaluation is very common. Risks can be determined by illness of workers, probability of catastrophic events, possible trials against the company, height of insurance fees etc. Advantages: For enterprises, the benefit evaluation is very common so that this instrument may have a high level of acceptance on this level. It is possible to evaluate the qualitative data, i.e. the procedures do not require that the risk or cost related criteria information be in numerical monetary form, and no preference information is needed (TemaNord 97). Disadvantages: The procedure does not solve the trade-off between costs and benefits. This is a great disadvantage because there is evidence that decision makers tend to “overweight” criteria that are directly measured with money (TemaNord 97). Nr.: A 4b Name: Risk-Benefit analysis of existing substances Nr.: A 4 Developed by: UK Government, Industry working group (1995) Addressee: MS Rapporteurs who work on risk management for the EU Context of guide: Under Regulation 793/93/EEC on existing substances the rapporteur is advised to suggest a risk reduction strategy if a substance is of concern. If the rapporteur suggests to implement market restrictions, he must additionally submit a detailed analysis of the advantages and drawbacks of this proposed measure. This report describes the methodology of risk benefit analysis for this purpose. Purpose / Aim: The aim of this report is to establish a general method with which the detailed analysis of advantages and drawbacks of a proposed market restriction measure can be evaluated. Methodology: See A3 Reference to substitution: Market restrictions can be one policy instrument to initiate a substitution. Therefore risk benefit analysis can be seen as a tool to quantify the (economic) impact of a proposed substitution in monetary terms. Example: After introduction of TBT-free paints, the price of paint is expected to increase by 0.66 pound per t. This leads to an increase of 10 mill. pounds annual cost for UK. A decision to ban TBT therefore implies a judgement that the value of environmental damage which such a ban would avoid would be in excess of these sums. A quantification of risk / environmental harm (cost-benefit analysis) is not implemented in the examples shown in the text. 27 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT Name: The use of decision aid methods in the assessment of risk reduction measures in the control of chemicals. Developed by: Tema Nord, Miljö Institute, Council of Nordic Ministers (1997) Addressee: MS Rapporteurs who work for EU Chemical Risk Assessment Context of guide: In the European Union assessment of risk reduction measures are necessary when, for example, listing of certain chemicals under marketing restriction Directive 76/769/EEC are under consideration or when a rapporteur of a MS suggests marketing and use restrictions under risk assessment for existing chemicals under Regulation 793/93/EEC. This report reviews the existing methods how to select the best alternative which are aggregative or disaggregative. A detailed discussion about the various nature of the methods is given in the introduction. The report shortly describes the advantages and drawbacks of the methods and what kind of result can be achieved. An overall procedure for decision making is proposed and illustrated in form of a diagram. Introduction to the different kinds of decision aiding tools which can be used in the context of chemical risk reduction is given. Purpose / aim: The aim of this report is to provide the rapporteur with information about existing decision aid methods. Methodology: The various methods are shortly described and discussed along the parameters transparency and consistency of decision. An overall procedure for decision making is proposed. The concept proposes to use the different tools in an order of complexity, i.e. starting with qualitative simple tools and applying more complex (quantitative) tools just in case that a consistent decision could not be achieved. The proposed steps are the following: Collect data and use a procedure with no preference or criteria level information (qualitative, no knockout. criteria); If this procedure does not lead to a consistent decision, use procedure with criteria level (quantitative in each criteria but disaggretative) If this procedure does not lead to a consistent decision, use ordinal preference information (i.e. ranking of the different criteria in order of importance) If this procedure does not lead to a consistent decision, use aggregative method Complexity of procedure and time consumption is increasing from step one to four. Reference to substitution: This report gives a broad introduction in decision aid methods, but substitution is not addressed directly. As in other cases substitution is one option beside emission control measures or other general risk reduction measures. The stepwise process for the application of the different models propose an order for using assessment tools which help at the state of choice making in the substitution procedure. Examples: In the appendix several examples of the various decision aid methods are illustrated for fictive chemicals to illustrate the proposed procedure. In all cases one option among emission control and others where market restrictions. In none of the examples different substitution possibilities were compared with each other. Nr.: A 5 28 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT Guidelines on Risk Management of the Hazardous Substances Committee concerning decisions with far reaching consequences Developed by: German Hazardous Substances Committee, published 1998 URL: http://www.baua.de/prax/ags/ags_leitfaden_rm.pdf Addressee: Stakeholders dealing with risk management, the Committee’s various sub-committees and working groups Context of guide: Discussions inside the Committee Purpose / aim: Background material, to standardize the risk management process and make it transparent. This document can be seen as a guide for major decision makers about substitution of chemicals at work places. Methodology: The Hazardous Substances Committee is responsible for all practical and administrative regulations concerning chemicals at the workplaces. It consists of members from all concerned groups. authorities (OSH, Environment, Health), employers, the producers and sellers of chemicals, the trade unions and the consumers. Its decisions can widely influence the use of chemicals. The committee felt the need to establish a common risk assessment and management strategy and to improve public transparency of its decisions. Especially the decisions to ban or restrict the use of chemicals and the proposal for substitutes have been lengthy and controversial and are targeted with this document. The four steps how to proceed for a risk management process are : 1. Creation of a project group (internal step) 2. Risk description: Quantitative and qualitative toxicological assessment including real exposure data and controversial opinions 3. Options for action and their potential for risk reduction 4. Socio-economic effects of the selected actions. Under step 2 “Risk description” the following criteria are used: Nr.: A 6 Basis for risk assessment Decision making aspects Current situation Risks absolute number of cases Costs Five general criteria. Benefits effects on the size of the staff Implementation guarantee competitive advantage through innovation availability of the substitute scenario 1 scenario 2 29 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT The overall number risk assessment is finally done with five general criteria: Overall assessment in the decision making process Assessment category Current situat. scenario 1 Risk acceptability for employees appropriateness distributive justice idea of precaution functional equivalence scenario 2 comments The proposed procedure is an integrated concept of risk assessment with parameters such as safety and health, economy, social aspects and technology. The environmental impact is integrated as far as it is important in the risk description. Examples: The whole assessment procedure is extensively demonstrated in one practical example “The use of ceramic fibre products” (Annex of 50 pages, only available in German). 30 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT Nr.: A 7 Name: Ökoeffizienzanalyse [Eco-efficiency analysis] Developed by: BASF Ludwigshafen (www.basf.de/de/corporate/sustainability/oekoeffizienz/) Purpose / Aim / Result : Staff in research and development and management who have to decide about different process technologies / production routes / product designs etc. need a tool to assess different options in order to find the most sustainable / eco-efficient option. For this purpose the ecoefficiency analysis helps to illustrate the impact of these options with respect to environment and economy. The result of the environmental analysis is the ecological fingerprint constructed out of a spider diagram with the 5 parameters emission, toxicity, risk potential, energy and raw material consumption. On the second stage the environmental parameters are aggregated to the indicator environmental performance and are combined with the parameter overall cost in a portfolio matrix. If this is done for two or more strategic options the most sustainable routes can be obtained (the least expensive with the lowest environmental drawback). The tool is on the one hand used for strategic decisions within the BASF-company and is on the other hand used to evaluate advantages / disadvantages of different products for the customer depending on the analysis boarders and standard for comparison applied. From the profile of advantages for the customer also conclusions about the expected market performance of a newly developed product can be drawn. The eco-efficiency states itself to be an independent consultant for customers of BASF. Additionally, the impact of proposed research targets on the overall performance can be evaluated by applying the method to the proposed product with changed characteristic. Methodology: The eco efficiency analysis tries to evaluate indicators for sustainability (SD). From the five indicators emission, toxicity, risk potential, energy and raw material consumption the parameter environmental drawback is derived with a set of statistical weights. Each indicator is derived from a weighted set of sub-indicators (e.g. emission is derived from air-/ water- and waste emission. Sub indicators of air emission are greenhouse potential, ozone depletion, ozone building potential and potential for acidification of the ground in accordance to norms of LCA). In the various levels the indicators are normalised on a scale from 0 to 1. Weighting among the different indicators is done by a relevance factor and a public factor. Whereas the second one describes the importance of the topic in the public, the first one describes the significance of the parameter when compared to the overall value in Germany (e.g. SO2 emission per service unit compared to SO2 emission in Germany). Therefore relevance factors are individually derived for each analysis and high burden are strongly weighed. Within each category different normalisation procedures are used, e.g. the resource consumption is normalised by applying the resource availability given in years until depletion. At the beginning of each analysis the system boundaries have to be well defined to have a decent standard for comparison, e.g. service unit. In the next step data are collected and material flows evaluated. Each data set is thereafter assigned to an effect category which are aggregated with the help of the relevance and public values. The result is the ecological fingerprint out of 5 parameters, which is further aggregated to the environmental factor. Examples : Short illustrative examples are: evaluation of the most sustainable strategy to produce Indigo. More examples on the internet: paints for furniture based on different curing mechanisms (i.e. UV, powder, PUR), recycling of car fuel tanks etc. 31 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT Nr.: A 8 Name: Eco-Check (product excellence) Developed by: Bayer, Leverkusen (www.sd.bayer.com/produkte/bayer_oeko_check_en.html) Purpose / Aim / Result : Staff in research and development and management who have to decide about different process technologies / production routes / product designs etc. need a tool to assess different options in order to find the most sustainable / eco efficient option. The result is a spider diagram which includes the indicators economy, health, ecology, eco-analysis, technology, public value. The overall diagram is called the “excellence diamond” due to its hexaedric form. Methodology: The eco check tries to evaluate indicators for sustainability (SD). The above mentioned six indicators are derived from sub-parameters, e.g. health is derived from general toxicity, risk of cancer, risk to unborn life and mutagenicity. All these parameters refer to the product use phase. Additionally the exposure caused by the product is assessed and weighted equally with the intrinsic parameters. The other sub-parameters will be listed. In the various levels the indicators are described on the scale of very high / high / medium / small / very small risk potential. Examples : Comment: The Eco-Check of Bayer is based on a rather general level and implements soft factors like public value. Also the economic indicator is not just evaluated on the basis of costs but also on the basis of market perspectives. Thus this instrument is rather helpful for strategic decisions of the higher management than for decisions which directly refer to the process / production. Nr.: A 9 Name: Pre-screening Scheme for Offshore Chemicals by OSPAR Developed by: Sub group SEBA (Sea Based Activities) of OSPAR1 (Oslo and Paris Commission). Addressee: Users of chemical in the off-shore plants at sea, contracting parties (states) of OSPAR co-operation. Context of guide: In June 2000 the reviewed “Harmonized Mandatory Control System for the Use and Discharge of Offshore Chemicals” was decided by OSPAR in OSPAR Decision 2000/2 (Predecessor PARCOM Decision 96/3). Part of this decision is a pre-screening scheme on a qualitative basis applicable for all offshore chemicals. The pre-screening scheme is laid down in more detail and with defined threshold values in OSPAR Recommendation 2000/4 which is not binding for the contracting parties. Similarly, a detailed proposal for data collection format in order to provide the authority with data and information about chemicals, is part of a Recommendation 2000/5 on a Harmonised Offshore Chemical Notification Format (HOCNF). Purpose / aim: The decision and its subsequent recommendations aim at application of the management mechanism (incl. the pre-screening) in order to “actively promote the continued shift towards the use of less hazardous substances (or preferably non-hazardous substances) and, as a result, the reduction of the overall environmental impact resulting from the use and discharge of offshore chemicals.” Methodology: The pre-screening system as laid down in OSPAR Decision 2000/2 and Recommendation 2000/4 for offshore chemicals is based on the following steps: information / data-sets on all chemicals used or discharged from offshore installations the identification of substances which should be replaced by environmentally less harmful substances, the prioritisation of short-term non-replaceable substances with regard to the necessary efforts for developing new products, Oslo and Paris Commission, that coordinates the co-operation of the contracting parties under the OSPAR Convention for the protection of the North –East-Altlantic with regard to pollution by ships, aeroplanes and from land based sources. Predecessor until 1996 was the Paris Commission (PARCOM). 1 32 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT the risk-related ranking of substances which are not required to be substituted in the short-term, but which should remain under constant supervision. In step (a) the substance inventory for offshore chemicals is addressed. The data requirements are laid down in the OSPAR Recommendation 2000/5 on the notification system HOCNF. The HOCNF requires data on trade names, use, discharge, proposed fate and composition of the preparations / articles in use by a company. Substance data are necessary for all chemicals occurring in the product. These are the data usually given in the SDS plus more detailed tests on biodegradability, tainting, adsorption tests (Koc-value), aquatic toxicity and mammalian toxicity test are required some of them on voluntary basis. The data evaluated by the contractor’s authorities have to be reported to the OSPAR Commission. In step (b) the following offshore chemicals should be considered for substitution if a less hazardous substance is available2: substances listed in Annex II of the OSPAR strategy (hazardous substance black list), substances with equivalent risks as in (1), inorganic substances with high toxicity (LC50 or EC50 < 1mg/l), persistent substances (biodegradation less than 20% during 28 days), substances which meet two of the following criteria: - not readily degradable (biodegradation < 70% during 28 days), - high bioaccumulation potential (log Pow 3 or BCF > 100), - high toxicity (LC50 < 10mg/l or EC50 < 10mg/l). In step (c) all substances which meet these criteria but no substitute is currently available are addressed. For these chemicals a prioritisation should be done in order to develop appropriate alternatives starting with the chemicals with highest priority. For these chemicals a temporary permission can be given by the authority. More detailed information on the relevant methods for testing are given in the notification format scheme (HOCNF) and a guideline for completing these3. In step (d) for all substances not meeting the above criteria a ranking according to their PEC/PNEC value must be done in order to give an indication of the relative risks of these offshore chemicals. This ranking list shall be subject to regular review. Substances which are on the OSPAR positive “PLONOR”-list have not to be considered for ranking. Reference to substitution: The pre-screening scheme is suitable for screening substances which need to be substituted. The system is a sector specific guidance for authorities and the operators of offshore appliances which substances should be substituted. Therefore this system gives discrete answers to the substitution measures. Also an incentive for using chemicals with low hazardous properties is given by excluding positively listed chemicals from the ranking procedure. In this context the definition of “availability” for substitution is mentioned with reference to the definition of availability in the definition of Best Available Techniques (BAT) in the OSPAR convention 1992 and Best Environmental Practice (BEP) in the OSPAR Convention 1992 related to substitution of products. In the Appendix 1 the term BAT is described as “state of the art” of processes, facilities or of methods of operation. The considerations outlined for assessment of BAT in this document refer to comparable processes which have recently been successfully tried out, scientific knowledge and understanding, economic feasibility, time limits in new and existing plants and nature and volume of discharge. In this context the meaning of availability, which is also discussed in the chapters on legislative instruments, is sharpened by giving a frame for a definition. Examples No examples are given in this context. 2 „Available“ in the context of substitution must be understood in the same sense as in the definition of Best Available Techniques in the OSPAR Convention 1992.....“ 3 OSPAR Guidelines for Completing the Harmonised Offshore Chemicals Notification Format (HOCNF) 33 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT Nr.: A 10 Name: Quick Scan Developed by: RIZA 98.005 / 98.006 for Ministry of Housing, Spatial Planning and Environment, NL Addressee: This assessment tool is on the policy level a help to fill gaps in data knowledge and to be able to decide about measure for risk reduction. At the same time the industrial community is provided with a tool to enable the assessment on the practical level. Context of guide: The screening method for hazardous substances was accepted by the Council of Ministers in December 2001 (SOMS 01b). The methodology is part of the Dutch Strategy on Management of Substances (SOMS), in which national regulations for chemicals used and sold in the Netherlands and recommendations for EU chemical policy are developed (SOMS 01). The Quick Scan must have been completed by industry in the Netherlands before the end of 2002 leading to validated substance profiles by the end of 2004. Purpose / aim: This screening method, the so called “Quick Scan”, enables a pragmatic answer to the question how to assess the risk of chemicals used and sold in the Netherlands. The purpose is to get a fast answer on hazardous properties of substances in use and to draw conclusions for the measures to be undertaken with respect to risk reduction measures. Furthermore, the Dutch Council of Ministers also proposes to implement this system in the new Chemicals policy in the EU as a prescanning method for the REACH-system (Registration, Evaluation and Authorisation of Chemicals) propose in the white book on Chemicals Policy. Methodology: The Methodology is based on a 4 step scheme: Assigning hazardous properties of the substance In the proposal for the Quick Scan certain criteria determine the limits of hazard categories for individual properties, which are P, B, T, He, C, M, R, Ho (persistence, bioaccumulation, toxicity, health damage, carcinogenicity, mutagenicity, reproductive toxicity, hormonal disruption). The information can be of 2 types, from international standardised sources (hard data) or information that provide an indication of the hazardous properties of substances from literature, accepted models and expert judgement (soft data). Fig. 2.4.4.: Schematic Scheme of the “Quick Scan” for substances proposed in the Netherlands. Classification of properties in categories of concern Criteria determining the limits of the hazard categories for the individual properties P, B, T, He, C, M, R, Ho that characterise a substance. The methodology is mainly based on criteria laid down in international agreements, i.e. the criteria for very high concern (vhc) comply with PBT and vPvB (‘very persistent, very bioaccumulating’) criteria of the EU and with the POP convention, for high concern (hc) criteria of the OSPAR strategy on hazardous substances (DYNAMEC) are applied and for criteria for concern (c) the current EU classification and labelling criteria for certain risk phrases such 34 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT as “very toxic for aquatic organisms” are used. For criteria He, C, M, R, and Ho certain threshold values enable a direct link to a category of concern, whereas P, B and T are assigned to a hazard class 1 to 4 according to threshold values in their individual categories, e.g. P3, B2, T4, and certain combinations of these give a result with respect to level of concern (see Fig. 2.4.5.). Fig. 2.4.5.: Assignment of PBT criteria to levels of concern Lack of data is handled with respect to the precautionary principle as very high concern and, as such, will be subject to restrictive measures if no data are available before the deadline of 2002. Other parameters like use pattern, risk of exposure or economic impact are not considered at this point. Classification of substances in categories of (in-principle) measures From the results of the concern categories certain conclusions for measures are drawn by considering different use categories (see Fig. 2.4.6.). Fig. 2.4.6.: Assignment of “in principle” measures on the basis of level of concern The matrix in Fig. 2.4.6. follows the principle, that vhc-substances must no longer be used. Thus, this group of substances will be banned from open professional use and in consumer products. A ban is also proposed for site limited use for vPvB substances complying with the POP convention and unless stringent conditions for preventing hazards and exposure are satisfied. High Concern substances are not permitted for consumer purposes and in open professional use, unless certain preconditions are satisfied. “This could be a mandatory target value, to be achieved by 2010, application of ‘best-available techniques, substitution, etc.” (SOMS 01b). Substances of Concern are permitted, provided that certain limit conditions are satisfied as above. 35 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT Balancing hazard risks versus social costs and benefits Once the ‘in-principle’ measures are in place, the actual implementation of the measures can be influenced by other type of information concerning the use of a substance besides hazard information. Balancing can be (un)certain social benefits (e.g. economic gains) against costs, and the (un)certain hazards and risks for man and the environment. Also technical feasibility of risk-reducing measures, the social (ir)replaceability of substances (less hazardous alternatives available?) and the spreading of the social costs and benefits can be considered. The SOMS 01b stresses the fact, that “it is the government that, ultimately, decides the scales in balancing”. The industry can include both ‘Quick Scan’ data and any number of other considerations in the implementing measures but the balancing of measures in a social perspective is a prerogative of the government. Results of the balancing like e.g. lacking possibilities of replacement are outlined to be non-static but rather dynamic with respect to changing social factors or technical progress and are therefore subject to permanent re-evaluation. Reference to substitution: The Quick Scan of the Netherlands provides a tool for achieving results on a risk assessment of substances in a pragmatic way and gives a basis for risk reduction measures from which one of the most important is the ban i.e. substitution of a substance. Examples No examples are given in this context. 36 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT Nr.: EL 1 Examples for Environmental Label Name: Blauer Engel (Blue Angel) URL: http://www.blauer-engel.de/ englisch/navigation/body_blauer_engel.htm Developed by: German Ministry of Environment (BMU) Product groups: More than 100 different product groups including services History / Aim: 1977 created in Germany, the Blue Angel was the first environment related label worldwide. It focuses on the support of environmental and consumer requests including special functionality aspects (e. g. limitation of flow rates for water taps). Even if the Blue Angel is a national label, it is accepted and used in many other countries. Methodology: Methodology and scope of criteria differ between the various product groups. The Blue Angel does not always consider complete environmental impacts during the life cycle of a product, but highlights a main award reason which is reproduced in the writing around the label logo. Criteria are developed by an independent board (“Jury Umweltzeichen”) which consists of representatives from environmental and consumer associations, industry, trade, handcraft, labour unions, associations of local authorities, science, media, church and Federal States together with the BMU and the German UBA (federal environmental agency). The certification and awarding of products with the "Blue Angel" logo is performed by RAL (German institute for quality assurance and classification e. V.). Reference to substitution: Chemicals classified as hazardous in accordance with Council Directive 67/548/EEC are excluded from use in many product groups. The German Blue Angel often uses the classifications in the German TRGS (technical rules for hazardous substances) in addition. For products like paints and varnishes, cleaning agents, fire extinguishers, hydraulic fluids and plumb, chemical contents are considered as the main environmental aspect. Main reasons for award such as “low content of hazardous substances”, “low emissions”, “free of cadmium”, “easy biodegradable” and similar appear in writing around the label logo. 37 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT Nr.: EL 2 Examples for Environmental Label Name: Nordic Swan URL: http://www.svanen.nu/Eng/default.asp Developed by: SIS Miljömärkning AB Product groups: ca. 60 product groups including services (e. g. tourism) History / Aim: Eco-label founded in 1989 by the Nordic Council of Ministers (Denmark, Sweden, Norway, Finland, Iceland). An eco-labelling organization was set up in each country to manage the scheme. The Nordic Swan is committed to sustainable development as a general goal. Methodology: The Nordic Swan methodology is orientated after ISO 14020 and 14024 standards which define general conditions and procedures for the development of environmental labels considering the whole life cycle of a product. The eco-labelling organisation of participating countries selects product groups and lays down the final criteria. The resulting criteria documents contain information on the market and on future criteria. To obtain the label, manufacturers have to complete a detailed product fact sheet. Reference to substitution: Nordic Swan criteria in the field of harmful substances exclude or limit the presence of substances classified by the authorities in official listings in the Nordic countries. Exclusion of substances can further be based on classifications like allergenic (e. g. raw material in floorings) or class A or AB from Nordic Wood Preservation Council regulations (e. g. windows). 38 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX III: STANDARDISED SHORT DESCRIPTION OF THE ASSESSMENT TOOLS FINAL REPORT Nr.: EL 3 Examples for Environmental Label Name: European Flower URL: http://europa.eu.int/comm/environment/ecolabel/ Developed by: The European Commission Product groups: At present 17 product groups including bed mattresses, copying paper, dishwashers, detergents for dishwashers, laundry detergents, footwear, indoor paints and varnishes, refrigerators, soil improvers, textiles,tissue paper products, light bulbs and others (further products under development). History / Aim: The EU Eco-label award scheme was launched in 1992 to encourage the production and consumption of green products at a European scale. Based on the positive experience from national labels, the idea was to have one integrated that would be consistent across the whole EU. The Community Label should promote transparency and simplicity, since the same criteria apply for the same product, regardless of the Member State in which it is produced or sold. Coordination between the Flower and other national schemes, particularly in the selection of product groups and the development and revision of the criteria needs to be ensured. The implementation of recognised environmental management schemes, such as EMAS or DIN ISO 14001, have to be taken into account, when assessing application and monitoring compliance with the criteria. The European Flower follows the “cradle to grave” approach, i.e. all environmental aspects during the lifetime of a product should be taken into consideration. Methodology: The EU Eco-label award scheme was set up by the Council Regulation 880/92/EEC of 23 March 1992. A new revised Regulation entered into force in 2000 streamlining the scheme, widening the scope of the scheme to services, introducing decreased fee structures, increasing the transparency of the Scheme and improving stakeholder involvement. The EUEB (European Union Eco-labelling board), which consists of the Competent Bodies and interest groups (representatives of consumer and environment NGOs, trade unions, industry, SMEs and commerce) is the central body of the scheme. The EUEB shall carry out preparatory work to determine whether the product group under consideration falls within the scope of the Community Eco-label and the European Commission gives mandates to the EUEB to develop and periodically review the Eco-Label criteria for a particular product group. The approved criteria are adopted as a Commission Decision and published in the L series of the Official Journal. A user´s manual for each product group should help manufactures to apply for the award. Reference to substitution: Substances classified as hazardous in accordance with Council Directive 67/548/EEC are normally excluded from labelled products. Further criteria could be based on additional substance lists or properties. Chemicals could be excluded from the use in a particular product, if effects on surface water are expected. Sum parameters like BOD are used in criteria for preparations (e. g. for laundry detergents). Criteria specifically related to chemicals aim at limitation of toxic residues in raw materials (e.g. pesticides in cotton for textiles), reduction of air pollution (e.g. VOC in paints and varnishes), water pollution (e. g. AOX in tissue paper) and exclusion of the use of harmful substances (e. g. pentachloro-phenol in shoes). 39 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT ANNEX IV 10 TECHNICAL CASE STUDIES Annex IV contains the full versions of the 10 technical case studies performed during this study in which substitution cases were analysed from the perspective of the downstream user of hazardous chemicals or materials. The cases cover a wide range of substances in different products and processes, serving functionalities like cleaning operations (metal parts, facades, textiles), coating and painting (marine anti-foulings, wood preservation), fire resistance (flame retardants in printed circuit boards), lubricants and process fluids (loss lubrication, mould release agents), energy storage (rechargeable batteries) and plasticisers (phthalates in toys). The individual cases are 1 2 3 4 5 6 7 8 9 10 Metal parts cleaning Cleaning of façades Textiles cleaning in laundries Marine anti-fouling coatings Wood preservation Flame retardants in circuit boards Loss lubrication in inland water Mould release agents Rechargeable batteries Plasticisers / phthalates in toys The case studies give an insight into typical controversial issues, decision-making and associated time scales. Each case offers different possibilities of interpretation, and it is not intended to judge whether substitution is the right risk reduction measure or not in a specific case. The purpose is rather to show how alternatives have been developed and how it was eventually decided whether to substitute a hazardous substance or not. The methodology applied is explained in detail in section 2.6.1 of the main report. Short summaries of the case study findings can be found in section 2.6.2, and a presentation and discussion of the key factors identified in the case studies is given in section 2.6.3 of the main report. 40 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT 1. CASE STUDY 1: METAL PARTS CLEANING 1.1. TECHNICAL AND CHEMICAL SCOPE The cleaning of metal surfaces is an integral and unavoidable part of many production and working processes. Metal surfaces have to be cleaned not only in the metal industry, but in so divergent industries as construction, car repair, technical services or food processing. The dirts to be cleaned are residues of other materials coming into contact with the metal surface during normal production with or without intention. These materials can be processing fluids, lubricants, protective layers, particles, rust or other typical dirts and dusts from industrial processes. This study covers only the metal industry including its main sub-branches mechanical engineering, car and steel industry. We will focus on the most common and important process, the removal of processing fluids (cutting fluids, rolling oils) from metal parts. Other less common or exceptional cleaning tasks are not covered because these processes require often quite different chemicals than for the removal of process fluids, e.g. strong acids to remove rust or scale. 1.1.1. Technological principles Metal parts cleaning can be carried out in a variety of ways depending on size and material of the part to be cleaned, type of dirt etc. When designing the cleaning process, the industrial user has to consider technical factors and process options such as: • • • • • • • • properties of the parts to be cleaned (material composition, size, surface and geometry); necessary degree of cleanliness; number of cleaning steps; quantity of parts to be cleaned per hour/per day; decentralised cleaning (close to the working places) or centralised cleaning; acceptable or necessary duration of the cleaning process; the requirements from further processing (gluing, electroplating, painting or coating); application of a universal cleaning system or differentiation according to the properties of the parts. The market for cleaning equipment offers a huge variety of alternative installations. A common and very simple solution for occasional cleaning tasks is a washing table. In advanced processes with high capacity fully automatised large installations are needed to clean very fast huge quantities of metal parts. The investment required varies between 500 € for a low cost washing table and more than 10 Mio. € for large scale installations. 41 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT Besides simple immersion of parts in the cleaning process, many technological features have been developed to accelerate the process or improve its effectiveness, including • • • • agitation of the cleaning vessel, agitation of the parts, agitation of spraying nozzles; heating of the cleaning agents high pressure spraying or high pressure pumping of the cleaning agent ultrasonic agitation Additional equipment is available for drying, exhaustion, recycling, separation, waste water treatment, explosion–protection etc. All this features can be combined and adopted to the industrial user’s demands. 1.1.2. Chemical scope Cleaning agents for metal surface cleaning can be separated into two large groups, the solvent based and the water-based products. The two main technological advantages of solvent based products are the cleaning efficiency for many common cleaning tasks and the fast and complete evaporation of the cleaning agent from the metal part without residues. Meanwhile, water based products have reached a comparable cleaning efficiency while avoiding the problematic evaporation of solvents. However drying needs longer, the wastewater requires treatment and chemicals must be added periodically to the aqueous cleaner to keep it effective. Specially designed cleaning agents as semi-aqueous cleaners, high boiling petrochemicals, isoparaffines, esters, dibasic esters, lactates, glycol ethers or supercritical CO2 gain a growing market share, to fulfil special cleaning demands. These developments make the market even less transparent. Organic solvents A solvent must be capable of dissolving another substance and forming a homogeneous mixture. The mixture is purely physical, i.e. no chemical reaction between the and the substance to be dissolved takes place. “Organic solvents”, i.e.hydrocarbons and related substances, are the most commonly used group of non-aqueous liquid solvents. Frequently used are aliphates, aromates, alcoholes, glycols, ketones, esters etc. Aliphatic hydrocarbons are often mixed with aromates - toluene, xylene -, because the cleaning efficiency of aromatic compounds is higher than of aliphates. The majority of industrially used organic solvents is volatile to enable the fast removal of the liquid. According to the definition in the EU-VOC-Directive a compound is volatile if the vapour pressure is higher than 0,1 mbar at 20° C. At this vapour pressure indoor air concentrations of VOC in the range of some mg/m3 are to be expected. 42 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT Chlorinated Solvents Chlorinated solvents are derived from hydrocarbons in which all or part of the hydrogen has been replaced by chlorine. These solvents are very stable, hardly or non-flammable and have a high solvency. Trichloroethylene (TRI, C2HCL3) and perchloroethylene (PER, C2CL4) are of major commercial significance in metal parts cleaning both worldwide and still also in Europe. Aqueous Cleaners Aqueous cleaners can be separated into three groups: Alkaline cleaners, acid cleaners and neutral cleaners. The typical metal surface cleaner is slightly alkaline (often called “neutral” or “light alkaline”) with a pH between 7 and 10,5 and contains a detergent as the main active ingredient. The mechanism of lifting soil from a surface by displacing it with surface-active materials that have a greater affinity for the surface than they do for the soil is known as detergency. Detergents rely on a combination of processes as solubilization, wetting, emulsification, deflocculation, sequestration and saponification. Semi-Aqueous Cleaners Semi-aqueous cleaning incorporates the principles of aqueous and organic cleaners. This is accomplished by combining a surfactant with hydrocarbon in particular, to form a cleaning blend. In its simplest form, semi-aqueous cleaning involves two steps: the organic component to dissolve the soil and the water component to remove the residues of the blend and any other water-soluble soils. 1.2. SCIENTIFIC EVIDENCE ON (ECO)TOXICOLOGICAL AND ENVIRONMENTAL IMPACT General considerations In this case study the substitution includes three possible situations: • • • the change from chlorinated solvents to organic solvents the change from organic solvents to water based cleaners the change from chlorinated solvents to water based cleaners The enterprises, which are planning a substitution, are confronted with two options, which makes a risk assessment more complicated. 43 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT The main environmental impacts which have to be considered in a risk assessment are: • • • • • • • the waste from the cleaning activity, typically a mixture of cleaning agent and dirt the emissions of the agent into the air discharge of waste water into the sewage system, containing parts of the dirt and the cleaning agent. the energy consumption of the process (e.g. for agitation of equipment, heating of the cleaning agents and drying of the parts) the water consumption the risks of spills or leakages during transport, storage or handling unwanted reactions with material or dirt and possible formation of toxic substances. Each Member State has a number of legal provisions and control procedures to reduce the impact of cleaning agents on the environment. Besides the environmental impacts, some serious occupational safety and health risks also need to be considered, mainly • • • Fire and explosion risk, Inhalation of volatile solvents Skin contact with both organic solvent and water based products. Chlorinated solvents For metal degreasing and cleaning there are two chlorinated solvents currently dominating, trichloroethylene (TRI) and perchloroethylene (PER). Both are colourless liquids and under practical conditions non-flammable (TRI has a flammable limit of 8%). Chlorinated solvents are hardly soluble in water, but can remain in ground water for a long time. Their biodegradability is very poor. Chlorinated solvents may stick to particles in water, which will cause them to eventually settle to the bottom sediment. TRI has been produced commercially since the 1920s in many countries by chlorination of ethylene or acetylene. Its use in vapour degreasing began in the 1920s. Currently, 80-90% of TRI worldwide is used for degreasing metals (IARC 95). TRI and PER quickly evaporate so they can be detected as a vapour in the ambient air and at work places. Breathing small amounts can cause headaches, lung irritation, dizziness, poor coordination, and negatively affects concentration. Inhalation over longer periods may cause nerve, kidney, and liver damage. Skin contact with chlorinated solvents for short periods may cause skin rashes. In 1995 the International Agency for Research on Cancer’s (IARC 95) has classified TRI and PER as "probably carcinogenic to humans” (Class 2A). In 2001 the Technical Progress Committee (working under the Directive on Classification, Packaging and Labelling of Dangerous Substances (67/548/EC)) has accepted the recommendation of the EU Working Group on Classification, Packaging and Labelling to change the current health classification of TRI (TRI) under the EU Dangerous Substances Directive from cancer category 3 (labelling 44 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT risk phrase R40) to category 2 (risk phrase R45) (ECSA 01). Chlorinated solvents for metal degreasing purposes often need stabilising additives to protect the solvent against decomposition by oxidation or acidification. This is especially the case in contact with light metals as zinc and aluminium. Also undesirable reactions with sodium hydroxide are mentioned as serious risks by the producers of these solvents (ECSA 01). Hydrocarbons Environmental hazards associated with emissions of organic solvents include the build-up of atmospheric ozone by photochemical oxidation (summer smog) (see VOC 99). Some organic solvents also contribute to ozone depletion in the upper atmosphere. The population can be exposed to solvents because of airborne concentrations in ambient air. Solvent use is also a potential risk for water and soil contamination. Most solvents are volatile and flammable. Their vapours can accumulate in confined places and generate an explosion and fire risk (ILO 02). Solvents, their vapours and mists enter the body by inhalation, by swallowing and through the skin. The most probable exposure route depends on the volatility and fat-solubility of the solvent. The health effects of the solvents are specific to each solvent. Many of them have a narcotic effect, causing fatigue and dizziness. High doses may lead to unconsciousness and even death. Exposure to large doses of solvents may slow down reaction time and affect rational judgement. Some solvents irritate the eyes and the respiratory tract. Solvents clean and degrease the skin, which is a very common cause of skin disorders and dermatitis. Solvents with capacity to dissolve fats penetrate the skin and enter the blood circulation. Some solvents may also damage the liver, kidneys, heart, blood vessels, bone marrow and the nervous system. Use of aromatics to enhance cleaning efficiency often leads to increased toxicity.4 4 As a relative index of solvent power the Kauri-Butanol-Value is used: benzene is equal to 100, and all other solvents are compared to it. Higher KB values imply better removal of oil and grease stains. Linear paraffins generally have relatively low KB values. 45 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT Aqueous Cleaners Water based metal parts cleaners contain a number of ingredients with (eco-)toxicological impact. Typical additives in a typical slightly alkaline cleaner with detergents are: Group Biocides Corrosion inhibitors Antifoaming agents Detergents Emulsifier, Demulsifier Softeners Complexing agents Function Biological Stability Corrosion protection Cleaning efficiency Cleaning activation Degreasing and cleaning Cleaning efficiency by softening the water Defloccation Eco Tox Toxic impact on organism and microorganism Toxic impact on organism and microorganism Low biodegradability in the water phase Low biodegradability in the water phase Biodegradability in the water phase Human tox (via skin contact) Toxic impact dep. on type of biocide Toxic impact dep. on type of biocide Skin irritation Skin irritation Skin irritation low biodegradability in sediments - Depending on the huge variety of chemicals used, a risk assessment must practically be done in a case by case approach. It is a widespread opinion among scientists and authorities that the overall risk of water based cleaning is lower than with hydrocarbons and chlorinated solvents (NOEL 99). 1.3. INITIATIVES AT THE POLITICAL LEVEL Metal surface cleaning has been adressed by a large number of regulatory and public activities. The first regulations were made to protect the worker’s health. Carbontetrachloride (CCl4) and Benzene were widely banned until the seventies. The first environmental regulations covered the emissions from solvents of both types and were enforced in the early seventies. Solvent emissions into the air, the water and as byproduct of the waste have caused public and administrative awareness. In general cleaning agents are process chemicals rather than a constituent of the final product. Accordingly the role of the private consumers of the final products is very weak (with some exceptions e.g. in the food industry, where contamination can happen by metal surface cleaning agents during food processing. Nevertheless the industrial clients of metal parts cleaning - like the car industry or the electronic industry - often have an own interest in substitution, especially if residues of cleaning agents affect their own processes negatively. 