Ref. Ares(2018)4184215 - 09/08/2018

Substitution of Chemical Substances of Potential Concern

Extract of Final Report

Disclaimer

The information and views set out in this report are those of the author(s) and do not necessarily reflect the official opinion of EASME or the Commission. EASME and the Commission do not guarantee the accuracy of the data included in this study. Neither EASME or the Commission nor any person acting on EASME's or the Commission’s behalf may be held responsible for the use which may be made of the information contained therein.

Table of contents

Abstract ...... vi

Executive Summary ...... vii

Synthèse ...... x

1 Introduction ...... 1

2 Mapping ...... 3

3 Profiling ...... 21

4 Identification and Analysis of Relevant POD Profiles ...... 24

5 Guideline for the Use of the Partnership Opportunities Database for the Purpose of Substituting Chemicals of Potential Concern ...... 33

6 Testing and Validation of the Guideline ...... 37

7 How the Network Can Support Businesses in the Substitution Process ...... 39

8 Guideline for SMEs on How to Approach Substitution ...... 42

9 References ...... 43

Annex 1 Simplified Analyses of Alternatives of the Selected Substances ...... 44

List of Abbreviations

AC Article Category AfA Application for Authorisation AoA Analysis of Alternative BHA Butylated hydroxyanisole BPA Bisphenol A BPR Biocidal Products Regulation CAD Chemical Agents Directive CAPEX Capital expenditures CAS Chemical Abstracts Service CMD Carcinogen and Mutagen Directive 2004/37/EC CORAP Community Rolling Action Plan COSME EU programme for the Competitiveness of Enterprises and Small and Medium-sized Enterprises CPR Cosmetic Products Regulation DBDPE 1,1'-(ethane-1,2-diyl)bis[pentabromobenzene] DEHP Bis(2-ethylhexyl) phthalate DIDP Di-‘isodecyl’ phthalate DINP Di-''isononyl'' phthalate DPHP Bis(2-propylheptyl) phthalate EASME Executive Agency for Small and Medium-sized Enterprises EBP Ethane-1,2-bis(pentabromophenyl) EC European Commission ECHA European Chemicals Agency EDC Endocrine Disrupting Compounds EEN Enterprise Europe Network LOUS List of Undesirable Substance MDI 4,4'-methylenediphenyl diisocyanate MOCA 4,4'-Methylenebis(2-chloroaniline) MTBE Methyl Tertiary Butyl Ether NeRSAP Network of REACH SEA and Analysis of Alternatives Practitioners NMP N-Methyl-2-pyrrolidone OPEX Operating expenses PACT Public Activities Co-ordination Tool PBT/vPvB Persistent, Bio-accumulative and Toxic substance / very Persistent and very Bio-accumulative substance PC Product chemical Category POD Partnership Opportunities Database POP Persistent Organic Pollutants PPPR Plant Protection Products Regulation Q&A Questions and Answers REACH Regulation (EC) No 1907/2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals RMOA Risk Management Option Analysis RoHS Directive 2011/65/EU ROI Registry of Intentions RPA Risk & Policy Analysts Ltd. SIN Substitute It Now! SME Small and Medium-sized Enterprise

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SU Sector of Use SVHC Substance of Very High Concern TMAH Tetramethylammonium hydroxide UV Ultraviolet light VOC Volatile Organic Compounds WHO IPCS World Health Organisation International Programme on Chemical Safety WKÖ Wirtschaftskammer Österreich

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Abstract

The presence of hazardous chemicals in processes and products is an obstacle to the development of a circular economy. SMEs may lack the resources to engage in the substitution of hazardous chemicals. Bringing together demand and offer of safer alternatives may facilitate substitution. This study explores the potential of the POD to promote contacts between solutions providers and SMEs interested in substitution. The authors selected 14 substances of potential concern and carried out simplified analyses of alternatives. These informed the review of existing relevant profiles on the database and the provision of guidelines for their improvement. Technical function(s) and end use(s) of the technologies should be prominent in the profiles, as well as their main economic, health and safety, and environmental advantages. Some adjustment could be made to the POD, such as the possibility to select a keyword “Substitution of hazardous chemicals” that would allow users to refine searches and to signal the potential of certain technologies as substitutes for chemicals of concern. The authors conclude that the POD is conducive to functional substitution, and a closer collaboration between EEN and ECHA would create synergies that would provide better support to SMEs interested in substitution.

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Executive Summary

Following the commitment of the European Commission towards developing a circular economy and the growing interest of industry stakeholders in substituting hazardous chemicals, the Executive Agency for Small and Medium-sized Enterprises (EASME) launched this study within the 2016 COSME Work Programme. It is one of several initiatives aiming to support businesses in dealing with chemical policy and, more precisely, it aims to facilitate contacts between solutions providers and SMEs interested in substituting chemical substances of potential concern (hereafter referred to as substitution). SMEs may lack the resources to engage in substitution initiatives and bringing together demand and offering safer alternatives has been seen as one of the measures that may facilitate substitution the most.

This could be achieved by providing guidance to the partners of the Enterprise Europe Network (EEN), to EEN staff and to SMEs on how to better use the Partnership Opportunities Database (POD) for the purpose of substitution. The POD is an internet platform maintained by the EEN that aims to connect SMEs to facilitate commercial deals, technology transfers and research projects. Each request and offer from the companies (clients) supported by the Network are described in profiles, varying according to the type of partnership sought/offered by the clients.

The first task of the project team was to identify between 10 and 15 substances of potential concern, to be used as case studies for the analysis to be carried out in the subsequent tasks. In order to ensure the selection of substances that are used in different sectors and for which substitution is driven by variable reasons, a list of criteria was prepared and agreed with the project steering group. A long list was compiled to include substances:

• Covered by different pieces of legislation; • With different functions, used in different applications and sectors; • For which substitution or consideration of substitution is driven by the high costs associated to risk management throughout their life cycles; • For which innovative alternatives have been/are being developed that may open up new market opportunities; • That can be/have been substituted through alternative non-chemical technologies; • That can be/have been substituted through organisational measures.

This long list was narrowed down through the consultation of databases, experts and SMEs. Ultimately, 14 substances were selected for further consideration. These include:

1. Silica flour 2. Chromium trioxide 3. Glutaraldehyde 4. Methanol 5. Bisphenol A 6. Hydrazine 7. N-Methyl-2-pyrrolidone 8. 4-Nonylphenol, branched and linear, ethoxylated 9. Toluene 10. Formaldehyde 11. Di-''isononyl'' phthalate 12. Brominated flame retardants e.g. Ethane-1,2-bis(pentabromophenyl) 13. Trichloroethylene 14. Tetrachloroethylene

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The second task consisted of identifying the functionalities of the selected substances and in assessing the availability and technical and economic feasibility of chemical and non-chemical alternatives. For the purpose of this study, the project team adapted and simplified the Analysis of Alternatives (AoA) that is part of an Application for Authorisation (AfA) under the REACH Regulation. Indeed, the primary objective was not the development of detailed AoAs but rather the learning of lessons and identifying of good practices to be communicated through guidelines intended for interested parties. For each selected substance, a minimum of three alternatives were identified and analysed. The lessons learnt were summarised in 10 simple steps, providing advice on finding and collecting information on the identities, the properties, the technical and economic feasibility, and the availability of potential alternatives.

The third task consisted of searching through the POD for profiles relevant to substitution and in reviewing these in order to highlight shortcomings and identify good practices. The project team searched through the POD by entering relevant words, such as “substitution”, “alternative”, “non- toxic”, “eco-friendly”, as well as the names of specific chemical substances. They also generated queries using some of the technology and market keywords available in the POD to filter profiles by technology and economic activity. Through this search strategy, the project team screened around 1,800 profiles (ca. 25% of the total number of 7,700 profiles present on the POD as of October 2017), of which 49 (ca. 2.7% of screened profiles) were deemed relevant to substitution.

The identified profiles vary in terms of quality and quantity of information provided, ranging from excellent profiles – with optimal use of title, summary, description and advantages and innovations sections – to profiles presenting too generic requests or offers. In particular, profiles failing to describe the technical functions and end uses of the technologies sought/offered are likely to attract less interest from prospective clients/partners. POD users searching for alternative (chemical and non- chemical) technologies to substances of potential concern may have difficulties in finding relevant profiles if these do not mention the substances that the technologies may substitute. Many profiles present bio-based or green chemistry technologies but fail to mention the substances they could replace or fail to describe what makes the technology offered safer from a health and environmental perspective. Even when enough information on the substances that could be substituted is provided, additional information on technical requirements of the technologies sought/offered, on the hazardous properties of the substances that the technology replaces, and the legislation and the standards the technology complies with/should comply with, would maximise the probabilities of a match between the profile creator and its client and prospective clients and partners. Moreover, while the case for adopting less hazardous and environmentally friendlier technologies may be implied, profiles highlighting the economic advantages of doing so are likely to attract most interest.

On the basis of the results of the first three tasks, the project team developed guidelines for the EEN partners on how to better draft profiles for offers of and requests for alternative solutions to the use of hazardous chemicals. The guidelines recommend that profile titles be sufficiently meaningful to enable Network partners and their clients to easily decide whether a profile is of interest and should therefore include information on technical function(s) and end-use(s) of the technologies requested/on offer. Where relevant, a profile should include the name(s) of the substance(s) or group(s) of substances which the offered/sought technology aims to substitute. This information should be given in addition to the main type of partnership desired and the location of the client. The guidelines further recommend that profile summaries complement the information provided in the title by listing the key characteristics of the technology and its main economic, health and safety, and environmental advantages. Profile descriptions can then describe the problem that the technology aims to solve and the state-of-the-art technologies currently in use. This will allow the comparison of the different solutions and will further highlight the advantages of the technology sought/offered.

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The guidelines were tested and validated by EEN partners and their recommendations and suggestions have been taken into consideration for their further elaboration and improvement.

It is also suggested that beyond the better drafting of relevant profiles, some adjustment could be made to the POD in order to facilitate the matching of companies interested in substituting chemical substances of potential concern with companies offering safer alternatives. The project team recommends that the POD provide the possibility of selecting a new specific keyword “Substitution of hazardous chemicals” that would allow the users to refine their searches and would signal the potential of certain technologies to substitute chemicals of concern.

The project team concludes that the POD, by listing opportunities offered and sought by companies active in all sectors, can become conducive to supporting functional substitution or, in other words, the consideration of solutions that go beyond the chemical-to-chemical approach, and instead look at the use of the substance as a means of identifying, evaluating, and selecting safer alternatives for achieving a particular function, end use or service. To make the most of this potential, it is recommended that a closer collaboration between EEN and ECHA be promoted, as this is likely to create synergies and ultimately provide better support to SMEs, and businesses more generally, interested in substitution. Such collaboration may take the form of training offered by ECHA to EEN staff and EEN partners on substitution issues. EEN is also in a better position to provide technical support to companies in testing potential alternatives before scaling up the production and adoption of the technologies, as such support requires direct knowledge of the companies’ circumstances. The Network could also be used to disseminate best practices with examples of successful substitution initiatives, and information on substitution-specific funding.

Finally, the project team prepared some practical hints and tips for SMEs interested in engaging in a substitution process, focusing on the use of the POD and on the collaboration with EEN partners.

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Synthèse

Suite au engagement de la Commission européenne en matière du développement d’une économie circulaire et à l’intérêt croissant des intervenants de l’industrie concernant le remplacement de produits chimiques dangereux, l’Agence exécutive pour les petites et moyennes entreprises (EASME) a lancé la présente étude dans le cadre du Programme de travail COSME 2016. Il s’agit d’une parmi plusieurs initiatives visant à aider les entreprises à mettre en œuvre la politique relative aux produits chimiques et, plus précisément, elle vise à faciliter la communication entre les fournisseurs de solutions et les PME souhaitant remplacer les produits chimiques potentiellement préoccupants (ci-après dénommé remplacement). Les PME n’ont pas forcément les ressources suffisantes pour participer à des initiatives de remplacement et le rassemblement de ceux nécessitant et ceux offrant une solution de remplacement plus sûre est considéré comme l’une des mesures qui pourrait faciliter le remplacement le plus.

Cela pourrait être atteint en fournissant des orientations aux partenaires du réseau Entreprise Europe (Entreprise Europe Network – EEN), au personnel EEN et aux PME sur la façon de mieux utiliser la base de données de recherche de partenaires (Partnership Opportunities Database (POD)) aux fins de remplacement. La POD est une plateforme internet gérée par l’EEN qui vise à relier les PME pour faciliter les accords commerciaux, les transferts de technologie et les projets de recherche. Chaque demande et offre des entreprises (clients) soutenus par le Réseau sont décrits dans un profil qui varie selon le type de partenariat recherché/offert par les clients.

La première tâche de l’équipe du projet était d’identifier entre 10 et 15 produits chimiques potentiellement préoccupantes à utiliser comme études de cas pour l’analyse à effectuer dans le cadre des tâches subséquentes. Afin d’assurer la sélection d’une variété de produits chimiques utilisées dans différents secteurs et pour lesquelles le remplacement est motivé par des raisons variables, une liste de critères a été préparée et convenue avec le groupe de pilotage du projet. Une longue liste a été dressée pour inclure des produits chimiques :

• Couverts par différents textes législatifs ; • Avec différentes fonctions, utilisés dans différentes applications et secteurs ; • Pour lesquels le remplacement ou la considération de remplacement est motivé(e) par les coûts élevés liés à la gestion des risques tout au long de leurs cycles de vie ; • Pour lesquels des solutions de remplacement innovantes ont étés/sont en cours d’être développées qui pourraient ouvrir de nouvelles possibilités de marché ; • Qui pourraient être/ont été remplacés par des technologies de remplacement non chimiques ; • Qui peuvent être/ont été remplacés par le biais de mesures organisationnelles.

Cette longue liste a été réduite en consultant des bases de données, des experts et des PME. En fin de compte, 14 produits chimiques ont été sélectionnés pour un examen plus approfondi. Il s’agit notamment de :

1. Farine de silice 2. Trioxyde de chrome 3. Glutaraldéhyde 4. Méthanol 5. Bisphénol A 6. Hydrazine 7. N-méthyl-2-pyrrolidone 8. 4-Nonylphénol, ramifié et linéaire, éthoxylés 9. Toluène

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10. Formaldéhyde 11. Phtalate de di- « isononyle » 12. Agents ignifuges bromés par ex. 1,2-bis(pentabromophényl)éthane 13. Trichloroéthylène 14. Tétrachloroéthylène

La deuxième tâche consistait à identifier les fonctionnalités des produits chimiques sélectionnés et à évaluer la disponibilité et la faisabilité technique et économique des solutions de remplacement chimiques et non chimiques. Aux fins de cette étude, l’équipe de projet a adapté et simplifié l’analyse des solutions de remplacement (AoA) qui fait partie d’une demande d’autorisation en vertu de la réglementation REACH. En effet, l’objectif premier n’était pas l’élaboration d’analyses (AoA) détaillées mais plutôt l’apprentissage des leçons tirées de l’expérience et l’identification de bonnes pratiques à communiquer par le biais de lignes directrices destinées aux parties intéressées. Pour chacun des produits chimiques sélectionnés, au moins trois remplacements ont été identifiés et analysés. Les leçons tirées de l’expérience ont été résumées en 10 étapes simples fournissant des conseils sur la recherche et la collecte d’informations sur les identités, les propriétés, la faisabilité technique et économique et la disponibilité de solutions de remplacement potentielles.

La troisième tâche consistait à consulter la POD pour des profils relatifs au remplacement et à les passer en revue pour mettre en évidence les lacunes et identifier les bonnes pratiques. L’équipe du projet a effectué des recherches dans la POD en saisissant des mots pertinents, tels que « remplacement », « alternative », « non toxique », « écologique », ainsi que les noms de produits chimiques spécifiques, et en utilisant certains des mots-clés relatifs à la technologie ou au marché disponibles dans la POD afin de filtrer les profils par technologie et activité économique. Grâce à cette stratégie de recherche, l’équipe du projet a étudié environ 1 800 profils (environ 25% du nombre total des 7 700 profils figurant sur la POD en octobre 2017), dont 49 (environ 2,7%) ont été jugés pertinents comme une solution de remplacement.

Les profils identifiés varient en termes de qualité et de quantité des informations fournies, allant d’excellents profils avec une utilisation optimale des sections « titre », « résumé », « description » et « avantages et innovations » à des profils présentant des demandes ou offres trop génériques. En particulier, les profils qui ne décrivent pas les fonctions techniques ou les utilisations finales des technologies recherchées/offertes sont susceptibles de susciter moins d’intérêt chez les clients/partenaires potentiels. Les utilisateurs de la POD cherchant une technologie alternative (chimique ou non chimique) pour les produits chimiques potentiellement préoccupants peuvent rencontrer des difficultés à trouver les profils pertinents si ceux-ci n’incluent pas les produits chimiques que les technologies pourraient remplacer. De nombreux profils présentent des technologies de nature biologique ou des technologies issues de la chimie verte mais ne mentionnent pas les produits chimiques qui pourraient être remplacés ou ne décrivent pas ce qui rend la technologie offerte plus sûre du point de vue de la santé et de l’environnement. Même lorsque suffisamment d’informations sur les produits chimiques pouvant être remplacés sont fournies, des informations supplémentaires sur les exigences techniques des technologies recherchées/offertes, sur les propriétés dangereuses des produits chimiques que la technologie remplace, ainsi que la législation et les normes auxquelles la technologie se conforme/devrait se conformer maximiserait les probabilités de relier le créateur du profil à son client ainsi qu’à des clients et des partenaires potentiels. De plus, alors que les avantages d’adopter des technologies moins dangereuses et plus respectueuses de l’environnement peuvent être implicites, les profils mettant en valeur les avantages économiques sont susceptibles de susciter le plus d’intérêt.

Sur la base des résultats des trois premières tâches, l’équipe du projet a élaboré des lignes directrices pour les partenaires EEN sur la façon de mieux rédiger les profils d’offres et de demandes de solutions de remplacement pour les produits chimiques dangereux. Il est recommandé dans les lignes directrices Substitution of Chemical Substances of Potential Concern | xi que le titre du profil soit suffisamment significatif pour permettre aux partenaires du réseau et à leurs clients de décider facilement si un profil les intéresse et qu’il devrait ainsi inclure les informations sur la/les fonction(s) technique(s) et la/les utilisation(s) finale(s) des technologies demandées/proposées. Le cas échéant, un profil doit inclure le(s) nom(s) du/des produit(s) chimique(s) ou du/des groupe(s) de substances que la technologie offerte/recherchée vise à remplacer. Cette information devrait être donnée en plus du type principal de partenariat souhaité ainsi qu’en plus de l’emplacement du client. Il est également recommandé dans les lignes directrices que les résumés sur les profils complètent l’information fournie dans le titre en énumérant les principales caractéristiques de la technologie et ses avantages principaux en matière d’économie, de santé et de sécurité et d’environnement. Les descriptions de profil peuvent alors décrire le problème que la technologie vise à résoudre et les technologies de pointe parmi celles actuellement utilisées. Cela permettra de comparer les différentes solutions et mettra davantage en évidence les avantages de la technologie recherchée/offerte.

Les lignes directrices ont été testées et validées par les partenaires EEN. Leurs recommandations et suggestions ont été prises en considération pour être développées et améliorées.

Il est également suggéré qu’outre une meilleure rédaction des profils pertinents, certains ajustements pourraient être apportés à la POD afin de faciliter l’appariement des entreprises intéressées à remplacer les produits chimiques potentiellement préoccupants, avec des entreprises offrant des solutions de remplacement plus sûres. L’équipe du projet recommande que la POD offre la possibilité de sélectionner un nouveau mot-clé spécifique « remplacement de produits chimiques dangereux » qui permettrait aux utilisateurs d’affiner leurs recherches et signalerait la possibilité de certaines technologies de remplacer les produits chimiques préoccupants.

L’équipe du projet conclut que la POD, en énumérant les opportunités offertes et recherchées par les entreprises actives dans tous les secteurs, peut devenir propice à soutenir le remplacement selon la fonction ou, en d’autres termes, la prise en compte de solutions qui vont au-delà de l’approche produit par produit et considèrent plutôt l’utilisation d’un produit chimique comme un moyen d’identifier, évaluer et sélectionner des remplacements plus sûrs pour réaliser une fonction, utilisation finale ou service particulier(e). Pour en profiter au maximum, il est recommandé de promouvoir une collaboration plus étroite entre l’EEN and l’ECHA, car cela est susceptible de créer des synergies et, au final, de fournir un meilleur soutien aux PME, et plus généralement aux entreprises, souhaitant remplacer un produit chimique. L’EEN est également mieux à même de fournir un soutien technique aux entreprises pour tester les solutions de remplacement potentielles avant d’intensifier la production et l’adoption des technologies, car un tel soutien nécessite une connaissance directe de la situation des entreprises. Le réseau pourrait également être utilisé pour diffuser les meilleures pratiques et des exemples d’initiatives de remplacement réussies et des informations sur le financement lié à une solution de remplacement spécifique.

Enfin, l’équipe du projet a préparé des conseils et des astuces pratiques pour les PME souhaitant entamer un processus de remplacement, qui se concentrent sur l’utilisation de la POD et sur la collaboration avec les partenaires de l’EEN.

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1 Introduction

The aim of this study is to facilitate contacts between small and medium-sized enterprises (SMEs) interested in replacing substances of potential concern and solution providers, through the development of guidelines on how to better use the functionalities of the Partnership Opportunities Database (POD) for:

• SMEs; • Enterprise Europe Network (EEN) partners; and • The EEN staff responsible for maintaining the POD.

The specific objectives are to:

• Identify 10–15 relevant chemical substances of potential concern to be replaced; • Develop and apply a methodology that identifies the functionalities of those chemical substances; • Identify at least 2–3 alternative solutions for each of the chemical substances to be replaced; • Define ways to better address the challenge of substitution of chemical substances of potential concern for SMEs in the POD (internal processes, guidelines); • Receive feedback from SMEs and EEN partners on the feasibility and the potential impact of POD in the field of chemical substitution; • Draw general lessons on how to facilitate the substitution of chemical substances of potential concern for SMEs.

In order to achieve the specific objectives, Risk & Policy Analysts, in collaboration with Wirtschaftskammer Österreich (WKÖ - the Austrian Federal Chamber of Commerce), was asked to carry out the following tasks:

• Task 1 – Mapping: through the consultation of industry associations, ECHA, experts, SMEs and other stakeholders, and considering the different reasons and needs of substitution, select a short list of substances to be used as the basis for the subsequent tasks; • Task 2 – Profiling: describe the functionalities of the short-listed substances and identify two to three alternatives; • Task 3 – Design new POD profiles:

− Subtask 3.1: Identify and analyse relevant POD profiles and provide recommendations for improvement; − Subtask 3.2: Draft guidelines to be used by EEN partners on how to use the POD for the purpose of substituting chemical substances of concern; − Subtask 3.3: Draft a short document on the challenges of substitution and on how the Network can support SMEs; − Subtask 3.4: Assist EEN partners in drafting 20 POD profiles, according to the developed guidelines;

• Task 4 – Testing and Validation: With the help of 10 EEN partners, test and validate the guidelines and revise them according to the feedback; • Task 5 – Guidance for SMEs: Draft general guidelines on how SMEs can engage in substituting chemical substances of concern.

As the initial step (Task 1), we identified 14 chemical substances of potential concern for which there may be enterprises interested in their substitution, and companies and research institutes developing

Substitution of Chemical Substances of Potential Concern | 1 or offering alternative solutions (less hazardous chemicals and/or new technologies). The substances were selected according to a number of criteria aimed at ensuring the selection of substances with different functionalities and for which there may be different chemical and non-chemical alternatives.

Simplified analyses of alternatives (based on the AoA of the applications for authorisation within the REACH Regulation) were carried out to identify the functionalities of the substances of potential concern and some safer alternatives for each application of the substances (Task 2: Profiling). The results of these first two tasks were used to provide recommendations on how to better profile offers and requests of alternative solutions to substances of potential concern (Task 3).

In order to test and validate these documents (Task 4), 10 EEN partners were asked to complete two exercises by following the developed guidelines. The feedback received was used to improve the documents.

The remainder of this report is structured as follows:

• Section 2 presents the results of Task 1 (Mapping), namely the selection of some substances of concern to be used for carrying out the subsequent tasks; • Section 3 presents the methodology followed and the lessons learnt by carrying out the simplified AoAs of the selected substances (Task 2 - Profiling). Annex 1 provides the AoAs of the selected substances; • Section 4 presents the search strategy followed to identify POD profiles relevant to the substitution of chemical substances of potential concern and the review of the identified profiles; • Section 5 presents the guideline for EEN partners on how to use the POD for the purpose of chemical substitution (this guideline is also provided as a stand-alone document); • Section 6 presents the challenges to substitution; • Section 7 presents the guidelines for SMEs on how to engage in the substitution process; and • Section 8 provides the references of the studies consulted by the project team.

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2 Mapping

2.1 Introduction

The objective of this first task was to identify between 10 to 15 substances of potential concern to be used as the basis of the analysis to be carried out in Task 2 (Profiling). The selection had to take into account the different reasons and needs for substitution, such as regulatory compliance, reduction of investments and operational costs and the opening of new market opportunities.

On this basis, a list of criteria for the selection of the substances was prepared and agreed with the project steering group:

• Substances covered by different pieces of legislation; • Substances with different functions, used in different applications and sectors; • Substances which substitution or consideration of substitution is driven by the high costs associated with their management throughout their life cycles; • Substances for which innovative alternatives have been/are being developed that may open up new market opportunities; • Substances that can be/have been substituted through alternative non-chemical technologies; • Substances that can be/have been substituted through organisational measures.

These criteria informed the consultation of databases, experts and SMEs. The results are presented in the following sub-sections.

2.2 Long list of Substances

2.2.1 Consultation of databases

The project team consulted the following databases:

• The Public Activities Co-ordination Tool (PACT)1; • The Registry of Intentions (RoI)2; • The Candidate list of Substances of Very High Concern for Authorisation3; • The Authorisation list4; • The Community Rolling Action Plan5; • The List of Restrictions6; • Annex II to Directive 2011/65/EU (RoHS); • The EU Pesticides Database7; • The Biocidal Active Substances8;

1 https://echa.europa.eu/pact 2 https://echa.europa.eu/registry-of-intentions 3 https://echa.europa.eu/candidate-list-table 4 https://echa.europa.eu/authorisation-list 5 http://echa.europa.eu/information-on-chemicals/evaluation/community-rolling-action-plan/corap-table 6 https://echa.europa.eu/substances-restricted-under-reach 7 http://ec.europa.eu/food/plant/pesticides/eu-pesticides- database/public/?event=homepage&language=EN 8 https://echa.europa.eu/information-on-chemicals/biocidal-active-substances

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• The Stockholm Convention on Persistent Organic Pollutants9; • SIN list10; • The Danish List of Undesirable Substances (LOUS)11.

Information from the Registry of Intentions was not included as some of the substances on the list were only undergoing minor changes, for example gaining skin sensation classifications or in some cases having classifications removed. Also, particular substances that might be of concern were likely to be covered by other substance lists.

By aggregating the entries in these databases, a list of 3,474 substances was compiled. For substances listed in at least three databases (138 substances), a search for their use descriptors on the ECHA registered substances database was carried out and use descriptors were added to the list when available. According to the defined criteria, the project team selected 51 substances for further consideration. These are listed in Table 2-1.

In order to select substances for which innovative alternatives have been/are being developed that may open up new market opportunities, the webpage on the LIFE projects on chemicals has been consulted. 12 For the purposes of this project, among the most interesting projects are:

• LIFE-COMBASE, aiming to develop an information system combining evidence-based decision support systems and computational toxicology modelling approaches. The ultimate aim is to promote the sustainable use of biocidal active substances13; • LIFE BITMAPS, aiming to establish a pilot plant for the treatment of tetramethylammonium hydroxide14; • MIDWOR-LIFE, aiming to analyse the non-toxic alternatives to long-chain fluorocarbons used in the textile finishing industry15; • LIFE Fit for REACH, aiming to support SMEs in their efforts to substitute hazardous substances16.

As a result, the following substance has been added to the list for further consideration:

• Tetramethylammonium hydroxide (TMAH) (CAS number: 75-59-2; EC number: 200-882-9): substance with numerous and diverse industrial and research applications, used in particular in the production of electronic products.