46 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT Chlorinated solvents Public awareness towards chlorinated solvents was first raised in the 1970ies. It was mainly triggered by two environmental discussions: the destruction of the ozone layer in the stratosphere caused by the use of CFC’s and HFC’s, and a wider risk perception of organochlorine chemistry in general, symbolised by the Seveso accident in 1976. Since then, all chlorine-based products came into the view of the public. Today the use of chlorinated solvents is directly limited and regulated in many ways. Chemicals like 1.1.1trichloroethane (C2H3Cl3) or CFC-113 (C2CL3F3) have been banned completely due to their ozone depleting effects. Also, many national laws (e.g. for ground water protection, waste disposal etc.) contributed indirectly but significantly to a reduced use of chlorinated solvents. For metal cleaning in the EU today only the two solvents TRI and PER remain. The effect of the restrictions and emission control measures can be seen in production and sales figures. Due to the regulative and technological measures the use of chlorinated solvent is declining steadily. From 1990 to 2000 the reduction was app. 30%. The following table shows the figures published by the producer’s association. It has to be taken into account, that the reduction of PER is mainly due to the technological improvements in dry cleaning (strict emission control, see case 3). For metal surface cleaning PER has partly become a substitute of TRI (e.g. in Sweden, see SLU 01) Chlorinated solvent market in Western Europe (ECSA 01) TRI PER Thousands of Metric Tons 1990 105 110 1993 94 84 1994 94 79 1995 106 86 1996 101 85 1997 93 71 1998 85 73 1999 79 74 2000 74 70 An overview on control and restriction for chlorinated solvents measures covers all risk aspects from transport over storage to several emission limits for the environmental media, for waste and the work place air. Strictly regulated is the storage and the maintenance of the storage systems in order to reduce the risk of soil and groundwater pollution by leakage and spillages. European directives and regulations as e.g. in the context of waste or disposal to water (as e.g. Council Directives EC/86/280 or EC/90/415) influenced the use of chlorinated solvents at a European scale. Numerous national regulations contribute to reductions in the use of TRI and PER: Sweden prohibited TRI (and Methylenchloride) in 1996, with some possible exemptions (SLU 01). Germany set the emission levels so low that chlorinated solvents can only be used in closed loop circle machinery. France accepts chlorinated solvents as a cause 47 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT for occupational diseases. Spain has enforced national storage, transport and emission regulations. Permits or licences for emissions to the water are common in the Member States. Norway has put a tax on PER, which leads to a price increase of app. 500% Organic solvents Hydrocarbons are the conventional alternative to halogenated hydrocarbons for metal parts cleaning. Due to safety and health induced restrictions about the acceptable amount of aromatics (benzene, but also toluene and xylene) their cleaning capacity was reduced and is in general lower than for chlorinated solvents. Other restrictions came via strict fire and explosion regulations, which required cleaning agents with a higher flash point. This raised the drying time, which is often undesirable from a technical point of view. Worker’s health regulations came again into view. Member states had a public discussion about solvents, starting in Denmark and the Scandinavian countries in the eighties, in the Netherlands in the nineties. In many Member States, OEL’s for widely used hydrocarbons (aliphates) and their mixtures were enforced for the first time. In the middle of the eighties and the beginning of the nineties the first studies how to reduce the emissions and the use of VOC in general, started in several Member States (SE 91; UK 93; NL 89). Nevertheless reports from different sources (EME 99) show that hydrocarbons are still the dominating cleaning agent. In 1999 the EU Directive 1999/13/EC on the limitation of emissions of volatile organic compounds due to the use of organic solvents in certain activities and installations (the socalled VOC Solvents Directive) entered into force.5 The Directive sets emission limit values and fugitive emission values for certain industries. Member States are required either to implement the set of emission limit values foreseen by the Directive, or to design and implement a National Plan to achieve the same reduction. The VOC-directive will trigger much stricter emission control measures and by this also support substitution indirectly. An Eco-label for “Industrial cleaning and degreasing agents” exists since 1998 for the Scandinavian countries (NOEL 99). It defines criteria for the least toxic ingredients of water based cleaners. Products containing solvents and chlorinated hydrocarbons are excluded from the eco-label award. In total the following chemicals are excluded: The products must not be subject to classification under regulations on health, environmental, fire or explosion hazards with the exception of products classified as corrosive, irritants or in accordance with the Swedish "Läs varningstexten" scheme. 5 One of the main reasons for this Directive were the ozone episodes during summertime in European cities. 48 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT Alkylphenoletoxilates, linear alkylbenzensulphonates, organic halogen compounds, petroleum based solvents, EDTA, DTPA, ftalates and fragrances must not be present in ecolabelled products. The criteria impose restrictions on the quantity of environmentally harmful substances and NTA/phosphorus in the products. Furthermore, the surfactants used must be readily and anaerobic degradable. Preservatives used must not be potentially bioaccumulative. A number of government industry agreements have been introduced in the nineties. Most of them were dedicated to household products. In France the target was to reduce the average VOC content of all paint types by 25% over the period 1986-91. The result was a fall of 16% in the solvent content per ton of paint in the time span of five years, despite a 20% increase in the quantity of paint sold (EUC 94). In the Netherlands covenants have been used to control solvent use. The target was to reduce emissions from VOCs to at least 50% of the 1981 level. This covers all sources except mobile sources and stationary combustion. In 1991, after three years of the accord, the average VOC content of paint had fallen from 36% - the 1981 level - to 21% (EUC 94). 1.4. INITIATIVES AND MOTIVATION AT THE ENTERPRISE LEVEL At the enterprise level the technology and the costs connected with equipment, cleaning agent, environmental and safety and health protection represent the main factors to decide about the cleaning agent. The following tables show the factors and arguments relevant for enterprises. Substitution from chlorinated solvents to organic solvents The technical advantages including the low explosion and flammability risks have to be balanced with the high environmental and health risks. Substitution from chlorinated solvents to organic solvents PRO SUBSTITUTION CONTRA SUBSTITUTION Cleaning efficiency MAIN ACTOR Industrial users, especially producers of high quality products Equipment producers More advanced and expensive cleaning equipment available, to reduce the emissions acc. to stricter regulations More advanced and expensive cleaning equipment necessary against fire and explosion Use of less cleaning agents through improved machinery design, more features Risks of spilling and soil contamination, storage obligations Prices for sludge (waste), Industrial users Industrial users, Cleaning equipment producers Industrial users, insurances, authorities Industrial users, authorities 49 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT Substitution from chlorinated solvents to organic solvents PRO SUBSTITUTION contaminated with chl. solv. Health hazards Health hazards by stabilising additives and spontaneous risks by decomposition CONTRA SUBSTITUTION MAIN ACTOR Less potential conflicts with authorities, workers, neighbours and the public Industrial users, technicians and HSE Substitution from hydrocarbons to water based cleaners In the case of substitution from hydrocarbons to water based cleaners the reduction of the fire and explosion risk as well as the reduced environmental and health risks form the main advantages. Substitution from hydrocarbons to water based cleaners PRO SUBSTITUTION CONTRA SUBSTITUTION Cleaning efficiency (image) Drying problems (time, quality) Fire and explosion risk More advanced and expensive waste water equipment Difficult sharpening of the cleaning agent Energy and water consumption Less risks of spilling and soil contamination Less health hazards MAIN STAKEHOLDER Industrial users (technical and quality view) Industrial users technical and quality view) Industrial users Industrial users (economic view) Industrial users (process handling) Industrial users (environmental view) Industrial users (environmental view) Authorities, workers, public, neighbours In such a multi-factor environment the substitution steps are necessarily case-to-case decisions inside enterprises. Some case have been reported where large industrial users substituted very early or in advance of coming regulations. Public descriptions are mainly available from the car industry and their large suppliers. 50 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT 1.5. ALTERNATIVES / SUBSTITUTES In the case of metal parts cleaning the substitution possibilities are so manifold and their history is so complex that it can be described only in principle and using types of substitutes. CHLORINATED SOLVENTS MAJOR ROUTE OF USE AND SUBSTITUTION Carbontetrachloride (CCL4) (1850 to 1940) Carbontetrachloride (CCL4) (1850 to 1940) 1,1,1,Trichlorethan and similar chlor. solv. (1920 to a very limited use today) Trichloroethylene (1920 to today, loosing market share towards PER MINOR USE AND ROUTE OF SUBSTITUTION Chlorofluorocarbons (CFC’ s) (1940 to 1980) Hydrochlorofluorocarbons (HCFC’s) (1975 to today)) Hydrofluoroether HFE’s and Perfluorocarbons (PFC’s) (1975 to today) As a main strategy, it becomes evident that less toxic alternatives of a similar chemical type are used for a longer period. The process integration is easiest, the production risks and the change costs are lowest. Substitution at the substance level which enables adaptation of the process without requiring additional investments in machines / technology, is generally preferred by the companies. 51 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT HYDROCARBONS MAJOR ROUTE OF USE AND SUBSTITUTION CRUDE SOLVENT Mixtures of all types mainly alkanes containing aromates SOLVENT MIXTURES with less impurities and without benzene (from 1960) SOLVENT MIXTURES without aromates (from 1980) SOLVENT MIXTURES without aromates (from 1980) MINOR USE AND ROUTE OF SUBSTITUTION Alcohols , Ketones , Esters, Ethers, Acids, all other hydrocarbon based alternatives SEMI-AEQUEOUS CLEANERS The same strategy can be seen in this case: it is significant that for a longer period less toxic alternatives of a similar chemical type are used. The initial reduction of toxicity was mainly achieved by separating toxic components from petrochemical cleaning products. Beginning in the early 1980ies the (eco-)toxicity of the whole substance group “Organic solvents “ became a public issue. Since then the search for alternatives is more intense and the technological options for cleaning agents have been expanded enormously. AQUEOUS CLEANERS MAJOR USE AND ROUTE OF SUBSTITUTION WATER WITH CAUSTIC SODA OR SOAP for special purposes (from 1850) WATER WITH EFFECTIVE DETERGENTS (from 1975) WATER WITH BETTER BIODEGRADABLE and LESS TOXIC COMPONENTS (from 1985) The growing market share of water based cleaners is based on the development of additives, to reduce or avoid the technological disadvantages as low cleaning efficiency, material compatibility, corrosion and longer drying time. Additive development is the key for market success of water based cleaners. 52 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT OTHER CLEANING ALTERNATIVES HC AND CHLORINATED SOLVENTS PRODUCTION PROCESSES AVOIDING DIRT AS CUTTING WITHOUT CUTTING FLUIDS CLEANING WITH SUPERCRITICAL CARBONDIOXIDE PLASMA CLEANING ULTRASONIC CLEANING The extension of cleaning options brings new mechanical /physical cleaning technologies into focus. The main pre-requisite to use these cleaning technologies is a good technical knowledge and a work or process organisation, which allows to select and define processes suited for such new cleaning technologies. 1.6. IMPLICATIONS OF SUBSTITUTION FOR BUSINESS PRACTICE The available chemical and technical options have been extended in the last twenty years, many “new” formulations and technologies are on the market. Both the requirements for the quality of the products (cleanliness) and the process control have become stricter with more advanced quality management systems. Additionally the demands from the regulative bodies - from environment over transport to health and safety - have become stronger. It is difficult to describe a common strategy of companies. Some assumptions about their internal “policy” and their considerations can be derived from journal articles and personal communication. The large operators are switching or have already switched to automatic and relatively closed installations using all three types of chemicals. All these types of cleaning agents need a detailed control of practical handling and risk reduction measures. These necessary organisational efforts have been made or are intended, if cleaning from process fluids plays an important role for the business. Other users in companies, where cleaning is still seen as a minor task in the whole process, seem to tackle the cleaning issue without a strategic background. They use the products and technologies, which are available on the market and are not connected with too much regulative restrictions. Larger strategic considerations about substitution are rare. A widespread opinion in companies is that regulative restrictions and the quality demands 53 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT will continuously become stricter. For suppliers of larger companies such as the car industry the demands from the quality or environmental management systems of their customers play a growing role. 1.7. CONCLUSIONS The main characteristic of the metals parts case can be summarised as follows: An intense discussion about the risk of chlorinated solvents started in the middle of the seventies, followed by a risk discussion about all types of organic solvents beginning in the eighties. Highlighted were the risks for soil, water and air pollution as well as occupational health problems. Since then the cleaning technology for metal surfaces cleaning has split up into a broad variety of different cleaning technologies and cleaning chemicals. The market for substitutes is currently very large and offers all options concerning types of chemicals and suitable cleaning equipment. This causes on the other hand reduced transparency. SME’s have serious problems to assess the different chemicals and cleaning technologies. The consumption of chlorinated hydrocarbons and aromatic hydrocarbons has decreased significantly, the use of aliphatic hydrocarbons with low flash points has been reduced and the water based cleaners have raised their market share in some countries above 50%. Cleaning agents are process chemicals, the main actors are grouped around the core industrial process: the user companies, the HSE-administration, the workers, the equipment producers and the chemical suppliers. The role of consumers of the final products is very weak. One general impression is, that the choice of the user companies still depends mainly on the functionality, but discussions and decisions about cleaning agents are becoming more and more strategic as aspects related to quality, health and environment are getting increasingly important. At the same time, due to the complex influence factors, in many cases the comparative risk assessment is very difficult. Often shifts of risks have to be considered. For a generalised case of substituting chlorinated solvents and hydrocarbons by water based products or cleaning technologies without the use of dangerous substances, the following factors have been identified as hindering or supporting key factors. Economics - Price of new equipment In many cases investments for new and more expensive cleaning equipment are necessary. These costs for investments in new cleaning equipment hinder substitution. 54 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT Technical functionality In some European countries water based cleaners are well established and technically as well as economically feasible. Reliable information is available for substitutes. However, there is some negative anticipation concerning the effectiveness and process integration of substitutes. A main technical risk of water based cleaners is seen in the potentially slow evaporation and the corrosion effect. This hinders substitution efforts. To avoid the anticipated bad performance, a good overview about the market and additional efforts such as careful selection and some tests of the practical functionality are necessary. Social factors While user companies select the cleaning method primarily based on functionality aspects, their decisions are becoming more and more strategic because aspects related to quality, health and environment are getting increasingly important for their customers. Risk Assessment The major substitute - water based cleaners - need a number of additives to work (tensides, biocides, corrosion inhibitors). This makes the toxic risk assessment difficult and causes assessment efforts in companies. The substitution with a water based cleaner might also imply, that the risk assessment has to take into account a shift to other environmental burdens as higher water and energy consumption as well as waste water pollution. Regulation For SME’s with smaller consumption of cleaning agents the administrative obligations to change do not trigger substitution substantially. For larger installations the regulatory push is unlike stronger. 55 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT Conclusions in table form The following table presents the key factors which have been identified in this case. It is a step towards an overall comparison of the cases. The aggregation level is higher and it should finally be a tool to identify the key factors of all ten cases. Single important factors overview Economics Costs for investments in new cleaning equipment hinder substitution Economics/costs hindrance of substitution (-) (++) (-) (+) (-) Technical functionality Performance of substitutes Technical functionality/performance Technical functionality/process integration Social factors/communication B2B Strong support of substitution hindrance of substitution Supposed less functional effectiveness hinder substitution efforts Social factors Increasing importance of environmental and health aspects support of substitution hindrance of substitution Risk assessment Complex water based alternatives need complicated risk assessments risk assessment/RA of alternatives/shift of risks Legislation Regulation Regulation support substitution for large installations but not in SME´s concerning large enterprises concerning small and medium enterprises concerning large enterprises & SMEs (aggregated score) strong support of substitution no influence (++) (o) (+) 1.8. LITERATURE Council Directive 86/280/EEC of 12 June 1986 on limit values and quality objectives for discharges of certain dangerous substances included in List I of the Annex to Directive 76/464/EEC Council Directive 90/415/EEC of 27 July 1990 amending Annex II to Directive 86/280/EEC on limit values and quality objectives for discharges of certain dangerous substances included in list I of the Annex to Directive 76/464/EEC ECSA, Solvents Digest 20, Brussels, April 2001 EMEP/CORINAIR Emission Inventory Guidebook - 3rd edition, 1.Sept. 1999 TRICHLOROETHYLENE (Group 2A), VOL.: 63 (1995) (p. 75), 5. Summary and Evaluation TETRACHLOROETHYLENE (Group 2A), VOL.: 63 (1995) (p. 159) EC 86/280 EC 90/415 ECSA 01 EME 99 IARC 95 56 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES ANNEX IV – CASE STUDY 1: METAL PARTS CLEANING FINAL REPORT 5. Summary of Data Reported and Evaluation ILO 02 NL 89 NOEL 99 SE 91 SLU 01 see ILO http://www.ilo.org/public/english/protection/safework/cis/products/ safetytm/solvents.htm Dutch Ministry of Housing, Physical Planning and Environment Control Strategy for Emissions of Volatile Organic Compounds, 1989 NORDIC ECOLABEL: Eco-labelling of industrial cleaning and degreasing agents, Criteria document, 15 June 1999 - 14 June 2003 Swedish Environmental Protection Agency, Strategy for Volatile Organic Compounds, Report 3897, 1991 Slunge, D. / Sterner, T.: Implementation of Policy Instruments for Chlorinated Solvents - A Comparison of Design Standards, Bans, and Taxes to Phase Out Chlorinated solvents, September 2001, Resources for the Future Discussion Paper 01–32 UK Department of the Environment, Reducing Emissions of Volatile Organic Compounds (VOCs) and Levels of Ground Level Ozone, A UK Strategy, 1993 Council Directive 1999/13/EC of 11 March 1999 on the limitation of emissions of volatile organic compounds due to the use of organic solvents in certain activities and installations UK 93 VOC 99 57 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 2: CLEANING OF FAÇADES FINAL REPORT 2. CASE STUDY 2: CLEANING OF FAÇADES 2.1. TECHNICAL AND CHEMICAL SCOPE 2.1.1. Technical scope Cleaning of façades made of stone or similar material is mostly done either in order to inmprove the appearance of commercial buildings or living houses, or as an essential preparation to save or restore historical buildings. The technical process of façade cleaning covers mainly the removal of undesirable mixtures of biological and non-biological material from the surface of the stone or from cracks and areas below the surface. The sources of contamination include non-biological soiling particles such as soot, vehicle exhausts and industrial chemical emissions or their reaction products, and old paints. In recent years the removal of graffiti has become a specialised sub-task in façades cleaning.6 Biological soiling is the result of organic growth on and within the stone. The four most important types of organism are algae, fungi, lichens and bacteria. Algae are the predominant form of biological soiling on building façades. Some organisms exude acids and other chemicals capable of dissolving some components of stones. Certain bacteria can oxidise or reduce chemical pollutants in the stone, thus aiding access of such pollutants to the stone interior. Due to the wide range of materials used (including e.g. sandstone, limestone, terracotta, faience or brickwork), it is inappropriate to adopt standardised specifications for cleaning operations. In principal the technologies used for façades cleaning can be structured in the following way: Energy input High Mechanically/Physically Abrasive Blasting Grinding High pressure washing Laser Minimum or medium abrasive technologies (e.g. calcium carbonat) Non abrasive Manual treatment Spraying with very low pressure Water soaking Thermically Reactive Chemically Abrasive/reactive Acids Alkali Low Non reactive Steam cleaning Hot water cleaning Non abrasive Chlorinated solvents Hydrocarbons Adhesives Pastes 6 Often cleaning enterprises offer a subsequent protection process against further soiling or graffiti. Such additional anti-graffiti treatment with chemicals is not part of the cleaning process itself and not dealt with in this study. 58 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 2: CLEANING OF FAÇADES FINAL REPORT These methods can be combined to accelerate or improve the cleaning effectiveness. The market for products and preparations aimed at the cleaning of façades is very scattered. An unknown number of construction companies, specialised painters, facility cleaners, restorers and enterprises from other areas are working in this area, using different technologies and cleaning agents. Different traditions, materials, technological options, budgets and local regulations determine the methods and economics of cleaning. Reliable market figures for equipment and chemicals used in this sector are not available. The technologies range from sand blasting, over the use of strong acids, to steam or high pressure washing with water with or without detergents. Even for very hazardous and strictly regulated chemicals like hydrogen fluoride it cannot be calculated, which amount of the European production goes into façade cleaners. Also e.g. for methylenchloride it is not possible to distinguish between amounts used in the construction industry vs. quantities spent for paint removal in house or at façades. No quantitative estimate about the number of companies involved or the number of workers exposed can be given. 2.1.2. Chemical scope The typical chemicals can be structured in the four groups of acids, alkalines, solvents and water based cleaners. Acids Acids commonly used for façade cleaning are hydrochloric acid (HCl), hydrofluoric acid (HF), phosphoric acid (H3PO4), nitric acid (HNO3). Acids are used to remove all types of soiling from the surface. They have a very high effectiveness and they clean very fast, however the risk to also cause damage to the façade material is very high. Acids can attack the substance of the stone and will destroy certain materials such as limestone. Some companies recommend to clean never more than 5 m² per operation. Alkalines Alkali based substances and preparations, for example caustic soda (Sodium hydroxide NaOH) or caustic potash (potassium hydroxide - KOH), are used to remove greasy dirt like soot, old and fresh paints and dirt in general. Aromatic and chlorinated solvents These substances are mainly used to remove old paints or graffiti. Chlorinated solvents are known as very effective remover of paints and similar surface materials, because they are able to dissolve most of the commonly used binder types in paints. The use of paint removers –not only for façades - is around some 30,000 tpa in Europe (TNO-STB 99). 59 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 2: CLEANING OF FAÇADES FINAL REPORT Water based washers with detergents Pure water can be used at high pressure or heated or as steam for mechanical removal. Detergents are added to improve the cleaning effectiveness of pure water. 2.2. SCIENTIFIC EVIDENCE ON (ECO)TOXICOLOGICAL AND ENVIRONMENTAL IMPACT The chemicals-related risk of the cleaning operation can be caused both by the chemicals used and by the dirt removed. Cleaning of façades produces waste which may contain particles of soot, or heavy metals, or risky biological material such as bird excrements. Acids The risk of strong acids used in open processes outside of buildings is obvious and the toxic potential of acids as HF and HCl is beyond doubt. Façade cleaning is an open manual process meaning that the risks of spillage, emissions and/or accidents are high. The major health concern regarding hydrofluoric acid is related to short-term exposure at work. Hydrofluoric acid is dangerous to humans because it cauterizes eyes and skin. In extreme cases, exposure to hydrofluoric acid can cause lethal damage to lungs or heart. Alkalines Alkalines can contain sodium hydroxide, potassium hydroxide, ammonia, tensides and accelerators. They are used to remove alkyds or oil paints and fatty contaminants. The toxic impact of alkalines for humans as well as for the aquatic environment are well studied and are closely related to the concentration. Solvents – methylene chloride Of all chlorinated solvents, methylene chloride (or dichloromethane) is the product with the least strict regulations. Methylene chloride is more easily biodegradable than other chlorinated solvents. Nevertheless it is suspected to be carcinogenic, and the EU has labelled methylene chloride as carcinogenic category 3, ‘Substances, that need attention due to their possible carcinogenic properties for humans’. The chemical has to be labelled as harmful (Xn), with the risk phrase R40 (possible risk of irreversible effects). 60 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 2: CLEANING OF FAÇADES FINAL REPORT Comparison of impact The three main risk categories connected to the use of façade cleaners are workers’ health, emissions to air and emissions to water and soil. In a rough comparison, the different substances in their typically applied average concentrations shows the following risk picture: Risk categories Workers health Human tox acute Human tox chronic Emissions Air Water hazards, acute aquatic toxicity Bioaccumulation Biodegradability Acids xxx x x xxx o o Alcaline xx x o xxx o o Chlor solv xxx xx xx xx xx xx Aromates Detergents xx xx xxx x o x x (skin) x x (dep.) x x Impact between o (= no concern), x (= low concern), xx(= medium concern) , xxx (= high concern) Compared to chemical methods, mechanical techniques like high pressure spraying or steam washing constitute new accident risks for the workers using the equipment. E.g. sand blasting which is widely used for large scale basic restoration bears high risks for the workers (silicosis and accidents) and produces large amounts of contaminated waste. 2.3. INITIATIVES AT THE POLITICAL LEVEL Various political initiatives to regulate façades cleaning have addressed general regulations for construction sites, separate treatment of wastes, waste water treatment, partial bans of certain chemicals, health and safety of workers and special regulations for the restoration of public buildings. No harmonised European legislation exists for this sector. Legal requirements differ not only between Member States but also at regional and even local level.7 Local and regional authorities responsible for construction, public health, environment, and workers health and safety have issued a considerable number of rules and technical guidelines for façade cleaning, often restricting the use of certain substances, with even more specific requirements for façades of buildings which are part of the cultural heritage. Like every construction work in a public area, façade cleaning normally has to be registered. Before starting the cleaning work, the construction enterprise has to apply for a permit which normally will require certain protection measures for the public (no access to the site, protection against the dust etc.), and regulations concerning the protection of soil and the disposal of waste and waste water e.g. in a mobile treatment equipment. 7 In the future, the preparation of a BREF about “Surface treatment using solvents”, facilitated by the EIPPCB, may provide recommendations and guidelines for best technologies also in façades cleaning. 61 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 2: CLEANING OF FAÇADES FINAL REPORT 2.4. MOTIVATION AND BUSINESS PRACTICE Cleaning companies are in general SME’s from the construction sector, mainly specialised painters enterprises. They are working at temporary construction sites. The equipment and the chemicals are selected by themselves except in rare cases where the building owner, the architect or the general contractor obliges them to use a certain technology and or specific chemical cleaning agent. The selection of the cleaning agent is based on an aspects such as • compatibility with the stone or surface material • effectiveness to remove the undesirable material • qualification and experience of staff • equipment available • price of the chemical • time for cleaning operations • regulations (national or local, especially for public buildings). In any case, the quality of instruction or training of workers concerning the risks from façades cleaning is crucial. A motivation to use less hazardous products could be to comply with the environmental regulations and the regulations on workers health. However, as seen in many studies about the use of chemicals in such companies, only a minority of companies which is actually able to comply with all regulations, including the priority of using the least hazardous substances. The majority has no real environmental or HS management system (SDS 99). Basic information is often missing, many workers receive only very limited instructions and training. Due to the large number of cleaning operations, strict enforcement of all regulations is impossible for purely quantitative reasons (number of sites in relation to number of inspectors). 2.5. SUBSTITUTION AND ALTERNATIVES There are two main alternatives for cleaners based on acids, strong alkalines, chlorinated solvents and aromatic solvents. Chemical substitutes are e.g. dibasic esters and similar chemicals with high effectiveness but slow mode of operation. The second and more common route is to switch to mechanical treatment with pressurised or heated water. More “exotic” alternatives such as laser cleaning or the use of CO2 are not covered here because they are applied rarely. Although sand blasting is widely used, it is not covered because it is an alternative for large scale basic restoration rather than cleaning. It attacks the surface quite drastically and has become increasingly unpopular for stone cleaning purposes. For historical buildings sand blasting is often completely banned, because abrasive blasting damages e.g. the outer fired surface of brickwork and the hand tooled finish of stonework. Water based high pressure cleaners operate at a pressure of 70 to 200 bar, with machines using between 5 and 25 litres per minute. Both cold water high pressure cleaners and hot water high pressure cleaners are used. For special purposes detergents are injected at around 1 to 5%. 62 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 2: CLEANING OF FAÇADES FINAL REPORT Hot water is used if the dirt contains a considerable amount of fats or oils. A hot water cleaner works with similar pressure and flow except that the water is heated to up to 100° C in a boiler, with some machines having an extra steam stage. Brushes, assorted lances and other accessories can usually be added to any of the above types of equipment. Substitution from chemical façade cleaning to the use of mechanical cleaning with water (high pressure cold and hot) (HOF 01, HSE 01) PRO SUBSTITUTION CONTRA SUBSTITUTION Speed of the working process Reduced cleaning effectiveness against strong staining, fats and oils Experience of workers with conventional methods More advanced and expensive application technologies and equipment Accident risks for workers: contact with high pressure water and / or with hot water Larger amounts of waste water Costs of water based cleaners Costs of energy for hot water cleaning Threat of freezing Premature decay Oxidation of masonry Environmental hazards Less chemical health hazards Costs of illness Selling of more (other, higher priced) cleaning equipment MAIN ACTORS Cleaning enterprises, workers Cleaning enterprises Cleaning enterprises Workers, Trade Unions, Costs of absence, Health and Safety Authorities Cleaning enterprises (Costs), Environmental authorities Cleaning enterprises Cleaning enterprises Enterprises, Owners Owners Owners Environmental authorities Workers, Trade Unions Workers, Trade Unions Equipment suppliers Regulations for restoration of historic Local and regional cultural buildings: physical treatment and heritage protection authorities strong wetting of the surface not accepted, but strong chemicals (in case of fragile surface structures) Regulations for restoration Local and regional cultural of historic buildings: physical heritage protection authorities treatment and strong wetting of the surface accepted, but no strong chemicals Costs for removal of Local and regional authorities contaminated waste Local and regional authorities Less risks of spilling and water contamination 63 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 2: CLEANING OF FAÇADES FINAL REPORT 2.6. Conclusions Façade cleaning is one of the sectors using highly toxic and dangerous chemicals manually in an open process. The decision about the techniques and chemicals used is mainly taken by the cleaning companies, based on their experience and skills. Restrictions come partly from the owners (public buildings) and local authorities. Information and recommendations to use the least hazardous products or to use water pressure cleaning are given from many actors, but it is hardly possible to get an overview about the development of the substitution process, because there are no statistics about the share of the different operation methods and the amount of chemicals used in façade cleaning. - Process integration The cleaning task changes with every construction site and sometimes even at one façade. Cleaning companies prefer a stronger and ‘one-for-all’ products in order to ensure the success of their operations. o Awareness The awareness of environmental or consumers NGO’s is comparatively low. The fact that this work happens often “in public areas” causes some awareness concerning the protection of the general public. + Risk information of alternatives The risk of alternatives is lower than conventional substitutes. Disadvantages of the alternatives arise mainly from technical or economic considerations and partly from a shift of risks. + Regulations In some areas with a high degree of enforcement of strict regulations concerning the waste, and the water protection will lead to the use of less hazardous substances. Especially the removal of waste closes partly the gap for illegal practices. Public heritage conservation authorities define and prescribe the methods for cleaning processes often in detail. Sometimes there are restrictions to use the public facilities such as public sewage systems. Single important factors overview Technical function Supposed less functional effectiveness hinder substitution efforts Technical functionality/process integration Social factors/awareness (public) hindrance of substitution (-) (o) (+) (+) Social factors Awareness of environmental and health aspects No support or hindrance of substitution Support of substitution support of substitution Risk assessment Lower risks from alternatives compared with conventional chemicals Risk information/RI of alternatives Regulative frame/legislation Regulation Enforcement of strict regulations concerning the waste 64 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 2: CLEANING OF FAÇADES FINAL REPORT 2.7. ECB 00 LITERATURE EUROPEAN CHEMICALS BUREAU / INSTITUTE FOR HEALTH AND CONSUMER PROTECTION: European Risk Assessment Report: Hydrogenfluoride, Luxembourg 2000 Façade Cleaning: For more than appearance’s sake, By: Kadlubowski, A. and Bynum, C., in: Hoffmann Architects 1/2001 HSE information Sheet: chemical Cleaners, Construciton information sheet No 24 (Revision 1), HSE UK 2001 HOF 01 HSE 01 TNO-STB 99 Tukker, A. /Simons, L. Ph.: Methylene chloride: Advantages and Drawbacks of Possible Market Restrictions in the EU., Final Report for DG III of the European Commission, Brussels, Belgium SDS 99 Study contract of DGV: SOC 97 201817: Assessment of applicability of Safety Data Sheets in SME’s in Austria 65 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 3: TEXTILES CLEANING IN LAUNDRYS FINAL REPORT 3. 3.1. CASE STUDY 3: TEXTILES CLEANING IN LAUNDRIES TECHNICAL AND CHEMICAL SCOPE 3.1.1. Technical scope Laundries may opt between the three main cleaning technologies of • dry cleaning, using Perchloroethylene (PER) and adequate equipment • dry cleaning, using hydrocarbons (different equipment than for PER required) • wet cleaning (using water, detergents and gentle agitation in special equipment). This study focuses on the risks and substitution alternatives of dry cleaning with PER as the dominating technology. The following diagram presents market shares of the three types of cleaning technologies in industrialised countries as reported by the International Committee of Textile Care (CINET). Market share of cleaning technologies (CINET 02; PCE stands here for PER) Dry cleaning was developed in the 19th century as a useful method to remove spots from textiles. At that time dry cleaning was performed by hand, using petroleum-based solvents. 66 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 3: TEXTILES CLEANING IN LAUNDRYS FINAL REPORT The developing dry cleaning industry first used turpentine and kerosene before moving to benzene and gasoline. All of these solvents were highly flammable and the reason for fires and explosions. In the 1930ies perchloroethylene (PER ) was introduced. It is still the dominating chemical as it is used by approximately 90% of all EU dry cleaners today. The selection of products for dry cleaning depends mainly on labelling of the textiles. In cases, where both dry cleaning or wet washing is classified as possible, the choice depends on the consumer’s personal decision. Before dry cleaning the garments are separated and visually inspected. If necessary the garments are treated with special spot cleaners. The dry cleaning core process comprises the three steps of washing, extracting of the solvent and drying. Agitation and heating are techniques frequently used to improve the cleaning effectiveness. After washing the solvent has to be extracted from the chamber and the garments are tumbled dry. Dry cleaning shops using older equipment have separate machines for washing and drying, leading to emission of PER during the transfer from the washing to the drying process. In advanced machinery there are several features to reduce the amount of solvent in the garments and to reduce emissions. Warm air is circulated through the chamber to vaporise the remaining solvent. Cool air is used to cool down the garments and the machinery to avoid evaporation and reduce wrinkles. Exhaustion equipments and carbon filters are used to reduce the remaining emissions. CINET classifies the current dry cleaning equipment into four categories: Type Type Type Type I: II: III: IV: Dry cleaning machine with water-cooling but without activated carbon filter Dry cleaning machine with refrigeration cooling and activated carbon filter Closed dry cleaning machine with refrigeration cooling without exhaust air Closed dry cleaning machine with refrigeration cooling and activated carbon. Installation of advanced techniques in many European dry cleaning shops led to significant reductions in use and emissions of PER. The PER producers estimate that a 90% reduction of PER consumption was achieved in 20 years, i.e. while in 1980 10 kg PER was needed to clean 100 kg textiles, today only 1 kg is needed (CHLORONL 01). 3.1.2. Chemical Scope Since the 1930ies the chemical industry produced chlorinated hydrocarbons in large quantities. At the beginning carbon tetrachloride was the preferred chlorinated hydrocarbon for dry cleaning; but due to its toxicity and aggressiveness to metals, textiles, and dyes, it was gradually replaced in the 1940s and 1950s by trichloroethylene and tetrachloroethylene (or "perchloroethylene" = PER = C2Cl4). In the 1960s, CFC 113, a chlorofluorocarbon solvent, was used in dry cleaning, but never reached a significant market share. Because of its potential to deplete ozone and cause global warming, its use is now banned in most countries under the Montreal Protocol. 67 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 3: TEXTILES CLEANING IN LAUNDRYS FINAL REPORT Perchloroethylene is a colourless liquid and under non-flammable practical conditions. Hydrocarbons currently used as substitute cleaning agents are based on a blend of C10 isoparaffins. The main two advantages in comparison to formerly used hydrocarbons (“white spirit”) is their higher flashpoint (above 50° C) and a negligible odour. The disadvantage of hydrocarbons is their lower solvency power (see chapter 3.5). 3.2. SCIENTIFIC EVIDENCE ON (ECO)TOXICOLOGICAL AND ENVIRONMENTAL IMPACT PER has serious environmental and health impacts which have been intensively studied. The main health-related issues are its toxic impact on the liver and the central nervous system, the accumulative potential and its suspected carcinogenic properties. Breathing small amounts can cause headaches, lung irritation, dizziness, poor coordination, and negatively affects concentration. Inhalation over longer periods may cause nerve, kidney, and liver damage. Repeated dermal exposure may result in dry, scaly, and fissured dermatitis (ILO 99). Skin contact with chlorinated solvents for short periods may cause skin rashes. Environmental aspects include the general risks associated with the production of chlorinated products, atmospheric emissions, PER’s aquatic toxicity and poor biodegradability, leading to long persistence of PER in ground water and soil. There are also two major concerns from consumers: the textiles show ongoing emission of PER for some time after dry cleaning, and PER was found in the fatty phase of food in the neighbourhood of dry cleaning shops. A 1987 US-EPA study on PER showed that, in addition to the numerous adverse health effects already known and outlined above, there was evidence of carcinogenity. In 1995 the IARC classified PER in group 2A, meaning that it is probably carcinogenic to humans (IARC 95), even if the evidence was less in comparison to trichloroethylene. Additionally, chlorinated solvents need stabilising additives to protect the solvent against decomposition by oxidation or acidification. The toxicity of the stabilisers might pose an additional risk which however cannot be covered here. 3.3. INITIATIVES AT THE POLITICAL LEVEL The starting point for political initiatives differed from country to country. The following facts, which had an influence for the different stakeholders to act, were identified: • • • • growing awareness of residues of a dangerous substance in people’s personal textiles; the smell of the textiles after PER cleaning; the phasing out of chlorinated solvents in certain areas (Consumers products, some open cleaning processes in industry such as adhesives, metal surfaces, printing); the general debate on chlorinated products (including CFC and the dioxin debate); 68 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 3: TEXTILES CLEANING IN LAUNDRYS FINAL REPORT • • • the identification of PER’s carcinogenic effects; the risk of very expensive spilling accidents with wide spread water pollution; in the Nordic countries the discussion about solvents at the work place. In public awareness the main risks were emissions to the environment (air, soil and water) and health concerns from consumers. The water pollution aspect was mainly raised by competent authorities. The occupational health aspect played no significant role in the public debate.8 Besides being dealt with in national regulations, dry cleaning operations are additionally treated under the recent VOC directive. As one relevant field of application this Directive addresses any industrial or commercial activity using VOCs in an installation to clean garments, furnishings and similar consumer goods, with the exception of the manual removal of stains and spots in the textile and clothing industry. The total emission limit values for new and existing plants will be 20 g/kg, expressed in mass of solvent emitted per kilogram of product cleaned and dried. To achieve the necessary emission reduction mainly design requirements on cleaning equipment were necessary. Austrian, German and Swedish regulations require technical features such as • Emission free solvent filling • Still tank rinsing • Emission free rake out • Safety volumes for groundwater protection • Cooling water temperature control • Double water separators • Emission limits inside the cylinder. 3.4. INITIATIVES AND MOTIVATION AT THE ENTERPRISE LEVEL The machine technology has been improved significantly, however the situation varies from country to country. Depending on the type of machines used in dry-cleaning shops it is technically possible to reduce the emissions and the specific consumption of PER by 90 per cent. Dry cleaning equipment is one of the few areas where it has been possible to find European aggregated data about the technological standard. On the basis of data provided by trade associations, machine manufacturers, solvent producers and distributors, CINET has estimated how the different machine technologies are distributed over the EU Member States (ECSA 01a): 8 For a general description about initiatives oriented towards chlorinated solvents the reader is referred to the Case Study on “Metal Parts Cleaning” (in Annex Section 1.3). 