9 http://chm.pops.int/TheConvention/ThePOPs/ListingofPOPs/tabid/2509/Default.aspx 10 http://chemsec.org/business-tool/sin-list/ 11 http://eng.mst.dk/chemicals/chemicals-in-products/assessment-of-chemicals/list-of-undesirable- substances/ 12 http://ec.europa.eu/environment/life/project/Projects/index.cfm?fuseaction=home.getProjects&themeID =27&projectList 13 http://www.life-combase.com/index.php/en/project 14 http://www.lifebitmaps.eu/index.html 15 http://www.midwor-life.eu/ 16 http://www.fitreach.eu/content/activities

Substitution of Chemical Substances of Potential Concern | 4

Table 2-1: Substances for further consideration from the consultation of databases Substance CAS number EC number Included in: Applications/functions Rationale of inclusion Bisphenol A; 4,4'- 80-05-7 201-245-8 PACT SVHC Binding agents, construction Under scrutiny for decades, targeted by different pieces of isopropylidenediphenol CoRAP materials, paint and varnish, legislation Restriction SIN process control agents, filling LOUS agents Formaldehyde 50-00-0 200-001-8 PACT CoRAP Adhesives and sealants, Wide use and consumers’ exposure Pesticide polymers, laboratory Biocide SIN chemicals and coating LOUS products Boric acid 10043-35-3 233-139-2 SVHC Insecticide, chemicals, mineral Biocide – Boric acid is also used widely Pesticide products, machinery and Biocide SIN vehicles, fabricated metal LOUS products and metals 1,2-dichloroethane 107-06-2 203-458-1 SVHC Pesticide, chemical Solvent – Useful to include a substance (with wide use in the Authorisation intermediate past) which is already regulated (Authorisation) and for which Pesticide SIN there may be a body of evidence on substitution 4-(1,1,3,3- 140-66-9 205-426-2 PACT SVHC Polymers, coating products Adhesives – Selected to ensure that the market for adhesives tetramethylbutyl) phenol SIN LOUS and adhesives and sealants and sealants is encompassed Anthracene oil 90640-80-5 292-602-7 SVHC Formulation of mixtures Electrode – This is subject to regulation (Authorisation) but Restriction and/or re-packaging may also be exempt for a number of electrode uses (based on Pesticide SIN ECHA Q&A 1195). It could be interesting to find out what substitution options have been considered by the supply chain Biphenyl 92-52-4 202-163-5 PACT CoRAP Heat transfer fluids, Quirk – This seems to have some non-mainstream applications Pesticide laboratory chemicals and which may be worth exploring LOUS washing and cleaning products Butylated hydroxyanisole 25013-16-5 246-563-8 PACT CoRAP Antioxidant and preservative To encompass food additives and packaging in the analysis (BHA) SIN LOUS in food, food packaging, animal feed, cosmetics, rubber, and petroleum products Diarsenic pentaoxide 1303-28-2 215-116-9 SVHC Wood preservation, glass and Arsenic compounds have been under regulatory pressure and Authorisation glass products, intermediate this has been selected as a representative compound Restriction SIN for other arsenic products

Substitution of Chemical Substances of Potential Concern | 5

Table 2-1: Substances for further consideration from the consultation of databases Substance CAS number EC number Included in: Applications/functions Rationale of inclusion

Methyl 4- 99-76-3 202-785-7 PACT CoRAP This substance is used in the To encompass pesticides, but it also finds uses in other areas hydroxybenzoate Pesticide following products: cosmetics which could be of interest (cosmetics) LOUS and personal care products, adhesives and sealants, biocides (e.g. disinfectants, pest control products) and perfumes and fragrances. This substance has an industrial use resulting in manufacture of another substance (use of intermediates) Methyl tertiary butyl ether 1634-04-4 216-653-1 PACT CoRAP Process control agents, raw To encompass fuel additives (MTBE) SIN LOUS materials and lubricants. This substance is used in the following products: fuels N,N-dimethylformamide 68-12-2 200-679-5 PACT SVHC Binding agents, paint and Solvent – This substance has been selected as a SIN LOUS varnish 'representative' of aprotic solvents which find wide use in pharmaceuticals and are also under (collective) regulatory pressure for their reprotoxic effect (endocrine disruption might also be a consideration) Propyl 4-hydroxybenzoate 94-13-3 202-307-7 PACT CoRAP Preservatives Propylparaben - Wide use in cosmetics and other products SIN LOUS and is a representative of the widely used paraben 'family' Toluene 108-88-3 203-625-9 PACT CoRAP Preservatives in cosmetics and It finds very wide use and is one of the most severely Restriction other. Solvent hazardous industrial chemicals LOUS Triclosan 3380-34-5 222-182-2 PACT CoRAP Antibacterial and antifungal Under scrutiny and scientific debate for a long time Biocide SIN agent Trixylyl phosphate 25155-23-1 246-677-8 PACT SVHC Lubricants and greases, Example of flame retardant substances CoRAP SIN hydraulic fluids, metal working fluids and polymers 1,3-propanesultone 1120-71-4 214-317-9 PACT SVHC Photo-chemicals and Batteries – Used as an additive in (lithium-ion) batteries SIN electrolytes for batteries,

Substitution of Chemical Substances of Potential Concern | 6

Table 2-1: Substances for further consideration from the consultation of databases Substance CAS number EC number Included in: Applications/functions Rationale of inclusion intermediates, scientific research and development, electrical, electronic and optical equipment and chemicals 1-Methyl-2-pyrrolidinone 872-50-4 212-828-1 SVHC SIN Process control agents, raw Solvent stripper – Used as a solvent in synthesis but also in LOUS materials, lubricants and paint strippers where it is supposed to be replacing catalysers dichloromethane. It is an aprotic solvent suffering the same pressures as DMF 2-(2H-benzotriazol-2-yl)-4- 36437-37-3 253-037-1 PACT SVHC pH regulators and water Example of UV stabilisers that find wide use (plastics, rubber, (tert-butyl)-6-(sec- SIN treatment products and coatings, etc.) butyl)phenol (UV-350) laboratory chemicals, formulation of mixtures and/or re-packaging, scientific research and development and agriculture, forestry and fishing, manufacture of: chemicals 2,4,6-Tribromophenol 118-79-6 204-278-6 PACT CoRAP Polymers and plastic products Brominated flame retardant (not one of the most well-known) SIN 2,4-Dinitrotoluene 121-14-2 204-450-0 SVHC Used to produce flexible Interesting uses in the manufacture of explosives, under Authorisation polyurethane foams, the intense regulatory pressure SIN explosives industry, plasticiser, deterrent coating, and burn rate modifier in propellants 2,6-Di-tert-butyl-p-cresol 128-37-0 204-881-4 PACT CoRAP Lubricants and greases, Example of lubricant additives SIN adhesives and sealants, coating products, inks and toners, polishes and waxes, leather treatment products and metal working fluids, printing and recorded media reproduction, formulation of

Substitution of Chemical Substances of Potential Concern | 7

Table 2-1: Substances for further consideration from the consultation of databases Substance CAS number EC number Included in: Applications/functions Rationale of inclusion mixtures and/or re-packaging, building and construction work and scientific research and development, textile, leather or fur, plastic products, furniture and rubber products 3-Benzylidene camphor 15087-24-8 239-139-9 PACT SIN UV filter UV stabiliser/filter that has been under scrutiny over its (3-BC); 1,7,7-trimethyl-3- LOUS potential endocrine disruption properties (phenylmethylene)bicyclo [2.2.1]heptan-2-one 4,4'-Methylenediphenyl 101-68-8 202-966-0 PACT CoRAP Adhesives and sealants, MDI is the least hazardous of the commonly available diisocyanate Restriction coating products and isocyanates but still hazardous and it is also subject to polymers, formulation of restrictions mixtures and/or re-packaging, manufacture of chemicals 4-Nonylphenol, branched 84852-15-3 284-325-5 PACT CoRAP Polymers, coating products Example of a PBT substance SIN and adhesives and sealants, plastic products and chemicals a-chlorotoluene/Benzyl 100-44-7 202-853-6 PACT SIN Impregnation products, Used in construction products chloride/α-chlorotoluene LOUS construction materials, paint and varnish, raw materials, laboratory chemicals, use as intermediate, scientific research and development Alkanes, C14-17, Chloro 85535-85-9 287-477-0 PACT CoRAP Polymers, coating products, RoHS - Used as a replacement of short-chain chloroalkanes. LOUS fillers, putties, plasters, Currently under scrutiny (RoHS) modelling clay, adhesives and sealants and metal working fluids, formulation of mixtures and/or re-packaging, mining and building and construction work. This substance is used for the manufacture of: plastic

Substitution of Chemical Substances of Potential Concern | 8

Table 2-1: Substances for further consideration from the consultation of databases Substance CAS number EC number Included in: Applications/functions Rationale of inclusion products, rubber products, textile, leather or fur, chemicals, fabricated metal products and furniture Benzophenone-3; 131-57-7 205-031-5 PACT CoRAP Cosmetics and personal care Potential endocrine disruptor used in cosmetics Oxybenzone SIN products, coating products, fillers, putties, plasters, modelling clay and finger paints, formulation of mixtures and/or re-packaging, manufacture of plastic products Beryllium 7440-41-7 231-150-7 PACT CoRAP Metals and pH regulators and To encompass electronics SIN water treatment products, used as intermediate, municipal supply (e.g. electricity, steam, gas, water) and sewage treatment, scientific research and development and offshore mining, metals, fabricated metal products, electrical, electronic and optical equipment and machinery and vehicles Bifenthrin 82657-04-3 Pesticide Pyrethroid insecticide Used in biocides and subject to debate among the scientific Biocide LOUS community Bis(2-methoxyethyl) ether 111-96-6 203-924-4 SVHC Polymers, laboratory Pharmaceuticals – Wide use. Applications for Authorisation Authorisation chemicals and have been submitted and there is work underway for its SIN pharmaceuticals, formulation substitution of mixtures and/or re- packaging, chemicals, plastic products and electrical,

Substitution of Chemical Substances of Potential Concern | 9

Table 2-1: Substances for further consideration from the consultation of databases Substance CAS number EC number Included in: Applications/functions Rationale of inclusion electronic and optical equipment Borax pentahydrate, 12179-04-3, 215-540-4 SVHC Biocide pH regulators and water Used in a great variety of uses disodium tetraborate 1303-96-4, SIN treatment products and metal pentahydrate/Disodium 1330-43-4 working fluids, intermediate, tetraborate formulation of mixtures pentahydrate/Disodium and/or re-packaging and tetraborate, anhydrous building and construction work, chemicals, mineral products (e.g. plasters, cement), machinery and vehicles, fabricated metal products and metals Cadmium oxide 1306-19-0 215-146-2 SVHC Metals, metal surface Representative of the cadmium compounds Restriction SIN treatment products and laboratory chemicals, intermediate, chemicals and electrical, electronic and optical equipment Carbon disulphide 75-15-0 200-843-6 CoRAP pH regulators and water Solvent – Building block in organic chemistry as well as an Pesticide SIN treatment products, polymers industrial and chemical non-polar solvent and laboratory chemicals, intermediate Chromium trioxide 1333-82-0 215-607-8 SVHC Adsorbents, pH regulators and Well-known problematic substance. Whilst it is subject to Authorisation water treatment products, REACH Authorisation, numerous applications for its continued SIN metal surface treatment use have been submitted products, non-metal-surface treatment products and laboratory chemicals Creosote oil, 90640-84-9 292-605-3 PACT Coating products and To encompass coatings acenaphthene fraction Restriction SIN adhesives and sealants. DBDPE; 1,1'-(ethane-1,2- 84852-53-9 284-366-9 PACT CoRAP Polymers, adhesives and This substance has been touted as a replacement for DecaBDE diyl)bis[pentabromobenze SIN sealants, coating products, (a flame retardant) but as it is under scrutiny, its use might ne] ultimately prove to be a case of regrettable substitution

Substitution of Chemical Substances of Potential Concern | 10

Table 2-1: Substances for further consideration from the consultation of databases Substance CAS number EC number Included in: Applications/functions Rationale of inclusion inks and toners and washing and cleaning products Deltamethrin 52918-63-5 258-256-6 Pesticide Insecticide To encompass insecticides Biocide LOUS Dichloromethane 75-09-2 200-838-9 PACT CoRAP Washing and cleaning Wide use as solvent, but classified as carcinogenic and subject Restriction products, coating products, to restrictions adhesives and sealants and extraction agents Methanol 67-56-1 200-659-6 PACT CoRAP Fuel, fuel additives, solvents Example of a fuel additive and as a substance used in cleaning LOUS and thinners, washing & products cleaning products Methoxychlor 72-43-5 200-779-9 PACT Pesticide Insecticide Example of an insecticide LOUS m-tolylidene diisocyanate 26471-62-5 247-722-4 PACT CoRAP Biocides, binding agents, Example of substances used in biocidal formulations LOUS impregnation products, paint and varnish, rust inhibitors, printing inks Nonylphenol 25154-52-3 246-672-0 Restriction SIN Antioxidants, lubricating oil Subject to scrutiny and debate for several decades LOUS additives, laundry and dish detergents, emulsifiers and solubilisers Octamethylcyclotetrasilox 556-67-2 209-136-7 PACT SIN Washing and cleaning Belongs to the siloxanes chemical group ane LOUS products, polishes and waxes, cosmetics and personal care products, semiconductors, non-metal-surface treatment products, lubricants and greases, textile treatment products and dyes, leather treatment products and laboratory chemicals Pentazinc chromate 49663-84-5 256-418-0 SVHC Coating products and Interesting uses in aerospace coatings octahydroxide Authorisation adhesives and sealants SIN

Substitution of Chemical Substances of Potential Concern | 11

Table 2-1: Substances for further consideration from the consultation of databases Substance CAS number EC number Included in: Applications/functions Rationale of inclusion Phenol 108-95-2 203-632-7 PACT CoRAP Biocides, paint and varnish, Very wide use LOUS laboratory chemicals, coating products, adhesives and sealants, polymers, and semiconductors Potassium dichromate 7778-50-9 231-906-6 SVHC Metal surface treatment Water treatment – uses in laboratories and research and Authorisation products, laboratory development activities and these may not be caught by the SIN chemicals, pH regulators and Authorisation process water treatment products, metals, non-metal-surface treatment products and pharmaceuticals Sodium dichromate 10588-01-9 234-190-3 SVHC Metal surface treatment Wide use. Whilst it is subject to REACH Authorisation, several Authorisation products, laboratory applications have been submitted SIN chemicals, leather treatment products, non-metal-surface treatment products and textile treatment products and dyes Strontium chromate 02/06/7789 232-142-6 SVHC Coating products and Interesting uses in the aerospace industry Authorisation adhesives and sealants SIN Styrene 100-42-5 202-851-5 PACT SIN Solvent in many products Solvent – Wide use without being the object of strong LOUS including paint, varnish, regulatory pressures cooling agents and lubricants, polymers, coating products and fillers Trichloroethylene 79-01-6 201-167-4 SVHC Manufacture of chemicals, Example of substances used in cleaning activities. Subject to Authorisation cleaning agent the REACH Authorisation, industry is under pressure to SIN substitute

Substitution of Chemical Substances of Potential Concern | 12

2.3 Consultation of Experts

A short questionnaire was developed and submitted to sixteen experts from the Commission services, European agencies, research institutes, trade unions, national authorities, industry associations and non-governmental organisations. The experts provided recommendations and suggestions on the substances to be included in the short-list for further consideration. All recommendations were in consideration of the selection criteria and were put forward for the purpose of this study only; they are not part of any regulatory prioritisation strategy.

Chromium VI compounds and formaldehyde were suggested by different experts. Both substances raised concern due to large workers’ exposure and both seem to satisfy all the selection criteria, namely:

• They are regulated by different pieces of legislation (chromium VI compounds by the Carcinogen and Mutagen Directive (CMD), REACH, RoHS, Biocidal Product Regulation (BPR), Toys Safety Directive; Formaldehyde by CMD, REACH, BPR, Cosmetic Products Regulation (CPR); • Their risk management entails significant costs for businesses; • They have applications for which alternatives have been developed: Iron (II) sulphate is a good alternative to chromium VI textile dye mordants; the use of paraformaldehyde (a polymerised form of formaldehyde) as dry sanitiser for instruments storage can be replaced by process change, storing the instruments in a disinfected, dry, covered container; • They have different functions, are used in different applications and sectors, namely: Chromium VI compounds are used as anti-corrosion agents, mordants, pigments, biocides in applications such as coatings, inks, wood-preservatives, in the manufacturing of chemicals and machinery sectors, in construction and textile and can be present as contamination in chromium III salts and form by oxidation of chromium III salts used as tanning agents in leather manufacturing; formaldehyde is used as an intermediate in plastics and for its bactericide properties as a binding material, disinfectant, preservative and embalming solution, in the manufacturing of chemicals sector, in wood-panels and in cosmetics.