69 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 3: TEXTILES CLEANING IN LAUNDRYS FINAL REPORT Machine Technology Split Europe 2000 Type Country Total Type I Machines II Dry cleaning Dry cleaning machine machine with water- with cooling but refrigeration without cooling and activated activated carbon filter carbon filter Austria Belgium Denmark France Greece Ireland Italy Luxembourg Netherlands Spain/ Portugal Sweden & Finland UK West Germany Total Per Machines 500 610 270 8.910 2000 570 24.000 20 900 5.700 890 7.500 4.700 56.570 100 % 0 0 4.025 7% 2000 0 6.650 12 % 2.900 30 200 0 800 315 0 3600 10 100 270 450 Type III Closed dry cleaning machine with refrigeration cooling without exhaust air Type IV Closed dry cleaning machine with refrigeration cooling and activated carbon 500 Source 400 100 8.280 1.200 180 20.200 180 75 200 20 market data Dow market data Dow Danish Association French Association Greek Association Dowling Union market data Dow market data Dow CINET market data Dow market data Dow Dowling DTV 500 1500 370 1.100 890 2.000 0 34.260 61 % 3.500 4.700 11.635 21 % The technological differences are clearly spread geographically over Europe. They show that the national public debate and the regulations significantly accelerate the process of technological innovation towards effective emission control. In no case substitution was followed as the strategy for risk reduction. 70 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 3: TEXTILES CLEANING IN LAUNDRYS FINAL REPORT The PER-producing industry sees a significant reduction of PER due to the better technologies in the dry cleaning sector. Use of PER in the dry cleaning industry in Western Europe (ECSA 01b): 1980 1990 1995 1999 160.000 tons/year 100.000 tons/year 80.000 tons/year 74.000 tons/year 500 g/year/ 300 g/year/ 250 g/year/ 230 g/year/ inhabitant inhabitant inhabitant inhabitant In this special case emission control contributes directly to a reduction of the use of PER, because the non-emitted PER can be used again. 3.5. ALTERNATIVES For some special purposes still TRI is still in use, but it cannot be considered as a serious alternative because its properties in terms of environment and health risks are probably worse than those of PER. Chlorofluorocarbon solvents are totally banned for the use in dry cleaning shops. The major alternatives for PER are the petroleum solvents (mainly isoparaffins) and wet cleaning. Niche products are propylene glycol ethers (trade name Rynex®) which has gained a small market share or CO2 cleaning which is still under development. The main functional disadvantage of petroleum-based solvents is their lower Kauri-Butanol (KB) value in comparison to PER.9 There are a number of other technical disadvantages of petroleum-based dry cleaning solvents. They generally have a lower vapour pressure than PER, therefore drying takes longer for garments cleaned with these solvents instead of PER. Isoparaffin solvents are generally deemed to be less toxic than PER. Because the vapour pressures are lower than PER, evaporative losses and exposure from inhalation will be lower. Traditional petroleum-based solvents have a distinctive odour. Linear and branched hydrocarbons have relatively low odours while naphthenes and aromatics have strong and mostly repelling odours. Gentle wet washing in special machines, using similar chemicals as in consumer washing powders, is another major alternative. For its increased use, a clear recommendation for wet cleaning would have to be given on the garment label. In 2002 CINET proposed such a new label (a bold “W” in a circle). E.g. viscose and acetate products can be wet cleaned at 30°C and reduced mechanical agitation. Nevertheless garment producers often recommend dry cleaning even when wet cleaning would also be possible, in order to avoid any problems with the consumers. As a relative index of solvent power the Kauri-Butanol-Value is used: benzene is equal to 100, and all other solvents are compared to it. Higher KB values imply better removal of oil and grease stains. Linear paraffins generally have relatively low KB values. (In some cases, e.g. for cleaning of leather textiles or non-fadeproof garments where less agressive agents are required, a lower cleaning efficiency can be an advantage.) 9 71 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 3: TEXTILES CLEANING IN LAUNDRYS FINAL REPORT Presently research institutes are studying the possibilities of cleaning with carbon dioxide, but this technology is still in a research phase (BEEH 01). Producers of propylene glycole ethers have won a small market share, claiming that their product is completely non-toxic, readily biodegradable and in the long term cost effective. The technology seems promising, and equipment manufacturers are now introducing the first machines which are specially designed for this product. The major “cleaning technology” for most of the garments is still the normal washing process with water and tensides (NEAL 99) in the households. Theoretically it would be possible to produce exclusively garments which can stand the normal washing process. However on a global market with high consumer needs in terms of design and wearing comfort this option seems not easily achievable. It would require a global approach and a change of consumer behaviour. 3.6. IMPLICATIONS OF SUBSTITUTION FOR BUSINESS PRACTICE The business of the dry cleaning shops has been influenced by the market development and by regulations. Presently no trend can be observed that the percentage of garments which require dry cleaning is declining. Rather, there are indications that their market share is growing. On the other hand in countries with strict emission control requirements many dry cleaning shops had to close. In Germany the new regulations were blamed to have contributed to the closure of ca. 50% of all cleaning shops, mainly smaller ones. The larger shops could afford to invest in the new technology. The price for a Type IV equipment is approximately 50.000 EURO, additional PER monitoring equipment can be added. 3.7. CONCLUSIONS The main characteristic of the case can be described in short: After a risk discussion about PER in dry cleaning in the late 1980ies and early 1990ies a number of EU Member states introduced stricter emission rules. Relevant actors finally accepted the emission control approach instead of substitution. The consumption of PER for dry cleaning was reduced by more than 50% since 1980, in some countries by 90%. The case is still continuing, still stricter emission control via national and EU-regulation is on the agenda and research might lead to new effective alternatives such as cleaning with propylene glycole ethers or CO2. Four major influence factors could be identified: - Costs of equipment Equipment manufacturers were able to offer advanced machinery complying with the stricter emission control standards. For the producers this was an opportunity to sell equipment with a much higher value per cleaning machine. For the owners particularly of small dry cleaning laundries the higher capital investment has been a significant economic barrier. 72 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 3: TEXTILES CLEANING IN LAUNDRYS FINAL REPORT -- Technical Functionality The two major substitutes - hydrocarbons and wet cleaning - have a lower functional effectiveness (less cleaning potential, slower evaporation and risks of garment damages). The suppliers of chemicals have not yet been able to provide an alternative with similar technological properties and at the same time lower risks. + Risk information The potential carcinogenic effect of PER has not been studied in depth. It is possible that PER will have to be phased out completely when new scientific evidence emerges. + Shift of risks Although their health- and environment-related risks are lower than for PER, petroleum based solvents have a very limited use in textile dry cleaning. This is mainly due to their large fire risk. A shift towards wet cleaning would evidently reduce all types of risks. Single important factors overview Economics Costs of equipment Economics/costs hindrance of substitution Strong hindrance of substitution Support of substitution Support of substitution (-) (--) (+) (+) Technical function Substitutes may have lower functional effectiveness Technical functionality/performance Risk information In-depth risk information on conventional chemical not available Risk information/RI of chemical/product Regulation Shift of risk Risk information/Shift of risks 3.8. LITERATURE Beeh, M./ Swerew, M: CO2 - introduction into the new technologies, Hohenstein Institutes, lecture at the CINET convention 2001 BEEH 01 CHLORONL01 EUROCHLOR: Chlorine Online: Some facts about chlorinated solvents, last modified November 2001 CINET ECSA 01b ECSA 01a IARC 95 02 http://www.cinet-online.net/figures ECSA, Solvents Digest 20, Brussels, April 2001 European Chlorinated Solvents Association: Annex to Perchloroethylene Risk Assessment Report 12 April 2001 TETRACHLOROETHYLENE (Group 2A), VOL.: 63 (1995) (p. 159) 5. Summary of Data Reported and Evaluation 73 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 3: TEXTILES CLEANING IN LAUNDRYS FINAL REPORT ILO 99 NEAL 99 US DHHS ILO/ CIS 1999: International Hazard Datasheets on International Hazard Datasheets on Occupation: Dry Cleaner Neal R.: Special edition on Dry-Cleaning, in: ECSA, Solvents digest, July 1999 US Department of Health and Human Services, Authors: Earnest, G./Spencer, A.: Lessons from Europe: Reducing Occupational Exposure and Environmental Emissions to Perchloroethylene in Commercial Dry Cleaning, Report No. ECTB 201-07, Cincinnati, 1995 74 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT 4. 4.1. CASE STUDY 4: MARINE ANTI-FOULING COATINGS TECHNICAL AND CHEMICAL SCOPE 4.1.1. Technological scope Roughness of the underwater hull of ships and boats reduces the speed of the vessel, resulting in increased time and energy consumption and costs. The International Maritime Orgaisation defines “fouling“ as the “unwanted growth of biological material on a surface immersed in water” (IMO 99, p 4). Fouling stands here for the process of growing of a “bio film” consisting of e.g. barnacles, seaweed, tubeworms and other organisms. To prevent this effect, marine anti-fouling coatings have been developed to keep a smooth surface. The currently dominating type of marine antifouling coatings for merchant ships are organo-tin compounds with tributyltin (TBT) as the major chemical constituent. Paint manufacturers estimate that over 70 percent of the worlds ocean-going fleet is painted with TBT as effective biocide. The widespread use of TBT paints for ships and leisure boats started in the late 1960s. At this time “free association” paints were applied, which released the biocide rapidly but demanded frequent reapplication. This type of coating was gradually replaced by ‘selfpolishing copolymer’ (SPC) formulations which provide a more constant release of the biocides. Additionally these paints allow application of thicker paint coatings, bonding the TBT biocide chemically throughout the coating and resulting in a reduced repainting frequency. According to the producer’s association (ORTEPA) the lifetime of TBT-SPC’s is more than five years. A number of factors influence the growing of the bio film. The growth is faster if the ship is not moving but laying in a port (e.g. military vessels). Warm water temperatures also accelerate the growth (MAMPEC 99). In an extreme scenario, non-protected vessels may gather up to 150 kg of fouling per underwater square meter in six months. A large crude carrier with 20,000 m² underwater surface would then bear up to 3,000 tons of fouling (IMO 99, p 4). 4.1.2. Chemical Scope The growing of a bio-film at the underwater body of ships can be prevented, reduced or decelerated in two ways: by the hull’s surface structure or a by a biocide. Biocidal protection is by far dominating, mainly based on heavy metals like tin, copper or zinc. In the 1960ies the major types of anti-fouling paints were mainly based on copper, combined with toxic heavy metals, e.g. lead, mercury or arsenic or their compounds. Alternatively or additionally organochlorine chemicals such as PCP or DDT were used in anti-fouling paints. Organotin compounds were first developed and applied as moth-proofing agents in the 1920. TBT was introduced as an additive to copper-based formulations from the late 1960s on. In practice TBT showed a superior biocidal effectiveness compared to copper. 75 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT Two principal approaches in the developments of alternative technologies can be distinguished. The first approach can be characterised as substitution of biocides by either less dangerous ones or by technological treatment of the surface. The second approach aims to avoid the leaching of any biocide. A major path is to protect the metal with a smooth and durable layer made of teflon or silicon (see section 4.5 for a description of alternatives). 4.2. SCIENTIFIC EVIDENCE ON (ECO)TOXICOLOGICAL AND ENVIRONMENTAL IMPACT When compared to other controversial toxicological discussions the scientific evidence of the ecotoxic effects of TBT is almost undisputed. A majority of scientific studies which were performed before regulations came into force gave evidence of its eco-toxicity (e.g. EEA 01, IMO 99, UBA 00). Consequently organo-tin compounds are categorised as “List 1” substances of Directive 76/464/EEC and they are mentioned on the OSPAR list of chemicals for priority action. Tributyltin and triphenyltin compounds are listed on Annex 1A of the international North Sea Declaration and also (with highest concern) as one of 37 priority substances in the list of the Water Frame Work Directive. Tributyltin is a suspected endocrine disrupter. TBT is highly toxic to many marine plants and animals. Populations of dogwhelk and other mollusc have collapsed after their reproductive function had been negativley affected by TBT. Female snails develop a masculine condition depending on the amount of TBT present in their tissues. Sterilisation of female dogwhelks occurs at TBT concentrations as low as 3–5 ng/l. Almost all females are affected, if the concentrations reach 10 ng/l. The phenomenon was characterised as ‘the best example of endocrine disruption in invertebrates that is causally linked to an environmental pollutant’ (VOS 00). The most contaminated areas are coastal regions such as port regions, estuaries and embayments with ship traffic. Uncertainty remains about the effects of accumulation of butyltins in top predators (dolphins, sea otters). Effects on humans are also studied with diverging results until now. Nevertheless limits for food and daily uptake were proposed by international associations. The WHO published a LOAEL of 0.25 mg/kg per day and a NOAEL of 0.025 mg/kg per day (UBA 00 p A4). While the effects as such are not disagreed upon, the degree of concern varies among the involved parties. The TBT-producers association ORTEPA did not put in doubt the scientific evidence found for oysters, dogwhelks, some mollusc populations and some types of snails. It rather argued that the concentration of TBT were continuously declining, that the risk concerns only some selected species and that no risk assessment of the substitutes (TBT-free marine antifoulings) is available. ORTEPA also stated that the populations of endangered species (e.g. the oyster population in the French Arcachon Bay) have recovered since the regulations became stricter. 76 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT Contrarily, IMO presented an overview of the efficacy of organotin regulations, showing that in many areas no declining TBT-concentrations can ne observed (IMO 99, p 16). Also other studies showed controversial results concerning the question whether TBT concentrations are really declining (UBA 00, p B20). Environmental NGO’s (e.g. WWF 00) argued for a strict and fast ban of TBT because of its high toxicity for all kinds of species. According to their evaluation of studies, in some areas the TDI (Tolerable daily intake) has been reached even for humans. The IMO formulated basic criteria for “a good biocide” in anti-fouling systems: • • • • • • Broad spectrum activity Low mammalian toxicity Low water solubility No bioaccumulation in the food chain Not persistent in the environment Compatible with paint raw material. 4.3. INITIATIVES AT THE POLITICAL LEVEL In 2001 the United Nation’s International Maritime Organization (IMO) has adopted a proposal by its Marine Environmental Protection Committee MEPC (IMO 99b), targeting at a total elimination of TBT-coatings for all types of vessels (new applications) by the year 2003. Calculating a lifetime of approximately five years, there will be no organo-tin paints on sea ship vessel from 2008 on. A convention has been agreed between the IMO Member States in October 2001, to phase out the use of TBT from 2003 to 2008. This convention comes into force if 25 states, representing 25% of the world merchant ships fleet, ratify the convention. First attempts to regulate TBT-based anti-foulings started approximately 15 years after the beginning of their massive use (EEA 01 p143, IMO ): 1982 1985 1986 France introduces legislation prohibiting the use of TBT paints on small vessels. First controls introduced in United Kingdom limiting concentrations of TBT in paints. Scientists report widespread imposex in dogwhelks on southern coast of UK correlated with TBT. 1987 United Kingdom announces further restrictions on TBT content of antifouling paint; retail sale ban of TBT paint for use on vessels < 25 m and on fish cages. 1987 PARCOM Recommendation 87/1 calls for similar ban over entire convention area (Northeast Atlantic). 1988 Prohibitions addressing small vessels less than 25 meters in length are adopted in the United States (Organotin Antifouling Paint Control Act - OAPCA). Free association paints were practically banned. 1989 Similar restrictions introduced in Canada, Australia and New Zealand. 1991 Harmonised ban on retail sale of TBT paint introduced at EU level. 90-92 Japan, Australia and New Zealand ban the use of TBT-antifoulings. 1994 Early reports of imposex in whelks from offshore areas of North Sea linked to shipping activity. 77 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT 1995 1997 1997 1998 1999 1999 2001 2002 2002 Ministerial declaration of fourth North Sea conference (Esbjerg) commits to working for global phase-out of TBT paint within IMO. Japan bands the production of TBT-paints. Concept of global phase out of organotin-containing paints agreed at MEPC’s 40th session OSPAR (Convention for the Protection of the Marine Environment of the Northeast Atlantic) prioritises organo-tins for action to cease all releases. Cessation of all releases organotins to marine environment, under OSPAR’s hazardous substances strategy in 2020. Deadlines for phase-out adopted under IMO Assembly Resolution A 895. EU’s Directive 1999/51/EC bans TBT for boats of less than 25 meters and “vessels of any length for use predominantly on inland waterways and lakes”. International Convention on the Control of Harmful Anti-fouling Systems accepted by the IMO assembly: In 2003 worldwide prohibition on new application of organotin antifoulants to all vessels and in 2008 the existing organotin antifouling coatings will be replaced on all vessels worldwide Ratification procedure starts. The convention comes into force if 25 states representing 25% of the merchant ships fleet, ratify the convention. EU Directive 2002/62/EC of 9 July 2002 calls for the approximation of laws in the Member States and amends the market restriction Directive 76/769/EEC banning the use of TBT from January 2003 on. Due to the worldwide character of the problem the legislation process has become international. However, up to now the more detailed regulations like limited bans, special handling regulations or permitting of alternatives are dealt with in national legislation. The use of TBT in marine anti-fouling has been banned in smaller vessels since 1990 in most European Member states and since 2000 for vessels used in inland waters. Council Directive 89/677/EEC of 21 December 1989 (amending for the eighth time Directive 76/769/EEC) restricted the use of arsenic, mercury and tin compounds. For “organostannic compounds” this restriction was made for boats less than 25 meters and for equipment used for fish farming. Sales to non-professional users are forbidden and a special labelling enforced. Finally in 2002 the EU restricted the use of organostannic compounds for anti-fouling purposes totally. The ban enters into force in January 2003. 78 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT 21. Organostannic compounds May not be used as substances and constituents of preparations intended for use to prevent the fouling by micro-organisms, plants or animals of: a) the hulls of boats of an overall length, as defined by ISO 8666, of less than 25 metres; ............... Such substances and preparations may be placed on the market only in packagings of a capacity equal to or greater than 20 litres, may not be sold to the general public but only to professional users ....... the packaging of such preparations shall be legible and indelibly marked as follows: 'Not to be used on boats of an overall length of less than 25 metres or on any appliances or equipment used in fish or shellfish farming.'' 'Restricted to professional users.''... Commission Directive 2002/62/EC of July 9, 2002 (excerpt) Council Directive 89/677/EEC of 21 December 1989 (excerpt) Organostannic compounds ... may not be placed on the market or used as substances and constituents of preparations which act as biocides to prevent the fouling by microorganisms, plants or animals of: (a) tall craft irrespective of their length intended for use in marine, coastal, estuarine and inland waterways and lakes; (b) cages, floats, nets and any other appliances or equipment used for fish or shellfish farming; (c) any totally or partly submerged appliance or equipment. 4.4. INITIATIVES AND MOTIVATION AT THE ENTERPRISE LEVEL IMPLICATIONS OF SUBSTITUTION FOR BUSINESS PRACTICE The main actors influencing the enterprise policy are the authorities, the scientific community (eco-toxicology), paint developers and the general public including environmental NGO’s. Some major actors at the enterprise level include • • • • ship owners of merchant ships, the ship yards, paint producers, fish farmers and similar enterprises using the marine environment. Other important actors are the owners of private leisure boats, the national navies as owners of military vessels and the classification societies. 79 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT Substitution from organo-tin paints to substitutes PRO SUBSTITUTION CONTRA SUBSTITUTION Speed of the ship Fuel consumption Restricted availability of substitute coatings and application techniques Trust in the durability of substitutes Need for more expensive advanced application technologies Selling of a technically well developed product Environmental hazards of the alternatives Economic competition with shipyards in countries with less restrictions Five-Years-Longevity matches with Five-Years-Classification schedules Higher rates of transfer of harmful aquatic micro organisms and connected problems of proper treatment and waste disposal in ship yards Expected higher coating frequency Selling of more (other, higher priced) coatings Public image Environmental Hazards Scientific evidence Current and expected regulations Current and expected regulations Costs for the removal of contaminated sediments in Harbours etc. Less risks of spilling and water contamination Health hazards MAIN ACTORS Ship owners (economy) Ship owners (economy, env.) Practicability for ship owners and ship yards (economy) Shipyards (knowledge, liability) and ship owners including navies Shipyards (costs, process handling), private ship owners Paint manufacturers (conventional product line) All actors dealing with risk assessment Ship yards Ship owners (economy) Ship yards, health concerns Ship yards (economy) Paint manufacturers (TBT-free product lines), NGO’s Public opinion towards the branch, NGO’s , Classification societies Environmental authorities, fishers, fish farmers and the public, NGO’s Scientific community, Environmental authorities, NGO’s Environmental authorities Environmental authorities Local and regional authorities Shipyards (environmental care) Shipyards (less potential conflicts with workers and auth.) In short, the world-wide availability and practical experience with TBT-coating works as a general market advantage, which favours the product presently dominating the market. 80 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT Existing technical experience with TBT-paints and economic considerations are key arguments for merchant ship owners to stick to TBT-based paints. Fear of increasing fuel consumption due to the growth of a bio-film is used by ship owners as an additional environmental argument10. Consequently the ship owners argued for a sensitive timing of the fade-out of TBT (INTERCARGO, VSM 02). Sealing of TBT-coatings is promoted as one alternative. Ship yards might be cautious to apply alternative solutions because the effectiveness and durability of alternatives is still under development and not finally proven. Although most of the paint producers offer TBT-free paintings, these products are on the one hand new, on the other hand more expensive. High competition in a world wide repair and maintenance market can be a hindering factor. For shipyards a positive expectation might be a higher frequency of dock visits as Lloyd’s Register formulates it: “Less efficient antifouling coatings, of course, spell more visits to the Many paint manufacturers try to bring effective alternatives on the market. Research into alternative anti-fouling chemicals is developing rapidly, however the development time is relatively short compared to the time needed to evaluate the real technical effectiveness. In general the paint manufacturers still have doubts about the performance of their substitutes (UBA 00 p B19). Nevertheless some of them have phased out the production of TBT already (WWF 01) (see PRODUCERS in references). Due to the coming regulations and the overwhelming evidence concerning the environmental hazards, for environmental authorities, fish farmers, NGO’s and the general public it is clear that TBT will be phased out completely. Problems arise in evaluating the risks associated with the alternatives. Only the physical solution - smooth and durable surface coating without biocides - is undoubtedly environmentally superior, but this solution is still very expensive. Up to now these products could gain a significant market share only for leisure boats. The actors connected to the shipping business see the expected ban from IMO very critical. Also the process of the preparation o the regulations is harshly criticised (ENSUS 2000): dry dock.” ”The question arose as to who is involved in the regulatory decision making process and are all parties properly informed ?" Is the voice of science and scientists involved? Are shippers' concerns being addressed? Has the general public been made aware of all the issues? The topic of TBT may be inherently controversial because certain participants in this debate believe their voice is under-represented by regulators looking into banning TBT.” While copper based alternatives are comparable to TBT in price, other tin-free systems are significantly more expensive due to development costs and presently low volumes. e.g. at ENSUS 2000 (EVANS 00): “Dr. Stewart Evans, Conference Chair, opened the day's events by citing this theme in his discussion on our joint responsibility in protecting the marine environment. He challenged the logic in banning TBT citing the benefits of the antifoulant such as: Reduced fuel consumption on ships, yielding lower atmospheric pollution. Reduced chances of invasions of exotic species.” 10 81 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT 4.5. SUBSTITUTION AND ALTERNATIVES The availability of effective and economically viable alternatives to TBT is one of the main barriers in this case. Today many preparations which were in use prior to the widespread introduction of TBT cannot be seen as acceptable alternatives any longer. Many currently available alternatives have specific environmental hazards, which makes the risk assessment a complicated matter. Research on substitutes is spread over a number of paint and coating producers, based on their own resources or supported by their governments, who are testing a large number of possible substitutes. Some of the research projects are organised and co-ordinated by NGO’s as the WWF (WWF 02), by authorities (KEMI 98) or by producers’ associations as CEPE (MAMPEC 99). Different sources estimate that the costs of TBT-free coatings are 2 to six times higher than for TBT-coatings or copper based systems (ENSUS, PROPELLER). Paint producers expect that the costs will decrease when higher quantities will be demanded. The technical functionality of an anti-fouling coating cannot be seen immediately after use. One research problem is the requirement for simulation of long term behaviour of the coatings. Newly developed products have not proven their durability in practice - only in simulation tests. There is widespread doubt about the longevity, effectiveness, costs and the ecotoxic risks of alternatives, and companies or private persons applying a certain coating need to rely on the manufactuer’s claims or vague references from the first pioneer users. Institutions like IMO, the Irish EPA or trade journals published an overview of advantages and disadvantages of the TBT-free alternatives. The least hazardous solution is a biocidefree non-sticky coating which simply forms a physical barrier to bio-film growth. Application technology and equipment can be very different for physical coatings. The Irish EPA stated 1998: “However, much research is needed in order to develop coatings with similar performance and, if possible, price as TBT coatings.” The listed alternatives are based on three sources, the IRISH EPA, a WWF study and a focus report of IMO. 82 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT List of TBT-free solutions based on IE - Irish EPA list about Anti-fouling alternatives WWF - Study on “Biocide-free anti-fouling paints” (WWF 01b) IMO 99 - Anti-fouling systems (IMO 99) Source Antifouling Alternative Advantages (according to the sources) Disadvantages (according to the sources) May cause galvanic corrosion of aluminium hulls Copper may leach out of paint in a year or two Requires movement of boat through water to provide fresh biocide at hull surface Causes galvanic corrosion of aluminium hulls unless primer coat used Most require professionally trained users Currently expensive GROUP 1: Use of other biocides IE Conventional Control of fouling by Free macrofouling organisms Association (Copper Paint) IE Ablative Ablation results in fresh layer of antifouling paints biocide at the hull surface with copper May provide over five years protection IE Metallic copper coatings IE IE IE IE May require professionally trained users Requires specialised application Treatment Antifoulant with Does not prevent build-up of bio-film organisms and grasses on hull copper thiocyanate Not as effective as cuprous oxide paints 5-hydroxytetraClaimed to double life of May leach from certain paints too cycline monoantifouling paints quickly (depending on the coating hydrochloride Stops biofilm-forming organisms matrix) Zinc oxide Boat owner can apply Low levels of generated peroxides antifouling paints Can be used on aluminium hulls are not very effective against Independent testing indicates micro-foulers, but are effective paints perform well against barnacle larvae Metallic copper thermal spray product Independent testing indicates that coatings perform well Hard coating resistant to scratching Can be applied to aluminium hulls Claimed to be effective for up to ten years Primarily for recreational boats Can be used for aluminium hulls GROUP 2: Biocide-free non-stick coatings IMO Non-stick Suitable for vessels with a coatings minimum speed of 30 knots IE Silicon coatings Difficult to repair damages IE: Requires professional application May have to clean less frequently used vessels Currently expensive Practicability for ships is questioned WWF Silicon coatings Fouling can be easily removed Very slippery surface (inhibits attachment) Frequently used high speed vessels may clean themselves Claimed to be non-toxic to nontarget organisms for vessels with a high average speed and high activity levels 83 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT IE Teflon and metallic copper paints Teflon hull wax Paraffin wax combined with polyurethane Prickly coatings IE WWF IMO Slippery surface Primarily used on recreational boats Boat owner can apply One season protection Six week protection Tests not completed or evaluated Effective Requires copper biocide Must manually clean hull before organisms firmly attach Must be reapplied Only for crafts operated in freshwater Increased water resistance of vessels Poor effectiveness to prevent macroalgae fouling GROUP 3: Fibre coatings WWF Fibre coats fixed Good effectiveness to prevent on an epoxy barnacle fouling coating GROUP 4: Self-polishing copolymers (SPC) WWF SPC without TBT Good effectiveness on ships with a high average speed Poor effectiveness on ships with a low average speed GROUP 5: Anti-corrosive paints WWF Anti-corrosive Tests not completed or evaluated paints GROUP 6: OTHER TECHNICAL SOLUTIONS IE Acoustical Good for micro and macro fouling antifouling organisms devices May be used without antifouling IE IMO Electricity IMO Cleaning paint Primarily for recreational boats IE: Good for micro and macro fouling organisms May be used without antifouling paint Primarily for recreational boats IMO: effective Very effective Must periodically clean hull Ineffective on concrete hulls Professional installation is recommended IE: Must periodically clean hull Ineffective on concrete hulls Professional installation is recommended IMO: Energy consumption, corrosion risk 4.6. Conclusions The application of organo-tin coatings has been subject to an intense debate since 1980, after the first serious environmental damages caused by TBT were detected. There is little scientific doubt about the ecotoxic effects of TBT, and it was widely accepted already in the middle of the 1980ies that the dominating ship coating technology, based on TBT as the effective substance, should be replaced as soon as possible. The regulations enforced in the EU in the 1980ies and 1990ies reduced the accepted uses of organostannic compounds for anti-fouling purposes step by step. First came prohibitions of TBT use on small vessels and boats for private use, ending in the year 2000 with an 84 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT amendment of the Directive 76/769/EEC stipulating a EU-wide total ban of TBT which will enter into force from 2003 on. Even a global ban issued by the supra-national maritime UNorganisation IMO has been adopted, but has not entered in force yet. The use of biocides at the underwater level of boats has one main advantage: a smooth surface guarantees that a vessel can keep its speed, which saves time, costs and energy. TBT is a very harmful but effective biocide to keep the surface free from fouling. A large number of substitutes with different characteristics has been developed and is marketed. However, there is still development time needed. During this time a number of actors will doubt and mistrust the technical comparability of the substitutes with TBT-coatings. Four major influence factors could be identified: -- Economics: High economic impact for the users For a merchant shipping line the speed of their freight ships is essential to keep the time schedules. The toxic coating is energy-saving and thus reduces operating costs. - Technical functionality: Development and effectiveness of alternatives A dominant technology, based on one effective substance, needs to be replaced by a number of alternative chemicals and technologies. The time needed for research and development, especially tests of the longevity, decelerates the process of substitution. ++ Public The main ecotoxicological effect of TBT – simply speaking the changing of sex – can be very well promoted in public campaigns. The difference is obvious especially in comparison to the industrially used chemicals as mould releases or metal parts cleaners. ++ Risk assessment: High impact of scientific evidence The evidence linking cause and effect is not controversial in the scientific community and one of the clearest examples for dose-effect responses. ++ Regulation The comparatively fast development and implementation of regulations, i.e. 20 years from the first findings to an agreement on a world wide ban, can be seen as consequence of the high scientific evidence and the high public concern. The comparatively fast and strict process of regulation is not listed as a key factor, but as a consequence of the scientific evidence and the public concern. 85 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT Single important factors overview Economics Costs implications caused by higher prices of substitutes and slower ships Economics/costs Strong hindrance of substitution Hindrance of substitution Strong support of substitution (--) (-) (++) Technical function The effectiveness of substitutes is under development Technical functionality/performance Social factors/awareness (public) Social factors Awareness of environmental aspects Risk information Strong scientific support on harm of conventional substances. Risk information/RI of chemical/product Regulative frame Fast implementation of regulation Strong support of substitution (++) (++) Regulative frame/legislation Strong support of substitution 4.6. LITERATURE Anti-fouling working group of CEPE: Utilisation of more environmentally friendly antifouling products, EC project 96/559/3040/DEB/E2, 1999 European Environmental Agency: Environmental Issue Report No 22: Late lessons from early warnings: the precautionary principle 1896 - 2000, Chapter 13: Tributyltin antifoulants: a tale of ships, snails and imposex, Copenhagen, 2001 Council Directive 89/677/EEC of 21 December 1989 amending for the eighth time Directive 76/769/EEC on the approximation of the laws, regulations and administrative provisions of the member states relating to restrictions on the marketing and use of certain dangerous substances and preparations Commission Directive 1999/51/EC of 26 May 1999 adopting to adapting to technical progress for the fifth time Annex I to Council Directive 76/769/EEC on the approximations of the laws, regulations, and administrative provisions of the Member States relating to restrictions on the marketing and use of certain dangerous substances and preparations (tin, PCP and cadmium) Commission Directive 2002/62/EC of 9 July 2002 adapting to technical progress for the fifth time Annex I to Council Directive 76/769/EEC on the approximations of the laws, regulations, and administrative provisions of the Member States relating to restrictions on the marketing and use of certain dangerous substances and preparations (tin, PCP and cadmium) ENSUS 2000 - Marine Science and Technology for sustainability, Conference September 2000, University of Newcastle upon-Tyne CEPE 99 EEA 01 EC 89/677 EC 1999/51 EC 2002/62 ENSUS 00 86 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT EVANS 00 ENSUS 2000 - Marine Science and Technology for sustainability, Conference September 2000, University of Newcastle upon-Tyne, Session 7: TBT-Ban What next? Clean Technology Centre: Inventory and tracking of dangerous substances used in Ireland and development of measures to reduce their emissions/losses to the environment / Best environmental practice guidelines A-5 Organo-tin, Cork 1999 Anti-fouling Systems moving towards the non-toxic solution, in: Focus on IMO, April 1999 Resolution A.895(21) adopted on 25 November 1999: Anti-fouling systems used on ships International Convention on the Control of Harmful Anti-fouling Systems on Ships, Adoption: 5 October 2001 IE EPA 99 IMO 99 a IMO 99 b IMO 01 INTERCARGO International Association of Dry Cargo Shipowners: Work programme 2002, p. 10 KEMI 98 Chemicals Inspectorate (Sweden): Antifoulingprodukter för yrkesmässigt bruk - Fartyg längre än 12 meter, 1998, (Antifoulings for commercial use - Vessels longer than 12 meters, 1998) Institute for Environmental Studies (IVM), Vrije Universiteit, Amsterdam: Development of a computer model (MAM-PEC) to predict marine environmental concentrations of antifouling agents, Amsterdam 1999 Green Effort for Existing Ships - Test of Tinfree Anti-fouling Paints Test Ship Programme, Project Presentation Current Statements to all aspects of antifoulings can be found at the website of the producers of organotins under www.ortepa.org. ORTEPA stands for “Organotin Environmental Programme Association” OSPAR strategy with regard to hazardous substances, OSPAR 98/14/1, Annex 34, OSPAR Convention for them Protection of the Marine Environment of the Northeast Atlantic. 1987. PARCOM Recommendation87/1 on the use of tributyl-tin compounds, 3 June 1987, Paris Convention for the Prevention of Marine Pollution from LandBased Sources. PARCOM Recommendation 88/1 on measures to reduce organotin compounds reaching the aquatic environment through docking activities, 17 June 1988, Paris Convention for the Prevention of Marine Pollution from Land-Based MAMPEC99 MARINTEK ORTEPA OSP 98 PAR 87 PAR 88 87 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 4: MARINE ANTI-FOULING COATINGS FINAL REPORT PRODUCERS for further information please look at the product information sheets and the homepages of producers of coatings and active substances as e.g. Akzo Nobel, Ameron, Arch Chemicals, Bayer, Ciba Geigy, Chugoku, Elf Atochem, Hempel, International Coatings , Jotun, Kansai, Lotrec, Mitsubishi, Nautix, Nordox, Sigma, Seal Coat, Star Marine etc. PROPELLER UBA 00 Cost factor limits teh use for the present, in: International Coatings: Ppropeller direct, May 1998, p.11 Environmental Protection Agency (Germany): Fachöffentliche Anhörung vom 14. März 2000 zu Produktion und Verwendung zinnorganischer Verbindungen in Deutschland (Stakeholder hearing on production and use of organotin compounds, March 2000) Vos, J. G., Dybing, E., Greim, H. A.,Ladefoged, O., Lambre, C., Tarazona, J. V., Brandt, I. and Vethaak, A. D., 2000. ‘Health effects of endocrine-disrupting chemicals on wildlife, with special reference to the European situation’, Critical Reviews in Toxicology Vol. 30, No 1, pp. 71–133. VERBAND FÜR SCHIFFBAU UND MEERESTECHNIK E.V.: Maßnahmen der EU zum Verbot von TBT-Schiffsfarben benachteiligen Werften im internationalen Wettbewerb (EU-Regulation concerning the ban of TBT penalize European shipyards), Press release July 16, 2002 Press release, “WWF battles marine pollution from anti-fouling paints”, March 2000 TBT-Verbot trägt Früchte - Größter Schiffsfarbenhersteller verzichtet auf TBT, Bremen, 21.11.2001 (TBT-ban effective - largest ship paint producers phases out TBT) Performance of biocide free antifouling paints - Trials on deep-sea going vessels, WWF 2001 Utvärdering av bottenfärger för fritidsbatar 2000 - 2001 (Evaluation of coatings for leisure boats), VOS 00 VSM 02 WWF 00 WWF 01a WWF 01b SJÖF 02 88 Kooperationsstelle Hamburg SUBSTITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 5: WOOD PRESERVATION FINAL REPORT 5. CASE STUDY 5: WOOD PRESERVATION 5.1 MARKET, TECHNOLOGY AND CHEMICAL SCOPE In this study wood preservation products are analysed which are commercially available for private consumers. Wood preservation products restricted to professional use are not considered. The substitution conditions between the private consumer and the professional sector differ significantly. In the consumers sector in general less toxic chemicals are used to reduce the risks. Nevertheless the risk can be higher than in industrial application, because consumers in general apply the product manually without protection. Market for wood treatment consumer products Consumer products for wood preservation are marketed in two main varieties: as pure preservation products and as finished wood products containing preservation chemicals. In general consumers use these products for first protection or maintenance of wood. Decay of wood is mainly expected in outdoor use, such as fences, poles, piles, garden furniture, wooden window frames, wooden wall and roof constructions, carports etc. Nevertheless a considerable part of the consumption goes to protection of wood inside houses. This is mainly that wood, which forms an elementary part of the construction (beams, wooden ceilings, window frames inside etc). These parts of a wooden construction are normally industrially pre-treated but might need maintenance after some years. The wood preservation products differ depending on the required application. Possible applications are outdoor protection or in-house use, long lasting preservation or short / medium time preservation, with(out) earth contact, affected by fungi (as Blue Stain Fungi, Slime Molds) or insects (as ants, bees or beetles etc.). These conditions influence basically the choice of the desired effect and in this way the choice of the biocide. Technological scope Wood preservation products are designed to protect the wood against premature decay. Wood becomes subject to degradation if is untreated, especially in outdoor applications or in inhouse areas with high moisture. Some types of wood possess naturally occurring resistance to decay (hardwood as beech, oak, ash, walnut etc.). However, the much cheaper and widely used conifers (softwood as spruce, fir, pine, larch, hemlock, cedar) show little decay resistance and extra protection is needed. Wood has mainly to be protected from the attack of decay and destruction by fungi and harmful insects. Both types of decay depend highly on two main environmental conditions: the degree of moisture and the general circumstances (ultraviolet radiation, rain, population of insects) in the environment. The picture below shows the attack of different fungi on Green Pine Sapwood (VTT 01). 89 Kooperationsstelle Hamburg SUBSTITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 5: WOOD PRESERVATION FINAL REPORT The degree of protection achieved depends on the specific effectiveness of the preservative used, the proper penetration and retention of the chemicals. Therefore, for each wood species chemical preservative and treatment methods are required to obtain long-term effectiveness, adequate penetration and retention. Very good penetration and retention can only be achieved by professional methods using high temperatures and pressure in industrial installations. Substances as chromates, copper, creosotes or pentachlorophenol and in exceptional cases even still arsenic are used. The effort of the process depends in a linear way on the amount of preservative used. A list as the following can be made nearly for every type of wood and preservative (WOOD 99). Preservative: Chromated zinc arsenate kg/m3 1.76 (0.11) 3.52 (0.22) 4.65 (0.29) 3.20 (0.20) 6.41 (0.40) 8.49 (0.53) 6.09 (0.38) 8.33 (0.52) 11.21 (0.70) Wood: Southern Pine sapwood stakes, pressure-treated Average life (year) or condition at last inspection 22.1 years 33.0 years 89% failed after 51-1/2 years 10% failed after 40 years No failures after 40 years No failures after 40 years 40% failed after 51-1/2 years 10% failed after 51-1/2 years No failures after 51-1/2 years Technology of consumer application Consumer application is a pure surface application. The simplest treatment is to apply the preservative to the wood with a brush or by dipping. Rough lumber may require as much as 40 litre of oil per 100 m² of surface, but surfaced lumber requires considerably less. The transverse penetration obtained will usually be less than 2.5 mm, although in easily penetrated species the end-grain (longitudinal) penetration is considerably greater. The additional life obtained by such treatments over that of untreated wood will be affected greatly by the conditions of service. Service life may be from 1 to 5 years for wood in contact with the ground. Preservative penetration and retention levels obtained by cold soaking lumber for several hours are considerably better than those obtained by brief dipping of similar species. However, preservative retention levels seldom equal those obtained in pressure treatment. Chemical scope In consumer products generally less hazardous and less toxic biocides against fungi and 90 Kooperationsstelle Hamburg SUBSTITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 5: WOOD PRESERVATION FINAL REPORT insects are used compared to professional preservatives. Typical currently used chemicals are Boron, Dichlofluanid, Tebukonazol, Butylkarbamat and Pyrethroides. For this study we focus on the effects of the replacement of Lindane by Pyrethroides as insecticides and the replacement of PCP by Dichlofluanid as main fungicide. These two substitutions took place in the eighties and nineties, they represent in many EU-Member States according to the few figures available the major stream of substitution. The development of successful products has to take five factors into account: • High and specific activity against the insects and fungi, • No negative influence on the wood, • Low toxicity against all other species, • Competitive prices and • Easy application. 5.2. SCIENTIFIC EVIDENCE ON (ECO)TOXICOLOGICAL AND ENVIRONMENTAL IMPACT There is a higher toxicity of the substances compared to the other case studies due to their desired biocidal effect. The non-controversial scientific evidence of the two ‘old’ products has become official in form of risk phrases and a large number of restricting regulations. PCP PCP is the primary synonym for Pentachlorophenol, an organohalogene compound, also commonly referred to as PCP (CAS 87-86-5). PCP is a synthetically manufactured chemical substance, which is recognised as being dangerous for both humans and the environment. Classification and labelling of PCP are harmonised at community level (Council Directive 67/548/EEC). PCP is classified as very toxic by inhalation and labelled “Very toxic by inhalation” (R26) and “Toxic to the skin” and at swallowing (R24/R25). It is classified as irritating to eyes, the respiratory system and skin (R36/R37/R38). PCP is classified as a category 3 carcinogen (R40), i.e. a substance of concern to man because of a possible carcinogenic effect. Additionally PCP is classified as dangerous for the environment and labelled as “Very toxic to aquatic organisms. It may cause long-term adverse effects in the aquatic environment” (R50/R53). PCP is included in List I of Council Directive 76/464/EEC on pollution caused by certain dangerous substances discharged into the aquatic environment. This list contains substances that are selected mainly on the basis of their toxicity, persistence and bioaccumulation. PCP contains dangerous impurities including up to 0.1% of polychlorodibenzodioxins and 1% to 5% of polychlorinated phenoxyphenols. PCP inclusive its impurities is contributing to the daily emission of dioxins into the environment. Dioxins are emitted when products treated with PCP, exposed to the sunlight and incinerated at the end of their useful life. PCP in sewage sludge is also a source of dioxins. (EU-PCP 99) 91 Kooperationsstelle Hamburg SUBSTITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 5: WOOD PRESERVATION FINAL REPORT LINDANE Lindane is the primary synonym for Hexachlorocyclohexane (HCH) also commonly referred to as benzene hexachloride (BHC) (CAS-Nr: 58-89-9 and 608-73-1 as group of alpha-, betaand gamma- HCH). It is, like PCP, an organohalogene compound. This substance is classified as a dangerous substance under Directive 67/548/EEC. Lindane is classified as toxic by inhalation and labelled as “Toxic by inhalation”, “Toxic at swallowing” and “Toxic at contact with the skin” (R 23/24/25). It is classified as irritating to eyes and skin (R36/R38). Lindane is classified as dangerous for the environment and labelled as “Very toxic to aquatic organisms”. It may cause long-term adverse effects in the aquatic environment. Lindane is, like PCP, included in List I of Council Directive 76/464/EEC on pollution caused by certain dangerous substances discharged into the aquatic environment. This list contains substances that are selected mainly on the basis of their toxicity, persistence and bioaccumulation. Lindane is found in air, water and soil samples throughout the world. Lindane is documented in human breast milk and amniotic fluid. It is not only used as a wood preservative but on pets, livestock, fruits and vegetables, cotton, wool, tobacco, plants and trees. DICHLOFLUANIDE Dichlofluanid (CAS-NR:1085-98-9, Formula: C9-H11-Cl2-F1-N2-O2-S2) is the trivial name for Sulfamide, N-((dichlorofluoromethyl)thio)-N',N'-dimethyl-N-phenyl (EINECS-Name). This substance is classified as a dangerous substance under Directive 67/548/EEC as harmful (R20) and labelled as “Harmful by inhalation” (R36) and irritating to eyes (R43). Dichlofluanid is classified as PCP and Lindane as dangerous for the environment and labelled as “Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment” (R50/53). Dichlofluanid is not included in List I of Council Directive 76/464/EEC. However, it belongs to List 2, i.e. pesticide. PYRETHOIDS – DELTAMETHRIN Pyrethroides is the name for a group of chemicals. The selected Deltamethrin is one of approximately 1,000 synthetic pyrethroides; 20 of them are marketed successfully as insecticides. Deltamethrin or Decamethrin (CAS-NR.: 52918-63-5) is the primary synonym for Cyclopropanecarboxylic acid, 3-(2,2-dibromoethenyl)-2,2-dimethyl-ester, cyano(3phenoxyphenyl) methyl ester and (1r-(1-alpha(s*),3-alpha)) (EINECS-Name). Deltamethrin is a synthetically manufactured chemical substance which is recognised as being dangerous for both humans and the environment. Deltamethrin is classified as “Toxic at Inhalation” and “Toxic at swallowing” (R23/R25). As all the three others Deltamethrin is classified as dangerous for the environment and labelled as “Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment” (R50/R53). 92 Kooperationsstelle Hamburg SUBSTITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 5: WOOD PRESERVATION FINAL REPORT 5.3. INITIATIVES AT THE POLICY LEVEL PCP and Lindane are completely banned for consumer products in wood preservation, but it is still accepted in professional use. Dichlofluanid and the Pyrethroides are classified and under discussion. However, they are not as strict regulated as the two older chemicals. Directive 91/173/EEC prohibits the marketing and use of PCP, its salts and esters in substances or preparations in a concentration equal to or greater than 0,1% by mass. This restriction does not apply to substances and preparations intended for use in industrial installations. Emission levels and/or discharges of pentachlorophenol (PCP) are pre-scribed by existing legislation for the treatment of wood: …in the treatment of wood. However, treated wood may not be used inside buildings whether for decorative purposes or not whatever their purpose (residence, employment, leisure); - for the manufacture of containers intended for growing purposes and any re-treatment and the manufacture of packaging which may come into contact with or other materials which may contaminate raw, intermediate and/or finished products intended for human and/or animal consumption and any re-treatment; - in the impregnation of fibres and heavy-duty textiles not intended in any case for clothing or for decorative furnishings; - as a synthesizing and/or processing agent in industrial processes; - by way of special exception. In any case Pentachlorophenol used alone or as a component of preparations employed within the framework of the above exceptions a) must have a total hexachlorodibenzoparadioxid (H6CDD) content below four parts per million (ppm); (b) these substances and preparations may not be placed on the market except in packages of 20 litres or more; c) be sold to the general public. The packaging of such preparations should be marked clearly and indelibly: "Reserved for industrial and professional use" (Directive 91/173/EEC). Austria, Denmark, Germany (since 1989), the Netherlands (since 1992) and Sweden (in the Act of Accession Sweden was exempted from EU legislation Dir. 91/173) restrict PCP even stricter than the EU. The EC Commission endorsed the German restriction (EU-PCP 94) and the Dutch one (EU-PCP 99). All these national provisions totally ban the use of PCPcontaining products for wood treatment and textiles. Due to the restrictions in European and national levels, the amounts of PCP for wood in the EC has decreased from 8,000 tonnes in 1986 to 2,000 tonnes in 1994. PCP is also included in the "Non-exhaustive list of agents, processes and work" against which young people must be protected EU (Directive 94/33/EC on the protection of young people at work). Lindane is not as strictly regulated as PCP. Lindane is still accepted in wood preservatives, 93 Kooperationsstelle Hamburg SUBSTITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 5: WOOD PRESERVATION FINAL REPORT although the available information shows a real replacement in marketed products by the Pyrethroides. Its use for agricultural purposes is banned since the beginning of 2001 (Amendment of EEC/91/414). The ban will cover all agricultural and gardening applications, but not the use in domestic products against insects. For Dichlofluanid and Deltamethrin mainly the classification and labelling and safety rules apply. 5.4. MOTIVATION PCP and Lindane were subject to a number of public scandals in the seventies and eighties. Accidents during production and use, the ubiquitous detection of these two chemicals in soil, food and human tissues and especially the content of dioxins has made them “prominent” as dangerous chemicals. Their use in wood preservatives was heavily criticised after the debate on chemicals and their impact on the environment after the Seveso accident. Consumer products as wood preservatives became a topic five to ten years after this first intense environmental debate. Producers of wood preservatives Producers had to react on consumers’ demands with regards to less risks for their health. Most of the producers finally started to market PCP- and Lindane-free products. Consumers The awareness of consumers towards wood treatment products is comparably high. These chemicals remain for a long period in the household and the private environment. The main toxic issue in PCP and Lindane is the amount of Dioxins. Dioxins are widely known outside the scientific and chemical expert’s discussion as ultra toxic. Substitution of a biocide means no change in the handling and application. New or special equipment is not required. Of course parts of the consumers had doubts concerning the degree of protection. The situation in Germany relating to the use inside housing of wood products treated with PCP has been illustrated by legal proceedings taken since 1984. More than 3,000 persons have filed complaints against managers of enterprises for having sold products which have damaged their health. Science There is no scientific controversy, that the replacement of PCP and Lindane is very reasonable from a toxicological view. However, the two substitutes are criticised as well. Dichlofluanid has raised concern in Denmark after an indoor use: 200 consumers sue the importer for diseases. The pyrethroides have shown a toxic potential especially to the nerve system of humans. However, the scientific opinion is still controversial discussed. Therefore, there is urgency to find less toxic products. Research is also going on in the technological field to find alternative solutions (COST 22). 94 Kooperationsstelle Hamburg SUBSTITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 5: WOOD PRESERVATION FINAL REPORT NGO’s Biocides have been a core element of many environmental NGO’s campaigns. One of the organisations PAN – the Pesticides Action Network – is focussed solely on pesticides. Other worldwide known NGO’s as the WWF and Greenpeace campaigned against some types of biocides in the least twenty years (WWF is known for TBT-campaigns, Greenpeace for campaigns against chlorinated chemicals). PAN has campaigned since 1985 against the ‘Dirty dozen” (PAN 95), an early step towards the POP convention agreed in 2001 in Stockholm. The overall exposition from pesticides is one of the strongest argument of the NGO’s. The use in consumer products, in construction and in agriculture makes traces of pesticides an unavoidable part of every humans daily life. 5.5. SUBSTITUTION AND ALTERNATIVES Dichlofluanid, as alternative for PCP, has gained the largest market share in Western Europe. Pyrethroides, which are an alternative for Lindane, has gained the largest market share. The arguments pro and contra substitution are listed in the following tables. Substitution from Lindane to Pyrethroides and from PCP to Dichlofluanid LINDANE TO PYRETHROIDES PRO SUBSTITUTION Risk of contamination by dioxins Long persistency and global findings detection Detection of Lindane in food and breast milk No contamination risk for pyrethroides Basic pyrethroides similar to natural origin Much less acute toxicity to warm-blooded animals Medium persistency of synthetic Pyrethroides Sensitive complex of blocking of nerve connections Effects not fully studied CONTRA SUBSTITUTION PCP TO DICHLOFLUANID PRO SUBSTITUTION Risk of contamination of PCP by dioxine Long persistency PCP in food and breast milk Risks of forming of dioxins during incineration High aquatic toxicity No contamination risk for Dichlofluanid Still a risk for humans CONTRA SUBSTITUTION Same risk for the aquatic environment 95 Kooperationsstelle Hamburg SUBSTITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 5: WOOD PRESERVATION FINAL REPORT 5.6. CONCLUSIONS / KEY FACTORS Scientific evidence on persistency and contamination of PCP and Lindane with ultratoxic dioxins resulted in a high sensibility and resistance of consumers to use such products in their private environment. Strict regulations for PCP and Lindane led to a strong decline of the use of these two products. Still the professional use is only limited, not banned. Less toxic products have substituted the incriminated products. The identification of hazards of the substitutes led to new concerns, but the concerns are not as alarming as with the old products. + Process integration For consumers there is no change in application technology (mainly brushing or dipping). The application needs no special additional equipment. ++ Awareness Very high awareness among consumers and the public was the main reason for substitution. The high toxicity, for a broader public proven in accidents, ubiquitous detection was clearer as in every other of the ten case studies. ++ Risk information The scientific findings about the persistency and the contamination of PCP and Lindane with ultra-toxic dioxins resulted in a high sensitivity and resistance of consumers to use such products in their private environment. Public scandals made the products widely known. ++ Regulations: Strict regulations reduced the use of PCP and Lindane to a minimum in consumer products for wood preservation. Even stricter exceptions for some EU-countries were endorsed by the EU-Commission. Single important factors overview Technical function No change of equipment required for substitutes Technical functionality/process integration Social factors Awareness of high toxicity Support of substitution Strong support of substitution (+) (++) Social factors/awareness (public) Risk information Scientific evidence on persistency and contamination of PCP and Lindane with ultratoxic dioxins Risk information/RI of chemical/product Regulative frame Strict regulations regarding conventional wood preservation Strong support of substitution (++) Regulative frame/legislation Strong support of substitution (++) 96 Kooperationsstelle Hamburg SUBSTITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 5: WOOD PRESERVATION FINAL REPORT 5.6. LITERATURE COST 22 COST Action E22: Environmental optimisation of wood protection (Combined research activity of EU 5 FRP, see the documents under http://www.bfafh.de/inst4/43/download.htm COMMISSION DECISION of 14 September 1994 concerning the prohibition of PCP notified by the Federal Republic of Germany (94/783/EC, OJ L 316, 9.12.1994, p. 43) COMMISSION DECISION of 26 October 1999 concerning the national provisions notified by the Kingdom of the Netherlands concerning the limitations of the marketing and use of pentachlorophenol (PCP), OJ L 22.12.1999, p. 15) OECD Environment, Health and Safety Publications, Series on Pesticides EPE 99, No. 11, Survey of Best Practices in the Regulation of Pesticides in Twelve OECD Countries (2001) Schonfield, A., Anderson, W., Moore: PAN's Dirty Dozen Campaign -- The View at Ten Years. Global Pesticide Campaigner, Volume 5, Number 3, September 1995 Ritschkoff, A.-C., Mahlberg, R.: Fate and biotransformation of biocides and biotransformation of biocides - A way to acceptable chemical wood preservation, Meeting of COST Action E22: Environmental optimisation of wood protection: Workshop on Optimising treatment levels and managing environmental risks, Reinbek, 8 – 9 Nov 2001 Forest Products Laboratory / United States Department of Agriculture: Wood handbook—Wood as an engineering material, Madison, 1999 EU-PCP 94 EU-PCP 99 OECD 01 PAN 95 VTT 01 WOOD 99 97 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT 6. 6.1. CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUIT BOARDS Introduction The production of electrical and electronic equipment (EEE) is a fast growing domain of the manufacturing industry. The sector came into focus of EU environmental policy because of the amount of waste from electrical and electronic equipment (WEEE) which for the early 1990ies was estimated at annually six million tonnes and expected to increase in the future (ENEA 95). In Germany alone the total amount of WEEE is presently estimated at approximately 1,8 Mio t/y (GerEPA 01)11. Although being relatively small, electronic communication systems, like mobile phones and cordless phones, contribute a large amount of WEEE as they have a short useful life-time of 2 to 4 years. Besides the growing number of electronic appliances on the market, there is also a trend towards increased use of electronics for advanced electronic control functions in complex products. E.g. the amount of electronics used in cars is increasing and is presently estimated at 4 to 8 kg per car (Öko 01). Printed circuit boards are an integrated part of all electronic devices like e.g. television sets, computers, stereos, (mobile) phones etc., and nowadays also most electrical devices contain circuit boards. A printed circuit board consists of the board with its conductive paths to which the electronic component parts are connected by soldering. The dominating material for electronic circuit boards are glass fibre reinforced epoxides (Ger EPA 01). These are classified as FR 4 type materials according to the US-norm NEMA which is the generally accepted norm in the electronic field. The industry processing circuit boards had a turn-over of approximately 7 billion € within the EU in 2001 with a rapid growth during the last years: between 1999 and 2001 the growth rate was 10.5% with the major contribution coming from growing demands in the information technology (IT) and telecommunication sector (FED 01), with both sectors now covering more than 70% of the market (others: automobile, industry electronics, military). Hazardous substances in Circuit Boards The main areas for which hazardous substances contained in circuit boards were discussed in the past are: • • • • the presence of organohalogens in the electronic component parts, the presence of lead in the solder used for connecting the component parts, monomer raw materials of epoxide, (brominated) substances in the resin matrix and in the surface lacquer to reduce flammability. 11 Circuit boards in Germany account for ca. 62.000 t of the German Electronic waste (data for 1999/2000, Ger EPA 01). 98 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT Problems related to hazardous substances arose from waste management, environmental or health aspects or combinations of these. a) Presence of organohalogens in electronic components The presence and potential substitution of organohalogens in electronic components is very difficult to address because the suppliers / producers of these components are globally acting companies with production plants distributed over the world. However, the topic is presently under debate in parallel to the substitution of lead. b) Presence of lead in the solder used for connecting the component parts The solder used for circuit boards typically consists of a mixture of 63% tin and 37% lead. The high lead content of circuit boards leads to contamination of the plastic containing waste stream (shredder light fraction) when the product is shredded at its end-of life stage. The lead contamination of this fraction often prevents its use in more advanced levels of recycling and makes its use as secondary fuel problematic. The draft Directive on restrictions of the use of certain hazardous substances in EEE (ROHS) proposes a ban of lead containing solder from electronic devices. Several substitutes e.g. alloys of tin with silver, copper and/or bismuth have been developed and introduced in the market. According to one producer of circuit boards the introduction of these in the market on a broad basis will not happen before the Directive has entered into force (VOGT 01). Main reasons are the slightly higher price of the substitute due to revamp costs in the soldering processes. Most companies will wait until investment in the processes are needed anyway and will then proceed with substitution in parallel with other technical adjustments. c) Monomer raw materials of epoxide resin The monomeric raw materials for epoxides, namely epichlorohydrin and bisphenol A, have hazardous properties. However, after polymerisation the resulting polymer is highly inert and is almost free of these monomer components (allowing the use of epoxide adhesive even for dental applications). It can be concluded that the hazardous properties of monomers are of concern mainly for occupational health during resin production and processing. d) Substances in the resin matrix and in the surface lacquer to reduce flammability. Nearly all electronic systems and their components must fulfil specific fire safety demands. For achieving this goal, so called flame retardants are added to the polymer matrix, in order to prevent inflammation of the material in the initial state of a fire. For flammability commonly the US-Norm of the Underwriting Laboratories (UL) is applied as a standard, in which a standard test procedure (UL 94) is described for the assignment of flammability to standard V0, V1 etc. The material identification is normally completed by this flammability 99 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT standard like e.g. FR4-VO for a glass-fibre reinforced epoxide fulfilling the criteria of the UL94-V0 standard accordingly. Problem focussing: TBBA in printed circuit boards Flame retardants are used in a large number of products from various industrial sectors, including electrical and electronic equipment, building materials, the transport sector, textiles and others. It is estimated that more than 50% of the flame retardant containing products contain brominated flame retardants (BFR). For epoxide circuit boards the main flame retardant (FR) is TBBA12, which is presently used for an estimated 90% of all circuit boards (Ger EPA 01). TBBA is the brominated homologue of the monomer compound bisphenol A. The main proportion of TBBA produced in Europe is used as flame retardant in circuit boards. The consumption of TBBA for circuit boards makes up approximately 70% of the 13.800 t of TBBA consumed in Europe in 1999 (BSEF 00). When added to epoxide resins TBBA is incorporated in the polymer network which lowers the diffuse emission of this toxic substance during use. In other products, e.g. for the use in housings of electronic devices, TBBA may also be used in additive form. 6.2. (ECO-)TOXICOLOGICAL AND ENVIRONMENTAL IMPACT OF BROMINATED FLAME RETARDANT The use of TBBA and other brominated flame retardants have been a topic of debate since years. The main reasons were the following: 1. Diffuse losses of brominated flame retardants from products in use. When TBBA is compared to other flame retardants which are used in additive from, the mobility during use is lower for TBBA because it is reactively bound in the matrix of the epoxide. However, this chemical fixation has no influence on risks during accidental fire or the waste phase. Brominated flame retardants lead to emission of toxic brominated dibenzodioxins and –furans and other brominated organic substances in case of fire accidents. Additionally acidic and corrosive gases like hydrobromic acid are emitted. The bromine content of the laminate is ca. 9 to 10%. The incorporation of the TBBA into the polymer matrix does not lower the emission of polybrominated dibenzo dioxins and furans in comparison to TBBA monomer (Det 00). In recycling, brominated flame retardants lead to high contents of bromine in the shredder waste which often prevents usage of shredder material for advanced recycling routes (e.g. usage of halogen containing material in recycling plants for precious metals is often restricted). An average bromine content of 3 to 7 % is reported for waste from circuit boards (Ger EPA 2001). Most brominated flame retardants have a fairly high toxicity, for a lot of them a concern for carcinogenic / mutagenic properties is discussed. Most BFR have a low (bio)degradibility or are transformed to other brominated tetrabromobisphenol A, also mentioned as TBBPA 2. 3. 4. 5. 12 100 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT 6. substances of concern. Therefore they are of concern when material is disposed on landfills, and several of these substances can be found in households dust and in other environmental media. TBBA was detected in different media from sewage sludge and in the food chain and human breast milk (Ger EPA 01). In several products BFR are used in a 1:1 combination with antimony trioxide (ATO) as a synergist. The ATO dust is of concern as it is suspected to be carcinogenic. However, most TBBA containing printed circuit boards produced today do not contain ATO anymore. In summary, the concern arises from the toxicological profile of TBBA (intrinsic properties) and the risk of exposure e.g. in the waste phase or during accidental fires. 6.3. REGULATIONS / INITIATIVES IN THE FIELD OF TBBA AT POLITICAL LEVEL Brominated flame retardants have been discussed intensively in EU legal initiatives. TBBA is presently due to Risk Assessment under EU-Directive 793/93/EC on existing substances but RA has not yet been finalised. Additionally brominated flame retardants are discussed in the draft WEEE and ROHS Directives as well as in the eco-labelling criteria for various electronic devices. The draft ROHS Directive contains a prohibition to use brominated biphenyl ethers (PBDE), but will not regulate TBBA. However, a revision assessment for TBBA is envisaged for 2003. In Germany, use of PBDE has been restricted by a self-binding declaration of the industry associations VKE and TEGEWA as early as 1986 (VKE 86). In the draft WEEE Directive, an obligation to dismantle all parts containing brominated FR before shredding is discussed which would induce increased recycling costs. Legislative initiatives in Germany and Denmark aim at prohibition of PBDE and polybrominated bipenyls (PBB) and see a need for further research on the (eco-)toxicological properties for other brominated FR like TBBA and hexabromocyclododecane (HBCD). Both Member States consider implementation of the criterion “halogen-free” in national eco-labelling for electronic devices etc. as well as on EU level (Dk EPA 01, Ger EPA 01b). The World Wide Fund for Nature (WWF) proposes a stepwise phase out of brominated flame retardants (WWF 96) starting with organobromine additives which are of very high concern due to the high mobility and followed by polymer bound organobromines like TBBA polymers. WWF highlights the quantitative relevance of brominated FR due to high production volumes when compared with the case of polychlorinated biphenyls which on the basis of similar substance properties concerning toxicity and stability use are now prohibited from being used. The ban of BFR is therefore argued for with reference to the precautionary principle, as all substances used will end up in the environment due to their wide-spread and diffuse use pattern. 101 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT 6.4. INITIATIVES AND MOTIVATION FOR SUBSTITUTION OF BR-FR AT ENTERPRISE LEVEL At the company level awareness is often less developed until the substances are regulated or at least public awareness has risen considerably. Once there is sufficient public attention, companies may be interested to introduce an alternative because they expect advantages for marketing of their product, thus realising a market-strategy to improve their competitive position. During this project, contacts were established with one circuit board manufacturer who is planning to switch to a bromine free circuit board. Unexpectedly, the company stated that upcoming EU legislation including the European Risk Assessment of TBBA did not play any role or is even unknown to the manufacturer. Rather, the initial motivation for substitution had arisen from disposal problems with their production waste from which the light fraction (mainly plastics) of the shredder output had to be declared as hazardous waste due to the bromine content and disposal was therefore expensive.13 From this cost aspect the manufacturers became aware of advantages of bromine free products. Other manufacturers of EEE also state to see opportunities to get an eco-label award for their products after a switch to bromine-free raw materials which will possibly lead to marketing advantages. Among suppliers, two main motivations were identified: one is to follow the demands of the market i.e. co-operate with their customers, the other one is to strive for a good market position once the market should switch to bromine free products. One barrier in such processes is that big end-customers tend to move more slowly as they avoid to become dependent on just one supplier who has developed the technical or chemical know how and who might raise prices. So just before introduction in the market these end customers often want to slow down the substitution process to leave time for other suppliers to achieve an equal state of know how. 13 The amount of production waste from circuit board manufacturing is relatively high due to 5 to 10% cutting scraps. 102 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT 6.5.ALTERNATIVES / SUBSTITUTES FOR TBBA The required functionality of reduced flammability can be achieved by different strategies, which are briefly outlined below. Base Case (brominated flame retardant): Brominated organic FR like TBBA release bromine upon heating. The bromine inhibits the radical chain reaction which is the basic chemical process of the flame. The function is to prevent flame initialisation in the early stage of a fire. Substitutes (bromine free FR): Phosphorus-based FR (phosphor esters and other P-compounds) inhibit the flame by carbonisation of the materials surface which prevents fresh material becoming available for the burning reaction (shielding effect). In contrast to brominated FR the inhibition process occurs in a solid phase reaction. Mineral flame retardants like aluminium hydroxide reduce flammability by i) reduction of flammable material in the bulk (“dilution” of flammable organic compounds), ii) the cooling effect of the inorganic material and iii) release of water upon heating which is an exothermic (heat consuming) process leading to a net cooling effect. Quantities needed for complying with flammability standards lie around 50 % for e.g. Al(OH)3. Product level ... material level ... substance level Also basic materials other than epoxides can be used. Some products like special foams change their shape upon heating due to melting and therefore withdraw from the flame before the material ignites. These materials are not relevant in the sector of circuit boards but rather in the sector of furniture. Also materials like polysiloxane, which has a reduced flammability, can be introduced. As low voltage applications are not of special risk of fire initiating, flame retardants can be unnecessary in these. This can be also achieved, if high and low voltage circuit boards are separated within one electronic device. E.g. when electronic devices have their transformer as an external unit they may not need internal FR accordingly. no subst. As shown above, a substitution strategy for TBBA in circuit boards can focus on different functional levels, from a substance (e.g. phosphorus compounds) via material substitution in case of polysiloxanes to constructional solutions which require a re-design of the product. 6.6. IMPLICATIONS OF TBBA SUBSTITUTES FOR BUSINESS PRACTICE The implications of the different substitutes for business practice are manifold and vary widely between the different substitution strategies. However, for all substitutes the crucial parameter to consider is the flammability and the standard testing procedure which will therefore be discussed first. The implications specific for the individual substitutes will be presented afterwards. 1. Aspects not specific to the type of FR: Flammability The flammability standard is assessed on the basis of the internationally common US-Norm of the Underwriting Laboratories (UL) UL94. According to this standard materials are 103 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT assigned to the V0, V1 or other flammability class. The underlying criteria is the time until self extinction after ignition with an external flame (V0 = 10s, V1 = 30s), with shorter times representing better resistance to fire. When introducing bromine free FR several aspects have to be considered with respect to flammability norm, from which the most important ones shall be briefly discussed: a) Although V1 standard is required for FR4 circuit boards, today most circuit boards comply with FR4-V0. V0 was introduced in the market voluntarily by the producers as an added value for the customer. Even if the norms would allow so, producers hesitate to go back to V1 as they fear damage to their reputation. Many experts conclude that most of the electronic devices are over-engineered concerning fire safety. A higher flammability standard results in higher amounts of flame retardant and often makes the introduction of alternative substances very difficult or even impossible. When changing from V0 to V1 the amount of TBBA needed would decrease by approximately 50% (Ger EPA 01). Some companies state that the standard test conditions represent just one single parameter of fire safety (flammability) while leaving out other important aspects like smoke density, emission of toxic gases etc. Several experts state that test conditions are best adapted to brominated flame retardants and their reaction mechanism but do not fully reflect the functionality of “fire safety” in a holistic perspective. Individual companies see no opportunity to change the very common UL-test conditions. In cases where only low voltage is applied (as for example in circuit boards in mobile phones or computer key boards), there is no special danger of fire and flame retardants would hardly be necessary at all. Again producers might risk bad reputation when not applying the highest fire safety standard to their products. Especially in Germany the US UL-Norm is important as many producers of electronics are also part of the supply chain to the German automotive industry which exports many of their products to the USA. Often producers do not even know whether their customers export their products. As a consequence, they do not differentiate between different purposes of the product. Furthermore, logistic and production costs would increase if two different materials were to be used. From this perspective the use of brominated FR in low voltage products can partly be considered as a logistic and organisational problem. Companies from the electronic sector state that they would prefer to use V1 materials for low voltage applications if these were available on the market, whereas producers claim that there is no demand for such material in the market (Ger UBA 01). b) c) 2. Phosphorus containing flame retardants After intensive research over several years with a wide range of inorganic flame retardants, phosphorous and nitrogen containing substances, the majority of electronic manufacturers now seem to favour phosphorous and / or nitrogen containing FR which are already in use as additives for thermoplastic materials. The main technical performance criterion the organophosphorous FR has to fulfil is the low flammability of the circuit board. For achieving the common flammability standard V0 104 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT approximately an equal amount of phosphorus FR has to be applied as is necessary for TBBA. Same as TBBA, phosphorous esters can also be reactively incorporated in the resin matrix. The material properties may therefore be more similar to the standard TBBA material when compared to inorganic FR and substitution is truly on a substance level. Experiences with phosphor compounds have been made in the sector of thermoplastics, where these substances are in use since several years. In contrast to brominated FR, these FR do not lead to formation of acid gases and heavy black smoke during fire. The resulting fire residues indicated less toxicity in toxicological tests with daphniae (BMBF 95) and in several other research projects summarised in Ger EPA 01. Data on toxicity of inflammation gases are difficult to interpret but indicate that phosphor / nitrogen containing materials, because of their degradation to HCN and NOx, have a considerable toxic potential which is similar to brominated materials. Pure phosphor systems showed the best results (Bro 99). Besides flammability, other performance criteria are also relevant, including the following: • Uptake of water The introduction of reactive phosphor compounds leads to difficulties with respect to water uptake because the material becomes more polar and hence uptake of water increases. High water uptake of water results in difficulties in wet dipping processes. Adhesive strength of the sandwich structure One manufacturer reported another disadvantage of the polar ingredient being that bonding strength of the material to the copper foil in the sandwich structure decreased so that a strength threshold of the customer’s internal standard value could not be reached anymore. However, testing showed that the adhesive strength achieved although below the norm - was technically sufficient and the customer could be convinced to change his internal norm accordingly (VOGT 01). • Also other technical performance criteria like heat resistance, surface conductivity, dielectric properties, glass transition temperature (temperature at which the material softens) etc. have to be fulfilled by the material (BMBF 95). One main requirement in the development of a phosphorous-based circuit board is that the laminate can be processed with the existing machines. Producers are flexible only to adjust process parameters so that they can switch to the alternative without additional investments (Leit 01b). In such a case, the strategic know-how of the new product lies mainly in the chemical composition of the resin mixtures rather than in the processing know how, meaning that other actors than just the circuit board manufacturer need to be involved the development (e.g. chemical suppliers of base material). The circuit board manufacturer contacted for this project reports that he convinced an important customer from the electronic sector to take part in the project before even starting his research for substitutes. In the definition phase of the project the customer suggested to follow an integrated approach, i.e. to develop a circuit board which is not only bromine-free but which additionally does not contain lead in the solder neither any halogen in the surface lacquer, focussing on a special electronic product with the aim to develop and launch a real „green product“ on the market. To make a visual difference, the new circuit board shall have a blue colour in contrast to the normally green coated products, both to allow for separation 105 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT during production and recycling and for marketing purposes (Leit 01b).14 Starting with these requirements the company searched for a laminate supplier who would be able to co-operate in this project. An informal co-operation was established which is not based on a legal contract of the partners. Test laminates are developed by the supplier and delivered to the circuit board producer, where they are tested in the laboratory and on the machines. The supplier is informed about the results and participated in the tests in some parts of the project. The supplier also started a very similar procedure with his suppliers (raw materials for laminates i.e. resins and additives like FR). Consultations were held down the supply chain including enterprises which synthesise the resin components. One important drawback of most phosphorous ester substitutes is that little is known about their (eco-)toxicological properties. A recent study on the subject of FR concluded, that an assessment of two common phosphorous ester alternatives was impossible because data for their toxic and carcinogenic properties and analytical data of environmental compartments were not available. It was however recommended to substitute TBBA because the substance is found in indoor dust and has a high eco-toxicity (Ger EPA 01). To overcome this dilemma two of the most promising phosphor ester alternatives were placed on the fourth priority list under Regulation 793/93/EEC on existing substances and will be subject to EU Risk Assessment in the next years. In the past, several other projects were focusing on phosphor nitrogen compounds and brought out products which were very expensive (in one case 4 fold price) or lead to technical problems during use and/or production (Ger EPA 01, BMBF 95). At present, one manufacturer states, that the price of his new developed product is approximately 30 % higher than that of the TBBA product. However, he expects the price to decrease with higher production volume of the raw materials and to be similar to TBBA products after implementation in series production (Leit 01b). Apart from costs for research on the substances, no process investments were necessary for introduction of the substitute (Diel 01). Although the new development of the bromine-free circuit board is stated to be very promising, one manufacturer of circuit boards stated that most of his customers want to switch to bromine free in parallel to introduction of lead free solder which is expected to become obligatory under the forthcoming ROHS Directive. From a technical point of view the two substitutions could be introduced one after the other without any extra efforts but customers might want to change to the “greener” product in one step, which would then be postponed until the ROHS Directive enters into force. As a result, the manufacturer states to have higher costs presently because he must maintain 4 different processes. He also states, that a switch to bromine-free and lead-free is not seen as likely without ongoing legal initiatives and / or introduction of R&D programmes in this field (VOGT 01). 14 At present, the new circuit board and raw material proved its technical performance in a “small” series production of 10,000 pieces and the product is assessed by the marketing departments of the electronic company (VOGT 02). 106 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT In conclusion, the substitution by organophosphorous substances is possible from a technical point of view. However, the price of the alternative product is presently higher, as its production is less cost-optimised and acceptance in the market is not fully established. 3. Mineral-based Flame Retardants, AL(OH)3 When using mineral-based flame retardants the high amount of inorganic material which is required to reach the flammability norm has to be considered. Due to the high content of crystalline salt, the resulting material is much harder. Therefore adaptation of production processes to the new material properties will become necessary. One producer states that multilayer boards containing a combination of Al(OH)3 and a phosphorus compound have been successfully developed and are in usage for the underground in London where only products with a low potential for emission of hazardous substances upon fire are allowed (ALUS 00). One manufacturer of circuit boards reported about technical difficulties when processing raw products containing inorganic FR. He states that difficulties arose, because the FR migrated out of the product in wet dipping processes which lead to shorter life-time of the baths and therefore higher costs. Additionally it was stated that process costs (e.g. maintenance costs of drilling machines) will increase if inorganic ingredients are used because the material is harder and the lifetime of the drill will decrease (VOGT 01). Overall, substitution with mineral-based FR is possible from a technical point of view but the high amount of inorganic filler has a strong impact on material properties which might result in increasing costs in some process steps. However, this substitution would be in contrast to a general trend in the market towards higher flexibility of circuit boards. Since material properties change significantly when mineral-based FR are used, this substitution can be seen as affecting not only the substance but also the material level. 4. Special materials In the last decade many projects / initiatives have been reported following different routes in order to substitute TBBA in circuit boards. A famous project was the “green TV” , which was commissioned by the German Ministry of Research (BMBF). Several manufacturers of TV-sets took part in this project and developed an environmentally optimised TV prototype. The company Loewe developed a circuit board which was based on polysiloxane which is a flexible elastomer with a low flammability. The circuit board has several other advantages e.g. in the recycling procedure for metal recovery (BMBF 99). However, the circuit board did not enter the market because of its high price due to the high costs of polysiloxane. 5. Constructional Solutions In some electronic devices (e.g. printers) the use of flame retardants can be reduced or prevented by putting the transformer (high voltage) in a separate box (Ger EPA 01). The 107 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT electronic device itself is therefore separated from the high voltage area, thus reducing significantly the risk of fire. In conclusion, it can be stated that several strategies for substitution of TBBA exist, each of which will imply its specific investments in know-how, substitute materials, processing technique and machinery. However, none of the alternative substances can substitute TBBA on a simple 1:1 basis. 6.7. ANALYSIS OF KEY FACTORS Economics All producers state that the decision for introduction of the alternatives for TBBA in printed circuit boards is dominated by cost aspects rather than technical aspects. The profit margins in this large volume sector are relatively small and costs are therefore a very dominant factor. For the time being, products with alternative flame retardants will be more expensive due to higher prices of the alternative flame retardant and alternative resin matrixes. Main economic aspects to consider are: • Extra cost caused by the substitute are hardly accepted by the customers Many customers in the field of printed circuit board stick to TBBA as long as no additional legal requirements or incentives / marketing advantages are present because switching to a substitute or using parallel products would result in increasing (logistic) costs which is a crucial point in this high volume market. • Large customers try to avoid dependence on one single innovative supplier Large companies have a strong interest to have a certain number of suppliers for a component or product in order to have a competitive system. If early introduction of a new substitute would imply “single sourcing” from one innovative supplier, the company may prefer to slow down the process until other suppliers can offer the same substitute. A typical project aiming at substitution of brominated FR in circuit boards will start with the requirement that the substitute laminate material can be processed on the existing machines. Otherwise much higher revamp costs would be required. • The substitute is accepted only if no extra investment in process technology is necessary. • Cost for waste disposal was the initial motivation for substitution One company started to develop Br-free products because of their parallel activity of recycling production wastes in their own recycling plant. Secondary wastes from recycling had to be disposed as hazardous waste in their district at high costs. • TBBA is also present in products where it would not be necessary Although not required by norms, many circuit boards for low voltage applications contain FR because the TBBA containing standard material is available at low price due to the high volume of production. Keeping two different material qualities in stock and working in two parallel lines would result in additional costs for storage and logistics. 