Other substances that were suggested for further consideration are:

a. Substances covered by different pieces of legislation:

• Di-''isononyl'' phthalate (DINP) (CAS numbers 28553-12-0 and 68515-48-0), certain restrictions apply under ANNEX XVII to REACH related to toys and childcare articles which can be placed in the mouth by children. Ongoing proposed harmonised classifications and labelling as Reprotoxic 1B; • Di-‘isodecyl’ phthalate (DIDP) (CAS numbers 26761-40-0 and 68515-49-1), certain restrictions apply under ANNEX XVII to REACH related to toys and childcare articles which can be placed in the mouth by children; • Bis(2-propylheptyl) phthalate (DPHP) (CAS number 53306-54-0), listed under REACH, CoRAP, as potential endocrine disruptor, for exposure of sensitive populations, high (aggregated) tonnage, Wide dispersive use; • 1,2-Benzenedicarboxylic acid, di-C10-12-branched alkyl esters (DIUP) (CAS number 700-989-5), listed under REACH CoRAP for suspected CMR properties, high (aggregated) tonnage, other exposure/risk-based concern; • Diundecyl phthalate, branched and linear (CAS number 85507-79-5), listed under CoRAP as suspected CMR, high (aggregated) tonnage, other exposure/risk-based concern;

Substitution of Chemical Substances of Potential Concern | 13

• 1,2-Benzenedicarboxylic acid, di-C11-14-branched alkyl esters, C13-rich (DTDP) (CAS number 68515-47-9), listed under CoRAP for suspected CMR, high (aggregated) tonnage, other exposure/risk-based concern.

b. Substances which have different functions, are used in different applications and sectors:

• 4,4'-Isopropylidenediphenol (Bisphenol A; BPA) and 4,4'-sulphonyldiphenol (Bisphenol S; BPS), (CAS numbers: 80-05-7 and 80-09-1), starting material for epoxy resins e.g. in cans and food cans, water pipes packaging and food packaging industry, water pipes; ink developer for thermal papers receipts, labels, tickets, etc. in the printing industry; starting material for certain plastics, polycarbonate-based materials, e.g.: beverage bottles, construction materials, electric components, etc. Several sectors: e.g. food packaging industry, construction sector, electronics, automotive; several other functions possible; several other applications possible; several other sectors concerned; • Perfluorooctanoic acid (PFOA, CAS 335-67-1, EC 206-397-9) , its salts and related substances, perfluorononan-1-oic acid (PFNA, CAS 375-95-1); nonadecafluorodecanoic acid (PFDA, CAS 335-76-2); henicosafluoroundecanoic acid (PFUnDA, CAS 2058-94-8); tricosafluorododecanoic acid (PFDoDA, CAS 307-55-1); pentacosafluorotridecanoic acid (PFTrDA, CAS 72629-94-8); heptacosafluorotetradecanoic acid (PFTDA, CAS: 376-06-7); including their salts and precursors, C6-based fluorochemicals (various CAS numbers), several functions, applications and sectors covered, depending on the substance, among which: production of fluoropolymer (e.g. PTFE) and fluoroelastomers, surfactants in the semiconductor industry, fire-fighting foams, wetting agents, cleaners; side-chain fluorinated polymers are used to provide a water, grease and soil protection, e.g. in textiles and leather, paper and cardboard, paints and lacquers, e.g. exterior and interior architectural paints and other uses • Brominated flame retardants e.g. ethane-1,2-bis(pentabromophenyl) (EBP) (CAS number 84852-53-9), flame retardant in plastic, textiles, several sectors concerned. c. Substances for which substitution or consideration of substitution is driven by the high costs associated with their management, throughout their life cycles:

The use of the two chlorinated solvents below can, in certain instances, lead to significant management costs (e.g. due to closed systems or other risk management measures, on-site recycling facilities, hazardous waste disposal):

• 1,2-dichloroethane (EDC) (CAS number 107-06-2) • Trichloroethylene (CAS number 79-01-6) and tetrachloroethylene/perchloroethylene (CAS number 127-18-4). d. Substances for which innovative alternatives have been/are being developed that may open up new market opportunities (e.g. bio-based substances):

Several alternatives to the use of substances listed in the other categories can potentially open up new market opportunities:

• For phthalates in plastics, there are various bio-based substances for certain applications; • For nonylphenol ethoxylates and 4-tert-octylphenol ethoxylates, there are various bio-based substances for certain applications;

Substitution of Chemical Substances of Potential Concern | 14

• Chromium trioxide (CAS number 1333-82-0), for certain applications: trivalent chrome technology, Physical Vapour Deposition (PVD)-based process, chemical vapour deposition, etc.

e. Substances that can be/have been substituted through alternative non-chemical technologies:

• BPA in thermal paper (CAS number 80-05-7), for certain applications: electronic receipts; • Flame retardants, various for certain applications: non-combustible end- products (e.g. mineral wools replacing flame-retarded EPS); • Lead chromate sulfochromate yellow (C.I. Pigment Yellow 34) and lead chromate molybdate sulfate red (C.I. Pigment Red 104) used in paints and road marking (CAS numbers 1344-37-2 and 12656-85-8), for certain applications: reflective materials such as reflective marking tapes or films.

Some experts suggested selecting chemical groups rather than specific substances, as this would help avoid regrettable substitutions (the situation in which a hazardous chemical is substituted with another chemical with the same or more severe hazardous profile).

Two reports published by the Swedish Chemicals Agency on the presence and risk of CMR in textiles and construction products were suggested for consultation purposes. KemI (2014) presents some examples of functional substances used in the production of textiles:

• Dyestuffs and pigments • Crease resistant agents • Anti-shrinking agents • Oil, soil and water repellents • Plasticisers • Flame retardants • Biocides for defined functionalities in articles, e.g. antibacterial agents • Stabilisers • Stiffening agents • Reactive resins for various finishing treatments • Organic solvents • Surfactants • Softeners • Salts • Acids and bases • Biocides as preservatives in the process or during storage and transport.

Moreover, contaminants and degradation products are recurrently found:

• Formaldehyde released from certain reactive resins • Polyaromatic hydrocarbon (PAH) impurities in pyrolysed products e.g. Carbon Black • Arylamines derived from certain azo dyestuffs and pigments • Toxic metals (e.g. heavy metals) due to impurities from the raw material.

Annex 7 of KemI (2014) presents a long list of hazardous substances identified in the screening project.

KemI (2016) lists the occurrence of hazardous substances by construction article. Some examples are:

Substitution of Chemical Substances of Potential Concern | 15

• 2,3-Epoxypropyl o-tolyl ether • Bisphenol A • Chlorinated paraffins • DINP • Formaldehyde • Tetrachloroethene • Tetrahydrofuran • Trisodium nitrilotriacetate • Tetrabromobisphenol A • Hexabromocyclododecane • N-Methyl-2-pyrrolidone • Toluene • Styrene • n-Hexane • Vinyl acetate • Phenol • N-Ethyl-2-pyrrolidone • Acrylonitrile • Octamethylcyclotetrasiloxane

Other specific substances that have been suggested are:

• Trichloroethylene (CAS number 79-01-6) • DEHP (CAS number 117-81-7) • Benzene (CAS number 71-43-2) • MOCA (CAS number 101-14-4) • Cadmium (CAS number 7440-43-9) • Arsenic (V) and (III) compounds. 2.4 Consultation of SMEs

During May 2017, we consulted (through an online survey) SMEs that had implemented or had considered the substitution of hazardous chemicals in their processes or products. Fourteen companies from Austria, France, Germany and Italy participated in the survey, suggesting substances and providing information on technical functionalities and potential alternatives. The responses are presented in Table 2-2.

Substitution of Chemical Substances of Potential Concern | 16

Chemical Product Technical Regulatory Economic New market Pressure Negative Alternative Non-chemical category function compliance* cost* opportunities* from impact alternative within on the company supply image* chain* ------PC14 Products for Electrolyte for 5 3 4 2 1 Phosphoric acid the treatment of electro-polishing Chromic acid-free metal surfaces aluminium electrolyte (POLIGRAT E284) for the electro- plating of aluminium PC8 Biocidal Biocide Bronopol products PC41 Products for Antifreeze 2-propyn-1-ol, the exploration or compound with production of methyloxirane petroleum and natural gas PC8 Biocidal Biocide Bronopol products

PC9a Coatings and Elastifiers 5 1 2 No substitute is paints, thinner, described colour remover PC35 Washing and Cleaning supplies 1 Disodium cleaning products carbonate, compound with hydrogen peroxide (2:3) PC3 Air treatment Absorbent 1 2 Sodium bisulfite products PC15 Products for Surface modifier 1 Tetrachlorethylene the treatment of non-metal surfaces PC9a Coatings and PH-regulating 1 5 3 2 n-Butyl- Table 2-2: Substances suggested by SMEs Substance Sector of use Chemical Product Technical Regulatory Economic New market Pressure Negative Alternative Non-chemical category function compliance* cost* opportunities* from impact alternative within on the company supply image* chain* precipitants, product for neutralizing agents hydrazines Anthraquinones SU6b Manufacture of pulp, PC20 Processing Catalyst 4 5 3 1 2 Adjust the paper and paper products aids such as pH fuel cell regulators, process flocculants, precipitants, clear yield neutralizing agents Tetrahydrofuran SU9 Manufacture of fine PC28 Perfumes, Solvent 5 Ethyl acetate or chemicals PC29 methyl tert-butyl Pharmaceuticals ether NMP (N-Methyl-2- SU9 Manufacture of fine PC28 Perfumes, Solvent 5 3 Alternative is still pyrrolidone) chemicals PC29 being sought Pharmaceuticals Dichloromethane SU9 Manufacture of fine PC28 Perfumes, Solvent 1 3 Ethyl acetate or chemicals PC29 methyl tert-butyl Pharmaceuticals ether 4-Nonylphenol, SU8 Manufacture of bulk PC9a Coatings and Surfactant 1 3 4 5 2 Can be branched and linear, chemicals (including petroleum paints, thinner, replaced by ethoxylated products) colour remover other wetting agents Toluene SU17 General manufacture, PC9a Coatings and Cleaning supplies, 24 5 31 e.g. machines, equipment, paints, thinner, Diluents, solvents vehicles, other transport colour remover, equipment, SU6a, SU8, SU12, PC1, PC4, PC13, SU15, SU18 PC21, PC35 n-Methyl-2-pyrrolidone SU17 General manufacture, PC9a Coatings and Cleaning supplies, 24 5 31 e.g. machines, equipment, paints, thinner, paint stripper vehicles, other transport colour remover, equipment, SU6a, SU8, SU12, PC1, PC4, PC13, SU15, SU18 PC21, PC35 4,4'- SU17 General manufacture, PC9a Coatings and Alloying element 2 4 5 3 1 Isopropylidenediphenol; e.g. machines, equipment, paints, thinner, Substance present in vehicles, other transport colour remover, various products equipment, SU6a, SU8, SU12, PC1, PC4, PC13, SU15, SU18 PC21, PC35

Substitution of Chemical Substances of Potential Concern | 18

Table 2-2: Substances suggested by SMEs Substance Sector of use Chemical Product Technical Regulatory Economic New market Pressure Negative Alternative Non-chemical category function compliance* cost* opportunities* from impact alternative within on the company supply image* chain* Bisphenol A SU12 Manufacture of plastic PC1 Adhesives, Resins 31 Epichlorohydrin resin products, including sealants (prepolymers) mol > 700 compounding and conversion Fatty acids, C18 SU12 Manufacture of plastic PC1 Adhesives, Hardener unsaturated products, including sealants compounding and conversion 2-Methoxy-1- SU0 Other PC9a Coatings and Coating agents methylethylacetate paints, thinner, colour remover N-Methyl-2-pyrrolidone SU12 Manufacture of plastic PC9a Coatings and Solvent, 1 4 5 2 3 Dipropylene glycol materials, including mixing and paints, thinners, plasticiser monomethylether. converting paint removers Good alternative as co-solvent for polyurethanes, poor plasticising properties Toluene SU9 Manufacture of fine PC9a Coatings and Solvent 1 5 4 2 3 Xylene (Reactive chemical products paints, thinners, mixture of paint removers ethylbenzene, m- xylene and p- xylene) No such replacement can be made Formaldehyde SU12 Manufacture of plastic PC9a Coatings and Plasticiser 1 5 4 2 3 2- materials, including mixing and paints, thinners, cloroacetammide converting paint removers Chromium VI SU15 Manufacture of metal PC14 Products for Other products, except machinery the treatment of and equipment metal surfaces Chlorine PC0 Other Other Cyanide *In order of importance from 1 to 5

Substitution of Chemical Substances of Potential Concern | 19

2.5 Proposed Substances for Further Consideration

2.5.1 Selection of 10–15 substances

The long list of substances identified through the consultation of experts and SMEs was analysed and 14 substances were proposed and finally agreed with the project steering group. The final selection tried to strike a balance between the recurrent recommendations by different experts and SMEs and the defined criteria, aiming to ensure the selection of substances with different functionalities and different chemical and non-chemical alternatives. The substances are:

1. Silica flour 2. Chromium trioxide 3. Glutaraldehyde 4. Methanol 5. Bisphenol A 6. Hydrazine 7. NMP (N-Methyl-2-pyrrolidone) 8. 4-Nonylphenol, branched and linear, ethoxylated 9. Toluene 10. Formaldehyde 11. Di-''isononyl'' phthalate 12. Brominated flame retardants e.g. ethane-1,2-bis(pentabromophenyl) 13. Trichloroethylene 14. Tetrachloroethylene

Substitution of Chemical Substances of Potential Concern | 20 3 Profiling

3.1 Introduction

The second task of the project consisted of identifying the functionalities of the selected substances and assessing the availability and technical and economic feasibility of chemical and non-chemical alternatives. The purpose of this exercise was to inform the review of relevant POD profiles and the development of guidelines for the use of the POD for chemical substitution purposes by EEN partners, the EEN staff and SMEs (Task 3 and 5).

3.2 Methodology

In order to identify and assess the technical and economic feasibility of potential alternatives, it is important to have a clear understanding of the functions and uses of the substances to be substituted. This is standard practice and the starting point for the AoA that is an integral part of an AfA under the REACH Regulation. An AoA entails extensive work that is usually prepared over several months. For the purpose of this study, we applied a simplified approach, as the primary objective was not the AoAs themselves but rather the learning of some lessons and good practices to be communicated through guidelines for the interested parties. We focused on four aspects:

• The identities of potential alternatives • Their physicochemical properties and hazard and risk profiles • The technical and economic feasibility • Their availability.

For each selected substance, we identified and analysed two to three alternatives. The results of the simplified analyses of alternatives are presented in Annex 1 of this study. The lessons learnt were summarised in 10 steps and are presented in the following section.

3.3 Lessons Learnt

3.3.1 Finding the identities of potential alternatives

Step 1. Check ECHA website to establish regulatory pressures and actions taken so far on the substance to be substituted. If under Authorisation (starting from the stage of nomination to the Candidate List, all the way to AfA being submitted), RMOA analysis or restriction, analyses of alternatives may be available (including in comments made by stakeholders during public consultation exercises).

Step 2. If the substance to be substituted has not been assessed in the past, more general literature searches are required. Potential information sources are:

• Known substitution portals (e.g. http://www.subsport.eu/substitution-steps) • General Internet searches

Step 3. Use ECHA’s registration database to establish physicochemical properties of the substance. If not registered, a range of online databases may be used:

• https://www.echemportal.org/echemportal/index.action

Substitution of Chemical Substances of Potential Concern | 21 • http://www.chemspider.com • https://pubchem.ncbi.nlm.nih.gov/

Step 4. Use ECHA’s Classification and Labelling Inventory to check the hazard classification for the substance.

Step 5. Check registration dossiers to determine the sectors of use and product categories that the substance is used in. Registration dossiers also provide exposure scenarios.

3.3.2 Collecting information on the properties of potential alternatives

Step 6. Use approach above to establish physicochemical properties of the identified alternatives (NB. it is useful to establish what key parameters are important for the selection of technically feasible alternatives).

Step 7. Use ECHA’s Classification and labelling Inventory to check the hazard classification for each alternative (harmonised and notified) (this should ideally be lower than the substance under substitution).

3.3.3 Collecting information on technical and economic feasibility

Step 8. For gathering information on the technical feasibility of the alternatives, check the alternative’s registration dossier to confirm whether the use of interest is identified as relevant. Also, if the substance to be substituted is subject to regulatory action, documents available on the ECHA site could provide information on the applicability and feasibility of alternatives. If such information is not available:

• Use substitution portals (see above) where case studies may be available; • Visit websites of relevant trade associations and key players in the market; • Undertake more general research (Google searches, patents, Google books, industry technical publications, etc.).

Step 9. For collecting information on the economic feasibility, check whether the substance to be substituted is subject to regulatory action. Documents available on the ECHA site could provide information on the cost (loadings, price per tonne, etc.) of alternatives. If such information is not available:

• Chemical supplier marketplaces (Alibaba.com) could be used (with due consideration to the volumes required and the qualities needed (e.g. pharmaceutical or food grade) • Prices of minerals can be found from the US Geological Survey (for the USA but useful for an indication of the order of magnitude) • Prices of bulk commodities are often available from places such as ICIS, Tecnon Orbichem, etc. (although most of such sources require payment for access to the latest data) • General searches with Google, using appropriate key words, can also be considered

3.3.4 Collecting information on availability

Step 10. The key source of data is ECHA’s registration database – but note that some natural products do not need to be registered. The research undertaken earlier on technical feasibility may also provide

Substitution of Chemical Substances of Potential Concern | 22 information on the quality of alternatives required and how this may affect availability. Where large amounts of information are available (e.g. the substance of concern is regulated) there may also be information on how quickly transition to an alternative can be achieved within documents on the ECHA website.

Substitution of Chemical Substances of Potential Concern | 23 4 Identification and Analysis of Relevant POD Profiles

4.1 Introduction

In order to develop guidelines on how best to use the POD for substitution purposes, as well as carrying out simplified AoAs to identify the key steps for defining the functionalities and uses of the substances to be substituted and their alternatives, we searched through the POD for relevant profiles, either presenting requests for, or offers of, alternative technologies to substances of potential concern. The identified profiles were then analysed in terms of the information provided and of the way information is organised within the profiles.

4.2 The POD Profiles

Table 4-1 presents the number of POD profiles by type17 as of 26 October 2017.

Table 4-1: POD profile type – Statistics (accessed on 26/10/2017) Number Profile type of % of total records Business Offer 5,146 67% Business Request 685 9% Research and Development Request 15 0.2% Technology Offer 1,590 21% Technology Request 249 3% Total records 7,685 100%

A Business Offer should be submitted when the client company18 wants to offer their products or services on external markets. A Business Request should be submitted when the client company is requesting the services/products of another company, is looking for products to complement its existing product range, or is looking for new projects to invest in. A Technology Offer is a description of a specific innovative technology, process, or specific know-how that the client is willing to make available to a prospective partner. A Technology Request is a description of a technology, process or specific know-how that is required by the client and that they are willing to source from a prospective partner. A Research and Development Request should be submitted when a client company wishes to find a partner to join a consortium for a research project under a specific call, funded by the European Union, or wishes to find a partner for a specific bilateral call (non-EU-funded), where at least one of the partners is based in an EU member state or in a COSME-signed country.19

Profiles are created by EEN partners based on the co-operation needs of the clients, which have been established through a business or technology review (possibly face-to-face). Once the profile creators finalise the draft profiles, these are submitted for internal review to other Network staff members. Internal reviewers check whether the profiles are in line with the profile drafting guidelines and their spelling and grammar. Profiles are revised accordingly and, once approved by internal reviewers, they

17 http://een.ec.europa.eu/tools/services/SearchCenter/Search/ProfileSimpleSearch 18 The end user. The business who are looking for or offering partnering opportunities. 19 EEN (2016): Profile Drafting guidelines v4.1. Available at: http://ictt.by/Docs/news/2017/02/2017-02- 27_01/EEN_Profile_Drafting_Guidelines__v4.1__EN.pdf

Substitution of Chemical Substances of Potential Concern | 24 are passed to a pool of external reviewers. These reviewers score the profiles from 0 to 5 on four criteria:

1. Clarity, coherence and understanding; 2. Advantages and innovation/expertise sought; 3. Guidelines and linguistic accuracy; and 4. Co-operation expectations.

On the basis of the final score, profiles are categorised as excellent (total score between 17 to 20), good (score of 14 to 16), sufficient (score of 10 to 13), rather poor (score between 5 to 9) and insufficient (0 to 4). Profiles with a total score of less than 10 are put on hold and sent back to the profile creators for redraft. External reviewers can also give a 0 (blocking score) for one of the criteria, signalling that the profiles may be of sufficient quality overall but are compromised by a certain issue (e.g. naming a brand or providing a patent number).

With regard to the database, a client user guide (named “Merlin”) can be downloaded20 from the POD portal, providing instructions to registered and unregistered users on how to use the database features. The guide is organised in four sections:

• Subscribing to the network; • Searching for profiles; • Managing expressions of interest; and • Searching for events.

There are two ways to search for profiles in the database:

• By using the Profile Search functionality; and • By creating a query.

Through the Profile Search functionality, a generic word search can be performed. Moreover, it is possible to narrow the search by profile type, profile country of origin and client requested (Figure 4-1).

By creating a query instead (once registered onto the EEN), it is possible to use market and technology keywords to search for business opportunities.

Each profile is composed of five broad areas:

• Profile details

− Title − POD reference − Summary − Description − Advantages and innovations − Technical specification or expertise sought − Stage of development − IPR status − Profile origin.

20 http://een.ec.europa.eu/tools/services/Help/OnlineHelp/Merlin_Client_UserGuide.pdf

Substitution of Chemical Substances of Potential Concern | 25 • Keywords

− Technology keywords − Market keywords − NACE keywords.

• Partner sought

− Type and role of partner sought − Type and size of partner sought − Type of partnership considered.

• Client

− Type and size of client − Year established − Already engaged in trans-national cooperation − Additional comments − Certification standards − Languages spoken − Client country.

• Dissemination

− Sector group − Restrict dissemination to specific countries.

Apart from the profile details, keywords play an important role in providing additional information about the business opportunity and in enhancing the search experience when using the database. There are three types of keywords: market, technology and NACE.

Market keywords are structured across nine main sectors (Level 1), 68 sub-sectors (Level 2) and 271 specific branches (Level 3). The nine main sectors are:

Figure 4-1: POD dashboard

Substitution of Chemical Substances of Potential Concern | 26 • 001 - Communications • 002 - Computer related • 003 - Other electronics related • 004 - Genetic engineering/molecular biology • 005 - Medical/health related • 006 - Energy • 007 - Consumer related • 008 - Industrial products • 009 - Other

Subsectors and specific branches are listed in Appendix A of the Merlin guide. Amongst the most relevant to this study is sub-sector “Chemicals and Materials (008001)”, subdivided into 23 specific branches:

• Plastic fabricators (008001001) • Homogeneous injections/extrusions (008001002) • Non-homogeneous injections/extrusions (008001003) • Fibre-reinforced (plastic) composites (008001004) • Other fabricated plastics (008001005) • Processes for working with plastics (008001006) • Coatings and adhesives manufactures (008001007) • Membranes and membrane-based products (008001008) • Speciality/performance materials: producers and fabricators (008001009) • Semiconductor materials (e.g. silicon wafers) (008001010) • III/V semiconductor materials (e.g. gallium arsenide) (008001011) • Speciality metals (including processes for working with metals) (008001012) • Ceramics (008001013) • Lubricants and functional fluids (008001014) • Other speciality materials (008001015) • Commodity chemicals and polymers (008001016) • Industrial chemicals (008001017) • Polymer (plastics) materials (008001018) • Speciality/performance chemicals (008001019) • Electronic chemicals (008001020) • Other speciality chemicals (008001021) • Agricultural chemicals (008001022) • Other chemicals and materials (not elsewhere classified) (008001023)

Technology keywords are divided into 11 main sectors (Level 1), 61 sub-sectors (Level 2) and 328 specific branches (Level 3). The eleven main sectors are:

• 001 - Electronics, IT and Telecoms • 002 - Industrial manufacturing, material and transport technologies • 003 - Other industrial technologies • 004 - Energy • 005 - Physical and exact sciences • 006 - Biological sciences • 007 - Agriculture and marine Resources • 008 - Agrofood industry • 009 - Measurements and standards • 010 - Protecting man and the environment

Substitution of Chemical Substances of Potential Concern | 27 • 011 - Social and economic concerns

Sub-sectors and specific branches are listed in Appendix B of the guide. Amongst the most relevant to this study are sub-sectors “Industrial Manufacture (002002)” and “Material Technology (002007)” in sector “002 - Industrial manufacturing, material and transport technologies”. These are subdivided into the following specific branches:

• Industrial Manufacture (002002):

− Cleaning (sandblasting, brushing) (002002001) − Coatings (002002002) − Drying (002002003) − Erosion, removal (spark erosion, flame cutting, laser/plasma cutting, electrochemical erosion, waterjet cutting) (002002004) − Forming (rolling, forging, pressing, drawing) (002002005) − Hardening, heat treatment (002002006) − Joining techniques (riveting, screw driving, gluing) (002002007) − Jointing (soldering, welding, sticking) (002002008) − Machine tools (002002009) − Machining (turning, drilling, moulding, milling, planning, cutting) (002002010) − Machining, fine (grinding, lapping) (002002011) − Mixing (powder, etc.), separation (sorting, filtering) (002002012) − Surface treatment (painting, galvanising, polishing, CVD, PVD) (002002014) − Extrusion (002002015) − Microassembly, nanoassembly (002002016) − Microengineering and nanoengineering (002002017) − Micropositioning, nanopositioning (002002018) − Micromachining, nanomachining (002002019) − Moulding, injection moulding, sintering (002002020)

• Materials Technology (002007):

− Adhesives (002007001) − Building materials (002007002) − Ceramic materials and powders (002007003) − Colours and varnishes (002007004) − Composite materials (002007005) − Fine chemicals, dyes and inks (002007006) − Glass (002007007) − Iron and steel, steelworks (002007008) − Materials handling technology (solids, fluids, gases) (002007009) − Metals and alloys (002007010) − Non-ferrous metals (002007011) − Optical materials (002007012) − Plastics, polymers (002007014) − Properties of materials, corrosion/degradation (002007015) − Rubber (002007016) − Stone (002007017) − Advanced textile materials (002007018) − Paper technology (002007024)

Substitution of Chemical Substances of Potential Concern | 28 − Carbon nanotubes (002007025) − Hybrid materials (002007026) − Biobased materials (002007027) − Nanomaterials (002007028) − Conductive materials (002007029) − Lightweight materials (002007030)

Other relevant specific branches within the same sub-sector are “Fire resistance/safety (002006004)” and “Materials, components and systems for construction (002006016)” in the subsector “Construction technology (002006)”.

Another relevant technology sector is “003 – Other industrial technologies”, in particular sub-sector “Chemical technology and engineering (003004)”. This is subdivided in the following specific branches:

• Agrochemicals (003004001) • Inorganic substances (003004002) • Colours, dyes related to chemical technology and engineering (003004003) • Electrical engineering and technology/electrical equipment (003004004) • Man-made fibres (003004005) • Organic substances (003004006) • Pharmaceutics (003004007) • Plastics and rubber related to chemical technology and engineering (003004008) • Soaps, detergents (003004009) • Special chemicals, intermediates (003004010) • Care, hygiene, beauty (0030040011)

Some safer alternatives may be described by using the keywords listed in sub-section “6 – Industrial Biotechnology (006007)” in sector “006 – Biological sciences”. The sub-section is subdivided in:

• Bio-composites (006007001) • Biobased chemical building blocks (006007002) Biobased high-performance materials (006007003) • Biobased materials (006007004) • Biological nanomaterials (006007005) • Biolubricants (006007006) • Bioplastics (006007007) • Biopolymers (006007008 • Bioprocesses (006007009) • Biotensides (006007010) • Downstream processing (006007011) • Fermentation (006007012) • Ionic liquids (006007013)

Three specific branches that could yield profiles relevant to chemical substitution are “Hazardous materials (010001004)” and “Protection against intoxication (010001006)” in sub-section “1 – Safety (010001)” and “Clean production/green technologies (010002015)” in sub-section “2 – Environment (010002)” of technology sector “010 – Protecting man and the environment”.

The NACE keywords are structured into 21 main sectors listed alphabetically (A–U), further broken down into 88 sub-sectors and 270 levels showing a total of 996 NACE keywords, in line with the Eurostat classification. NACE keywords are used to describe the sector(s) of activity that applies to the POD client advertising the business opportunity.