108 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT Technical functionality Smooth integration of the substitute in the running process plays a major role. Generally, the substitution at the substance level (low innovation depth) is preferred because the effort and costs for this substitution (e.g. costs for revamp of machines) are lower (see above economic aspects). When innovation depth is very high (e.g. switch to a completely different material) suppliers may not be able to substitute due to lack of know-how or appropriate machinery, thus eventually loosing their market upon substitution. In conclusion, all technical aspects are dominated by cost aspects in this case. Social Factors Since producers of printed circuit boards mostly have engineering skills but limited chemical knowledge, for successful substitution an intensive information exchange or collaboration along the supply chain is necessary, going back even to producers of the basic polymer resins. Japanese manufacturers are presently pioneers in this substitution case due to their advantage of having all members of a supply chain are combined under one international consortium (“in-house-shops”). One important Japanese manufacturer envisages a phase out of halogenated compounds in all of his products by 2003 although the new material is expected to be 20 to 30% more expensive (UBA 2001). In contrast, the process in the European market is described as slow and the actors’ behaviour is more or less passive (Ger EPA 01). Japanese manufacturers rely on a marketing effect especially in Europe if they introduce “green products”. European producers may eventually be driven by Japanese successes in due course. • A successful development of a bromine-free circuit board was realized in a project in which all actors from resin manufacturers to the manufacturer of electronic products were involved. For successful substitution all actors along the supply chain must be involved • Eco-toxicological profile is not a primary motivation at company level The decision at the company level is mainly driven by marketing, economic and regulatory issues in contrast to the political level where initiatives are derived from risks to environment and health. Risk Assessment The number of experiments and reports about intrinsic properties of the substances is much higher for TBBA than for its alternatives. This is the result of the high production volume of TBBA and the long history of this substance also in debates about toxic and bio-accumulative properties. Lack of data in case of the alternatives results in an uncertainty whether the environmental / health benefit are substantial and if these substances might become subject of concern in the future. 109 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT To overcome this dilemma the EPA of UK followed a concept based on a prioritising methodology for all substances used as FR i.e. evaluation of substances with same functionality. The prioritising methodology was based on a ranking in the parameters production volume, (eco-)toxicological hazard and risk (expressed in PEC/PNEC). Lack of data was overcome by QSAR modelling of substance properties. As a result it was recommended to put certain substances on a priority list under 793/93/EEC, with priority given to brominated phenols and organophosphorus compounds. Also for Al(OH)3 a detailed study of the speciation and environmental fate of aluminium is recommended to ensure further validation for future substitution activities (EPA UK 2001). Knowledge on risks of substitutes is lower than for the substance presently used For TBBA a lot of research on (eco-)toxicological properties has been done in the past in contrast to many substances considered as substitutes. Regulatory Frame The two draft Directives in the area of electric and electronic equipment (WEEE and ROHS) are have a strong impact on substitution not only because of the proposed ban of lead in electronics, but also with respect to brominated flame retardants as these substances are also addressed. On the other hand, the flammability UL standard as a non regulative instrument is highly important as its requirements are very difficult to achieve by substitutes. • The upcoming WEEE Directive puts pressure on the electronic industry as in its Annex an obligation to dismantle all parts containing bromine is suggested. This will lead to higher cost for recycling which under the concept of producer responsibility will have to be paid for by the manufacturers. The lead ban proposed in the draft ROHS Directive might also stimulate the simultaneous substitution of brominated FR. Upcoming legislation has a strong influence • A common standard/norm is adapted to the properties of the former substance The internationally common flammability standard UL-94 V0/1 focuses on flammability only, although this is just one parameter representing safety in case of fire. E.g. smoke formation and emission of hazardous substances in case of fire are not referred to. The brominated substances have a good performance in the flammability criterion but perform less well than the alternatives with respect to other parameters. Factors not belonging to a category Focussing: Substitution of TBBA by phosphorous ester substances After intensive research with inorganic FR, phosphor and nitrogen containing substances in the recent decade the majority of the manufacturers seem to favour phosphorous and / or nitrogen containing FR which are already in use as additives for thermoplastic materials (Ger EPA 01). 110 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT Therefore this section will focus on the substitution TBBA --> phophorous ester FR for deeper analysis. All aspects discussed in the former Chapter are also valid for this substitute. The aspects that had a major influence in this case are written in bold letters. The aspects are weighted as described: ECONOMICS A) Extra cost caused by the substitute are hardly accepted by the customers Material / process / logistic cost & invest: Economics / material price strong hindrance of substitution hindrance of substitution support of substitution (--) (-) (+) (--) (0/+) (+) (--) (+) (-) (+) (--) (0) B) Large companies try to avoid dependence on one single innovative supplier C) Cost for waste disposal was the initial motivation for substitution Economics / Costs / Environmental Costs Technical functionality Technical functionality Awareness TECHNICAL FUNCTIONALITY D) Integration of substitutes into running process is very difficult. E) TBBA is also present in products where it would not be necessary strong hindrance of substitution slight support of substitution SOCIAL FACTORS F) Growing public concern about “ptb” substances led to substitution initiatives support of substitution G) For successful substitution all actors along the supply chain must be involved Communication / Complexity Risk Assessment strong hindrance of substitution RISK ASSESSMENT H) Ubiquitous presence of TBBA in environmental media supported search for alternatives support of substitution I) Knowledge on risks of substitutes is lower than for the substance presently used Risk Assessment / RA not existent Legislation hindrance of substitution REGULATORY FRAME J) Upcoming legislation has a strong influence support of substitution strong hindrance of substitution K) A common standard/norm is adapted to the properties of the former substance Standardisation MISCELLANEOUS L) Companies will switch to substitute only in combined action with other substitution measures Unexpected influence / timing can be positive or negative to substitution 111 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT 6.8. Literature Interview at Martinswerk Bergheim, Germany, 21.12.2000 Halogenfrei flammwidrige duroplastische Werkstoffe für die Elektronik, Report of the German Ministry of Research, 01 ZH 90028, Bonn, Germany Ergebnisse des Forschungsverbundprojektes “Grüner Fernseher”, Zentralverband Elektrotechnik- und Elektroindustrie (ZVEI), 1996, Frankfurt Brown N., Aggleton M., Alternatives to halogens in PCB laminates, Reinforced Plastics 43, 1999, 44-49 Bromine Science and Environmental Forum, Major Brominated Flame Retardants Volume Estimates for 1999, 27.7.2000, Bruxelles Dettmer F., Bromorganische Flammschutzmittel, Thesis, Aug. 2000, Technical University Braunschweig, Germany telephone interview with representative of Dielektrika, 06.11.01 Action plan for brominated flame retardants, Danish Environmental Protection Agency, March 2001 Information Document to Priority Waste Stream Project Group on WEEE, ENEA Italian National Agency for New Technology, Energy and Environment, Rome 1995. Oral presentation held on FED seminar 28./29.9.2001, Aschaffenburg Öko-Recherche GmbH, authors Leisewitz A., Kruse H. and Schramm, 2001, Substituting environmentally relevant flame retardants: Assessment fundamentals, Report N° 25/01, 26/01 and 27/01 of the German Umweltbundesamt (UBA) ALUS 00 BMBF 95 BMBF 96 Bro 99 BSEF 00 Det 00 Diel 01 Dk EPA 01 ENEA 95 FED 01 Ger EPA 01 Ger EPA 01b Proceedings of a workshop series on flame retardants at German Umweltbundesamt, 29.5.01 and 06.06.01, Berlin Leit 01 Leit 01b NEMA 98 Öko 01 ROHS 01 http://www.zev-leiterplatten.de/markt.htm Journal Leiterplatten 12/2001, 19-24 National Electronic Manufacturer Association, NEMA LI 1.1983, USA, in: Industrial laminating thermosetting products, 1998 Heavy Metals in Vehicles II, Ökopol GmbH, Report to DG Environment, 2001. Proposal for a Directive on the restriction of use of hazardous substances in 112 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 6: FLAME RETARDANTS IN PRINTED CIRCUT BOARDS FINAL REPORT electrical and electronic equipment. Institutional Dossier 2000/0159 (COD), 14.11.01. UK EPA 01 UL 94 VKE 86 VOGT 01 VOGT 02 VOGT 01 WEEE 01 WWF 96 Review of environmental hazards of flame retardants, National centre for ecotoxicology & hazardous substances UK, July 2001 Classification of flammability according to NEMA 89 Letter of the “Verband der Kunststofferzeugenden Industrie e.V., 22.12.1986 Interview at company Vogt-FUBA, Gittelde Germany, 31.10.01 telephone interview of representative of company Vogt-FUBA, 14.03.02 report to oral presentation of representative of VOGT-electronic, Febr. 2001 Proposal for a Directive on waste electrical and electronic equipment. Institutional Dossier 2000/0158 (COD), 14.11.01. Polybrominated Flame Retardants: a Case for Phase-out, WWF Submission to OSPAR meeting, Cadiz, Oct. 1996 (DIFF96/11/NGO.1). 113 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT 7. CASE STUDY 7: LOSS LUBRICANT IN INLAND WATER 7.1. TECHNICAL AND CHEMICAL SCOPE Lubricants in and around surface water are used in a wide range of activities and applications. Both loss lubricants and lubricants for closed systems (hydraulics and gear oils) are used. The activities cover inland shipping, harbour activities, dredging, lubrication of locks and bridges, hydro-electricity plants, pumping stations, waste water treatment plants, waterfront construction etc. A long time ago diffuse pollution sources had been recognised as a problem in water pollution. In the Netherlands for example it is estimated that up to 70% of the total water pollution can be attributed to diffuse sources. Consequently, the focus of environmental organisations, water quality management institutes and governmental policy makers have focused on pollution by diffuse sources. One of the sources which adds significantly to surface water pollution is the use of loss lubricants, greases and 2-stroke fuels by professional and recreational shipping activities on inland and coastal waters. Additionally, lubricants from accidental spills, leaky closed systems and burst tubes contribute to water pollution. From a total lubricants market of 5 million tons in Western Europe, approximately 15% (equivalent to 750.000 tons) is discharged to the environment as loss lubricants; most of it is polluted into inland waters. Inland water is one of the most sensitive environmental system. Freshwater reserves are limited and essential to life. Feshwater is often used as drinking water, for example the river Rhine. It is known that already small amounts of mineral oil stains both fish and other aquatic species and drinking water [LLINC 01]. Most of the commonly used lubricating agents are derived from mineral oil. Mineral oil based products do not biodegrade easily. This can be solved by two strategies: firstly reduction of the amount emitted to the surface water and secondly improving the properties of lubricants in order to reduce harm to the environment. Currently, synthetic and vegetable oil based lubricants are available, which are biodegraded in the surface water. Their technical performance has been proved in many applications. The substitution of conventional lubricants through biogradable ones is the focus of this case study. The discussion on bio-lubricants and the development of the first products is around fifteen years old. It started with the replacement of loss lubricants in chain saws. Other applications followed like hydraulic oils, motor and gear oils, concrete release agents, cooling lubricants and others. Up till now regulations cover only a small part of applications. The application of lubricants in inland water had not come into focus before the nineties. Less than 1% of the lubricants applied in this sector can be classified as non-toxic and biodegradable. According the FEDIOL Federation the current EU market for bio-based lubricants and hydraulic fluids amounts to approximately 100,000 tonnes a year, while the total potential market is estimated at 1,5 Mill. tonnes [FED 00]. 114 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT 7.1.1. Technological principles Lubricants facilitate the effective operation of mechanical equipment, reduce friction and wear, and are used for the transmission of force. There are two kinds of lubricants: 1) Loss lubricants are, by definition, used in non-closed systems. The direct surroundings of the lubricated part are, therefore, exposed to diffuse and small emissions of lubricating agents frequently. The extent, duration and frequency of exposure depend upon the equipment, the use of the equipment and hygiene. 2) Lost lubricants are used in closed systems. These lubricants come to environment by accident, i.e. by leakage or breaking of tubes or hoses. In this case the direct surrounding of the lubricated part is exposed to emissions of lubrication agents rarely. However, in case of exposure, huge amounts of lubricants may reach the environment. Additives are used to improve the performance of lubricants. The number of and variety in chemical compounds used as additive is enormous. Commonly encountered categories of additives are [KROP 02]: • Anti-oxidants to slow down the oxidation of the base oil, • Viscosity modifier to balance changes and improve the viscosity versus temperature behaviour of the lubricant, • Friction modifier, to reduce frictional forces (prevent stick-slip and noises), • Pour point depressants, to prevent co-crystallization or paraffinic compounds • Dispersants to keep oil-insoluble solid particles (resulting from wear and external contaminants) in suspension and to prevent agglomeration, • Corrosion inhibitors to prevent the metal machine parts from being corroded, • Extreme pressure/anti-wear (EP/AW) additives to secure functionality and reduce wear in high-pressure conditions, • Antifoam agents to prevent the lubricant from foaming, • Demulsifiers and emulsifiers to prevent the formation of water-in–oil emulsions and • Adhesives to increase viscosity to prevent unnecessary oil loses sue to drainage, dripping or spraying of lubricants. 15 The technical requirements for the use of a lubricant is normally defined in the specifications of the constructor of machinery and the standards development (DIN and VDMA in Germany, AFNOR in France, ASTM in America). In order to control the behaviour during use it is necessary to control the oxidation behaviour, hydrolytic stability, range of working temperature, control of the physico-chemical and environmental characteristics during use, compatibility with materials and seals, corrosivity and wear and friction properties. 7.1.2. Chemical scope The variety in lubricant types is large and the composition of each type depends on the application and the desired functionality. Secondly, the number of additives used to affect 15 Polymers are often used for this purpose. 115 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT the functionality of lubricants is enormous. Common lubricants base on mineral or synthetic oil. Mineral oils are complex mixtures of substances consisting of paraffinic, naphthenic and aromatic hydrocarbon chains of medium length. The composition is essentially determined by the origin. The oils are obtained through fractional distillation or cracking and hydrogenation. Mineral oil based lubricants are toxic to humans and aquatic eco-systems. First of all the mineral oil components may contain polycyclic aromatic hydrocarbons (PAHs). Especially the heavier oil fractions which are used in lubricating agents possess a relatively large amount of PAHs. It is generally known that these compounds are toxic to both the environment and to humans (carcinogenic). Furthermore PAHs will sediment on the bottom of the river and will accumulate in the sediment as a result of their poor degradation properties. PAHs belongs to the list of priority substances of the European Water Directive 2000/60/EC. The group of synthetic oils is very divers in their composition. It contains synthetic hydrocarbons, esters and polyglycols. They typically derive not from natural oils but from chemical syntheses. Fatty acid esters are produced through esterification or interesterification of natural resources like plant oils. They are used in the lubricant and food industry. Bio-lubricant is the short term for easily biodegradable and non-toxic lubricants. It is not imperative that they are based on vegetable oils. Lubricating products not only consist of oil or grease, but also contain small amounts of additives. Although, the amount of additives usually is small, they are known to be harmful to the environment and humans, for example chlorinated paraffins. In general terms lubricants might consist of the following ingredients: • Ingredient type Grease Gear oil • Base oil 60-95% 75-95% • Thickener 0-20% • Solid lubricant 0-20% 0-5% • Additive package 0-10% 0-10% • Adhesives 0-20% 0-10% Base oils determine the properties of the lubricant product. Furthermore, they act as a carrier for the additives. Thickeners are used in greases to achieve the specific grease consistency. Often used materials are calcium and lithium soaps (e.g. stearates) and inorganic materials like bentonite. Solid lubricants are added to increase performance. Common solid lubricants are graphite and molybdenum disulphide. Additives cover a wide range of chemicals and guarantee the technical performance and help to fulfil the criteria of technical standards. 116 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT The additives in lubricants can be subdivided in the following types and compositions: Generally used percentage in lubricants Pour point depressant 0,05 - 1 % Anti foaming 0,1 - 0,5 % Detergent/dispersant 1-5% Anti-oxidants 0,2 - 4 % Extreme pressure and < 5 % anti-wear additives Corrosions-Inhibitors 0,01 - 2 % Biocides 0,1 % Total in weight % additives Additives Greases Hydraulic fluid Transmission / gear oil 0,05 - 1 % 1-5% 0,2 - 4 % <5% 4% > 10 % 1-5% 0,2 - 4 % 0,1 - 5 % 0,1 % 2-5% 0,05 - 1 % 0,1 - 0,5 % 0,2 - 4 % <5% 0,01 - 2 % (0,1 %) 1-3% Because of the wide range of additive types and their chemical character only some examples are given. Anti-oxidants are often present in petrochemical oils as N-,S-,Oheterocyclic compounds. This is not the case in vegetable oil derived based fluids. Amine and phenol derivates are especially used because they possess a synergistic behaviour. The phenols are able to regenerate the more efficient amine antioxidants. Corrosion-inhibitors are for example: petroleum sulfonates, synthetic alkylbenzenesulfonates, carboxylic acid derivates and amides and imides. Typical antifoam agents are silicones and siloxanes, polyalkyleneglycols and phosphates [KROP 02]. Usually lubricants contain additives from two groups: for the modification of the base oil (viscosity, pour point) and for affecting primarily the metal surface (performance: friction and wear). Meanwhile additives for extreme pressure and anti-wear purposes are developed and available, which are biodegradable and non-toxic [ZW 01]. 7.2. SCIENTIFIC EVIDENCE ON (ECO)TOXICOLOGICAL AND ENVIRONMENTAL IMPACT The total emission of lubricants to the environment is large. Statistics show that 45% is lost in use, 32% is collectedand 23% is unaccounted for. Similar statistics are not (yet) available for water related activities, but will most likely show a similar trend. Emissions of hydraulic and gear oils constitute by far the largest part. Loss lubricant emissions are smaller but unavoidable by definition. In the case of loss lubricants the problem of environment burden is the most important one. Loss lubricants are dispersed in a relatively uncontrolled way into the environment and pollute surface water. Conventional lubricants are based on mineral oils and contain toxic and poorly biodegradable substances, like ecotoxic additives. Each litre of waste oil released into the environment may contaminate one million litres of drinking water. It is well known that mineral oils degrade poorly under normal environmental conditions. They have therefore a high potential to accumulate in the environment. Mineral oils are also known to taint water and fish, making it unsuitable for consumption. A number of synthetic 117 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT oils have good biodegradable characteristics, and they have a low toxicity potential to aquatic organisms. As a rule of thumb it can be stated that mineral oils are biodegradable by 20-30% and bio-lubricants by 90% in water. Vegetable oils are not toxic to aquatic organisms. Their biodegradability is fast and complete. Metal soaps used in greases are commonly based on stearates, the main component of a natural soap. They are highly biodegradable. The only important impact to the environment is the metal contained in the soap. Sometimes inorganic thickeners are used (clay-like materials). They are not biodegradable, not toxic to aquatic organisms and they often are a natural substance. Similar arguments are applicable for solid lubricants. However, they do increase the amount of solid waste in the water. Contained adhesives are often polymers. They usually do not biodegrade and are often non-toxic. Additives Lubricants contain a wide range of chemical additives. They are often present in small amounts. Their biodegradability and aquatic toxicity varies significantly. Some additives are quite soluble in water and its solubility might even increase due to the presence of other solubility increasing substances. It is therefore difficult to mention anything in particular on biodegradation and aquatic toxicity on the used additives. Some of them have clearly an eco(toxicological) impact on environmental hazards some additive are on the EU list of priority substances for aquatic environments according EC decision No 2455/2001/EC, such as lead compounds, octyl and nonyl phenolates and chlorinated paraffins [KROP 02]. The following table gives an overview of the biodegradability and aquatic toxicity of the main components of a grease applied in a system where loss to surface water may occur. Component Base oil mineral Synthetic Vegetable Thickener metal soap Inorganic Solid lubricant graphite Molybdene sulphide (MoS2) Additives Adhesives (polymers) Biodegradability in general poor substance dependent Good Good No No No substance dependent poor Aquatic toxicity in general toxic substance dependent not harmful In general not toxic not toxic not toxic not toxic very large variation In general not toxic In the frame of the LLINCWA-Project nearly 90 additives and thickener for lubricant were classified concerning the health and environment hazards [KROP 02]. Mineral oil based products like lubricants have a negative influence on the physical, chemical or biological characteristics of water. The dangerousness of hazardous substances and mixtures can be classified into water hazard classes (‘WGK’) according to the German System [FME 99, VwVwS]: 118 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT • • • • WGK 1 : slightly hazardous to water WGK 2 : hazardous to water WGK 3 : extremely hazardous to water or rated as ‘non-polluting’ to water . The water hazard potential is rated according to the properties of the substances, in particular acute oral toxicity for mammals, toxicity for aquatic organisms (mostly fish and bacteria) as well as degradability [FME 99]. Bio-lubricants are classified in a lower class than common lubricants. Pollution due to diffuse emission of lubricants to the surface water should be tackled by two strategies. Firstly, minimisation of the amount emitted by looking for alternative lubricating techniques and effective measures to prevent lubrication losses. Secondly, in case of unavoidable losses only non-toxic biodegradable lubricants should be used. The environmental and occupational health objectives in this substitution case are: • reduction of diffuse pollution of lubricants and greases, • increased use of biodegradable lubricants, • reduction of environmentally hazardous additives, • protection of freshwater reserves, • reduction of substances harmful to humans and • increase in use of agricultural resources. 7.3. INITIATIVES AT THE POLITICAL LEVEL On the European level an important force for bio-lubricants derives from the EC Water Directive 2000/60/EC and the Decision 2455/2001/EC establishing the list of priority substances in the field of water policy and amending Directive 2000/60/EC. Every Member State has laws and regulations, correlated to protection of different environment partitions like water. They refer indirectly to loss lubricants as a possible pollutant, but this case has a low awareness. In some European countries local regulations and strategies foster the use of bio-lubricants. In Denmark all machines which are working in the area of the mud-flats has to be filled with bio-lubricants. In Portugal and Finland 2-stroke engines in drinking water areas has to filled with easily biodegradable oils, 66% and 99% respectively. In the Netherlands the VAMIL-law promotes the installation of environmental friendly machines filled with bio-hydraulic fluids and oil. Companies accrue a financial benefit by better write-off conditions. In Germany the public administration is a leader in using bio-lubricants in different application areas. It is laid down that in all public orders the use of bio-lubricants has to be chosen. A market introduction program for bio-fuels, bio-lubricants and hydraulic fluids exists for the sector of agriculture and forestry [BML 00]. The German agency for Renewable Primary Products (FNR) has created a ‘positive list’ for biolubricants and hydraulic fluids [IFAS 01]. From 30 July 2002 onwards preparations like hydraulic oils and lubricating oils and greases need to be labelled on environmental hazards. A label to the preparation is given if all classified substances are present above a certain concentration. Its consequences for 119 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT hydraulic oils and lubricating oils and greases will be discussed shortly. Products or preparations entering the market may be classified as dangerous, flammable or on health hazards. For this classification systems the well known R-phrases are used. For environmental hazards such a classification scheme on products was not known yet, but directive 1999/45/EC of the EU has changed this aspect. One substance on its own could already receive one of the existing R-phrases on environmental hazards, like R50 to R53 and certain combinations thereof for the water compartment. If they are toxic in water, they will also receive a general label N and a symbol. The new EU Directive extends the labelling for preparations to environmental hazards to water and ozone compartment. Many hydraulic oils and lubricating greases and oils are based on mineral oils which are often not readily biodegradable and toxic. Since they are present in very high amounts (i.e. often more than 80%) the product must be labelled as N and R51/53. Many Bio-lubricants on the other hand are readily biodegradable and not toxic to the living organisms in water. These products will therefore not receive an environmentally hazard label. Eco-labels There are for some Ecolabel for bio-lubricants. In Germany exists a ‘Blue Angel’ for “readily biodegradable lubricants and forming oils”, for “chain saw lubricants” and for “hydraulic fluids” all issued by the German Federal Office for the Environment [RAL UZ48, 64 and 79]. It defines criteria for the biodegradability and toxic ingredients of lubricants. Products containing poor biodegradable or eco-toxicological compounds, e.g. special additives are excluded from the eco-label award. Other countries promote ecolabel too, like Painter Hundertwasser (Austria), Blossom Symbol (Europe), Nordic Swan (Nordic Countries), Green Cross/Green Seal (USA), Maple Leaf (Canada), Ecomark (Japan), Green Tree (Hungary). 7.4. INITIATIVES AND MOTIVATION AT THE ENTERPRISE LEVEL As an alternative to mineral oils, which are non-toxic, bio-degradable and high-grade product lines, are available for almost all applications in many European countries, e.g. The Netherlands, Germany, Belgium, France, Denmark, Sweden and Finland. Most of the mineral oil companies developed alternative products on vegetable or synthetic oil base. They want to be prepared, when regulations get stricter or the demands increase on customer side. Only a few companies are very active in the area of inland water and shipping (e.g. Panolin AG, Fuchs). So far, the environmentally acceptable lubricants play only a minor role in the market. Only about 4% of some 1.2 million lubricants used in Germany each year are "bio-oils". Bio-oils replace approx 5% of hydraulic oils and 25-30% of loss lubricants. The market share of biolubricants is very low, i.e. around 1 %, especially in water-related applications [ULL 01]. But the forecast for future potential is promising: According to a study carried out by Frost & Sullivan, the share of bio-lubricants is set to triple by 2006 [in WAG 01]. Users do not trust in the technical performance and wait for bans or other legislation measure. In the public sector there are some exceptions. In Germany for instance the "Watercraft" Department of the Federal Institute of Hydraulic Engineering has drawn up plans, performance specifications and tender documents for the purchasing of watercraft for 120 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT the Marine Board and officially assists other federal departments. Environmentally acceptable lubricants have been used increasingly on board of official vessels since the beginning of the 1990's. The Government takes a lead role in protecting the environment and in supporting innovative technologies. Although several legislative movements compel various industries to reduce emissions, market participants must rely on consumer awareness to promote their products. Low-priced products, like mineral oil based lubricants, continue to pose a threat to manufacturers of biodegradable lubricants. 7.5. ALTERNATIVES / SUBSTITUTES Traditional lubricants are mineral oil based products. Their use is accompanied by environmental risks. These risks can be reduced by substitution with biodegradable, nontoxic loss lubricants on synthetic or vegetable oil base. These oils are classified as base oils. According to ISO/DIN 15 380 there are four groups: HETG (native base oils), HEPG (poly glycols), HEES (synthetic esters) and HEPR (poly alpha olephin and other hydrocarbons). Rapeseed oils (HETG) are always recommended for use if there are no other special requirements regarding temperature and oxidation stability. Native greases and oils can be processed into synthetic esters through further refining. The combination of fatty acids and alcohol make ester and water. A distinction can then be made between saturated and unsaturated synthetic ester. If comparisons are made between the various hydraulic fluids; it is evident that all biodegradable base oils have a clear advantage over mineral oils when it comes to viscosity; native oils (HETG) have the highest viscosity index and so perform better at a given temperature. The temperature at which the fluids can be used is lower for native oils than it is for mineral oils, whilst saturated synthetic ester is able to reach higher temperatures and so suit the requirements of the compact design of modern installations. A further important quality is oxidation stability which fundamentally effects the oil’s durability and allows longer intervals between oil changes. Synthetic esters, especially saturated synthetic esters, have excellent properties whilst native oils do not meet the requirements of the VDMA. Experience has shown that the interval between oil changes can be 5 times longer using synthetic esters. In this way, operating costs can be reduced by using biodegradable lubricants [KEI 01]. Synthetic Oils: Synthetic oils are high quality basic oils that are produced with defined chemical and physical properties for various applications, such as motor oils. These are won as paraffin based basic oils by hydro-cracking long-chained paraffins. The unsaturated compounds, which are a contaminate, are hydrogenated through the addition of hydrogen. Synthetic oils are used as a carrier liquid for additives. Vegetable Oils and their Derivatives: Vegetable oils are oils based on renewable raw materials, such as rape-seed, soya, cocoanut, palm-seed, sunflower, etc.. From a chemical point of view, these are triglycerides of natural fatty acids. Vegetable oils are won by raising the above mentioned plants. In lubricants, vegetable oils are used as a carrier or basic raw material. Neat oils are more or less only 121 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT recommended for low tech applications. Vegetable oil esters are produced from vegetable oils by chemical processes (e.g. interesterification). They can be used as a carrier or basic raw material, or in combination with pure vegetable oils to meet certain requirements (e.g. low viscosity, to improve spraying properties, etc.). This group is discussed controversial concerning the environmental properties. Poly alkylene glycols are an interesting group of substances which probably require fewer additives than other biodegradable groups of substances, whereas poly- -olephins are tribologically ineffective and therefore could lead to problems caused by the toxicity of additives. The products are sometimes mixed with synthetic ester fluids. Users should make further inquiries as seal and hose manufacturers have observed occasional problems with mixed products. A further aspect is the specific weight of poly- -olephins. They are heavier than water. In construction activities with gravel dredgers; after a while a strong poly- -olephin layer could be seen on the bed of dredged waters [KRS 01]. Bio-lubricants on synthetic oil base or fatty acid ester base can contain additives too. Concerning hazardous additives the same problems can occur like with ‘normal’ lubricants. But mostly the supplier and manufacturer select less harmful compounds for reaching the criteria of biodegradation and toxicity. Technical scope of substitutes The technical performance of bio-lubricants in inland water activities was studied intensively in the LLINCWA-project [LLINC 01]. Many other R&D projects developed the biolubs with high technical standard and demonstrated their suitability in practice [FNR 99]. There are a number of benefits from using biolubricants in place of common mineral oil products, including: • high biodegradable, also after long time of use, • low toxicity, • high viscosity index, • lower friction index than mineral oils, reduce energy consumption, • high flash point, low VOC-emission during production and use, low vaporization losses, • good lubricating properties, longer lifetime of machines and • good adhesive ability on different metal surfaces. Less oil losses during operating. Beside technical advantages the use of biolubricants can have financial benefits for example in the case of oil accidents/spills. Practical examples demonstrated cost savings between 25,000 - 50,000 € due to reduced requirements for remediation measures by the environmental authorities [HORN 01]. 7.6. IMPLICATIONS OF SUBSTITUTION FOR BUSINESS PRACTICE The amount bio-lubricants and hydraulic fluids has been extended in the last ten years. Today the market for substitutes offers products with all options concerning different demands. Most suppliers offer bio-lubricants in their product range. The technical Poly alkylene glycols and poly- -olephins: 122 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT performance is proven in practise and in laboratory test with standards measures. Concerning some chemical-physical and technical parameters bio-lubricants on vegetable oil base perform inferior than mineral or synthetic oil based products. In some cases additional devices are necessary for the use of bio-lubricants like special filters, especially in closed systems. Usually it is requested that suppliers of equipment and products guarantee for the technical performance. The requirements for the environmental friendliness of process products like lubricants have become stricter in some cases, for e.g. by demand from regulative bodies in environmental sensitive areas. Overall this factor is less important in the area of loss lubricants in water activities than in other areas like agriculture or forestry. There is still a considerable lack of legislative standards. The big supplier enterprises do not force the bio-products by specific marketing. They only want to be prepared when customers ask for bio-lubricants. Organisations using bio-lubricants have to pay more for the products. The price per litre is around 2 to 3 higher than for a mineral oil based lubricant. Costs occurring over the entire life cycle might be less compared with conventional products due to longer machine running times etc. However, this message is very difficult to communicate. Bigger enterprises like shipping companies are served with complete lubrication-services from the suppliers of lubrication agents. In this case it is difficult to introduce new products. The substitution process is easier, if technical engineers decide on products to be purchased; especially if the company has to pay for water pollution (shipping). In the public sector of some countries bio-lubricants are preferred, for example in the area of harbour (ships, locks and others). The basic requirement for substitution in the area of loss-lubrication is information on water activities. The dissemination of information and rising of awareness about disadvantages of loss lubricants on mineral oil base and the available alternatives is important. The fear of bad performance has to be overcome. Positive examples and references are convincing, like the LLINCWA project has demonstrated. Addressees would be shipping companies, owners, authorities and other customers. 7.7. CONCLUSIONS Lubricants in and around surface water are used in a wide range of activities and applications. Both loss lubricants and lubricants for closed systems (hydraulics and gear oils) are used. The activities cover inland shipping, harbour activities, dredging, lubrication of locks and bridges, hydro-electricity plants, pumping stations, waste water treatment plants, waterfront construction etc. Lubricants facilitate the effective operation of mechanical equipment, reduce friction and wear, and are used for the transmission of force. Lubricants used for such activities can pollute the surface water. Conventional lubricants are based on mineral oils and contain toxic and poorly biodegradable substances. The discussion on bio-lubricants and the development of the first products is around fifteen years old. It started with the replacement of loss lubricants in chain saws. Regulations cover up to now only a small part of applications. The application area inland water had not come into focus before the nineties. Consequently, there are few, mainly regional regulations up to now to avoid water pollution from lubricants. Market introduction support programs exist. 123 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT The new regulation for labelling will increase the awareness of environmental hazardous substances in lubricants. Less than 1% of the lubricants applied in this sector can be described as non-toxic biodegradable (Netherlands, Germany, Belgium, France and Spain). - Costs The price of bio-lubricants is higher (two to three times) than for conventional products. The user structure is characterized by two major groups: private owners of inland ships with high competitive market pressure, and public authorities operating locks and bridges etc. Both users are very sensitive to the price of the product. - Awareness - public Obviously the problem of water pollution through lubricants has still a low awareness. The reason might be that the risk by lubricants is seen as negligible in relation to other water polluting substances (waste water, industrial pollutions, sea and coast pollution by oil). + Communication B2B The technical functionality of bio-lubricants is proven in different application areas, a large number of practically tested products exist. There is an exchange of such experience between public authorities and others promoting this substitution. + Regulation Regulation plays an important role in the substitution process. However, it has not been applied consistently throughout Europe. Most important factors of this case study are presented in the table below. Single important factors overview Economics Higher price per litre for alternative product hinder substitution Economics/costs hindrance of substitution Hindrance of substitution Support of substitution (-) (-) (+) Social factors Relatively low awareness of water pollution through lubricants Social factors/Awareness Increasing importance of environmental and health aspects Social factors/communication B2B Regulation Regulation plays an important role in the substitution process. However, it has not been applied consistently throughout Europe. Legislation/Regulation Neutral to substitution (+) 7.8. LITERATURE BML 00 German Federal Ministry of Consumer Protection, Food and Agriculture: Directive for the market introduction program for ‘Biogenic fuels and lubricants’ from 7. December 2000. 124 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT CHRIS 01 Christiansen. M. (German Federal Institute of Hydraulic Engineering): Introduction of environmentally compatible lubricants – Some examples of state-owned ships in Germany. In: Llincwa-Workshop report ‘Environmentally acceptable lubricants and hydraulic fluids contributing to surface water protection’. Koblenz, 8th October 2001. Directive 1999/45/EC of 31. May 1999 concerning the approximation of the laws, regulations and administrative provisions of the Members States relating to the classification, packaging and labelling of dangerous preparations Water Directive of the European Parliament and of the Council of 23. October 2000 establishing a framework for Community action in the field of water policy. EC 99/45 EC 2000/60 EC 2455/2001 Decision of the European Parliament and the Council of the 20. November 2001 establishing the list of priority substances in the field of water policy and amending Directive 2000/60/EC. FED 00 FME 99 FEDIOL (EC Oilseed Crushers’ and Oil Processors’ Federation): Manifesto on ‘non-food’ oilseeds. May 2000. German Ministry of the Environment, Nature Conservation and Reactor safety: General Administration Regulation of the Water Management Act on classifying water hazardous substances into Water Hazard Classes (VwVwS) from 17 May 1999. German Agency for Renewable Primary Products (FNR): Status seminar on biodegradable lubricants and hydraulic fluid. Mannheim 1./2. December 1999. Ordinance on Protection against Hazardous Substances “Classification and Labelling”. German Federal Agency for Occupational Safety and Industrial Medicine. January 2000. Hornscheidt, G.A. (C. Bechem GmBH): Ten years of biolubs. In: LlincwaWorkshop report ‘Environmentally acceptable lubricants and hydraulic fluids contributing to surface water protection’. Koblenz, 8th October 2001. Institute of Fluid Power Drives and Controls at University of Aachen: Supplier and product list for lubricants and hydraulic fluids based on renewable resources (2001). http://www.rwth-aachen.de/ifas or FNR http://www.fnr.de. Keiemburg R. (TotalFinaElf): Biodegradable lubricants contributing to highest quality and security standards. In: Llincwa-Workshop report ‘Environmentally acceptable lubricants and hydraulic fluids contributing to surface water protection’. Koblenz, 8th October 2001. Krstic, M. (Kleenoil Panolin AG): Discussion documentation in: LlincwaWorkshop report ‘Environmentally acceptable lubricants and hydraulic fluids contributing to surface water protection’. Koblenz, 8th October 2001. FNR 99 GefStoffV HORN 01 IFAS 01 KEI 01 KRS 01 125 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 7: LOSS LUBRICATION IN INLAND WATER FINAL REPORT KROP 02 Krop, H. : "Health and environmental hazards of commonly used additives in lubricants". Report. Publisher IVAM-Chemiewinkel, Universiteit of Amsterdam, May 2002. LLINCWA-Project: “Loss lubrication in Inland and Coastal Water Activities”. Technology Transfer project funded by Innovation-program of the EU. German Institute for Quality Assurance and Labelling: ‘Blue Angel’ for Rapidly Biodegradable Lubricants and Forming Oils. Last version April 2002. Ullmer, S. (ISSUS-Hamburg): Market situation „Biolubs“. In: Llincwa-Workshop report ‘Environmentally acceptable lubricants and hydraulic fluids contributing to surface water protection’. Koblenz, 8th October 2001. Wagner, H. (Fuchs Petrolub AG): Biolubricants - Practice, wishes and realities. Transparency of lecture at the Llincwa-Workshop report ‘Environmentally acceptable lubricants and hydraulic fluids contributing to surface water protection’. Koblenz, 8th October 2001. Zwinselmann, J: New generation of EP/AW additives. In: Llincwa-Workshop report ‘Environmentally acceptable lubricants and hydraulic fluids contributing to surface water protection’. Koblenz, 8th October 2001. LLINC 01 RAL UZ 64 ULL 01 WAG 01 ZW 01 126 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT 8. 8.1. CASE STUDY 8: MOULD RELEASE AGENTS TECHNICAL AND CHEMICAL SCOPE General In concrete casting, mould release agents are used to release mould of the hardened concrete. Other appellations for mould release agent are form oil or concrete release agent. They are auxiliary agents to prevent surface damage of the concrete as well as the formwork. Concurrently, a good surface quality shall be performed without negative influences on the concrete itself. Release agents are used on construction sites or during the manufacture of precast concrete. In the European Union an annual 80,000 tonnes of release agent are used. Traditional release agents are based on mineral oil (petroleum), here called MORAs. Organic solvents may be added mainly to reduce the viscosity and further additives are commonly supplemented. They all may be hazardous to the environment and to workers’ health. As a result of the most commonly used way of application, i.e. by spraying, the products are dispersed in a relatively uncontrolled way into the environment. Environmental issues connected to release agents include: • emissions of volatile organic compounds (VOC) to the atmosphere, • emissions to soil and water, • poor biodegradability of these oils in the environment, • generation of hazardous waste, wastewater treatment and • use of non-renewable resources. Release agents cause health and safety hazards: inhalation of organic compounds and oil mist, skin irritations and diseases due to skin contact, allergies, accidental ingestion (choking), odour nuisance and fire- and explosion risks. Nowadays release agents based on vegetable oil, so-called ‘VERA’ (VEgetable Release Agents), are on the market. They perform as good as traditional oils. VERAs can be considered as a non-toxic, environmentally friendly class of products which are significantly less harmfull in terms of environmental and health hazards compared with mineral oil based products. Historical developments Until the eighties little attention was paid to mould release agents. They were not expected to affect the concrete. Health and environment impacts were ignored. Consequently, all kinds of mineral oil products were utilized including used motor oil or diesel from petrol stations, that was often diluted with solvents for better application.16 Sold products consisted of simple mineral oil distillates, some included solvents on aromatic hydrocarbon base. 16 In some European countries this is still common practise. 