Substitution of Chemical Substances of Potential Concern | 29 4.3 Search Strategy

In order to identify the POD entries relevant to the substitution of chemical substances, the project team entered keywords in the Profile Search Function and, in addition, generated some queries by using some of the technology keywords in the Advanced Search Function reserved for logged in users21. The keywords used in the Profile Search Function were:

• “hazardous materials” (94 records); • “hazardous chemical” (935 records); • “non-toxic” (50 records); • “substitution” (11 records); • “svhc” (2 records); • “phthalate” (3 records); • “cadmium” (9 records)); • “chromium” (10 records); • “formaldehyde” (19 records); • “silica flour” (0 records); • “glutaraldehyde” (0 records); • “aldehyde” (3 records); • “methanol” (7 records); • “bisphenol” (10 records); • “hydrazine” (2 records); • “NMP” and “pyrrol” (for NMP (N-Methyl-2-pyrrolidone; 0 records); • “nonylphenol” (1 record); • “toluene” (4 records); • “DINP” (0 records); • “ethane-1,2-bis(pentabromophenyl)” and “EBP” (0 records); • “trichloroethylene” (0 records); • “tetrachloroethylene” (0 records); • “safer” (43 records); • “alternative” (325 records); and • “eco-friendly” (172 records)

The technology keywords used to generate the queries were:

• 10001004 Hazardous materials (12 records); • 10002013 Clean production/green technologies (34 records); • 06002003 Enzyme technology (28 records); • 03004003 Colours, dyes related to chemical technology (8 records); • 002002002 Coatings (78 records); and • 02006003 Fire resistance/safety (16 records).

These searches have resulted in the identification of 49 POD profiles, including:

• 15 technology offers; • 6 technology requests; • 28 business offers; and • 0 business request.

21 Searches were performed between 6 November 2017 and 8 January 2018.

Substitution of Chemical Substances of Potential Concern | 30 Through this search strategy, we screened around 1,800 profiles (around 25% of the total number of profiles present on the POD in October 2017), of which around 2.7% were relevant to substitution of chemical substances. The marginal benefit of carrying out additional searches for different terms decreases with each search and, although other words could be used when presenting a request or offer for alternatives to chemical substances of concern, we tried to search for words that are likely to be used.

4.4 Analysis of the Relevant POD Profiles

Error! Reference source not found. presents titles and summaries of the 49 relevant profiles found while the full profiles are reproduced in Error! Reference source not found. to Error! Reference source not found.. Titles, summaries, descriptions and all other sections of the profiles were reproduced as found on the database (including grammatical errors), if not for some format adjustment. Each table is followed by a short analysis of the different elements constituting the profile, in particular, of the description, technical specification or expertise sought (in the case of technology requests), and advantages and innovations (in the case of technology offers). We underlined the parts of the profile that are relevant to substitution.

In summary, the identified profiles vary in terms of quality and quantity of information provided, ranging from excellent profiles with optimal use of title, summary, description and advantages and innovations sections to profiles presenting requests or offers that are too generic. In particular, profiles failing to describe the technical functions and end uses of the technologies sought/offered are likely to get less interest from prospective clients/partners. More specifically, POD users searching for alternative (chemical and non-chemical) technologies to substances of potential concern may find it difficult to find relevant profiles if these do not mention the substances that the technologies may substitute. Indeed, our search is likely to have identified those profiles that, although not perfect or comprehensive, did describe to a certain extent the substitution capabilities of the technologies offered/sought. Moreover, when presenting technologies which may have better health and environmental profiles, any certification or standard backing these claims would add value to the description. Many profiles present bio-based or green chemistry technologies but fail to mention the substances that could be replaced or fail to describe what makes the technology offered superior from a health and environmental perspective.

Other technologies that may be alternatives to chemical substances of concern and currently have a profile in the POD may have remained “hidden”, due to profile descriptions failing to provide enough information. Even when enough information on the substances to be substituted or that could be substituted is provided, additional information on technical requirements of the technologies sought/offered, on the hazardous properties of the substances that the technology replaces/should replace and the legislation and the standards the technology complies with/should comply with would maximise the chances of a match between the profiler and prospective clients and partners. For example, the offering of BPA-free plastics, while it may catch the attention of prospective partners, does not provide information on the alternative substances or technologies used to deliver the technical functionality bisphenol A is used for. Moreover, prospective partners may be searching for technologies that go the “extra mile”, in this case searching for plastics not containing any bisphenols (other bisphenols, e.g. bisphenol F or bisphenol S, have been used to substitute BPA but have the same hazardous properties or have raised the same level of concern and are the object of further toxicological studies).

Many of the businesses behind profiles offering alternative technologies to chemical substances of potential concern are searching for commercial agents and distributors in different EU Member States. While the case for adopting healthier and environmentally friendlier technologies may be implied,

Substitution of Chemical Substances of Potential Concern | 31 profiles highlighting the economic advantages of adopting the technologies are likely to raise the most interest. Some of the profiles reviewed go as far as quantifying, in percentage terms, the cost reductions achievable when compared with the old technology.

In searching for relevant profiles, the creation of queries by using technology and market keywords, results in finding more specific profiles, while searching for relevant terms through the Profile Search function yields the most results, which may or may not be relevant to the substitution of chemical substances. Many of the reviewed profiles do not exhaustively use technology and market keywords, missing out on the added value of this POD feature.

Finally, all profiles should be proof-read, possibly by a native English language speaker or by a person with an equivalent level of competence, as many of the reviewed profiles have syntactic errors that may prevent the description of the technology offered/sought being understood.

Substitution of Chemical Substances of Potential Concern | 32 5 Guideline for the Use of the Partnership Opportunities Database for the Purpose of Substituting Chemicals of Potential Concern

5.1 Introduction

This Section presents the proposed guideline for the EEN partners on how best to profile on the POD technologies offered/sought for the purpose of substituting chemical substances of potential concern. This guideline is also provided as a stand-alone document (project deliverable). The instructions are listed and summarised in Figure 5-1. The following recommendations should be seen as complementary to the Profile Drafting Guidelines developed by EEN and the general rules for writing a good profile:

• Keep it clear and concise • Check spelling and grammar • Make sure that the profile is consistent • Profiles should be anonymous • Avoid repetitions • Avoid marketing speak • Write in the 3rd person.

5.2 Who is This Guideline for?

This guideline serves as a reference document for all actors involved in the creation and review (profile creators, internal and external reviewers, EASME) of profiles regarding both offers or requests of business services and technologies aiming to, or with the potential to, substitute chemical substances of concern used in processes or products.

It aims to provide a clear path through the process and seeks to ensure that the resulting profiles maximise the chances of matching prospective partners. This includes use of data fields already in the system, optimal exploitation of internal nomenclatures and good drafting of the profile.

5.3 Title

According to the EEN Profile Drafting Guidelines, the title should be sufficiently meaningful to enable Network partners (and their clients) to decide whether to read further. Therefore, in the case of technologies that may be safer alternatives to chemical substances of concern, the title should present technical function(s) and end-use(s) of the technologies requested/on offer. When relevant, it should include the name(s) of the substance(s) or group(s) of substances that the technology aims to substitute. This information should be given in addition to the main type of partnership desired and the client’s country of location.

When describing the technical function and the applications of the technology, especially if it is a chemical alternative, the use of the use descriptor lists for the Sectors of Use (SU), the Chemical Product Categories (PC) and the Technical Functions (TF) in the guidance on information requirements and chemical safety assessment (Chapter R.12: Use description) developed by ECHA are

Substitution of Chemical Substances of Potential Concern | 33 recommended, to ensure consistency across different databases (e.g. ECHA registered substances database, REACH applications for authorisation, ChemSec Marketplace). These are available at: https://echa.europa.eu/documents/10162/13632/information_requirements_r12_en.pdf

These help in describing the role of the substance, the product types used by the end-users and the sectors of the economy or market area where the use takes place.

5.4 Summary

In line with the EEN Profile Drafting Guidelines, the summary should complement the information already provided in the title by:

• Naming the client’s country of location and the main business area; • Listing the key characteristics of the technology (including the sector(s) of use and possible technical applications) and its main economic, health and safety and environmental advantages; • Describing what types of partner the client is looking for.

5.5 Description

In the description, additional information can be provided on:

• The client and its expertise; • The problem that the technology helps solving, including the description of the technical applications and the sector(s) of use; • The state of the art of the existing technologies, including information on the hazardous properties of the substances that the technology replaces and the technical requirements/performances of the technology sought/offered; • The legislation and the standards that the technology complies with; • The economic advantages of adopting the technology.

The description of the problem that the technology aims to solve facilitates the description of the technology specifications and its advantages. When possible, these should be described comparing the performances of the technology sought/offered with other technologies

(e.g. the new technology has lower environmental impacts because it does not contain biocides; the new technology reduces operating costs because it does not require the maintenance of safety equipment and uses 30% less energy; the new technology should be compatible with the marine environment).

The hazardous properties of the substances that can be substituted by the technology sought/offered should be mentioned

(e.g. the mainstream technologies make use of substances with persistent, bio-accumulative and toxic (PBT) properties; the new technology avoids the use of diisocyanates (skin and respiratory sensitisers) in the manufacturing process).

Information on the hazardous properties of chemical substances can be found on the classification and labelling inventory maintained by ECHA at: https://echa.europa.eu/information-on-chemicals/cl- inventory-database

Substitution of Chemical Substances of Potential Concern | 34 Mentioning the relevant legal requirements and standards that the technology complies (or should comply) which may also help in maximising the partnership opportunities

(e.g. the technology does not rely on the use of Substances of Very High Concern (SVHCs) under the REACH Regulation); the technology should meet the UN-EN ISO xxx standards; the technology is certified EU Ecolabel; the technology should comply with the Food Contact Materials legislation).

Highlight any economic advantages the technology achieves/should achieve, reflecting on the savings obtainable by eliminating the handling of hazardous substances, materials and wastes. When possible try to quantify, in absolute terms (e.g. price per quantity of the new material) or in relative terms (e.g. savings achievable by the new process in percentage when compared to the traditional process).

Advantages and Innovations

In the Advantages and Innovations section (or in the Technical Specification or Expertise Sought, depending on the type of partnership sought), the EEN partners should help the clients by summarising the key strengths of the technology offered/requested in bullet points. Example:

Italian company seeks partners for distribution services agreement for tin-free anti-fouling coating system for maritime applications.

The anti-fouling system has the following advantages:

• Contains no organotins or other chemicals with persistent, bio-accumulative and toxic (PBT) properties or toxic to the aquatic environment; • Completely safe to handle - needs no extra safety procedures; • Not reliant on sensitive atmospheric conditions - your ship will spend less time in dry dock; • Non-porous and does not support marine growth; • Requires no additional conditioning period - you can return to sea within 35 hrs of application; • 100% solid, extremely hard, does not wear off and does not shed; • Encapsulates any rusting of the surface to provide a very strong adhesive bond; • Reduces operating costs and has a reduced carbon footprint; • Requires no special application methods and can be applied anywhere; • Has a smooth high gloss finish designed to ensure optimum micro-texture and greatly improved hull dynamics, to reducing operating costs; • Available in a full range of livery colours.

5.6 Other Recommendations

EEN partners should encourage the use of all the main relevant technology and market keywords. Their use maximises the number of matches. These can be found at: http://een.ec.europa.eu/tools/services/Help/OnlineHelp/Merlin_Client_UserGuide.pdf

EEN partners should also encourage clients to back any safety claim, such as “environmental friendly” or “non-toxic”, by providing a description of the technology that would allow any prospective partner to judge the veracity of the claims. Finally, the whole profile should be proof-read, possibly by a native English language speaker or by a person with an equivalent level of competence.

Substitution of Chemical Substances of Potential Concern | 35

Figure 5-1: Summary of the guideline for the use of the POD for hazardous chemicals substitution purposes

Substitution of Chemical Substances of Potential Concern | 36 6 Testing and Validation of the Guideline

6.1 Introduction

In order to test and validate the guideline for using the POD to substitute chemical substances of concern, we asked 10 EEN partners, familiar with chemicals and chemical substitution issues, to carry out two exercises each: one for a profile presenting a technology or business request; one for a profile presenting a technology or business offer. We asked them to draft the title and summary on the basis of the profile description provided, following the guideline presented in Section 5. The exercises are presented in Annex 2.

The EEN partners were then asked to score the guideline on clarity, comprehensiveness and usefulness (on a scale from one to five) and to provide suggestions and recommendations for the improvement of the guideline. The testing and validation were carried out in two rounds, between which some of the suggestions of the first four EEN partners were accepted and embodied into the guideline. At the end of the second round, further improvements were done on the document. All recommendations and the scoring results are presented in the following sub-section.

6.2 Assessment Results and Suggestions for Improvement

The guideline scored fairly well in clarity, comprehensiveness and usefulness (scoring on average 3.9, 3.7 and 3.9 respectively). All scores are presented in Table 6-1, Table 6-2 and Table 6-3.

The consulted EEN partners suggested bringing the document in line with the EEN Profile Drafting Guidelines. These were reviewed by the project team and the guidance document for drafting profiles relevant to chemical substitution was revised accordingly.

One partner recommended shortening the document, as profile creators, internal and external reviewers and EEN staff should be familiar with the POD terminology and should not need a glossary and the profile structure. These sections have been deleted.

Two Network members suggested differentiating between business offers/requests and technology offers/requests. However, the guidance document has to be seen as complementary to the EEN Drafting Profile Guidelines. While these provide suggestions by type of profile, the information to be provided is consistent throughout the profile types, and in particular for the technology/product/service object of the profile. Moreover, some of the EEN partners suggested to add instructions that are already provided in the existing EEN guidelines for drafting profiles (e.g. number of characters available, use of acronyms, avoid commercial talk). Complementarity to the existing guidelines have been highlighted by using bold and underlined text.

With regard to the profile description, one EEN partner suggested including a short description of the state-of-the-art technology solutions, in line with the EEN Drafting Profile Guidelines. Another partner suggested to improve the formatting of the guideline adding some additional space between the paragraphs. Both recommendations have been added to the guideline. A summary in the form of a picture has also been suggested. This is presented in Figure 5-1.

The partners appreciated the provision of the examples, which make clearer the elements to include in each section of the profile.

Substitution of Chemical Substances of Potential Concern | 37 More in general, the EEN partners that provided feedback stressed the need and recommended the provision of training focusing on the substitution of hazardous chemical substances and the interface between chemical legislation and occupational health and safety legislation.

Table 6-1: Is the guideline clear? Please score on a scale from 1 to 5. 1 2 3 4 5 Not clear at all Clear Very clear EEN partner 1 EEN partner 2 EEN partner 3 EEN partner 4 EEN partner 5 EEN partner 6 EEN partner 7 EEN partner 8 EEN partner 9 EEN partner 10 Average score 3.9

Table 6-2: Is the guideline comprehensive? Please score on a scale from 1 to 5. 1 2 3 4 5 Not comprehensive Comprehensive Very at all comprehensive EEN partner 1 EEN partner 2 EEN partner 3 EEN partner 4 EEN partner 5 EEN partner 6 EEN partner 7 EEN partner 8 EEN partner 9 EEN partner 10 Average score 3.7

Table 6-3: Is the guideline useful? Please score on a scale from 1 to 5. 1 2 3 4 5 Not useful at all Useful Very useful EEN partner 1 EEN partner 2 EEN partner 3 EEN partner 4 EEN partner 5 EEN partner 6 EEN partner 7 EEN partner 8 EEN partner 9 EEN partner 10 Average score 3.9

Substitution of Chemical Substances of Potential Concern | 38 7 How the Network Can Support Businesses in the Substitution Process

7.1 Introduction

This Section provides further recommendations, beyond the guideline for drafting relevant profiles, on how the Network can assist companies, and in particular SMEs, in substituting chemical substances of potential concern.