127 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT In the nineties the impact of the release agent on concrete surface quality was recognised. The development of the mineral products took place, while water based emulsions became more common. The ecological awareness of users increased and the regulations for handling chemicals became stricter. Hence, the demand for better concrete release agents was generated. Especially the demand for release agents with high biodegradability fostered the development of a new group of alternatives based on vegetable oil. Nowadays, ‘bio’ release agents formulated with fatty acid esters, derived from different vegetable oils are available on the market. In particular the emulsions based on fatty acid esters are suitable substitutes for precast factories, where solvent-containing MORAs are often used. VERAs perform as well or even better than the traditional oils. This study focuses on the substitution of MORAs by VERAs. Exceptions are not covered, such as less common or demoulding techniques with special laminated moulds or folia where no release agent is necessary. They are too expensive and their market share is low. 8.1.1. Technological principles Release agents are used in concreting to enable separation of forms from hardened concrete. The releasing actions of these agents can be classified into two basic categories: • physical or • chemical actions. Most of the well formulated release agents have both characteristic properties. Physical release Physically acting release agents can also be called barrier type release agents. They create a barrier between the form and concrete to hinder concrete from sticking to the form. The physical property of the hydrophobic effect of oil and water depends on the thickness of the coating. Therefore, purely physically active form oils are usually applied heavily which causes problems with bug holes and staining. MORAs act as physical release agents. Chemical release Chemical release is based on the saponification reaction between Ca-ions of fresh concrete and fatty acids of release agent. In this reaction a thin layer of insoluble calcium salts are formed in the concrete-form-interface, which contributes to easy release. Chemical release reaction is very effective compared to a purely physical one; consequently, the amount of chemically active release agents needed is much smaller. Theoretically, a layer of 2 microns is sufficient for good release. Fatty acids originate from plants or animals. They are also often added to mineral oil based form release agents to improve their performance. These type of products are called chemically active release agents. Application and performance Release agents are normally applied by spraying or wiping onto the inside of the formwork before fresh concrete is placed. Typical spraying equipment are hand held spraying devices (construction site) or automatic spraying units (precast factories). It is important to apply release agents in a thin film. To achieve good results attention has to be paid for the jet 128 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT direction and equipment, like spray pressure or kind of nozzle has to be followed. Many technical criteria have to be fulfilled by concrete release agents. The properties of the finished concrete can be influenced by type of release agent, type of mould and accuracy of application: • • • • • • • • • Releasing abilities (under different temperatures conditions), Visual appearance of concrete surface (e.g. porosity, colour, dusting), Durability of the concrete (compressive strength), Interaction with the concrete (e.g. time of setting), Adherence of the finished product (paints, plasters, etc), Long efficiency and rain resistance after spraying, Compatibility with different types of mould material (wood no discharge of wood sugar, steel shutterings no rust, plastic good adhesion), Temperature and heating stability ( no altering of viscosity, etc) and Contamination of moulds after demoulding ( easy cleaning, no sticking residues). Consequently, the demand concerning performance of mould release agent is high, particularly in precast factories. These claims are made particularly for substitutes. Substitutes are expected to perform better than the conventional products. The price per litre is a very important factor for choosing the product despite the fact that the relative contribution of release agents is negligible compared with other production costs in the building sector. 8.1.2. Chemical scope Typical release agents are based on mineral oil (petroleum). Today the types of base of release agents vary from recycled mineral oils (or simpler distillates) to high quality (cleaned up first refineries and synthetic oils). Volatile organic solvents may be added to reduce the viscosity and to control the application rate. Release agents often contain additives to ensure the technical performance, e.g. corrosion inhibitors or anti-foam agents. There are water based emulsions available too. The application is still accompanied by certain health and environmental hazards, although the newly developed mineral products are much less hazardous than the ones formerly used [SUM 99]. The following description of the chemical scope is structured in two parts: main ingredients and additives according to the report from DBC 01. Main Ingredients Mineral oils (paraffin and naphthene based): Mineral oils are complex mixtures of substances consisting of paraffinic, naphthenic and aromatic hydrocarbon chains of medium length. The composition is essentially determined by the origin. The oils are optained by fractional distillation or cracking (splitting large molecules) and hydrogenation. As a rule, the mineral oils used in concrete release agents are 129 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT highly hydrogenated which allows the content of aromatics to be kept very low. Their flashpoint is clearly higher than 100°C. Synthetic oils: Synthetic oils are high quality basic oils that are produced with defined chemical and physical properties for various applications (e.g. motor oils). These oils are extracted from basic oils as paraffin by hydro-cracking long-chained paraffins. The unsaturated compounds, which are a contaminate, are hydrogenated through the addition of hydrogen. Synthetic oils are used as a carrier liquid for additives. Vegetable oils and their derivatives: Vegetable oils are based on renewable raw materials (rape-seed, soya, cocoanut, palm-seed, sunflower, etc.). From a chemical point of view, these are triglycerides of natural fatty acids. Vegetable oils are won by growing the above mentioned plants. In release agents, they are used as a carrier or basic raw material to separate the concrete from the formwork. Neat oils are usually applied for low tech applications. Vegetable oil derivatives are produced from vegetable oils by chemical processes (e.g. interesterification). They can be used as a carrier, basic raw material or in combination with pure vegetable oils to meet certain requirements, such as low viscosity and increased spraying properties). Organic solvents: The solvents used in concrete release agents are thin-liquid, volatile, complex hydrocarbon mixtures. These de-aromatised white spirits have a residual aromatic content of less than 0,1 % by volume. These solvents are extracted from petroleum fractions by hydrogenation and hydro-cracking. Solvents are used in release agents to control viscosity and the thickness of the film. This class of substances also has very good spreading (creep) behaviour on formwork. After the release agent has been applied, the solvent evaporates in a defined manner. Waxes and resins are materials for special demoulding tasks. Additives Fatty acids: Fatty acids are generally understood as unbranched chains of carboxylic acids. Typical representatives are those of natural origin with 12 to 22 C-atoms. Fatty acids are won by cracking vegetable oils and animal fats. They are very weak acids and represent the starting product for surface-active agents, lubricants, cosmetics and foods. Stearolic acid, oleic acid or mixtures of higher fatty acids are used in concrete release agents. Their functionality is achieved by a chemical release effect that occurs when free lime in the fresh concrete forms a Ca-soap on the surface of the concrete. The physical release effect of the base oils is chemically reinforced through this reaction. Fatty acid esters: Fatty acid esters are produced both directly (e.g. from jojoba oil) and indirectly through esterification or interesterification of natural resources. They are used in the lubricant and food industry. Fatty acid esters are used as additives in concrete release agents on a mineral oil base. Depending on the type of ester, their main function is to either reduce pores or 130 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT improve the release effect. In release agents, that are free of mineral oils, fatty acid esters are used both as an additive for the above mentioned reasons or as base oils because of the favourable ecological properties of fatty acid esters. Emulsifiers (surface-active agents): These are so-called surface active substances. This is the designation for chemical compounds which strongly concentrate on interfaces in order to reduce surface tension. This makes immiscible liquids (e.g. oil/water) miscible, i.e. an emulsion forms. In this case a surface-active agent works as an emulsifier. The number of available surface-active agents is extremely large. Surface-active agents can be natural, partially or completely synthetic in origin. They can also be divided into anionic, cationic, non-ionic and amphionic surfaceactive agents, depending on their effect. Applications for surface-active agents or emulsifiers are extremely diverse and are indispensable for the formulation of release agents in emulsion form. They are used as a spreading agent and as an additive to suppress pores on the surface of concrete in non-aqueous release agents. Mainly fatty acid esters (ethoxylated and non-ethoxylated), fatty alcohol ethoxylates and fatty amine ethoxylates are used. Corrosion inhibitors: These are products that are suitable for passive corrosion protection that can be used to protect equipment and facilities. Calcium sulphonate, succinic acid semi-ester, fatty amines or imidazoline derivatives are typical corrosion protection agents used in release agents. As rule of thumb mould release agents contain two to five additives to guarantee the technical performance. 8.2. SCIENTIFIC EVIDENCE ON (ECO)TOXICOLOGICAL AND ENVIRONMENTAL IMPACT The current problems with the use of mineral-oil based release agents can be divided into two main categories: working conditions and the environment impacts. The substitution covers tree possible situations: 1. the change from mineral oil based release agents which contain solvents and/or aromatic hydrocarbons to less dangerous MORAs (occupational health), 2. the change from poorly biodegradable MORAs to readily biodegradable MORAs (environment) and 3. the change from mineral oil based to vegetable oil based release agents (occupational health and environment). The first situation can bring advantages concerning the working situation. The environmental impact could decrease for instance by less VOC emission. Problematic soil and water pollution by mineral oil still occurs. The second option seems to be more beneficial for the environment as it solves the problem of degradability (commonly used application). The third option improves both categories, i.e occupational health and environment. Consequently the focus of this case study is laid on the change from mineral oil based to vegetable oil based release agents. 131 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT 8.2.1. Workers’ health and safety issues connected to release agents Application of mould release agents is still associated with health risk, although the quality has improved considerably. Additionally, the quality level of mould release agents varies throughout the EU. A large number of release agents are mineral oil based and may contain relatively large amounts of solvents. In the majority of the cases release agents are atomised. This results in the formation of oil droplets in the air and evaporation of the solvents. Furthermore the release agents may contain additives which may result in allergies. Most critical is the exposure of workers in prefab productions. Thus, care should be taken in handling and working with release agents. Solvent vapours or sprayed mist may cause high concentrations of hydrocarbon vapours to form under certain conditions, when using concrete release agents in closed spaces. These concentrations can be monitored in working environments. Their concentration will depend on the specific means of production, the safety measures taken at the construction site as well as the ingredients in the composition of the release agent. Release agents may bring about the following health and safety hazards: • • • • • • • Inhalation of volatile organic solvents (VOC), Inhalation of oil mist, Skin diseases resulting from skin contact with mineral oil, aromatic hydrocarbon, organic solvents, Allergies caused by single components (additives etc.), Accidental ingestion (choking), Odour nuisance and Fire and explosion risk. Solvents, their vapours and mists have various negative effects on human health. Many of them have a narcotic effect, causing fatigue and dizziness. High doses may lead to unconsciousness and death. Exposure to large doses of solvents may slow reaction time and affect rational judgement. Solvents enter the body by inhalation, swallowing and through the skin. Solvents degrease the skin, which is a very common cause of skin disorders and dermatitis. When skin is damaged they enter the blood circulation. Some solvents may also damage the liver, kidneys, heart, blood vessels, bone marrow and the nervous system. Irritation of eyes and respiratory tract is possible. Most of the solvents are volatile and flammable. Vapours of solvents can also accumulate in confined places and generate an explosion and fire risk [ILO 02]. 8.2.2. Environmental aspects connected to release agents Environmental hazards associated with organic solvent emission include the build up of atmospheric ozone by photochemical oxidation (Summer Smog) and ozone depletion in the stratosphere [VOC 99]. The use of mineral oil based release agents is also linked to water and soil pollution; the biodegradability of most mineral oil based solvents is inferior to products based on vegetable oils. Other problems are the generation of hazardous waste, wastewater treatment and use of non-renewable resources. 132 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT The main environmental impacts, which have to be considered in a risk assessment, are: • • • • Emissions of VOC from release agents into the atmosphere, Risks of spills or leakages during transport, storage or handling, Risks of soil and water contamination with mineral oil and Discharge of waste water contaminated with release agents into the sewage system. Mould release agents are classified as readily biodegradable, potentially biodegradable or biodegradable in principle. Biodegradability is a chemical alteration of organic substances up to mineralisation and/or the formation of biomass caused by the action of micro organisms. Biodegradability is an important factor for determining the affects on the environment. Various test methods have been developed to determine biodegradability (CEC, OECD), particularly in aqueous systems. However, the results of these tests are often transferred without problems to other environmental media, such as soil. Within the EU-project Sumovera it was verified whether this is an acceptable practise. The biodegradability of mould release agents with mineral and vegetable oil base was compared in soil. Within the observed period the two VERAs had an average of biodegradation of 40 to 60 %, depending on the contamination level. For the mineral oil based products no degradation could be observed [LAN 98]. The results demonstrate that data from the usual OECD and CEC-tests cannot be used to estimate environmental friendliness in all environmental areas. Mineral oil based products have a negative impact on the physical, chemical or biological characteristics of water. The danger of hazardous substances and mixtures can be classified into water hazard classes (‘WGK’) according to the German System [FME 99, VwVwS]: WGK 1 : slightly hazardous to water, WGK 2 : hazardous to water, WGK 3 : extremely hazardous to water or rated as not hazardous to water (nwg.). The water hazard potential is rated on the properties of the substances: 1) acute oral toxicity for mammals, 2) toxicity for aquatic organisms (mostly fish and bacteria) and 3) degradability [FME 99]. Typically MORAs are classified in WGK 1 or 2, VERAs in WGK 1 or as not hazardous to water. Waterborne emulsions Water based release agents could contain a number of additives. Some of these ingredients have eco(toxicological) impacts. They are listed below: 133 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT Group Emulsifier Function Support the fixity of the emulsion Corrosion protection, specially for steel moulds Biological Stability to ensure the self life in tanks Application by spraying Increase frost resistance Corrosion inhibitors Preserving agents/ Biocides Antifoaming agents Alcohols (in winter grades) Human Tox (via skin contact) Poor biodegradability in the Skin corrosive, degreasing and irritating water phase, harmful to environment Skin corrosive, Toxic impact on organism + micro organism, harmful degreasing and irritating to environment Toxic impact on organism Skin diseases, toxic and micro-organism impact depending on type of biocide Low biodegradability in the Skin irritation water phase Often VOC Solvent emissions in ambient air Eco Tox For the classification of mould release agents different systems exist. The German system concludes seven categories according to the regulations on hazardous substances [GIS 99] (see chapter 5). The German enterprises are barely aware of the classification system and the acceptance is low [WOER 02]. In the Netherlands a ranking system has been developed in co-operation with the suppliers’ organisation BLF. This ranking concludes five categories which refers to occupational health aspects and to the biodegradability [SUM 99]. Both systems give advice for substitution within the group of mineral oil based release agents. 8.3. INITIATIVES AT THE POLITICAL LEVEL Every Member State has a number of legal regulations and control procedures to reduce the impact of mineral oil on the environment. Laws and regulations that refer to different environment compartments (air, water and soil), can be indirectly applied to mould release agents as possible pollutants. Especially in ‘drinking water production areas’ and in ‘nature preservation areas’, regulations regarding the use of oils are often more strict. In these cases the responsible local authority sets limitations in building permits. Pertaining to mould release agents the use of readily biodegradable products can be claimed. In 1999 the Directive 1999/13/EC on the limitation of emissions of volatile organic compounds entered into force due to the use of organic solvents in certain activities and installations (the so-called VOC Solvents Directive; [VOC 99]). The Directive sets emission limits for certain industries. Member States are required either to implement the set of emission limit values foreseen by the Directive, or to design and to implement a National Plan to achieve the same reduction. The new EU Directive 1999/45/EC extends the labelling for preparations as an environmental hazards. This approach will change the labelling practice for mould release agents based on mineral oils. To sale a product with the label “N” (dangerous to the environment) and the symbol “dead fish” on is practical impossible. Hence some additives will not be used any 134 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT longer in release agents [WOER 02]. In addition, some concrete release agents must have respective danger warnings printed on their labels according to the regulation system of the German Hazardous Substance Ordinance [GefStoffV 00]. Products that contain more than 10% by mass hydrocarbons must be labelled „Harmful if swallowed” (Xn with R65), if the viscosity of the concrete release agent is less than 7 mm2/s at 40°C and depends on a certain surface tension. Other constraints affect fire and explosion regulations, which required release agents with a higher flash point. The labels of solvent based release agents with a flash point between 21°C and 55°C must have the danger warning „Flammable” (R 10) and the relevant safety advice (Sphrases) because of their flammability. Only one Eco-label for “readily biodegradable lubricants and forming oils” exists, i.e. the ‘Blue Angel’ issued by the German Federal Office for the Environment [RAL UZ64]. It defines criteria for the biodegradability and toxic ingredients of release agents. Products containing poor biodegradable or eco-toxicological compounds are excluded from the eco-label award. 8.4. INITIATIVES AND MOTIVATION AT THE ENTERPRISE LEVEL Over the last decade construction and precast companies have faced an increasing demand from clients and legal authorities as well as from their own employees, for environmentally sustainable and safer products. Laws have become more strict and therefore costs have increased. In this respect, a number of problems connected to traditional mineral-oil based release agents can be solved by using alternative products like VERAs: Problem with traditional release agents They are flammable They irritate the skin They have a strong smell They attack working clothes, shoe-soles, plywood moulds etc. • They may contain volatile solvents which can damage workers' health • They are poorly biodegradable and pollute the soil at construction sites • They generate hazardous waste which is very expensive to get disposed of • • • • Advantage of VERAs They are not flammable They do not or hardly irritate the skin They have a mild smell They do not attack working clothes, shoesoles, plywood moulds etc. They do not contain volatile solvents They are readily biodegradable in the environment They generally do not produce hazardous waste • • • • • • • The development of alternative mould release agents like VERAs started parallel in the Netherlands and in Switzerland around 1990. One Swiss company developed a innovative ‘high tech’ VERA and introduced it on the European market expecting an economic advantage. Additionally, they aimed to fulfil the demands from their customers for products with better concrete performance [WOER 02]. In the Netherlands today several institutions, organisations or companies claim to be the initiators, or claim to have been the major driving force for the further development of the alternative VERA products [IVAM 02]: 135 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT • • • • An ester producer developed the ester that led to a successful VERA-product. They also hold the patent, and thus claim to be the initiator. A release agent producer bought the ester from the supplier and developed the products that were successfully introduced to a small number of companies. This took about 5 years of developing work. They convinced the end users to use VERAs. One building company and its contractors pressured suppliers to come up with product less harmful than mineral oil based products. The first was a prefab company. Problems with their waste sludge was the 'trigger'. They had to pay lots of money to the waste collectors, because mineral oil was detected in a too high concentration in the sludge. The second building company had to face a high financial claim resulting from an oil-spill on a construction site. Ground water protection played a role for certain companies, but the risk of financial claims due to soil pollution (oil spills) was more important. In the Netherlands, the 'polluter pays' principle holds as far as soil pollution is concerned. the Dutch Ministry of Environment granted a 'pilot study' on the possibilities of using VERAs, within the framework of the KWS 2000 project. The reduction of VOC-emissions was the main interest of the ministry [NL 89]. Significant differences among countries and enterprises on the implementation of VERAs can be observed, particularly concerning the influence of employers and employees. For example, in France the power is exclusive to the management, while in the Netherlands the employees have a decisive impact on purchasing decisions. Both the French employers and the Dutch employees are not very eager to purchase VERAs. The former because of their conception of the costs involved and the latter because of their (unwarranted) belief that VERAs are technically inadequate. Both arguments suit for Germany as well. One reason for this are bad experience of companies which tested the ‘earlier’ vegetable oil based products in the seventies. These release agents were ‘low tech’ products with bad performance. In other countries a low awareness for environmental protection had hindered the use of VERAs like in Finland and Portugal [Shere 98]. Today, this has changed a bit. The role of licensees in the adoption process was important in Portugal and the Netherlands. In these countries, only two companies each hold licensees for VERAs. This fact causes dissension and opposition among manufacturers and the other suppliers. These problems do not occur in every country. In Germany this is a minor fact because there is no punishment when patents are invaded. As described in case study 1 for metal cleaning agents, mould release agents are process chemicals and not a compound of the final product. The technical performance and the quality of the finished concrete are the most important points. In enterprises the main factors to decide on are technology and costs connected with mould release agents, equipment, environmental and safety and health protection. The following tables show the factors and arguments relevant for enterprises. 136 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT PRO SUBSTITUTION Less risks of spilling and soil and water contamination Prices for sludge (waste), contaminated with mineral oil Less health hazards like skin diseases, thereby less potential conflicts Technical performance Substitution from MORAs to VERAs CONTRA SUBSTITUTION MAIN STAKEHOLDER Industrial users Higher price per litre, costs for new equipment (e.g. stainless nozzles) Industrial users (environmental view), insurances, authorities Industrial users, authorities Workers, professional association, insurances, trade unions and authorities Industrial users (technical and quality view, apprehensions) Application (more care Industrial users (technical and recommended, change of habits) quality view), workers Industrial users Less fire and explosion risk, storage obligations 8.5. ALTERNATIVES /SUBSTITUTES Traditional release agents are mineral oil based products, often diluted with solvents to facilitate application. The use of traditional release agents is accompanied by certain health and environmental risks (see chapter 2.). These risks can be reduced by substitution of MORAs by VERAs. A set of criteria was developed in the EU-Project SUMOVERA in order to properly define VERAs [SUM 99]. These criteria refer to raw materials, biodegradability, toxicity and volatility. In table 1 the criteria for VERAs are given. A product is called VERA in case it meets these criteria. Table 1: Criteria for VERAs Major components Additives (together max. 5%) Raw Biodegradability material ready biodegradable 75% according to OECD (w/w) vegetable oil inherent biodegradable according to OECD R-phrases none Volatility vapour pressure < 10 Pa at 20°C vapour pressure < 10 Pa at 20°C Product ready biodegradable 70% according to OECD (w/w) vegetable oil none in relation to sensitisation, carcinogen, mutagenity or possible reprotoxic or aquatic effects none vapour pressure < 10 Pa at 20°C 137 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT Technical scope of substitute: The technical performance of VERAs was studied intensively and compared with MORAs within the framework of the SUMOVERA project [SUM 99]. According to the project results vegetable oil based mould release agents (VERA) perform very well. The Performance of VERA products was studied both in laboratory tests and in pilot applications. The releasing ability of VERA products is even better than that of conventional mineral oil based products. VERAs are chemical active release agents. This leads to a smaller amount of release agent needed. Several advantages are achieved with lowered amounts of oil: better concrete surface quality, savings in costs, cleanliness of moulds and working environment. Additionally, concrete proved to have better frost-salt resistance and lower waterpermeability when demoulded with VERA. VERA did not impair the adherence of possible finishes either. A comparison on the performance of VERAs and MORAs is shown in table 2. By using non-toxic, readily biodegradable mould release agents further savings can be made in waste handling and by offering healthier and safer working environment for workers. Table 2: Performance of VERA compared to standard release agents (MORA) Advantage Performance non dusting even colouring (with heated forms) Reducing imperfections in concrete Corrosion protection Compatible with all concrete admixtures no interference with subsequent treatments Application no thickening or settling at cold temperature Sprayable at temperatures below -7°C non evaporating at high ambient temperature usable even after long delay before casting no thickening in galvanised sprayers form wetting ability (emulsions) Occupational health/environment no VOC- release no drying out of skin skin irritation unlikely mild odour not combustible /flash point >90°C ready biodegradable in soil low amounts needed VERA modern microemulsion ++ to + ++ to + ++ ++ + ++ + ++ ++ + ++ ++ + + ++ ++ ++ ++ simple rape oil based o o (-) + ++ + o to o o ++ + + Mineral oil based RA high quality low quality with fatty (diesel) acids ++ + + + ++ + + + + ++ ++ + o to + to o + o + + ++ + + + ++ ++ ++ o o + to o + to o + + to o + o Legend: advantage is ++ + fully present present with reservation o - not present contrasting properties 138 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT The way of substitution MORA by VERA is not the only possible one. Less dangerous or hazardous MORAs are available. For replacements within this product group, other classification systems for release agents give aid, e.g. GISBAU system from the German building trade association: Figure 1: German classification system for concrete release agents [GIS 99]. VERAs normally belong to product code CRA 10. Other Demoulding Alternatives Other technical solutions without any release agents are not prevalent. This are moulds with special coatings, where no release agent has to be applied. The figure 2 shows the scheme of these possibilities. These techniques are up to now more or less exotic. The Teflon-laminated moulds are very expensive and have to be handled very carefully. This is not so easy on construction sites. Moulds for pillars and the special folia are expensive and produce a lot of waste. 139 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT Figure 2: Other demoulding alternatives 8.6. IMPLICATIONS OF SUBSTITUTION FOR BUSINESS PRACTICE The amount of available alternative release agents has been developed significantly over the last decade. Today there is a broad variety of VERAs on the market offering products with all technical features. Great knowledge and experience with VERAs ensures good technical support. Overall 30 suppliers offer VERAs on the Germany market. In the Netherlands 10 suppliers cover 95% of the market. In other countries the availability is narrower, but VERAs are available. The confidence of users in these product group is not very high. Both the requirements for the quality of the products and the process control have become stricter due to increased internal management systems (environmental, quality and occupational health). Additionally the demands from the regulative bodies - from environment over transport to health and safety - have become stronger. All in all these factors are in the case of mould release agents less powerful than in other industrial areas. In some cases building companies themselves look for alternative products when problems arise. This may be skin diseases of workers or need of investment for precautionary measures related to fire- and explosion risks or storage. Here the enterprises accrue directly a benefit by substitution MORA by VERA. Beside all advantages, the company which decides to switch to a VERA, has to pay more at first. The price per litre is around 1,5 to 2 higher than for a MORA. This influences the decision process differently depending on the corporate structures. In bigger companies with a central purchase - the decisions for materials are based on ½ Cent (€). In this case a costbenefit calculation is often needed to establish a VERA. In smaller companies where e.g. the production manager or the foreman decide directly which product will be purchased, the substitution process is much more easier. Some companies don’t decide on the costs only, they promote their ‘responsible and green image’ by using environmental friendly products. 140 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT VERAs require an accurate handling to guarantee the good performance and to balance the higher price per litre. The user has to apply a thin film and moulds has to be cleaned carefully in particular when emulsions are utilized. Instead, workers maybe have to change their application habits. An inducement could be, that a removing of surplus with rags can be omitted when VERAs are applied rightly. This is often an unloved working step and it needs time and money. The basic pre-requisite for a substitution MORA by VERA is the need for comparable information. The dissemination of information and awareness rising about disadvantages of MORAs and the available alternatives is very important. Addressees are not only user companies but also customers, authorities and workers. 8.7. CONCLUSIONS Mould release agents are based on different mineral oils containing also a number of additives. Groundwater and soil at construction sites and waste water from prefab enterprises can become polluted, additionally there is a risk of skin diseases and other health problems for workers. The substitution products are made from vegetable oils (partly mixed with water) with better biodegradability, less skin irritation and no solvents emissions. These products have been developed firstly in the Netherlands, a country with high percentage of concrete use in the building sector and a shortage of workforce in the construction sector. The discussion on risk played a smaller role than functionality and price. Although Dutch enterprises (and few in other countries) use these products since years without any technical problems the technology could not win a remarkable market share in other European countries (0% to 5%). The mineral oil based release agents have been improved over the last ten years, e.g. by reducing the aromatic hydrocarbon and solvent content. - Costs The price of the substitute is approximately twice as much as for the conventional mould release agent. Although the cost factor in relation to other costs of a building is negligible, this plays a role for the procurement. The higher price could be balanced by a lower consumption, but this regards an exact thin application, that can often not put in practice. - Liability The substitutes have not an established standing on the market, they have not proved their practical long-tem effectiveness under different circumstances. A number of technical and economic risks are anticipated by the decision maker in the construction enterprises. For example a low optical quality of visible concrete surfaces leads to high repairing costs for the construction company. + Technical functionality Tests confirm the good technical performance of substitutes compared with conventional substances despite the pessimistic anticipation of enterprises regarding the substitutes. -- Awareness Mould release agents have very low public awareness. Mould release agents are auxiliary chemicals. The application of moulds is often carried out by unqualified workers in many 141 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT countries. The awareness, the motivation and influence of such a work force is too weak to bring potential health problems on the agenda. The role of building owners is also weak. + Regulations To avoid the pollution of groundwater some regional public administrations oblige construction enterprises in some protected areas to use products with a good biodegradability. But this is far not enough to change the market situation. Most important factors of this case study are presented in the table below. Single important factors overview Economics Higher price per litre for alternative product hinders substitution. Economics/costs Liability hinders the substitution caused by the lack of long-term experience with substitutes and the potential risk of repariring visible concrete surfaces with low optical quality. hindrance of substitution hindrance of substitution support of substitution (-) Economics/liability (-) Technical functionality Supposed less functional effectiveness hinder substitution efforts Technical functionality/performance Social factors Legislation (+) (--) (+) Social factors Low importance of environmental and health aspects Strong hindrance of substitution Regulation Stricter legislation (environmental and occupational health) support of substitution 8.8. LITERATURE Deutsche Bauchemie e.V.: Concrete Release Agents and the Environment. Report second edition, June 2001. Directive 1999/45/EC of 31. May 1999 concerning the approximation of the laws, regulations and administrative provisions of the Members States relating to the classification, packaging and labelling of dangerous preparations German Ministry of the Environment, Nature Conservation and Reactor safety: General Administration Regulation of the Water Management Act on classifying water hazardous substances into Water Hazard Classes (VwVwS) from 17.05.1999. German Institute for Quality Assurance and Labelling: ‘Blue Angel’ for Rapidly Biodegradable Lubricants and Forming Oils. Last version April 2002. Ordinance on Protection against Hazardous Substances “Classification and Labelling”. German Federal Agency for Occupational Safety and Industrial Medicine. January 2000. DBC 01 EC 99/45 FME 99 RAL UZ 64 GefStoffV 142 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 8: MOULD RELEASE AGENTS FINAL REPORT GIS 99 German Association of construction industry, Working group GISBAU, Classification system for concrete release agents, in WINGIS 1.9, Frankfurt/Main. Landwehr, J. & Goetz, D. (1998): Biodegradation and mobility of mould release agents in soil – a comparison between vegetable oil based and mineral oil based release agents. Report on a study from University Hamburg, Institute of Soil Science), Germany. see ILO http://www.ilo.org/public/english/protection/safework/cis/products/ safetytm/solvents.htm Research and Consultancy on Sustainability and Chemical Risks (Chemiewinkel), University of Amsterdam, J. Terwoert, personnel information 23.09.2002. Dutch Ministry of Housing, Physical Planning and Environment Control Strategy for Emissions of Volatile Organic Compounds, 1989. B&A Groep: Le Blansch,K., Broekhuizen, P.v., De Herr, B.: Country Case Study Sumovera – The Netherlands in the Frame of the EU Shere+-Project, 1998. SUMOVERA: Application of Vegetable-Oil based Concrete Mould Release Agents (VERA’s) at Construction Sites and in Precast Concrete Factories. State-of-the-Art Document. Council Directive 1999/13/EC of 11. March 1999 on the limitation of emissions of volatile organic compounds due to the use of organic solvents in certain activities and installations. WOERMANN Concrete chemicals GmbH (Dortmund), Dr. M. Schnalke. Interview - personnel information 13.08.2002. LAN 98 ILO 02 IVAM 02 NL 89 SHERE+98 SUM 99 VOC 99 WOER 02 143 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT 9. 9.1. CASE STUDY 9: RECHARGEABLE BATTERIES Introduction For a long period of the 20th century rechargeable batteries were based on the two main technologies of nickel cadmium (NiCd) systems and the even older technology of lead acid batteries. The performance of these battery systems has been constantly improved on the basis of rather empirical knowledge. In the mid 1980’s the growing electronic industry produced an increased demand for smaller sized, sealed, consumer type battery cells for mobile appliances, power tools etc. For the increased demand a growth from 1 billion cells in 1990 to 2.5 billion cells in the year 2000 has been reported (Nor 00), with further increase expected from future introduction of new portable applications. For rechargeable batteries of this small type, nickel-cadmium cells (NiCd) were favoured because the lead acid systems have a rather unfavourable performance due to their low power density.17 Consequently the NiCd cell became the dominating battery system in this area. However, it is seen as problematic because cadmium is a hazardous substance, and strong concerns were raised by the diffuse release of cadmium into the environment for which NiCd batteries are believed to be one of the most important sources. In 1996, NiCd batteries were the most important application for Cd metal with a portion of 69% of the European cadmium consumption (TRAR 02). This figure is expected to be even higher today. It was not until the 90ties when alternative battery systems for small sized cells became available, the important types being nickel metal-hydride (NiMH) and lithium ion (Li-ion) batteries. The production rates of these new cell types grew rapidly in the last decade while NiCd production remained more or less constant (Nor 00). At present, however, NiCd batteries are still the dominating cell type if counted by cell number.18 9.2. (ECO-)TOXICOLOGICAL AND ENVIRONMENTAL EFFECTS OF Cd AND NiCd BATTERIES RISK OF CADMIUM Cadmium, which accounts for approximately 15 % of the cell weight in NiCd cells, is classified as a hazardous substance under Directive 67/548/EEC on Classification, Packaging and labelling of dangerous substances. Major concerns related to cadmium are the following: • Acute and chronic toxicity of cadmium is given due to toxic effects of cadmium in the kidney and liver which inhibits essential enzymatic processes. Also effects on the human skeleton system with deformation of the crystalline structure of the bones were reported However, when counted by value and by volume, lead acid batteries make it by far the largest market for rechargeable batteries, because these are used in almost all appliances for starter batteries in vehicles where they are favoured due to low costs. 18 Apart from “consumer type” batteries which account for approximately 75 % of the market, the remaining 25 % are larger industrial cells used in stationary and vehicular backup systems for e.g. continuous power supply or emergency lightning (data from 1999). 17 144 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT • • • after chronic exposure of humans via seafood in which cadmium accumulated strongly (so called Itai-Itai-desease, Kor 92). A carcinogenic effect has been suspected but has not been verified yet (Römpp 95). Cadmium exhibits a high eco-toxicity and accumulates in sediments. For fish, a bioconcentration factor of approximately 1000 is reported (Kor 92). NOEL19 and PEC values are presently under discussion under the EU risk assessment. Beside cadmium traces in fertilisers (Kor 92), the diffuse release of cadmium from NiCd batteries is believed to be a major source for ubiquitous cadmium release into the environment. The use of cadmium in other applications, as there are colour pigments, galvanic anti corrosion plating, stabilisers for plastics and use as an alloying element for steel, has been constantly decreasing, accounting now for ca. 20% of the EU cadmium consumption (TRAR 02). The disposal stage is the main environmental issue to consider for NiCd batteries as is outlined in the draft discussion paper of the targeted risk assessment on cadmium(oxide) used in batteries (TRAR 02). NiCd batteries are listed as hazardous waste under entry 160602 in the list of hazardous waste pursuant to Article 1(4) of Council Directive 91/689/EC. NiCd batteries contribute to the diffuse cadmium emissions from waste disposal facilities, the main paths being atmospheric emissions from incineration and leaching from landfills into groundwater. The latter is of particular concern because this emission source will not be stopped even after a cadmium ban or 100% collection rate and it is estimated to have effects over the coming 100 years or even longer (TRAR 02). Exact figures on municipal wastes are rare, but from random analyses it is estimated that cadmium from batteries causes approximately 85% of the cadmium input into the household waste (Sch 97), while other sources report 10-65% (TRAR 02). The typical life time for consumer type batteries is reported to be 3-10 years. The Risk Assessment under Directive under EU Regulation 793/93 on cadmium was not yet completed when this study was finalised. Cadmium production The global cadmium production lies around 17,000 t/y which is comparable to e.g. silver. Cadmium is a by-product of zinc ores which typically contain 0.1 to 0.4 % cadmium (Römpp 95). As a consequence, Cd availability depends on the demand of zinc and cadmium will thus continuously be extracted even if the cadmium demand should vanish. It has been argued that NiCd batteries are the most environmentally conscious way of coping with this by-product of zinc production. However, this would require to use cadmium in a closed loop, i.e. to collect and recycle nearly all used batteries at their end-of-life stage. Recycling The recycling of NiCd batteries is technically possible. Industry states that cadmium can be recycled at a recovery rate of 99,99% (TRAR 02). However, the collection of end-of life batteries is seen as the crucial point, especially in the case of small consumer batteries. The 19 NOEL: No Observed Effect Level 145 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT collection efficiency for small consumer cells throughout Europe are reported to be low. For the base year 1996, the total amount of NiCd batteries recycled in Europe was estimated by the industry to be about 337 tonnes at a total consumption of 2733 t (1999: 3600 t) i.e. 12% (TRAR 02). Nor 00 states that the world wide recycling figures (2000 t in 1998) match fairly well with the amount of cadmium used in industrial batteries (2,500 t/a). Collection schemes for these big industrial cells are well established in most cases, and recycling is technically possible because the cadmium electrode can be dismantled easily. For small consumer cells both the collection and the recycling is more difficult, because these consumer batteries are widely distributed over European households and, when collected, will enter the recycling plant in a mixture with other cell types, making separation necessary. Dismantling of the electrodes before recycling is nearly impossible as these batteries are sealed. Thus, the waste stream of mixed batteries allows for poor recycling efficiency only. For Germany it was reported for 1999 that from the total battery collection (industry & consumer) of 6.901 t an amount of 1.318 t were recycled, while the remaining 5.583 t were treated as waste (GRS 00). At the same time, existing recycling capacities would be insufficient for recycling of all batteries presently spent (Nor 00). 9.3. REGULATIONS / INITIATIVES IN THE FIELD OF CD AND NICD BATTERIES ON POLITICAL LEVEL The main aspects of NiCd discussed under Battery Directive 91/157/EEC were waste management and safety of chemical substances. The Battery Directive 91/157/EEC is presently under revision, with possible directions being either an increased collection efficiency or a phase-out of cadmium in batteries with the aim to lower diffuse releases of cadmium into the environment. Also initiatives for supporting research of alternatives could be identified. Phase-out of Cd The Battery Directive 91/157/EEC, which was initiated by Council Resolution of 25.01.1988 (OJ C 30), prohibits the marketing of batteries which contain more than 0,025% mercury by weight.20 On behalf of cadmium, the Council Resolution stated that “the use of cadmium should be limited to cases where suitable alternatives do not exist”. A working document of DG Environment on a revised EU battery Directive proposed a ban of cadmium containing batteries from 2008. Discussions about this draft were controversial, with some Member States strongly supporting the Cd phase out, while other countries and several battery associations argue strongly against it. In 2001 the proposal for a revised battery Directive was rejected by the Commission. While the Risk Assessment for Cd was still ongoing, the Danish Minister of Environment suggested to follow the precautionary principle and substitute Cd by a less harmful metal, In 2000 the Commission sent a first legal warning to 10 EU governments because they failed to implement the limitation of mercury content in consumer batteries into national law. 20 146 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT which would be in line with the White Paper on EU policy on chemicals (Dan 01), expecting that more environmentally friendly alternatives will be available for all applications by then. Recently, the German Environmental Protection Agency similarly announced that they consider diffuse losses of cadmium as the main environmental problem of the battery sector, and advocated a European phase-out of cadmium under the revised battery Directive (Ger EPA 02). On the other hand, some industry representatives claimed that, for the foreseeable future, NiCd batteries were the only economically feasible technology for many applications, and argued that a decision on NiCd batteries before finalisation of a EU Risk Assessment would not be consequent. Instead, several industry groups, including cadmium suppliers, battery manufacturers and recycling associations, undertook efforts towards more efficient collection and recycling instead of a Cadmium ban. For that purpose, they founded the coalition group CollectNiCad, which promotes the collection and recycling of NiCd batteries21. A parallel discussion of NiCd batteries took place under Directive 2000/53/EC on end-of-life vehicles, which in its Article 4 (2) prohibits the use of cadmium in cars after 1 July 2002. From this stipulation, the NiCd battery industry and French automotive manufacturers claimed for a derogation under Annex II of the Directive. The case was decided by Commission Decision 2002/525/EC of 27 June 2002, stating that after 31 December the placement on the market of NiCd batteries shall only be allowed as replacement parts for vehicles put on the market before this date. Another initiative with respect to NiCd batteries at the political level is their exclusion from eco-labelled products. The final report for the European Eco-label for Consumer Goods (Sch 97) suggests that eco-labelled products should not contain cadmium and lead and substances which are classified as (very) toxic, carcinogenic, mutagenic and toxic for reproduction. A revised study for the European Eco-Label (2001) on batteries has been completed but work is presently suspended (EU-Lab 01). The German national eco-label Blue Angel restricts the containment of cadmium in rechargeable batteries to traces of 10 ppm (Ger EPA 01). Collection Schemes The Battery Directive 91/157/EEC presently in force asks the MS to ensure the efficient organisation of separate collection and, where appropriate, the setting up of a deposit system. In 1997, it was decided to revise this Directive, mainly because of the low collection and recycling efficiency: despite the obligation to separately collect the batteries already since 1991, only 300 t NiCd batteries of the 13,000 t consumed annually were recycled in the year 2000. Before 2000 the collection rate was even lower with less than 5% (End 01). In 1999 the industry coalition group CollectNiCad offered a self binding commitment to the Commission in which they promised to increase collection to 5,000 t/a portable NiCd batteries per annum within 5 years (CNC 99) if the Commission would stop the initiatives towards a NiCd ban. CollectNiCad claimed that this amount would represent a collection rate CollectNiCad is supported by the International Cadmium Suppliers (ICdA), EPBA, Association of European Accumulator Manufacturers (Eurobat), European Association of Metals (Eurométaux) and the European Battery Recycling Association (EBRA). 21 147 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT of 75% for portable NiCd batteries, corresponding to an annual amount of ca. 6,670 t NiCd batteries.22 The draft for a revised Battery Directive suggests to collect 75% of all consumer batteries, because experience from the old Directive which addresses just NiCd batteries, has illustrated that consumers are unable sort the batteries correctly when disposing them. Rather, experts should sort the batteries from the mixture after collection of all battery types (Dan 01). The target of 75% for all consumer batteries is considered as unrealistic and much too expensive by the battery producer associations EPBA and Eurobat23 (EPBA 01). In contrast the Battery Recycler Association EBRA states that these targets could be easily achieved with a marginal effect on battery prices. All industry associations agree that a Cd phase-out would not be a reasonable route to cope with the recycling problems (End 01b). Directive 91/157/EEC led to national activities for collection schemes in Member States. E.g. in Germany, in 1998 a joint take-back system “Gemeinsames Rücknahmesystem Batterien” (GRS) was founded by 419 producers and importers, with the aim to fulfil the collection and recycling targets of a self binding declaration of German battery producers and also to comply with the German Battery Directive, which prohibits the disposal of batteries via the municipal waste. Similar collection schemes were founded in other Member States. Collection efficiency within the German collection scheme was reported to be 8,980 t (i.e. 29 %) in 2000, from which 1/3 were recycled and the rest disposed. Apart from large, non-portable industrial batteries which are easier to collect and recycle, only 990 t of portable NiCds were collected and recycled as reported by GRS to the EU Commission (TRAR 02). For the same year the French collection organisation reported of collection and recycling of 144 t of consumer sized cells. Concerning take-back of electronic appliances under the proposed WEEE Directive, some manufacturers are presently discussing a differentiation of recycling costs for products containing different battery types, because they expect lower recycling costs for products not containing NiCd batteries. When, as a consequence of producer responsibility, these additional recycling costs will be included in the product price, the price of NiCd containing products is expected to increase. Another point of discussion is the question whether treatment of batteries in metallurgical plants is a feasible recycling option or not. Steel furnace operators state hesitate to use this material as it could lead to additional cadmium emissions (EAF 00). Supporting research for alternatives Directive 91/157/EEC asks Member States to draw up programmes to promote research with the aim to reduce the dangerous substance content and to use less-polluting substitute substances in batteries and accumulators, and also to research into methods of recycling. DG Environment’s working document on a revised Directive specified this further by proposing to 22 Calculation for the total amount of portable NiCd batteries based on sales, assumed average product lifetime and collection per inhabitant in the EU. Obviously, estimations on the total waste potential are controversial between Commission and industry. 23 Eurobat represents 85% of EU producers. 148 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT mandate the Member States to initiate “the promotion of research on and marketing of batteries and accumulators substituting those containing mercury, cadmium and where possible those containing lead.” In Japan the government followed a policy to support development of alternatives to NiCd batteries already during the 1980´s. This programme has strongly stimulated the development of e.g. NiMH cells for which Japan presently dominates the world market. On the other hand, in France R&D programmes were initiated on electrical vehicles which are produced by large automotive manufacturers in France. The battery type chosen for these programmes was based on the NiCd technology (Öko 01). 9.4. INITIATIVES AND MOTIVATION FOR SUBSTITUTION OF NICD BATTERIES AT ENTERPRISE LEVEL Intensive research on alternatives for NiCd batteries started in the 1980’s. At that time, NiCd technology was not believed to be able to cope with the increasing demand of portable accumulators with high power density. Cadmium is a rather rare element, and rising prices or even a shortage of cadmium were foreseen due to the increasing demand that was expected for the market introduction of new portable electronic products like mobile phones, camcorders and portable computers. Especially in Japan, rechargeable batteries had come to be considered as strategic components among the large industrial groups which produce a large portion of the world’s portable electronic equipment. Unlike France, whose R&D programmes for electric vehicles where based on NiCd technology, in Japan intensive R&D programmes for alternative cell systems were started with strong support by the Japanese Ministry of Trade and Industry. The research resulted in the successful introduction of the new battery chemistries, NickelMetal-Hydride (NiMH) and Lithium ion (Li-ion). This policy has eventually resulted a strong domination of Japanese companies in the production of rechargeable consumer size cells. The NiMH cell was commercially launched in 1991 as a high capacity cell. With its very good performance its market had a rapid growth. However, some of the leading battery producers hesitated to increase their production, because the new cells competed with their own NiCdcell production which was very cost efficient, and the expected cadmium shortage was already eased at that time. Other NiMH producers who were not engaged in NiCd production saw their chance to enter the battery cell market and invested in new production facilities. As a result, the expanding volumes in the market were covered by the new technologies whereas the NiCd production remained fairly constant. While the original motivation to develop cadmium free cells was triggered by the fear of a raw material shortage, meanwhile environmental concerns had led to restrictions of using cadmium in other areas such as pigments, stabilisers, corrosion protection etc. which eased the pressure for cadmium shortage. Environmental concerns related to cadmium contained in the batteries themselves emerged at a later stage only. Today, the production of the different cell types is mainly driven by performance and market aspects (price, costs and related profit margin) which is further discussed in Chapter 7. 149 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT 9.5. NiCd BATTERIES AND SUBSTITUTES All rechargeable batteries in use comprise two electrodes whose electrochemical reactions are coupled. The cathode is identical for NiCd and NiMH, both having a nickel electrode where the redox conversion of Ni+II(OH)2 to Ni+III(OOH) takes place. As the reaction proceeds in solid state, the electrode is hardly susceptible to deformation which prevents memory effects. To substitute a NiCd system by a NiMH system, only the corrosponding anode needs to be changed. This anodic process is different for each cell type and is described separately in the following. NiCd Technique: The basic reaction at the cadmium anode is the conversion of Cd+II(OH)2 to Cd (oxidation state 0) via a dissolved species in a dissolution/precipitation reaction. Therefore, electrode geometry can change over time and memory effects are more likely to occur. Recycling: The recycling of NiCd batteries is technically possible but is at present mainly done for large cells used in industrial stationary applications24. The recycling of sealed consumer type batteries is still low. Collection, transport and recycling of small NiCd batteries need to be adequately controlled to avoid releases of toxic cadmium to the environment and exposure of humans. NiMH Technique: The metal hydride anode is based on a sintered alloy containing typically Ni, Co, Mn and Al and a portion of rare earth elements like La, Ce, Nd and Pr. This electrode is able to store hydrogen which in the cell reaction is generated by dissociation of water as the cell electrolyte. Both reactions are solid phase reactions and thus electrode geometry is kept constant over the charging and discharging cycle. The energy density of the NiMH anode has successfully been further increased by introduction of a Ni foam electrode instead of the former sintered Ni electrode. The foam has 95% porosity and is filled with a slurry of a high density Ni hydroxide material (Bau 96). The increase in electrode surface enabled higher cell capacities, which raised broad interest among battery producers who started to produce these cells by 1991 (Nor 01). Today, both types of Ni electrodes are offered on the market depending on the battery performance required in the specific application (high currents vs. high power density). Performance: NiMH cells have approximately twice the capacity of NiCd batteries. Therefore, NiMH could cope with the technical demands of high capacity applications like portable 24 like Uninterrupted Power Supply (UPS) systems or for emergency lightning of buildings 150 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT computers and mobile phones quite well. The use of NiCd within this market segment is negligible today (Nor 01). In “power tool” applications (e.g. drills and hybride vehicles) which require low internal resistance, i.e. high electrical currents, the introduction of NiMH was more difficult because the conductivity of the foam electrode material was a limiting factor. Furthermore, the electrode suffers from capacity loss at high discharge rates (EAF 00). However, when using cells with the “old” sintered electrode, the high Ampere performance can cope with the demands. Although NiMH batteries with sintered electrodes still have a higher power density than NiCd, the advantages of the NiMH over NiCd-technology are smaller in the power tool sector than in the high capacity sector (EAF 00). Only recently, the conductivity limitation of foam electrodes could be overcome as can be seen from the introduction of high capacity NiMH in electric vehicles and professional power tools (Nor 00). The full availability of NiMH for power tool applications is still seen controversial by different stakeholder, which however appears to be based mainly on economic considerations rather than a technical problem. When compared to NiCd batteries the higher self discharge rate and the higher sensitivity to temperature are disadvantageous (Sch 97). Recyclability: The absence of Cd and other hazardous metals allows for recovery together with steel scrap which already contains Ni as a valuable alloying element. Unlike NiCd, the separate recycling of NiMH could be self-financing (EAF 00). Li-ion Technique: In lithium ion batteries a lithiated cobalt oxide is used as electrode material. The second electrode is the Ni hydroxide electrode as described above. Also cells with other materials such as e.g. manganese oxide are present on the market leading to a high variation of cell ingredients of the commercially available cells. The main advantage of Li-ion cells is their higher voltage with typically 3.6 V depending on the exact material choice (NiMH and NiCd 1.2 V). Performance: Due to the high voltage, the energy density is about 30% higher than for NiMH systems. The electrolyte is a flammable liquid which leads to increased risk of fire or explosion during overcharging or overheating but these problems could be mostly overcome. A recent introduction on the market is the Li-polymer battery, which contains a polymer or gel type electrolyte which leads to higher power densities and prevents risk of fire. Recycling: Practical experience with Li-ion recycling is scarce because of the recent introduction of this cell type. Principally, Li-ion batteries contain a large amount of cobalt in their positive electrode. Since Co is a valuable metal, the recovery is expected to be cost efficient. However, certain organic ingredients which differ between the various producers will have to be considered during the recycling procedure with respect to environmentally sound treatment and workers health. 151 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT In both substitution cases (NiCd --> NiMH, NiCd -->Li-ion) a product containing a hazardous substance is substituted by a product containing less hazardous substances, i.e. substitution proceeds at a product level. 9.6. NiCd IMPLICATIONS OF NICD SUBSTITUTION AT ENTERPRISE LEVEL Price & Costs: Even in case of an immediate substitution of NiCd, production of Cd will not stop since cadmium is a by-product in zinc ores. A ban could turn Cd from being a valuable raw material to a hazardous waste, thus causing economic problems for producers who may have stockpiled Cd at high price in times of shortage (see above). Presently, most of the cadmium contained in NiCd batteries is still in the technosphere, representing a considerable stock of cadmium. Collection and recycling of the NiCd batteries will be cost intensive procedures especially in the light of the decreasing demand in the market. If collection efficiency will remain as low as presently, most of the cadmium stock in the technosphere will end up in the waste stream. NiMH Technical impact: NiCd and NiMH cells share the same fundamental manufacturing processes. The Nickel positive electrode, the separator, the electrolyte, the can & the cover/seal mechanism can all be manufactured on essentially the same equipment, and are sufficiently close to be manufactured on the same lines with only minor tooling and settings changes. The negative electrode however does require some different machinery to switch from a Cd mixture to a metal hydride alloy (EAF 01). Price & costs: Beginning from 1995 the Li-ion battery was introduced on the market and experienced a rapid growth which was even faster than for NiMH. Competition between the two new cell types has driven the NiMH price down and pushed the NiMH technique out of the high price segment of high capacity batteries, forcing it to compete directly with NiCd cells in the low price segment (Nor 00). Today the price of NiMH is comparable to NiCd if calculated on a "Cost-per-Watt.Hour" basis but higher on a price-per-cell basis. NiCd cells can be sold with a higher profit margin because production facilities are well established, and raw material costs for NiMH are presently 20 % higher than for NiCd. The price gap might further narrow when the NiMH technology will become more mature and cost-optimised. Since NiMH ourperforms NiCd in many applications where battery performance is important (EAF 01), NiMH will often offer the better solution if both costs and technical aspects are taken into account. Overall, the technical performance of NiMH is presently better for almost all applications but built-up of production capacities for NiMH will take some years. 152 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT Li-ion Technique: The performance of Li-ion for high capacity applications is much better than for both NiCd and NiMH, but development for high power tools has not reached the status of market introduction yet. In a long-term perspective, Li-ion is seen as the most promising technique also for power tools. Price & Costs: Presently Li-ion batteries are more expensive. The technology is still under development and hence less cost reduced. On a long time perspective, Li-ion batteries will be favoured both economically and technically, as the raw material costs are low and they have a high potential due to their high voltage i.e. high energy density. Production costs are expected to decrease when the decision for the best cell chemistry has been met and larger capacities for series production will have been built up. A rapid decrease of prices could already be observed due to the increasing production capacities over the last few years. General Perspectives Some companies may want to proceed directly from NiCd to Li-ion production which is said to be the most promising technique in the future. Using NiMH as an interim technology is not favoured especially by companies who would have to invest in research or to pay for licences for NiMH technology developed by their competitors. Product Examples Mobile phones vs. cordless home phones: For mobile phones mainly NiMH and Li-ion batteries are used because they lead to a better performance in stand-by times and running times at same battery size with Li-ion having approximately 4 times higher power density (NiMH ca. 2 times) than that of NiCd (Sch 97). Although the technical demands are very similar, cordless phones for home use are still dominated by NiCd technology. In this product group the inferior technical performance of NiCd (e.g. shorter running times) is less important for the customer because of the rather “stationary” home use, and hence the price is a dominating factor. Phone manufacturers prefer NiCd since they can be offered either at lower price or with higher profit margins. The product group of home phones is especially sensitive to battery price, because the battery price has a higher contribution to the overall product price than for mobile phones. No technical reasons to stick to NiCd technique are evident as both application have very similar technical features. Power tool applications: Similar to the case of mobile phones and cordless phones, different battery systems are used in the power tool market. The market can be differentiated into segments requiring different battery characteristics, taking into account professional and private users and their different reaction to price structures (EAF 01): At the “low end” of the scale there are cordless power tools (e.g. cheap screwdrivers & drills 153 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT with basic performance) for whose customers price is the key objective. As better performance is of minor importance for the private consumer’s choice, the NiCd battery with its lower cost per cell value is favoured in this segment. At the “high end” of the scale is the professional power tool, demanding the highest performance available, the lowest internal resistance, maximum operating time, lowest temperature capability and fast recharging time. For these highly demanding tools, the better performing NiMH cell is used because the customer in his decision will consider the price per Wh basis. Especially in the professional sector, customers are often able to decide with the background of their experiences made with previous tools. This high-end segment represents only a small portion (~20%) of the total cordless tool market. In between these extremes there is a range of consumer tools in which various battery system are used. Nor (00) estimates that for power tools the NiCd and NiMH market shares could be of comparable size by 2006. Any legislative changes in the field of NiCd are anxiously observed by the producers of high power tools who are waiting for the best moment to launch NiMH cells on the NiCd market (Nor 00). On the one hand it will be an advantage to be the first on the market, on the other hand launching an even slightly modified product on a large scale is costly. The product examples show that, both for the high capacity and the high power tool sector, the cadmium-free NiMH technology is superior to NiCd from a technical point of view. 9.7. ANALYSIS OF THE CASE Analysis of alternatives For the case of cadmium in consumer batteries the substitution takes place on a product level, i.e. the NiCd battery is displaced by other cell systems. The following main key factors could be identified: Economics • Industry enforced development of alternatives due to an anticipated resource shortage Rechargeable batteries have come to be considered as strategic components among Japan´s large industrial groups which produce a large portion of the world´s portable electronic equipment. In the light of increasing demand a raw material shortage of Cd for Ni-Cd batteries was foreseen and became the driving force for the development of alternatives. • Recycling of alternative is cheaper as it does not contain hazardous substances The absence of cadmium and other hazardous metals in NiMH enables the recovery together with steel scrap which already contains Ni as a valuable element. Unlike NiCd, the separate recycling of NiMH could be self-financing. • Price of alternative is dominated by competition – and not by cost or technical aspects. 154 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT Beginning from 1995 the Li-ion battery was introduced on the market and experienced a rapid growth which was even faster than for NiMH. Competition between the two new cell types has driven the NiMH price down and pushed the NiMH technique out of the high price segment of high capacity batteries, forcing it to compete directly with NiCd cells in the low price segment. • Alternatives have been readily developed but not introduced in all product segments due to cost and price reasons At the present state the alternative NiMH are only introduced in high-end products. Although the price gap between NiMH technology and NiCd has been lowered, the price difference still hinders the introduction of NiMH in the low price segment. Production capacity, existing recharging technique, customer demand / marketing and other factors may also play a role here. No technical reason is evident for keeping NiCd technology. • Manufacturers avoid to cannibalise their old product with their new substitute Manufacturers of NiCd cells may hesitate to promote NiMH as it would cannibalise their own product which enables higher profit margins. Competitors who do not produce NiCd can act as a driving force more easily. • Substitution is not proceeding because companies wait for an even better or more economic alternative in the future NiMH cells are well developed for all applications. However, Li-ion technique is said to have the highest potential in the future, both from a technical and cost point of view, but further development is necessary and expected to take several years. Some companies may want to switch directly from NiCd to Li-ion without investing in NiMH production in between. • Substitution is not proceeding because companies do not want to pay license fees for patents Some companies may want to proceed directly from NiCd to Li-ion production which is said to be the most promising technique in the future. Using NiMH as an interim technology is not favoured especially by companies who would have to invest in research or to pay for licences for NiMH technology developed by their competitors. • The substitution might lead to a zero or negative price of the original material A Cd ban for batteries could turn Cd from a valuable raw material into a hazardous waste. Producers who have stockpiled Cd at high price in times of shortage are interested to slow down or even stop legislation because otherwise they would loose the value of their investments or would even become owners of large amounts of hazardous waste. Technical functionality • Most technical aspects identified are dominated by economic considerations and have already been discussed above. • Improved technical performance and not environmental considerations supported introduction of substitute 155 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT Communication / Awareness • Concern about cadmium in the environment brought NiCd batteries as the main Cd application into focus of the debate Regulatory framework • Ineffective waste collection schemes lead to legislative initiatives Low efficiency of separate waste collection especially in the field of small consumer cells have led to proposals for more stringent legislation by several Member States, aiming at Cd phase-out because enhanced waste collection is not expected to be a sufficient solution. • Governmental R+D programmes can have a strong influence on substitution In Japan the government followed a policy to support development of alternatives to NiCd batteries during the 80´s. This programme has strongly stimulated the development of e.g. NiMH cells for which Japan presently dominates the world market. In contrast to this, in France a governmental programme supported the broad introduction of NiCd technology for electrical vehicles, while no comparable efforts to develop alternatives were undertaken. • Substance of concern is increasingly banned for eco-labelled products The German Blue Angel restricts the containment of cadmium to traces of 10 ppm for eco-labelled products like e.g. lap tops, computers. Focussing: Analysis of NiMH as an alternative In the following the analysis will focus on the substitution of NiCd batteries by the NiMH cell in power tool applications, as this cell technique is fully developed for also for this application. 156 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT NiCd battery --> NiMH battery As the Li-ion technique is still under development, many conclusions would have to be drawn on expectations especially when the power tool market is concerned. ECONOMICS a) Development of alternatives was promoted due to an anticipated resource shortage Economics / resources strong support of substitution (++) (+) b) Recycling of alternative is cheaper as it does not contain hazardous substances costs Economics / Environmental- & Health Economics / competitors Economics / market support of substitution c) Price of alternative is dominated by competition – and not by cost or technical aspects. both aspects of substitution hindrance of substitution (+/-) (-) d) Alternatives have been readily developed but not introduced in all product segments due to cost and price reasons e) Manufacturers would cannibalise their old product with the new substitute Economics / competitors Economics / invest costs Economics / licenses strong hindrance of substitution (--) (--) (--) (--) f) Substitution is not proceeding because companies expect an even better / economically more feasible alternative in the future strong hindrance of substitution strong hindrance of substitution g) Substitution is not proceeding because companies do not want to pay for licenses h) The substitution might lead to a zero or negative price of the original material Economics / environmental costs strong hindrance of substitution TECHNICAL FUNCTIONALITY i) Improved performance (and not environmental considerations) supported introduction of substitute Technical functionality support of substitution (+) COMMUNICATION / AWARENESS i) Concern about cadmium in the environment brought NiCd batteries as the main Cd application into focus of the debate. Legislation / political discourse Legislation support of substitution (+) Regulatory framework k) Ineffective waste collection schemes lead to proposal for phase-out legislation strong support of substitution (++) (--/++) (+) l) Governmental R+D programmes can have a strong influence on substitution m) Substance of concern is increasingly banned from eco-labelled products Gov. initiatives / Support of research Government initiatives strong support/hindrance of substitution support of substitution 157 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT 9.8. Bau 96 LITERATURE Baumann W., Muth A., Batterien. Daten und Fakten zum Umweltschutz, Springer Berlin – New York, 1997. http://www.collectnicad.org/html/set_mission_ove.html Letter of the Danish Minister for Environment and Energy Sven Auken to EU Commissioner Margot Wallström, 31.08.2001. ENDS Daily 02/08/99. ENDS Daily – 17/10/00. ENDS Daily –10/05/01. ENDS Daily –30/04/01. ENDS Daily –20/04/01. http://europa.eu.int/comm/environment/ecolabel/ Letter of representative of Electric Arc Furnace plant, UK. EPBA Position Paper of 17.04.01, via www.epba-europe.org Award Criteria of the German Blue Angel for rechargeable alkali-manganese batteries, RAL-UZ 92, http://www.blauer-engel.de/deutsch/navigation/body_blauer_engel.htm http://www.umweltbundesamt.de/uba-info-daten/daten/batt-cd.htm www.grs-batterien.de of the “Gemeinsames Rücknahmesystem Batterien”. Korte F., Lehrbuch der Ökologischen Chemie, 2nd edition, Thieme Verlag Stuttgart, Germany. Letter from representative of Moltech Company from 19.03.01. Substitution of rechargeable NiCd batteries. A background document to evaluate the possibilities of finding alternatives to NiCd batteries. – Prof. Dag Noréus, Arrhenius Laboratory, Stockholm University, August 2000. Council Resolution of 25.01.1988 (OJ C 30). Heavy Metals in Vehicles II, Ökopol GmbH, Report to DG Environment, 2001. Falbe J., Regitz M., Römpp Chemie Lexikon, 9th edition, Thieme Verlag CNC 99 Dan 01 End 99 End 00 End 01 End 01b End 01c EU-Lab 01 EAF 00 EPBA 01 Ger EPA 01 Ger EPA 02 GRS 00 Kor 92 MOL 01 Nor 00 OJC 30 Öko 01 Römpp 95 158 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASE STUDY 9: RECHARGEABLE BATTERIES FINAL REPORT Stuttgart, New York. Sch 97 Scholl, G., Baumann W., Final Summary Report for European Ecolabel for Batteries for Consumer Goods, Institut für ökologische Wirtschaftsforschung (IÖW), Institut für Umweltforschung (INFU). Draft RAR Cadmium metal and Cadmium oxide, Discussion paper on the targeted risk assessment on Cadmium(oxide) as used in batteries. February 25, 2002. TRAR 02 159 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT 10. SUBSTITUTION OF PHTHALATES IN TOYS Scope Phthalates are predominantly used as plasticisers in products made from soft PVC. Phthalates in toys made of soft PVC became subject of public concern, because they can be dissolved out of the plastic matrix upon intense chewing and sucking by little children, leading to direct exposure via oral intake. 10.1. INTRODUCTION Safety of toys is a serious aspect of the protection of health of consumers, and in particular the health of children. According to Council Directive 88/378/EEC (Annex II) on the approximation of the laws of the Member States concerning the safety of toys, “the users of toys as well as third parties must be protected against health hazards and risk of physical injury when toys are used as intended or in a foreseeable way, bearing in mind the normal behaviour of children”. Special attention is given in this Directive to the dangers to babies and children under 36 months, since it is the typical behaviour of this group is to put things in their mouths and chew and suck on them. That is why toys which could foreseeably be placed in the mouth, even if they are not intended to be used in this way, must be labelled with corresponding warnings. For some toxic elements including arsenic, cadmium and lead, the Directive has set limits for the bioavailability. Organic compounds, which are added to polymers e. g. as stabilisers, colour pigments or plasticisers, are not regulated in this Directive. Various materials like wood, textiles and plastics are used in the manufacturing of toys. About 20% toys on the market contain or are made from flexible PVC (RPA 2000). Typical toys made from PVC are dolls, squeeze toys, soft figures and inflatable toys. Also toys intended to be placed in the mouth, like teethers and pacifiers, could contain PVC. To impart the desired softness and flexibility of the plastic, PVC contains between 10% and 60% of plasticisers, usually phthalates which are alkyl esters of phthalic acid. Until the prohibition of phthalates in certain toys, the predominantly used phthalate in this application has been di(isononyl)phthalate (DINP). In some cases di(2-ethylhexyl)phthalate (DEHP) was used as the primary softener in toys, and often it can be found in small quantities in addition to DINP (GP 97). Due to adverse effects shown in animal testing, the use of phthalates in consumer products has been criticised for the last 20 years. In the mid 1980s, some first health concerns originated due to their use in food wrapping material. Since plasticisers are not chemically bound on the matrix, they can migrate from the product into the food thus leading to exposure of consumers. As a result of the discussion, migration of compounds from plastic into foodstuff has been limited by Directive 90/128/EEC relating to plastic materials and articles intended to come into contact with foodstuffs. 160 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT Since plasticisers can leach or evaporate from products into every surrounding media, consumers are also exposed via infusions (medical devices), indoor air (floor and wall covering and car interior) or the environment (outdoor applications) or even directly through the sucking of plastic parts. Public awareness became highest for toys made from PVC which are destined to be placed in the mouth, like teethers for chewing which are given to very young children to soothe them when their first teeth are erupting. Upon chewing, the additives can be extracted and subsequently ingested by the children. Due to possibly adverse effects of DEHP and DINP, NGOs and consumer associations called for phase out of phthalates or even PVC from these kinds of toys and childcare articles and also for other toys for very young children, which are actually not intended to be placed in the mouth, but which could be used in this way, as this is the normal behaviour of babies (BEUC 00). 10.2. SCIENTIFIC EVIDENCE ON (ECO)TOXICOLOGICAL AND ENVIRONMENTAL IMPACT 10.2.1. Environmental risk DINP and DEHP (also known as di-octylphthalate, DOP) are high volume chemicals predominantly used as plasticisers in PVC (ECPI 01). During the lifetime of the products the additives can leach from the matrix and enter the environment. Although easy degradable under laboratory conditions, they accumulate in soils and sediments, since they are not degradable if adsorbed on particles and in the absence of oxygen. Today phthalates can be found in every environmental media (RA DEHP 01). Due to their potential risk to human health and the environment, five phthalates25 are currently subject to risk assessments in accordance with Regulation 793/93 on existing substances. The risk assessment reports on DINP and DIDP (rapporteur France) and DBP (rapporteur The Netherlands) have been finalised in 2001, while the reports on DEHP (rapporteur Sweden) and BBP (rapporteur Norway) are still in progress. Concerning environmental risks, the rapporteurs identified a need for further information or testing to determine the impacts of DEHP (RA DEHP 01) and DBP (RA DBP 01)26, but at present they saw “no need for risk reduction measures on DINP and DIDP beyond those which are being applied already” (RA DINP 01, RA DIDP 01). 25 di-(2-ethylhexyl) phthalate (DEHP), di-(iso-nonyl) phthalate (DINP), di-iso-decyl phthalate (DIDP), dibutyl phthalate (DBP) and butylbenzyl phthalate (BBP) DBP is classified as dangerous for the environment (N, R50) under Directive 67/548/EEC (28th ATP) 26 161 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT 10.2.2. Risk for human health While carcinogenic effects of DEHP in rats and mice were not seen as relevant for humans27, the suspicion that they were toxic to reproduction was confirmed. Observed testicular effects in several repeated dose toxicity studies in rats, mice and ferrets were considered as adequate to support the possibility that these effects can occur in humans. The lowest identified NOAEL28 of 3.7 mg/kg bw/d29 on testicular effects has been used for risk characterisation30. Based on toxic effects and human exposure, the rapporteurs of the EU risk assessment identified a need for limiting the risk for DEHP to consumers, especially children (RA DEHP 01). Since August 2001 DEHP as well as DBP have been classified as toxic for reproduction under Directive 67/548/EEC.31 For the risk characterisation of DINP a NOAEL of 88 mg/kg bw/d has been used. This value, which is related to liver and kidney effects found in a chronic study, does not justify classification. Also, no potential for endocrine disruption could be found. Based on these data, the EU risk assessment for DINP results in “no need for risk reduction measures beyond those which are being applied already” (RA DINP 01). Similar conclusions were made for the present applications of DIDP (RA DIDP 01). 10.2.3. Risk of sucking and chewing PVC-toys by very young children Initial investigations of phthalates in toys were carried out by the US Consumer Product Safety Commission (CPSC 83), who found relevant releases of DEHP from toys. As a result, the use of DEHP in toys was reduced voluntarily, with DINP as the major replacement product. 10 years later, new concern have arisen over the evident release of DINP from toys and its possible adverse effects. In order to assess the risk within this particular case, scientists need to know how much of the critical substances can reach a child`s body. Several interested parties tried to quantify the amounts of phthalates extractable from toys by sucking and chewing. In the light of widely differing results from various in vitro as well as in vivo methods, which take less or more into account the mechanical treatment by chewing, the European Commission has invited the EU Scientific Committee on Toxicity, Ecotoxicity and the Environment (CSTEE) to give advice on risk assessment and suitable test methods. Based on maximum emission rates, CSTEE compared extractable amounts and NOAELs in a margin of safety (MOS) approach (Table 1). MOS values for DEHP and DINP give rise to concern because they are smaller than the 27 1982 DEHP was classified as possibly carcinogenic to humans by the International Agency for Research on Cancer IARC. The observed effects were explained by the rodent specific peroxisome proliferation, which is not seen as relevant to human (IARC 00) NOAEL = No Observed Adverse Effect Level 28 29 30 milligram per kilogram bodyweight per day the Technical Meeting has not reached consensus yet on the use of this NOAEL in the RAR 31 DEHP: toxic for reproduction Cat. 2 (R60, R 61); DBP: toxic for reproduction Cat 2 (R61) and Cat. 3 (R62) 162 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT recommended safety margin of 100 (Table 1). Other tested phthalates (e. g. DIDP) show a much lower emission rate with resulting high MOS values, which can be explained by the low concentration of the plasticiser in the investigated products. In its opinion statements from April and November 1998 the CSTEE concluded that in spite of great uncertainties, “clear concern” arises due to the low MOS for DEHP, respectively “some concern” for DINP (CSTEE 98b). Uncertainties were seen mainly in the poor reliability of the applied migration rates. Table 1: Margin of safety approach for phthalate migration from soft PVC toys, excerpt from CSTEE: Opinion expressed at the 6th CSTEE plenary meeting (26/27 November 1998), Data available since the 16th of June 1998 Phthalate critical effects NOAEL value Maximum Intake dose MOS emission rate mg/kg bw/d Tg/10 cm²/3h Tg/kg bw/d DINP Increased liver and 15 1600 200 75 kidney weight DEHP Testicular damage 3,7 1600 200 19 DIDP Increased liver 25 140 17.5 1420 weight MOS = Margin of Safety = NOAEL/Intake The NOAEL for DINP used in this approach is based on a study on chronic toxic effects seen in male rats after exposure to DINP. These data are meanwhile not regarded as relevant to humans. The EU risk assessment concluded that for infants and babies, MOS values are considered sufficient for all endpoints (RA DINP 01). However at the time of the described approach the EU risk assessment has been in an early stage and the CSTEE chose the lower NOAEL of 15mg/kg bw/d for DINP, justified with a precautionary standpoint (CSTEE 98b). The outcome of the EU risk assessment confirm the findings of the CSTEE concerning DEHP. Corresponding to a systemic NOAEL of 2 mg/kg bw/d the rapporteurs identified “concern for the testicular, fertility and RTD endpoints for the oral exposure route to toys and childcare articles”. Exposure of infants and babies via indoor air, caused by the use of soft-PVC flooring and vinyl wall covering, was seen as an additional aspect of concern (RA DEHP 01). Although the EU risk assessment identified no risk for the present use of DIDP, extrapolations indicate that the replacement of other phthalates in toys by DIDP in the future could lead to new concern (RA DIDP 01). In its opinion (CSTEE 98a) the CSTEE recommends to assess the risk of the use of other plasticisers before introducing them into the toys in question. In fact the alternative plasticisers have not been investigated as well as the phthalates. For most of the substances, acceptable daily intakes (ADI) are not available. Reliable migration rates are not determinable. All identified risk were based on worst case scenarios with great uncertainties. New risks that could arise from the use of substitutes were difficult to predict. The main problem was the lack of a validated method to determine migration rates of phthalates and other plasticisers, which would allow the comparison of released amounts with acceptable intakes. 163 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT 10.3. INITIATIVES AT THE POLITICAL LEVEL The public debate on the use of phthalates in toys for very young children has been dominated by two groups. Environmental and consumer associations criticise the use of these plasticisers and even PVC at all, while the producers and most of the users of phthalates and PVC try to defend their economic base. NGOs try to raise public awareness on the problematic properties of phthalates, particularly for the sensitive group of infants and young children, with the aim of building up public pressure on manufacturers towards substitution of phthalates or even PVC. Since it is difficult to establish clear cause and effect relationships for endocrine and similar long-term effects, NGOs ask for a phase-out of such substances in sensitive applications based on the precautionary principle. In 1997 Greenpeace tested toys throughout Europe for release of phthalates upon chewing and sucking, and accused those manufacturers and retailers in public whose products showed particularly high concentrations of DEHP or DINP (GP 97). Although the market volume of phthalates used in toys intended to be placed in the mouth is almost negligible32, the phthalate producers, represented by ECPI33, defend the use of phthalates in toys on principle, emphasising the benefits of PVC. ECPI describes the use of phthalates in toys as not harmful to children, reasoning that despite phthalates have been used for more than 40 years, there is no known case of health having been affected by phthalates. They further argue, that the observed testicular effects in rats were not relevant for humans, since comparable tests with primates did not show reproductive effects. In their view, limited toxicological data for other plasticisers do not allow recommendation of alternatives, and even the use of PVC-free material is not safe, since all alternatives will contain potentially migrating additives. In the opinion of the phthalate supporters, the safety of toys could be rather ensured by the incorporation of migration limits for phthalates into appropriate legislation analogue to the foodstuff regulation (ECPI 01). Against this background, a number of studies were published and several political initiatives undertaken, eventually leading to substitution of phthalates in toys: The outcome of a US CPSC investigation about DEHP releases from toys 1983 caused manufacturers and retailers of toys in the USA to reduce the use of DEHP. As a consequence, also in Europe a decrease of DEHP containing toys was detectable between 1990 and 1996 (CSTEE 98a). While most of the European countries did not react to the American investigation, in 1986 the Swiss Federal Office for Health (Bundesamt für Gesundheit) prohibited the use of DEHP in toys and other articles for children under 3 years of age (BAG 02). The main substitute for DEHP in these cases was DINP. In 1997, Danish and Spanish (1998) authorities undertook first initiatives to limit the use of phthalates in infant and baby toys in general. They informed the European Commission 32 while 37,000 t of PVC and 7,100 t of phthalates were used in toys for children under three years of age, only 18 t of PVC and 2,9 t of phthalates were used in Terms intended to be placed in the mouth (RPA 00). Overall consumption of phthalates as plasticiser in Europe is around 800,000 tpa (RA DEHP 01) European Council for Plasticisers Intermediates, a sector group of CEFIC 33 164 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT under Article 8 of Directive 92/59/EEC (Safety of products) of the risk presented by certain soft PVC teething rings and figures. In 1998 Austria adopted a national law prohibiting certain toys containing phthalates, followed in 1999 by the Greek, Danish and Swedish authorities. Further Member States introduced national restrictions after the recommendation of the Commission (98/485/EC), based on the conclusion of the CSTEE (CSTEE 98a) raising concern about the use of DEHP and DINP as plasticisers in toys intended to be placed in the mouth, and inviting Member States to monitor the level of phthalate migration and to take the measures required to ensure a high level of child health protection. As already mentioned, a suitable method to monitor the recommended migration limits is still lacking. Differently from regulations for plastic material which come into contact with foodstuff, where migration levels34 are observed through validated methods which simulate the use conditions for the products35, Member States were not able to ensure the safety of toys by controlling phthalate migration (CSTEE 99, CSTEE 00). As a consequence, withdrawal and prohibition of phthalate containing products, regardless of a proved exposure, seemed to be the only way to ensure a high level of child health protection, which was done by the Greek, Danish, Swedish, Finnish, Italian, French and German authorities in 1999. Most of the actual national measures of these countries do not focus on toys intended to be placed in the mouth, but go partly beyond the scope of the recommendation by including all toys, which must be expected to be used by children of less than three years of age and likely be sucked and chewed by them. Since not every European authority adopted corresponding legislation, the resulting differences between the Member States called for action to harmonise the EU-market. In November 1999 the Commission presented a proposal for amendments of Directive 76/769/EEC (marketing and use restrictions; 22nd amendment) and Directive 88/378/EEC (safety of toys), to implement a permanent ban for the use of phthalates in toys intended to be placed in the mouth. The proposal has been discussed controversially since then, as there was no consensus among Member States whether a phthalate ban in toys or the setting of limit values (with standardised testing procedure) were to be preferred. With respect to testing of migration rates, a standardised method (“head-over-heals” method by TNO) has now been developed and validated (JRC 01), which however can be used only to determine the migration of DINP so far. It is intended to integrate this testing method, together with new evidence from the ongoing Risk Assessment, in a new proposal to be presented to the European Parliament. The final decision concerning phase-out or migration limit values for phthalates has still not been taken yet (DG Ent 02). Since it must be expected that an amendment of a Directive will take several years, this cannot be a suitable way to prevent a “serious and immediate risk”, which was concluded from the findings of the CSTEE for the presently living children of the questioned age. To 34 total: 10mg/cm² respectively specific migration limits for several substances, laid down in Directive 90/128/EEC 35 Directive 82/711/EEC and 85/572/EEC 165 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT implement a directly operating measure, in December 1999 under the emergency procedure of Directive 92/69/EC the Commission adopted Decision 1999/815/EC, stating a preliminary ban of the marketing of soft-PVC toys and childcare articles intended to be put in the mouth and which contain one or more of six phthalate plasticisers36. All Member States had to transfer this Decision into their national legislation within a few months. In that decision, the Commission appealed to the precautionary principle. Because of the preliminary character of the ban the WTO-agreement is not violated (COM 00a), since the Sanitary and Phytosanitary agreement declares that “in cases where relevant scientific evidence is insufficient, a Member may provisionally adopt sanitary or phytosanitary measures on the basis of available pertinent information” (WTO, article 5.7). Although the migration rates of four phthalates did not result in an actual risk for the use in toys, the decision is extended to six phthalates37. But substitution of the critical substances DEHP and DINP on a substantial level by any other common phthalate, which would have been the simplest way, was not considered to be safe: replacement of DINP by another phthalate would cause higher exposure of that substance, while exceeding of the recommended limit value could not be controlled at the time. Therefore the European Commission considered to lower this risk by an extended ban: the (preliminary) prohibition of phthalates as substitutes, to exclude this kind of substitution. At that time the EU risk assessments of phthalates were in an early stage and the risk for consumers did not allow to wait for the outcome of the risk assessments. Hence preliminary risk reduction measures were anticipated for a small segment of the phthalate market. The validity of the decision must be extended every three months until a permanent solution (for example with the proposed amendments) is implemented. Presently, the 10th prolongation of the emergency ban (Commission Decision 2002/372/EC) is in force. No comparable ban exists outside the EU, but due to uncertainties regarding risk assessments of the use of DINP in toys the US CSPC requested industry to remove phthalates from soft PVC rattles and teethers. A corresponding requirement of retailers makes it impossible for manufacturers to sell phthalate containing items (RPA 00). Health Canada, the federal health department of Canada, published an advisory for parents and caregivers to even dispose of those toys and to prevent their children from sucking of other soft PVC toys, and supplied a positive list of teethers and rattles without DINP (HC 98). 