7.2 Adjustments to the POD

To facilitate the matching of companies interested in substituting chemical substances of potential concern and companies offering safer alternative solutions, some adjustment could be made to the POD.

A first adjustment could be to provide a method of signalling the relevance of the profiles to the substitution of hazardous chemicals. This could be done by adding, for example, a technology keyword such as “Substitution of hazardous chemicals”. This would allow prospective clients and partners to easily identify relevant profiles, with the additional opportunity to narrow down the number of identified profiles by searching for e.g. name of the relevant substances or hazardous properties.

An alternative approach would be to develop a parallel POD dedicated to the substitution of chemical substances. While requiring more efforts and resources, this would provide advanced search functionality dedicated to substitution-relevant profiles, making the “substitution POD” similar to the Marketplace developed by Chemsec. While Chemsec’s Marketplace and the EEN POD are different in nature (the POD does not aim to showcase specific companies, products or services but its objective is to help companies in finding international business partners), a “substitution POD” could replicate some of the characteristics of Marketplace. Marketplace22 is an online platform dedicated to advertising safer alternatives and requests for safer alternatives to hazardous chemicals. While the general search function works similarly to that of the POD (results are based on semantic searches that provide the adverts most closely linked to the search term used; for example, search term “chromium” results include “chrome plating“), the advanced search is broken down into a number of criteria that can be chosen or left blank. The first level of search is the substance or process name. These can be searched for:

• Type of alternative wanted – alternative material, chemical substitute, technical or process solution; • Technical function; • Sector of use; • Material article category; • Legal requirements, standards or third-party labels.

The results are brief descriptions of the alternatives, which can be clicked on to find out more detail.

Even the terms and conditions of use of Marketplace could inspire those for a “substitution POD”. Namely, Marketplace aims to provide safer alternatives to hazardous substances. Alternatives that are

22 https://marketplace.chemsec.org/

Substitution of Chemical Substances of Potential Concern | 39 considered not to be within the scope are: solutions/equipment for safe handling of hazardous chemicals; solutions/processes that reduce the amount of a hazardous chemical; bio-based chemicals are not considered safer alternatives per se, as Marketplace focuses on the intrinsic properties of a substance; other types of sustainability innovations e.g. to reduce carbon emissions. There are minimum criteria that must be met for an advert to be placed on Marketplace. Substances that meet the criteria of SVHC, according to those laid out in REACH, cannot be promoted on Marketplace. This means that substances are prohibited if they are on the REACH candidate list, on the SIN list, have category 1 CMR properties in line with the criteria outlined in CLP, fulfil the PBT/vPvB criteria of REACH, or fulfil the WHO/IPCS definition of EDCs. If there is a possibility of regrettable substitution due to problematic properties such as persistence, neurotoxicity or sensitisation, or if data is lacking but the substance is structurally similar to well-known problematic compounds, then alternatives may also be prohibited from advertisement. Concentration limits also apply, meaning that substances that meet any of the above criteria cannot be intentionally added at any concentration. Contaminants that meet the above criteria at above the concentration of 0.1% w/w, or the specific concentration limit stated in CLP if it is stricter, are also prohibited. Such terms and conditions may be adapted to apply to technologies to be profiled on the “substitution POD”.

Upon considering the pros and cons of the two approaches, we recommend the addition of the keyword “Substitution of hazardous chemicals”, that would allow searches to be refined and the potential benefits of certain technologies to be signalled. By not creating a parallel “substitution POD”, profiles relevant to the substitution of hazardous chemicals would remain amongst the profiles of other technologies, products and services and could be found by businesses that, although not searching for safer alternatives to hazardous substances, may consider substitution upon finding a relevant profile. Moreover, a parallel POD focusing on substitution may narrow the range of opportunities offered, attracting providers of chemical-to-chemical substitution solutions. The POD instead, by listing opportunities from and for companies active in all sectors, may facilitate functional substitution23, where a company that was searching for a functionally equivalent chemical substitute may find instead an alternative technology providing the end use function or even the service of the product or process the substance is used in. Having profiles searching for or advertising safer alternatives to hazardous substances along with profiles on other technologies ensures that the scope of the initiative is not limited to regulatory compliance but supports substitution on the basis of economic and market opportunities considerations.

7.3 Training of Profile Creators, Internal and External Reviewers and EEN Staff

Beyond the provision of the guideline presented in Section 5, profile creators, internal and external reviewers and EEN staff should ideally attend training on substitution. The ECHA is stepping up its efforts on substitution24 and capacity building is one of the action areas of the strategy to promote substitution. EEN staff have participated in training on chemical safety and chemical policy in the past25 and their participation could be extended to trainings focusing on substitution.

23 Tickner JA, Schifano JN, Blake A, Rudisill C, Mulvihill MJ., 2015, 'Advancing safer alternatives through functional substitution', Environ Sci Technol. 2015 Jan 20;49(2):742-9. 24 ECHA (2018): Strategy to promote substitution to safer chemicals through innovation. Available at: https://echa.europa.eu/documents/10162/13630/250118_substitution_strategy_en.pdf/bce91d57-9dfc- 2a46-4afd-5998dbb88500 25 For example: https://newsletter.echa.europa.eu/home/-/newsletter/entry/2_14_european-wide-network- supports-innovative-smes and https://newsletter.echa.europa.eu/home/-/newsletter/entry/1_13_een and https://een.ec.europa.eu/succes-story/getting-ready-reach

Substitution of Chemical Substances of Potential Concern | 40 ECHA recognises the importance of providing technical support to companies testing potential alternatives before scaling up the production and adopting the technologies. However, this support requires knowledge of the companies’ circumstances and the EEN is therefore better positioned to provide such support. Furthermore, as suggested by ECHA’s strategy to promote substitution, the EEN could also be used to disseminate best practices and examples of successful substitution initiatives and information on substitution-specific funding.

In conclusion, closer collaboration between EEN and ECHA is likely to create synergies and ultimately to provide better support to SMEs and businesses more generally.

Substitution of Chemical Substances of Potential Concern | 41 8 Guideline for SMEs on How to Approach Substitution

8.1 Introduction

This Section provides some practical hints to SMEs interested in starting the substitution process of hazardous chemicals in their processes or products. We compiled four simple steps based on the results and conclusions of this study. They therefore focus on the use of the POD and on the collaboration with EEN partners.

8.2 Substituting Hazardous Substances

Step 1. Consider substitution! The substitution of hazardous substances in your processes and/or products is an opportunity and a source of innovation. It may help you in creating a healthier and safer working environment, and improving workers’ satisfaction and motivation. It will improve the sustainability of your business and the image of your company and may give you the opportunity to enter into new market niches and access public and private funds. Engaging in substitution of hazardous substances may be costly in the short-term but can deliver cost savings in the longer term and will create value.

Step 2. Focus on the function. A sound understanding of the technical functions and applications of the substance to be replaced in your processes and products will not only facilitate the subsequent steps but will also allow you to consider alternative technologies and solutions that go beyond the mere substitution of a chemical substance with another one, albeit with less hazards. Do not look only for a functionally equivalent chemical substitute, but search for other means to achieve the end use function (in the material, product or process) or even to achieve the service delivered by the process or product the substance is used in.

Step 3. Search through the Partnership Opportunities Database (POD). The POD, maintained by the Enterprise Europe Network (EEN), is one of the world’s largest business databases, where you can explore a wide range of opportunities in Europe and beyond. Search for the substance you want to substitute and/or for the technical function(s) and/or end use(s) of the substance. You may be able to find companies offering readily available safer alternative technologies and looking to enter into commercial agreements. Alternatively, you may find like-minded businesses searching for research or technical co-operation partners to share resources and skills to carry out exploratory research or further develop new solutions and technologies.

Step 4. Contact your local EEN partner. If, while searching through the POD, you found an interesting opportunity or even if your search was not successful, get in touch with your local EEN contact point. You can find it by selecting the country and city closest to where your business is based. The Network is active in more than 60 countries worldwide and has over 600-member organisations, all renowned for their excellence in business support. They will either send an Expression of Interest to the Network partner who has entered the profile you are interested in, or they will assess your needs and create a profile with your requests.

Substitution of Chemical Substances of Potential Concern | 42 9 References

ECHA (2018): Strategy to promote substitution to safer chemicals through innovation. Available at: https://echa.europa.eu/documents/10162/13630/250118_substitution_strategy_en.pdf/bce91d57- 9dfc-2a46-4afd-5998dbb88500 (Accessed: 22/02/18)

EEN (2016): Profile Drafting Guidelines, Version 4.1 – Updated: 29 November 2016, Enterprise Europe Network.

EEN (2015): Profile Drafting Guidelines, Updated: 10 April 2015, Enterprise Europe Netowrk.

KemI (2016): Hazardous chemicals in construction products – Proposal for a Swedish regulation. Report from a government assignment. Report 4/16, Swedish Chemicals Agency, Stockholm 2016. Available at: http://www.kemi.se/global/rapporter/2016/report-4-16-hazardous-chemicals-in- construction-products.pdf (Accessed: 22/02/18)

KemI (2014): Chemicals in Textiles – Risks to human health and the environment. Report from a government assignment. Report 6/14, Swedish Chemicals Agency, Stockholm 2014. Available at: http://www.kemi.se/global/rapporter/2014/rapport-6-14-chemicals-in-textiles.pdf (Accessed: 22/02/18)

Tickner JA et al (2015): Advancing safer alternatives through functional substitution, Environ Sci Technol. 2015 Jan 20;49(2):742-9.

Substitution of Chemical Substances of Potential Concern | 43 Annex 1 Simplified Analyses of Alternatives of the Selected Substances

A1.1 Substance 1: Silica flour

A1.1.1 Identity of the substance

Table9-1: Identity of silica flour Name of substance Silica flour (non-nanoscale) Synonyms Micronized α-Quartz Crystalline silica Crystallized silicon dioxide Quartz dust Quartz silica Silica dust EC Number 238-878-4 CAS Number 14808-60-7 Molecular formula SiO2 O=Si=O REACH Registration tonnage band Not registered (naturally occurring) Silicon dioxide registered at 1,000,000+ tonnes per annum Sources: ECHA website, https://echa.europa.eu/registration-dossier/-/registered-dossier/15556 (accessed on 28 July 2017) NTP website, https://ntp.niehs.nih.gov/ntp/noms/support_docs/silicaflour_oct2009.pdf (accessed on 28 July 2017)

A1.1.2 Functionality and applications

Table9-2: Functionality and applications for silica flour

General description of functionality Silica flour is the very finely divided, highly purified form of crystalline silica (SiO2). Silica flour is produced through the iron-free grinding and key physico-chemical of selected quartz sand with a high SiO2 content in ball or vibration mills. parameters Silica flour is generally used as an inert filler or a filtration material Family the substance belongs to Natural mineral

Substitution of Chemical Substances of Potential Concern | 44 Table9-2: Functionality and applications for silica flour Manufacture of sodium silicate Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) Product category PC0 Other Industrial/Professional/ Consumer Industrial Description Sodium silicate with weight ratio SiO2/Na2O R=1.6÷2.5 is produced by direct reaction of siliceous sand with sodium hydroxide and water. Sodium silicate is obtained by mixing raw materials at first into a dissolution vessel and then into a reactor in which the reaction between siliceous sand and sodium, hydroxide occurs. The reactor is heated by saturated steam and works under pressure. When the reaction time is spent the batch is transferred into a vessel and then filtered. Sodium silicate is mainly used in detergents, binders, anticorrosives, defocculates, zeolites, adhesives, cement, coagulant aids, and catalyst bases Glass manufacture Sector of Use SU13: Manufacture of other non-metallic mineral products, e.g. plasters, cement Product category PC0: Other Industrial/Professional/ Consumer Industrial: formulation and uses Consumer: Use of articles Description Glass fibres, mainly used for composite reinforcing or in decorative textiles, are made from fine ground silica flour Paints and Plastics, Polymer Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) Compounds, Rubber, Sealants and SU11: Manufacture of rubber products Adhesives SU12: Manufacture of plastics products, including compounding and conversion SU13: Manufacture of other non-metallic mineral products, e.g. plasters, cement SU16: Manufacture of computer, electronic and optical products, electrical equipment SU19: Building and construction work Product category PC1: Adhesives, sealants PC9a: Coatings and paints, thinners, paint removes PC9b: Fillers, putties, plasters, modelling clay PC32: Polymer preparations and compounds Industrial/Professional/ Consumer Industrial: formulation and uses Professional: Application of formulations containing silica flour (coatings and inks) Consumer: Use of articles and application of formulations (coatings and inks) – generally, not sold directly to general public Description Crystalline silica, as quartz and cristobalite, in its finest flour form is used as reinforcing filler. Silica flour provides resistance against abrasive actions and chemical attack. Self-cleaning exterior wall coatings and heavy-duty offshore or marine paints are typical examples. It can

Substitution of Chemical Substances of Potential Concern | 45 Table9-2: Functionality and applications for silica flour be found in products such as surface coatings, abrasives, plastics, grouts, and mastics as well as glues for roof and floor tiles and silicon rubber. The intrinsic properties of silica flour promote its use in plastics for encapsulating electronic components (epoxy resin castings and adhesives) Ceramics Sector of Use SU13: Manufacture of other non-metallic mineral products, e.g. plasters, cement Product category PC0: Other Industrial/Professional/ Consumer Industrial: formulation and uses Consumer: use of articles Description Typical everyday products such as tableware, sanitaryware, porcelain, ornaments and wall and floor tiles, but also high-tech ceramics, contain silica flour that has been ground to fine sizes to form a major constituent of frits for ceramic glazes where it is the most common glass former and serves to control the fusibility and viscosity, which are dependent on the amount of silica in the glaze; coarser grades help to control shrinkage. Silica flour is also used in clay bodies to modify shrinkage, porosity, and strength and as a void filler in silica-based refractories Foundry and Investment Casting Sector of Use SU15: Manufacture of fabricated metal products, except machinery and equipment Product category PC7: Base metals and alloys Industrial/Professional/ Consumer Industrial: formulation and uses Consumer: Use of articles Description Quartz and cristobalite flours are the main components in investment casting (also called precision casting) for the production of specialist products such as jewellery, dental bridges, aviation turbines and golf clubs, where silica flour acts as a refractory material and an additive enhancing easy parting from moulds. Silica flour is particularly used in the steel foundry in dressing for moulds and cores and also as essential ingredient in the moulding sand mixtures. It is also used to obtain elevated temperature strength, high density and resistance to metal penetration in cores Filtration Sector of Use SU23: Electricity, steam, gas water supply and sewage treatment Product category PC37: Water treatment chemicals PC40: Extraction agents Industrial/Professional/ Consumer Industrial Description Closely sized silica sand is the principal filtration medium used by the water industry to extract solids from wastewater Construction Applications, Sector of Use SU9: Manufacture of fine chemical Specialities and Commodities SU12: Manufacture of plastics products, including compounding and conversion