10.4. INITIATIVES AND MOTIVATION AT THE ENTERPRISE LEVEL While public debate on the use of phthalates in toys for very young children was going on, substitution of phthalates or PVC in many cases took place on a voluntary basis. Some manufacturers finally were forced to replace phthalates in their products by the national implementations of the Commission Decision. 36 37 with a limit of 0.1% w/w DINP and DEHP, also banned: di-iso-decyl phthalate (DIDP), dibutyl phthalate (DBP), Di-noctylphthalate (DNOP) and butylbenzyl phthalate (BBP) 166 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT The first substitution of DEHP by DINP in toys, initiated by a voluntary agreement of the American toy industry in 1983, affected manufacturing of toys in the whole world. More then 10 years later, the offensive publishing of retailers and manufacturers in Europe by Greenpeace, who analysed relevant releases of DINP and DEHP from trademark toys (GP 97), prompted some big companies to withdraw the criticised products from the market. Probably their big assortment enabled these companies to react immediately by removing all PVC-containing infant and baby toys, since other materials were available and it was not necessary to find phthalate-free PVC-products. This means that substitution was not at the substance level concerning chemical additives, but rather at the material level. Some companies extended substitution of PVC also in toys for older children and even their whole assortment (RPA 00) to avoid being further criticised and to improve their image, expecting that consumers would associate “PVC-free” with “environmentally friendly”. But not every company gave in to the Greenpeace demands. Particularly companies who were specialised and dependent on processing PVC, predominantly smaller companies, were less willing to undergo the high effort and risk of substitution in the light of the controversial statements about health risks. Represented by associations of toy manufacturers and retailers in Europe, together with phthalate and PVC industry, they questioned the analytical data presented by Greenpeace which were claimed to be disproved by own investigations (agpu 98). With several investigations and publications the PVC industry attempted to resist a negative environmental image (agpu 02). 10.5. ALTERNATIVES / SUBSTITUTES Two strategies are suitable to substitute phthalates as plasticisers in PVC: • • Substitution of the plasticising agent by other substances with same functionality. Substitution of the plasticised polymer by other soft materials. As mentioned above, strategy a) replacement of the concerning DINP and DEHP by another phthalate would require the lowest efforts and costs. Since this way was blocked because of the extended ban, manufacturers of baby toys who intended to keep PVC in their processes had to look for alternative plasticisers which are not based on phthalic acid. While 50-100 different types of plasticisers are available on the market (ECPI 01), only acetyltributylcitrate (ATBC38) and alkylsulfonic phenyl esters (APE39) appear to be relevant for the use in toys intended to be placed in the mouth. Under strategy b) polyolefins, especially polyethylene (PE) and ethylene vinyl acetate (EVA) have been used as alternatives for soft-PVC in toys. These materials do not need plasticising agents, since flexibility is adjustable by varying the chain length of the polymer molecules respectively the content of vinyl acetate. In some other cases silicon and latex are used (pacifiers and bottlenippels). 38 39 trade name Citrofol B, Jungbunzlauer GmbH, Germany trade name Mesamoll, Bayer AG, Germany 167 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT Even wood and textiles have been used in toys for very young children and intended to be placed in the mouth. Because of the very different properties of these materials (non flexibility of wood and low elasticity of textiles), they are not comparable to soft-plastic toys and will not be further considered here. 10.5.1. Technical performance ATBC and APE are suitable as plasticisers in PVC toys, with ATBC presently being the main substitute for phthalates. ATBC enhances resistance to UV radiation and increases colour stability (Jung 02). For both substances the efforts to adapt the mixture and the processing are relatively low. • APE has the advantage of shorter processing times and a better resistance to hydrolysis and has been proved for the rotational moulding process of emulsion PVC (Bay 01), which is used for doll heads and hollow figures Also adipates, which are used in food wrapping material, appeared to be suitable for the use in toys intended to be placed in the mouth. A potentially higher migration rate may be the reason why adipates could not be found in this application (RPA 00). • If PVC is substituted by another material, a certain effort is necessary to find a suitable material and than to adjust or even renew the technical equipment. Since the toy market represents a high variability of products, a standardised solution for every application does not exist. Materials and their variations must be chosen regarding the process, the product and the use. The most common alternatives to PVC in toys are polyolefins in different modifications40, followed by EVA. Compared to PVC these materials show a lower durability and a lower resistance to abrasion when used in teething rings. Finally they are not as flexible as soft PVC (RPA 00). 10.5.2. Health aspects Since the discussion on the use of phthalates in toys has been focused on the health of children, environmental impacts of phthalates, PVC and alternatives will not be considered in this substitution case. With respect to strategy (a), far less toxicological information is available for the alternative plasticisers ATBC and than for phthalates which belong to the best investigated substances. Neither acute nor long term toxicity nor sensitising potential are evident from the available data. Since ATBC has been mentioned as promising candidate for substitution of phthalates in toys, the CSTEE dealt with citrates in detail. In its opinion (CSTEE 99) it annotated the limited database, which does not allow to perform a proper risk assessment for ATBC. The RPA report nevertheless concludes “that ATBC may be preferable to DINP on health grounds” (RPA 00). APE was not assessed by the CSTEE. 40 for example: LDPE (low density polyethylene), HDPE (high density Polyethylene), Metallocene etc. 168 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT Both substances are admitted as additives in plastic materials which are placed in contact with foodstuffs. ATBC is furthermore used in food as a flavouring agent, which should be considered for the extrapolation of child exposure. Available information on the migration potential of ATBC from PVC is diverse, however indicating a comparable rate to DEHP. Corresponding data on APE have not been published. A high resistance to saponification may lead to a lower release of hydrolysis products, but this was not considered in the investigations on the phthalates. Concerning the replacement of PVC by other polymer materials (strategy b), the main advantage of the alternatives PE and EVA is that no additives are required to achieve flexible properties. Even if these plastics contain colouring and stabilising agents with potentially hazardous properties and unknown migration potentials, they are less complex than PVC mixtures and their overall content of additives is much lower. This route of substitution seemed to be more certain, since most opponents to the use of PVC in toys prefer PE and EVA as harmless materials and as suitable substitutes (Dk EPA 01). The use of latex in toys could be seen as problematic, since a sensitising potential of gloves made from latex is known. 10.5.3.Economic aspects Strategy (a): Raw material costs will increase when the high production volume chemical DINP is substituted by other plasticisers. Since ATBC has a price 3-4 times higher than DINP (about 0.8 EURO per 1kg) and the content of ATBC in the product is similar to DINP, increased costs for the finished product must be expected, for example +3,9% if the plasticiser content is 16% (RPA 00). The costs for reformulation and adjustment of the technical equipment is relatively low. Strategy (b): Substitution of the PVC will cause high investment costs, especially if the available machines are not compatible with the new material. In addition the raw material costs increase up to 160% (RPA 00). The majority of the toys on the European market are produced in Asia, mainly China. Even European toy companies have their production sites in Asia. Over 80% of these companies are small enterprises employing fewer than 50 people. While only a very small share of the market is effected by the EU restriction, some of the national restrictions include many more products (RPA 00). 10.6. IMPLICATIONS OF SUBSTITUTION FOR BUSINESS PRACTICE Both substitution strategies, the replacement of plasticisers as well as the replacement of PVC, have been accomplished to phase out phthalates from toys for very young children. Although the limited technical performance of alternative materials was criticised, many toy manufacturers decided to exchange the material, while some perhaps gave up the small market segment of toys intended to be placed in the mouth. Most of the questioned PVCproducts disappeared from the stores. Especially in teethers, phthalates together with PVC were substituted by entirely different plastics. One reason may be that NGO´s and consumer 169 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT associations recommended to avoid soft-PVC toys in general, since the finalised product gives no hint of the used plasticiser and consumers are not able to identify phthalate containing PVC. Where exchange of material was too expensive or alternative materials are not compatible with the required process (which is obviously the case in the production of doll heads by rotational moulding), manufacturers replaced the phthalates by allowed plasticisers (toycomp 02) although toxicological assessment of these alternatives is somewhat uncertain. Possibly, for economic reasons phthalate containing soft-PVC is still used in products for older children, or for markets outside the EU. 10.7. ANALYSIS OF KEY FACTORS In the following, key factors which were identified for the substitution case of phthalates in soft PVC toys for infants and babies are analysed in the main categories as introduced in CHAPTER X. 10.7.1. Categories Economics • In spite of higher costs, toy manufacturers substituted phthalates or even PVC, however Obviously, the effectively high investment costs and increased raw material costs, induced by the replacement of PVC, does not hinder toy manufacturers to select this route. Since the emergency ban on phthalates in certain toys pertains a very small segment of the European toy market only, the markets of the raw materials are not really affected even if national restrictions and commitments of toy companies included more products. In fact, despite an ongoing environmental debate on phthalates and PVC in all applications, no decrease of market volume is perceivable in consequence of the emergency ban (ECPI 02). In future, a deflection of demand for DEHP can be expected in consequence of the classification as “toxic for reproduction cat. II”. Other phthalates, predominantly DINP and DIDP, will likely be the common alternatives. Technical functionality • Substitutes with equivalent functionality are available. With ATBC and APE, two substitutes for phthalate plasticizers are available which require relatively low efforts of process adjustment. For substitution at the material level, a certain effort will be necessary to find a substitute material for PVC, and to adjust or even renew the technical equipment on which the toys are produced. no effect on the market volume of phthalates and PVC can be observed. 170 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT Communication/awareness • The sensitive issue of health safety for children facilitated the application of the precautionary principle. Public awareness appears as the main push factor in this case study because of the high priority which is given to the issue of children safety in the public debate. The campaign of the NGO´s awoke great resonance which called for action in the national and European institutions. Even without an evident danger the application of the precautionary principle was considered to be adequate, since a serious risk for the sensitive group of infants and babies could not be excluded because of the great uncertainties resulting from the available scientific data. Expecting new concern arising from other the use of other phthalates as substitutes for DEHP and DINP, the ban was extended to overall six phthalates. While this simplest way of substitution was excluded, more far-reaching strategies like substitution of the material became more attractive. • The polarised debate hindered the routine negotiations on legal amendments, but prompted the Commission to initiate an emergency procedure which supported substitution initiatives at national level and inside companies Although the main controversy was about the use of phthalates in toys intended to be placed in the mouth, neither NGOs nor industry restricted the debate within this scope. Industry was worried about the signalling of the campaign for other applications of phthalates, while indeed some opponents aimed at questioning the use of PVC in general (GP 99). Thus the discussion was dominated not only by the intention to protect the health of children, but by the more far-reaching question whether PVC in general is an acceptable material or not. Against this background, the authorities had to focus on consumer protection. To work out a suitable strategy to prevent children from health damage was difficult because of the great uncertainties of the scientific findings: while some authorities adopted a ban of phthalates in toys intended to be placed in the mouth, others decided to accept available tests to observe the migration limits recommended by the CSTEE (98/485/EC). These strong positions delayed a decision on the proposed amendments on the Directives 76/769/EEC and 88/378/EEC, but finally substitution was supported since many companies anticipated legal restrictions, many authorities adopted national bans for the use of phthalates in toys and the Commission implemented a preliminary ban valid for all Member States. On the basis of their respective perception and assessment of risk, today neither industry nor NGOs are content with the situation. While for BEUC the adopted bans are insufficient but rather should be extended to all phthalates and many more toys (BEUC), industry criticises the ban as inadequate and the described risk as unfounded. Toxicological assessment • Prohibition of substances was favoured by the authorities due to lack of a validated analytical method for exposure measurement The question of the risk of exposure for children by chewing and sucking of toys 171 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT remained unclear for a long time, since none of the available tests was assessed as adequate to distinguish between safe PVC-toys and unsafe PVC-toys(CSTEE 99). In the opinion of many Member States and the European Commission, prohibition of phthalate containing products seemed to be the only way to ensure a high level of child health protection. • Even high efforts for toxicological investigation do not give unambiguous evidence on risk Phthalates, especially DEHP, belong to the best investigated substances on the market. Nevertheless, it is not possible to definitely prove or disprove a risk for the use of these substances in toys intended for chewing and sucking, since scientific data leave open questions which can be interpreted in different ways. E.g. transferability of animal testing on human beings, margins of safety, effects of additional exposure are topics which lead to completely controversial interpretations and strategies based on the same data. The results of the now available European risk assessments on phthalates, which indicate different conclusions for the use of DEHP41 and DINP42, are not really considered by the opposing parties: industry still insists that the use of all phthalates is harmless in all applications, while NGOs still claim that all phthalates could cause harm in general. The availability of toxicological data alone does not necessarily affect the process of substitution. • plasticiser in the finalised product supported substitution of the material Because of great uncertainties in the toxicological assessment of alternative plasticisers, the CSTEE did not recommend any substance as a substitute for DINP and DEHP (CSTEE 99). Substitution of the material seemed to be preferable to avoid negative outcomes in the future. Furthermore concerned consumers, who would not be not able to identify phthalate-free PVC, would prefer other materials too. Uncertainties about alternative plasticisers and the impossibility to identify the used Legislation • Substitution of phthalates in toys intended to be placed in the mouth was supported by national restrictions and complemented by a European emergency ban Even if most of the concerned products were replaced voluntarily by industry, finally the preliminary ban ensured that phthalate containing toys intended to be placed in the mouth were effectively removed from the European market. 41 42 conclusion i): there is a need to reduce the risk... conclusion iii): there is no need to reduce the risk... 172 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT 10.7.2. FOCUSSING: SUBSTITUTION OF PHTHALATES TOGETHER WITH PVC BY POLYOLEFINS The majority of the products affected by the EU emergency ban has been replaced by toys made from materials other than PVC, predominantly polyethylene. Therefore this section focuses on the substitution of Phthalate/PVC through polyethylene. Economics a) Substitution at the substance level causes higher material costs, substitution at the material level causes higher material and investment costs. Economics/possible effects on the market Technical functionality b) hindrance of substitution support of substitution (-) Technical functionality Communication/awareness Substitutes with equivalent functionality are available. (+) c) The sensitive issue of children health safety facilitated the application of the precautionary principle Awareness & Communication / sensitive issue strong support of substitution (++) d) The polarised debate hindered the routine negotiations on legal amendments, but prompted the Commission to initiate an emergency procedure which supported substitution initiatives at national level and inside companies. Awareness & Communication polarised positions Toxicological assessment delay but finally support of substitution (+) e) The prohibition of substances was favoured by the authorities due to lack of a validated analytical method for exposure measurement Risk assessment / lack of analytical methods support of substitution indifferent (+) g) Risk assessment different interpretations of available data Even high efforts for toxicological investigation do not give unambiguous evidence on risk (o) h) Uncertainties about alternative plasticisers and the impossibility to identify the used plasticiser in the finalised product supported substitution of the material Risk assessment lack of RA for alternative substances Legislation Legislation support of substitution of material (+) i) Substitution of phthalates in toys intended to be placed in the mouth was supported by national restrictions and complemented by a European emergency ban. support of substitution (+) 173 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT 10.8. LITERATURE agpu 98 agpu 00 BAG 02 Bay 01 BEUC 00 COM 00a CPSC 83 http://www.agpu.de/news030498.htm http://www.agpu.de Bundesamt für Gesundheit, Informationsschreiben Nr. 43, Switzerland, 2002 Bayer AG, Polymer additives: Mesamoll®; www.experts4additives.de, 2001 BEUC position on Phthalates in Toys & Baby Products, BEUC/X/046/2000 Communication from the Commission on the precautionary principle, COM (2000) 1 final, Brussels, 2.2.2000 Hanson R. L.: Phthalate ester migration from polyvinyl chloride consumer products. Phase 1 final report. Report prepared for the US Consumer Product Safety Commission. 51 pp, 1983 EU Scientific Committee on Toxicity, Ecotoxicity and the Environment (CSTEE): Phthalate migration from soft PVC toys and child-care articles. Opinion expressed at the CSTEE third plenary meeting, Brussels, 24 April 1998 EU Scientific Committee on Toxicity, Ecotoxicity and the Environment (CSTEE): Opinion on Phthalate migration from soft PVC toys and child-care articles – Data made available since the 16th of June 1998, opinion expressed at the 6th CSTEE plenary meeting, Brussels, 26/27 November 1998 EU Scientific Committee on Toxicity, Ecotoxicity and the Environment (CSTEE): Opinion on the toxicological characteristics and risks of certain citrates and adipates used as a substitute for phthalates as plasticisers in certain soft PVC products EU Scientific Committee on Toxicity, Ecotoxicity and the Environment (CSTEE): Opinion of the CSTEE on validation of test methods for phthalate migration – Opinion expressed at the 17th plenary meeting, Brussels, 5 September 2000 EU Scientific Committee on Toxicity, Ecotoxicity and the Environment (CSTEE): Opinion on Chapters 6 and 8 (on risk issues) of the RPA EDT/99/502498 Final report – July 2000; Opinion expressed at the 22nd CSTEE plenary meeting, Brussels, 6/7 March 2001 EU Scientific Committee on Toxicity, Ecotoxicity and the Environment (CSTEE): Opinion on the report: Validation of methodologies for the release of diisononylphthalate (DINP) in saliva simulant from toys (2001 EUR 19826 EN), Expressed at the 25th CSTEE plenary meeting, Brussels, 20 July 2001 Harmless substances can replace harmful phthalates, Danish EPA, Updated CSTEE 98a CSTEE 98b CSTEE 99 CSTEE 00 CSTEE 01a CSTEE 01b Dk EPA 01 174 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT 22/10/01 DG Ent 02 ECPI 01 ECPI 02 IARC 00 Jung 98 GP 97 GP 99 HC 98 JRC 01 Telephone interview of representative of DG Enterprise, March 2002 http://www.ecpi.org/plasticisers/index.html, last updated on 24 September 2001 Telephone interview of representative of ECPI, February 2002 IARC Monographs on the Evaluation of Carcinogenic Risks to Humans Some Industrial Chemicals (Volume 77) (15–22 February 2000). Jungbunzlauer: Citrofol®, 1998, www.jungbunzlauer.com Greenpeace Hintergrundinformation: Kinderspielzeuge aus Weich-PVC: Umweltgift in Kindermund! November 1997 www.greenpeace.de/GP_DOK_3P/BROSCHUE/ARGUMENT/C03AR01.HTM#4 Health Canada, Advisory, 1998, http://www.hc-sc.gc.ca/english/protection/warnings/1998/98_85e.htm Validation of methodologies for the release of di-isononylphthalate (DINP) in saliva simulant from toys, European Commission, General Directorate Joint Research Centre, EU report EUR198826 EN 2001 RISK ASSESSMENT: bis(2-ethylhexyl) phthalate, Consolidated Final Report, September 2001 RISK ASSESSMENT: 1,2-Benzenedicarboxylic acid, di-C9-11-branched alkyl esters, C10-rich and di-“isodecyl”phthalate Finalised report of May 2001 RISK ASSESSMENT: 1,2-Benzenedicarboxylic acid, di-C8-10-branched alkyl esters, C9-rich and di-“isononyl” phthalate, Draft of February 2000 RPA in association with RiTox: The Availability of substitutes for Soft PVC Containing Phthalates in Certain Toys and Childcare Articles, Prepared for the European Commission Directorate-General Enterprise, Contract No: ETD/99/502498, July 2000 personal communication, German toy manufacturer, March 02 Agreement on the application of sanitary and phytosanitary measures. RA DEHP 01 RA DIDP 01 RA DINP 01 RPA 2000 toycomp 02 WTO 175 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT ANNEX V Conference Summary Substitution of Hazardous Substances in Processes and Products Conference 13/14 of June 2002, Hamburg 13 JUNE 2002, 02 p.m. – 06 p.m. Mr. Peter Friesel (Senate of Hamburg, Department for Environmental Protection) opened the Conference. He referred back to the Weimar Statement of the European Environmental Ministers from 1999, identifying fundamental deficits in the European Chemicals Policy. The Commission’s White Paper on a New Chemicals Policy in Europe is a response to this and encourages the substitution of dangerous by less dangerous substances where suitable alternatives are available. Referring to the substitution process of perchloroethylene by the ozone-depleting 1,1,1-trichloroethane, Mr. Friesel however pointed out that substitution has not always led to a decrease in environmental risk and hence careful assessment is needed. Mr. Lothar Lissner (Kooperationsstelle Hamburg) presented the preliminary results of the current study on substitution of hazardous substances in products and processes, launched by DG Env in 2000. He introduced the current range of definitions of “substitution” to the conference. Mr Lissner illustrated the methodological approach of the study, which aims to identify the major drivers of substitution based on the analysis of policies, strategies and guides from different actors as well as 10 case studies. Finally he presented a number of findings concerning the typical scenarios in substitution cases and the behaviour of actors in such cases. Mr. Rob Donkers (DG Environment) introduced the key elements of the Commission’s proposal for a New Chemicals Policy in Europe. He pointed out that various of these elements will work as direct or indirect drivers for substitution of hazardous chemicals in the market, e.g. the obligation on producers to define the intended use of their products, the authorisation regime for substances of very high concern, involving down stream users systematically in risk assessment and softening requirements to R+D activities with new chemicals at the same time. Mr. Joachim D’Eugenio (DG Environment) introduced to the EU Water Framework Directive and its goal to reach good water quality status in European surface water by 2015. The Commission has carried out a comparative risk based identification procedure to determine 33 priority substances for which environmental quality targets and specific measures on community level shall be proposed in 2003. These measures may include substitution as on part of emission control. Mr. D’Eugenio pointed out, that also the EU IPPC Directive includes a requirement on substitution like it is for example operationalised in the 176 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT BREF on tanneries. Substitution requirements in other pieces of legislation, e.g. in the EU Waste Directives (WEEE and RoHS) and the Chemicals at Working Place Directive were mentioned as well. In the following discussion the following points were made: Mr. Axel Singhofen (Assitant of the Greens in EU Parliament) stated that the current legislation on existing substances is a structural barrier to substitution since the question “how big is the risk” plays a pre-dominant role. The focus should be shifted to questions how and when can we act. In addition he pointed out that substances in articles are not sufficiently covered in the current legislation. Mr. Tom Feijtel (Procter and Gamble) emphasised the need to include i) the life cycle perspective and ii) other than only toxic impacts when deciding on substitution, in order not to shift risks from one life cycle stage to another or from one impact to another. He stressed the need to avoid a purely hazard-based approach. Mr. Julian Lageard (Intel) asked the representatives of the Commission to briefly outline how the various pieces of legislation triggering substitution (e.g. like the ROHS Directive) would be integrated with other pieces of legislation (e.g. Existing Substance Directive). Mr. Wolf-Rüdiger Bias (BASF) pointed out that industry is seeking to make profit and hence the key driver for substitution is innovation not legislation. Ms. Ute Meyer (Aktionskonferenz Nordsee) expressed her expectation that REACH will increase the availability of substance data and that this in turn may provide a clearer picture on the needs and options of substitution. Mr. Kenneth Geiser (University of Massachusetts) pointed at the need to understand substitution as a step that may influence a whole system of integrated production chains and material flows. Following these presentations, a panel discussion “TOWARDS A COMMON SUBSTITUTION POLICY” took place with Mr Rob Donkers as moderator and the following panelists: Mr. David Chesneau, European Chemical Industry Council (CEFIC), Mr Thorsten Zellmann, Robert Bosch GmbH (D), Jan Koch, Artifex Dr. Lohmann GmbH & Co., (D), Stefan Scheuer, European Environmental Bureau, Estefanía Blount, ISTAS-CC.OO., E, Eva Eiderström, Svenska Naturskyddsföreningen, S, and Arnold van der Wielen, Ministry for the Environment, NL. The contributions of the panelists and some participants in the plenary during the following panel discussion can be summarised into some key statements: Mr. David Chesneau (CEFIC) defined substitution as one of the tools for risk management and emphasised that it is more important to develop a common idea on the purpose of substitution rather than a perfect definition: “If we believe that the substitution principle is a risk management tool …I see no reason why there shouldn’t be extensive co-operation?” Mr. Stefan Scheuer (EEB) sees substitution as a methodology within the authorisation procedure under REACH. Legislation is in his opinion the key driver, however liability should be developed as to serve as an economic driver in parallel. He questioned whether 177 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT a definition of substitution is really needed and whether it is not much more important to draw consequences from the recently published study by EEA “Late lessons from early warnings”. Mr. Thorsten Zellmann (Bosch) pointed out that a company like Bosch, manufacturing electric components for automotive and various machinery, usually do not have experts on chemistry or toxicology at their disposal. Hence he sees the need for easy to understand guidance on which assessment requirements exist, and which data are needed for that. The flexibility to use less hazardous substitutes is very much case-dependent, general answers are not possible. Mr. Jan Koch (Artifex Dr. Lohmann GmbH) emphasised the need for better information in the supply chain coming through to small and medium sized chemical enterprises, since they have to rely on the information which they receive from their suppliers. He would particularly appreciate if suppliers would be more competent and willing to offer advise on less hazardous substitutes existing in the market, before hazardous substances get into the focus of the public debate. Ms. Estephania Blount (ISTAS-CC.OO, Spain) pointed out that most exposures occur at working places and usually substitution of hazardous chemicals does not happen if it is not mandatory. According to Ms. Blount’s understanding substitution often is a socialtechnical process which has a cultural and an organisational background. Hence it is important that workers participate in the process and contribute their expertise to the definition of problems and finding solutions. In order prevent risks at the working place more effectively, centralised data bases on available substitutes would be helpful to practically implement substitution on company level. Ms. Eva Eiderström (Svenska Naturskyddsföreningen) introduced to the private Ecolabel “Bra Miljöval” being quite successful in the Swedish market and having also impact on global scale. One of the key success factors was to identify and co-operate with those players in the market who are powerful enough to trigger substitution in products from competitors through using the “Bra Miljöval” label. According to Ms. Eiderström’s opinion co-operation between NGOs and first movers in the market on the one hand and regulatory measures targeting the laggards on the other are complementary strategies, both needed to promote substitution. Mr. Arnold van der Wielen (MINVROM) introduced to the “Quick Scan” approach as applied in the Netherlands. Based on available data on substance properties the “existing substances” are sorted into four management groups, each of these linked to a set of “in principal”-measures. In addition, the Netherlands recently had made the attempt to reject the permission for setting up a new production line for a substance (a brominated flame retardant) for which the producer could not provide data on the inherent properties of the substance. Finally Mr. Van der Wielen pointed at Dutch experience, that associations of downstream users can develop quite some power in asking suppliers for better information. In the plenary discussion the following points were made: • Mr. Michael Warhurst (WWF) expressed the concern that industry often does not really 178 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT consider the basic rules of chemistry when substituting a hazardous substance (like e.g. nitromusks, nonylphenol or prioritised brominated flame retardant) by substances which are not less hazardous by their chemical structure (polycyclic musks, octylphenol, brominated flame retardant not yet prioritised). • • Mr. Axel Singhofen (Greens in EU Parliament) stated that the thereis “a lack of driving to the better alternative and forcing the companies to actually ban then the other ones”. Ms. Ute Meyer (Aktionskonferenz Nordsee) stated that there is a need to develop a more common understanding on the type and level of hazards that should trigger substitution. Mr. Rob Donkers (DG Environment) closed the panel session in highlighting the challenge to come forward with a flexible system motivating industry to take the initiative. 14 JUNE 2002, 09 a.m. – 03.30 p.m. Mr. Martin Wirts (Ökopol) presented an overview on existing approaches and instruments to compare hazards, risks, costs and benefits of substances or other solutions with each other as a basis for product design or decision taking on risk reduction measures. Mr. Wirts highlighted three key questions to be considered when applying assessment tools: Which are the criteria to consider and which are the most important ? How to aggregate or to balance the criteria against each other? What are the views of the relevant stakeholders in the field? Mr. Tom Feijtel (Procter and Gamble) presented the product assessment concept as applied by Procter and Gamble. He highlighted the need of a holistic approach with regard to all three dimensions of sustainability in stating that only products offering a competitive performance and value will survive to deliver environmental benefits. In addition he expressed concerns that “hazard based substitution” may lead to undesired results, e.g.: Dose considerations would be omitted even though they may be the major determinant of the risk. Impacts from the entire life-cycle and possible non-toxic but nevertheless relevant environmental impacts may be ignored. Mr Feijtel mentioned also a substance which was substituted with a safer but more expensive one, but the customers didn’t accept that and the product had to be withdrawn from the market. The results from the working group sessions were summarised in the plenary: • WG1 – Plasticisers in Polymers The approach to substitution may differ depending on the level of hazard. The regulatory situation, the relevance of exposure scenarios and the need to search for more information in case of very hazardous substances may be different compared to other dangerous substances. If substitution is needed, it can be useful to draw up an action plan on national level covering a certain functional type of chemicals (e.g. all plasticisers), including three steps: compiling a risk profile (hazard and exposure information) , analysing economical and technical aspects and carry out “real life” implementation projects. Better risk communication on supply chain and means to overcome the competitive advantage of hazardous “high-tonners” (like e.g. DEHP) 179 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT against its alternatives were considered important challenges for the future. • WG 2 – Hazardous substances in circuit boards The initial discussion about which substitution case to focus on (lead in solder; brominated flame retardants) gave an indication that obviously pending legislation is a relevant trigger to push substitution efforts. Then focusing on tetrabromobisphenol A (TBBPA) in circuit boards, it turned out that all participants had almost the same scientific database, facts on risk profiles where accepted by all sides, but nevertheless conclusions differed widely as to whether this was a clear case for substitution or not. Also there were diverging views whether one should wait for the results of the EU Risk Assessment, or whether steps to promote substitution should be initiated already at this stage. Besides legislation, a range of instruments to trigger substitution was identified, including public procurement, R&D programmes, liability and accountability, eco-labelling and awareness-rising in general. Companies obtain their orientation on innovation direction by networking, corporate environmental staff, associations, customer requests and last but not least from environmental NGOs. WG 3 – Textiles Textile production is one of the most globalised industrial activities. The four main steps of the production - growing or producing of the raw material (natural or synthetic), preparation (cleaning, spinning ), pre-tratment (dyeing, printing, bleaching etc) and finishing (easy care, water repellent etc) - are done by suppliers in different companies and different countries. European Union Member States import these products and have a limited influence on the production process. The main approach to substitution has been up to now the control of undesirable residues of substances in the final product (in the frame of labels as Oeko-Tex, EU-Label, Nordic Swan). On the other hand many less hazardous textile chemicals have been developed in Europe and are exported to the textile producing countries. The options to successfully promote substitution in these countries seem to be: a better information about alternatives from the European Union to these countries, positive lists and import control. WG 4 – Metal Parts Cleaning Metal parts cleaning is a wide spread activity, the technology and the use of chemicals depends on the material and the dirt. A wide range of possible chemical alternatives is available, mainly petrochemicals and water-based cleaners. Application of less hazardous alternatives is for example promoted through regulatory requirements, improved communication on available alternatives and environmental and health and safety hazards of the conventionally used products. However several factors could be also an obstacle to substitution: The supplier does not provide full information to his clients, how to reduce the needed volume of cleaner and which substitutes may be available in the market. Environmental protection and protection of workers health may need conflicting measures. Finally public pressure is not available as a driver in this field. • • After the working group reports to the plenary, Ms. Inger Schörling (Member of EU Parliament) presented the EU Parliament’s current view on substitution. Ms. Schörling sees substitution as a key instrument to implement the precautionary principle. Hence it should apply to all chemicals and needs to be fixed in upcoming EU legislation. Ms. Schörling highlighted public opinion as an important driver for policy and hence the need to make good quality information on chemicals available to the public. 180 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT At the end of the conference, Mr. Andreas Ahrens (Ökopol) presented a brief reflection on what had been discussed during the 1.5 days. In addition to the points mentioned above, the following key aspects and questions were highlighted on the conference: • Substitution needs a goal and needs a definition. Is substitution a tool to manage or to reduce or to prevent risks? Or is it a key instrument or a strategy within chemicals policy to achieve prevention or reduction of risk? • The scope of substitution needs some more detailed consideration. Should it cover only the very hazardous or all dangerous substances? • Are different substitution approaches needed for intermediates in chemical production, for chemical manufacturing aids in industrial processes or for chemical products in wide spread use or substances in articles.? • Who can be the drivers for innovation? Are there different incentives necessary for traders, formulators or for industrial users, or consumers. • In substitution processes beside the environmental and health protection issues the economical feasibility and the social acceptability also plays a role. • Can or will substitution happen in co-operation? • When must substitution start – after early scientific warnings or is a full risk assessment necessary? • How can be dealt with the problem of chemicals imported with articles? Mr. Joachim D’Eugenio, expressing his thanks to all participants for their valuable contributions, closed the Conference at 3.30 p.m. 181 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT Conference Programme (DAY 1): TOWARDS A COMMON SUBSTITUTION POLICY SPEAKERS / CHAIR Welcome and introduction Joachim d’Eugenio EU-Commission, DG Environment Unit for Water, the Marine and Soil Freie und Hansestadt Hamburg, Department for Environment and Health SUBSTITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROCESSES Main preliminary results of the study “Substitution of Hazardous Chemicals in Products and Processes” The Substitution Approach in the “White Paper on Future Chemicals Policy” The Substitution Approach in Other Policy Areas Peter Friesel, Environmental Protection Unit SPEAKERS / CHAIR Lothar Lißner Kooperationsstelle Hamburg Rob Donkers, EU-Commission, DG Environment Chemicals Unit Joachim d’Eugenio, EU-Commission, DG Environment, Unit for Water, the Marine and Soil Questions + Discussion TOWARDS A COMMON SUBSTITUTION POLICY PANEL DISCUSSION PANEL DISCUSSION: How co-operative can Substitution Policy be? Chair: Rob Donkers Participants: David Chesneau, European Chemical Industry Council (CEFIC), B Thorsten Zellmann, Robert Bosch GmbH, D Jan Koch, Artifex Dr. Lohmann GmbH & Co., D Stefan Scheuer, European Environmental Bureau, B Estefanía Blount, ISTAS-CC.OO., E Eva Eiderström, Svenska Naturskyddsföreningen, S Arnold van der Wielen, Ministry for the Environment, NL. 182 Kooperationsstelle Hamburg SUBSITUTION OF HAZARDOUS CHEMICALS IN PRODUCTS AND PROZESSES ANNEX IV – CASESTUDY 10: PHTHALATES IN TOYS FINAL REPORT Conference Programme (DAY 2): SUBSTITUTION IN DETAIL ASSESSMENT STRATEGIES AND CASE STUDIES SESSION CHAIR Assessment Strategies and Decision Making Tools – an overview Assessment Tools at Company Level SUBSTITUTION IN DETAIL - CASE STUDIES Case Study 1: PLASTICISERS IN POLYMERS Case Study 2: CHEMICALS IN TEXTILES Case Study 3: PRINTED CIRCUIT BOARDS Case Study 4: METAL PARTS CLEANING TOWARDS A COMMON UNDERSTANDING OF SUBSTITUTION Workgroup reports Conclusions for further substitution policy Reflection on Results of the Conference Closure of the Conference PLENARY SESSION Joachim d’Eugenio, Unit for Water, the Marine and Soil EU-Commission, DG Environment Tom Feijtel, Procter&Gamble WORKING GROUPS Martin Wirts, Ökopol Chair: Andreas Ahrens, Ökopol Introduction into the substitution scenario: Kerstin Heitmann, Ökopol Chair: Eva Lechtenberg-Auffarth, FIOSH D, Introduction into the substitution scenario: Lothar Lissner / Wolfgang Kruschak, Otto Versand GmbH Chair and introduction into the substitution scenario: Joachim Lohse, Ökopol Chair: Tim Tregenza, EU-OSHA Introduction into the substitution scenario: Klaus Kuhl, Kooperationsstelle Hamburg CONCLUDING PLENARY SESSION WG Rapporteurs Inger Schörling, EP, Committee on the Environment, Public Health and Consumer Policy Andreas Ahrens, Ökopol Joachim d’Eugenio, Unit for Water, the Marine and Soil EU-Commission, DG Environment The presentations are available on the Internet Website http://www.rrz.uni-hamburg.de/kooperationsstelle-hh/contentengl/arbeitsgebiete/ersatzstoffe/politik/substitutioneu/conrmoreinfo.htm 183 Kooperationsstelle Hamburg