Substitution of Chemical Substances of Potential Concern | 46 Table9-2: Functionality and applications for silica flour SU13: Manufacture of other non-metallic mineral products, e.g. plasters, cement SU19: Building and construction work Product category PC1: Adhesives, sealants PC9a: Coatings and paints, thinners, paint removes PC9b: Fillers, putties, plasters, modelling clay PC32: Polymer preparations and compounds PC0: Other Industrial/Professional/ Consumer Industrial/ Professional/Consumer Description The construction industry is founded on silica sand and flours. There are a host of specialist applications including cement manufacture, silica and aerated concrete blocks, flooring and rendering compounds, artificial marble, white line markings, roofing felt and cement and resin injection systems where inertness and abrasion resistance are required Cosmetics Sector of Use SU9: Manufacture of fine chemicals Product category PC39: Cosmetics, personal care products Industrial/Professional/ Consumer Industrial/Professional/Consumer Description Silica flour is used industrially as an abrasive filler in soaps and as an coarse inert filler in toothpaste Cleaning, polishing and metal Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) finishing formulations SU15: Manufacture of fabricated metal products, except machinery and equipment Product category PC14: Metal surface treatment products PC25: Metal working fluids PC35: Washing and cleaning products Industrial/Professional/ Consumer Industrial Description Silica flour is used as an abrasive filler in polishing products, scouring powders and in gels used in the metal finishing industry Pharmaceuticals Sector of Use SU9: Manufacture of fine chemical SU20: Health services Product category PC29: Pharmaceuticals Industrial/Professional/ Consumer Industrial/Professional/Consumer Description Silica flours are used as fillers for a broad range of pharmaceuticals Food additive Sector of Use SU4: Manufacture of food products Product category PC0: Other Industrial/Professional/ Consumer Industrial/Professional/Consumer Description High purity silica flour is added to food products as an anti-caking agent separator. Products

Substitution of Chemical Substances of Potential Concern | 47 Table9-2: Functionality and applications for silica flour such as corn chips are dusted with silica flour to increase their shelf life and prevent adhesion of the chips. E551 silicon dioxide may also be used to remove protein and yeast in beer and wine production and as anti-foaming agent. Products that contain E551 include processed cereal-based foods and baby foods; vegetable oil pan spray; seasonings and condiments; sweeteners; drinks and sauces; ripened cheese; processed cheese; dairy analogues; fat and emulsions including spreads; confectionery including breath refreshing microsweets; decorations, coatings and fillings; sugars and syrups; chewing gum Oilfield chemicals Sector of Use SU2b: Offshore industries Product category PC41: Oil and gas exploration or production products Industrial/Professional/ Consumer Industrial Description Silica flour is used in oil well cements to inhibit strength retrogression at elevated temperatures. It can also contribute as a cement extender by increasing low shear viscosity and preventing cement sedimentation. At elevated temperatures changes in the hydration phases produced by the cement-water reaction can cause strength retrogression. The addition of silica flour can adjust the phase transformations and inhibit this strength reduction and the associated increase in permeability that occurs in set Portland cement. Sources: 3V Tech website, http://www.3v-tech.com/en/technologies-and-solutions/14/sodium-silicate (accessed on 4 August 2017) World of Chemicals website, http://www.worldofchemicals.com/media/silica-flour-market-forecast-2016-2024/370.html (accessed on 4 August 2017) NTP website, https://ntp.niehs.nih.gov/ntp/noms/support_docs/silicaflour_oct2009.pdf (accessed on 28 July 2017) FILCOM website, http://www.filcom.nl/en/products/silica-flour (accessed on 28 July 2017) IMA website, http://www.ima-europe.eu/sites/ima-europe.eu/files/minerals/Silica_An-WEB-2011.pdf (accessed on 28 July 2017) Indian Bureau of Mines website, http://ibm.gov.in/writereaddata/files/07092014130101IMYB_2012_Quartz%20&%20other%20Silica%20Minerals.pdf (accessed on 9 August 2017) CDC website, https://www.cdc.gov/niosh/docs/81-137/default.html (accessed on 28 July 2017) Waikato Ceramics website, http://www.potterysupplies.co.nz/shopexd.asp?id=377 (accessed on 6 August 2017) Imerys website, http://www.imerys-oilfieldsolutions.com/Silica.html (accessed on 28 July 2017) Dupré Chemicals website, http://www.dupreminerals.com/portfolio/z300-silica-flour/ (accessed on 31 July 2017) Kent and Surry County Councils, http://webcache.googleusercontent.com/search?q=cache:AOTdk2T84PsJ:consult.kent.gov.uk/file/3203326 (accessed on 4 August 2017) Food-Info website, http://www.food-info.net/uk/e/e551.htm (accessed on 10 August 2017) EC Food Additives website, https://webgate.ec.europa.eu/foods_system/main/index.cfm?event=substance.view&identifier=253 (accessed on 10 August 2017) Nanoshel: https://www.nanoshel.com/graphite-nanoparticles-and-nanopowder/ (accessed on 4 October 2017)

Substitution of Chemical Substances of Potential Concern | 48 A1.1.3 Potential alternatives

Table 9-3: Identification of potential alternatives for silica flour Application 1 Manufacture of sodium silicate Name/description of alternative Silica sand (i.e. a coarser form of silica) can be used as a raw material Identifiers (if chemical substance) Substance name EC Number CAS Number Silica sand (quartz) 238-878-4 14808-60-7 Description of applicability of According to literature, the main raw materials for the production of soluble silicates are quartz sand (or other silica sources), alkali alternatives carbonates (e.g. soda ash Na2CO3, potash K2CO3), alkali hydroxides (e.g. NaOH, KOH, LiOH), water and fuels / energy, (e.g. oil, gas, electricity). Thus sand can be considered an alternative form of silica raw material input Application 2 Glass manufacture Name/description of alternative Silica flour is a key raw material and acts as a glass former. Other types of glass fibres may be possible to generate, however, for those made with silica, replacing the substance would not be possible. Some newer compositions with low or no silica content may be based on aluminium oxide or aluminium oxide/yttria oxide garnet. Continuous single-crystal sapphire fibres (α-Al2O3) offer an impressive performance as rein-forcing fibres in ceramic and metal matrix composites Identifiers (if chemical substance) Substance name EC Number CAS Number Aluminium (III) oxide/Sapphire fibres 215-691-6 1344-28-1 Yttria-alumina-garnet (Y3Al5O12) - - Description of applicability of Continuous glass fibres can be formed from melts with a wide range of compositions and viscosities. Pure silica fibres are formed from alternatives highly viscous melts, silicate glass fibres with 50–70% SiO2 are formed from moderately viscous melts, aluminate glass fibres with 50– 80% Al2O3, as well as yttria-alumina-garnet (YAG) glass fibres are formed from inviscid melts. Commercial glass fibres are made for a variety of applications from pure silica rods and from silicate melts containing 50–70% SiO2 and 10–25% Al2O3. Sapphire fibres are manufactured according to the EFG technique (edge-defined, film-fed growth), have a very high melting point (more than 2000 °C) and are chemically almost neutral. Therefore, it can be used in extremely aggressive environments. Sapphire fibres are suited for chemical processing plants where reactions have to be monitored. Sapphire is also well suited for Er:YAG lasers. Overall, alternative glass fibres are best suited for ‘niche’ applications rather than commercially voluminous ones Application 3 Paints and Plastics, Polymer Compounds, Rubber, Sealants and Adhesives Name/description of alternative The mineral fillers most commonly used in rubber, plastics and coatings include: - Calcium carbonate - Kaolin clay - Talc - Wollastonite - Mica - Baryte

Substitution of Chemical Substances of Potential Concern | 49 Table 9-3: Identification of potential alternatives for silica flour - Diatomite - Feldspar - Nepheline syenite - Pyrophyllite - Dolomite (marble flour)

Synthetic fillers may include: - Precipitated calcium carbonate - Carbon Black - Synthetic silicas (fused silica) - Calcium Sulphate - Alumina Trihydrate (ATH) - Magnesium Hydroxide - Glass (fibres, spheres, hollow spheres, and flakes) - Synthetic polymers (polyamide, polyester, aramid, and polyvinyl alcohol fibres)

Natural polymers may include: - Cellulose fibres - Wood flour and fibres - Flax - Cotton - Sisal - Starch Identifiers (if chemical substance) Substance name EC Number CAS Number Calcium carbonate 207-439-9 471-34-1, 7440-70-2 Kaolin 266-340-9 66402-68-4 Talc (Mg3H2(SiO3)4) 238-877-9 14807-96-6 Wollastonite 237-772-5 13983-17-0 Mica 601-648-2 12001-26-2 Baryte (barium sulphate) 231-784-4 7727-43-7 Diatomite (kieselguhr) 272-489-0 68855-54-9 Feldspar (group minerals) 270-666-7 37244-96-5, 68476-25-5 Nepheline syenite 609-369-8 37244-96-5

Substitution of Chemical Substances of Potential Concern | 50 Table 9-3: Identification of potential alternatives for silica flour Dolomite 240-440-2 16389-88-1 Carbon black 215-609-9 1333-86-4 Calcium sulphate 231-900-3 7778-18-9 Aluminium hydroxide (Alumina Trihydrate) 244-492-7 21645-51-2 Magnesium hydroxide 215-170-3 1309-42-8 Description of applicability of There are many potential alternatives and not all can be fully addressed; some common alternatives are hereby discussed. alternatives Several minerals fulfil the requirements for use in polymer applications, i.e., they are abundant, low cost, colourless, inert and readily produced with the required particle sizes and shapes. Fillers are produced from these natural mineral sources by mining, followed by a variety of processes such as comminution (dry or wet), purification (beneficiation), classification, calcination, surface treatment and drying.

Calcium carbonate fillers can be differentiated as ground natural carbonate (GCC) vs precipitated carbonate. Precipitated calcium carbonate (PCC) is produced for applications requiring any combination of higher brightness, smaller particle size, greater surface area, lower abrasivity, and higher purity than is generally available from ground natural products. Both GCC and PCC are available with stearate surface treatments for better compatibility with polymer matrices.

Kaolin clay is available in a number of grades, airfloat clay which is the variety most commonly used in the rubber industry; water- washed clay; delaminated clay; calcined clay and surface coated clays.

Talc products are processed using various combinations of dry grinding, air separation and flotation depending upon the quality of the crude ore and the properties required for intended applications. The talc most often used as filler is commonly called platy talc.

The filler uses for wollastonite are dictated by the length of individual needles in the ore and the extent to which this shape is preserved during milling of the finished products. Wollastonite can be used in applications vulnerable to cracks/tears.

Most filler grade mica is first collected as flakes by flotation from ore that contains several minerals. Dry-ground products are air milled from flotation concentrate that has been partially of completely dried. Flaky micas provide good electrical isolation, superior dielectric strength and excellent thermal resistance.

Precipitated silica is produced by the controlled neutralisation of sodium silicate solution by either concentrated sulfuric, hydrochloric or carbonic acids and can be manufactured and used in nanoforms. Fused silica may be used in epoxy systems subject to extreme temperature fluctuations. The use of select high-performance fillers with low thermal-expansion coefficients in epoxy potting compounds makes it possible to minimize divergence in the thermally-induced shape distortions of potting compounds and metals. This is an indispensable prerequisite for applications vulnerable to cracks and tears (large moulded components or complex geometries).

Substitution of Chemical Substances of Potential Concern | 51 Table 9-3: Identification of potential alternatives for silica flour

Filler uses for baryte generally require high brightness, high purity, and fine particle size. The highest quality filler grades are made by flotation, followed by wet grinding, bleaching with sulfuric acid, washing, drying, and milling.

Diatomite products are generally differentiated by process and particle size. Flux-calcined diatomite is calcined at about 1200 °C with sodium carbonate or sodium chloride. Coarse fractions sold for filtration uses and fine fractions as white fillers. Calcined diatomite, also known as straight-calcined, is heated to between 870 °C and 1100 °C. Calcination generally turns the white to off-white natural diatomite pink from iron oxidation, so it is used primarily for filtration applications and seldom as filler. Natural diatomite products are gently crushed and milled to retain the frustule shape and then screened and air classified to remove impurities and to segregate products into coarse fractions for filtration applications and fine fractions for filler uses.

Floated feldspar finds limited use as filler in polymers despite its low vehicle demand, and resistance to abrasion and chemical degradation. Although the performance properties of feldspar and nepheline syenite are similar, the latter is more often used because it is available in a broader range of fine grinds (325 mesh to 1250 mesh) and it has generally higher brightness. Feldspar has a high dry brightness, high hardness, good heat stability, is inert and is easy to disperse. The main application for Feldspar is as general filler in self-levelling floor screeds, paints, polymers, adhesives, polishes and rubbing compounds. It is primarily used as an alternative to silica flour because it has good opacity - which reduces the requirement of white pigment in light coloured formulations.

Pyrophyllite products are natural blends of quartz and pyrophyllite along with minor amounts of mica and kaolin. Quartz-induced abrasion generally restricts the use of pyrophyllite in polymers, although the fine platy nature of the pyrophyllite, mica and kaolin components can otherwise contribute to physical properties in a manner similar to kaolin or talc.

Several fillers are produced by chemical synthesis. This is generally used where the desired mineral is not readily available in nature and/or when high purity, special shapes, or finer sizes than obtainable from comminution are required. The main synthetic processes used involve precipitation from a solution or gas phase. In a few cases the filler may be a by-product from another process Application 4 Ceramics Name/description of alternative When used as the glass former in frits, it cannot be possible to find non-silica alternatives for commercial ceramics. Alternatives for refractories are discussed under foundry applications below Identifiers (if chemical substance) Substance name EC Number CAS Number - - - Description of applicability of - alternatives Application 5 Foundry and Investment Casting Name/description of alternative Replacements for silica flour in foundry applications (refractory raw materials and parting compounds) include:

Substitution of Chemical Substances of Potential Concern | 52 Table 9-3: Identification of potential alternatives for silica flour - Zircon flour - Graphite - Chromite - Olivine - Talc - Mica Identifiers (if chemical substance) Substance name EC Number CAS Number Zircon (zirconium silicate (ZrSiO4)) 233-252-7 10101-52-7 Graphite 231-955-3 7782-42-5 Chromite ((Fe, Mg)Cr2O4) 308-539-6 98072-82-3 Olivine ((Mg, Fe)2SiO4) group minerals 215-281-7 1317-71-1 Talc (Mg3H2(SiO3)4) 238-877-9 14807-96-6 Mica 601-648-2 12001-26-2 Description of applicability of Zircon flour is a highly refractory material and is primarily used for coatings in steel foundries. Good quality zircon flour suitable for alternatives foundry work should contain minimum 64% zircon oxide (ZrO2), 30 to 35.5% silica and maximum of 0.5% TiO2 + Fe2O3. Refractory uses of zircon require low interstitial water content. This translates into low loss on ignition. Excessive internal radiation damage to zircon crystals (metamict zircon) can cause an increase in the loss on ignition of a zircon product. It has a specific gravity of about 4.5 and a pH value of the water-based coating of not more than 9. The high heat conductivity, about double that of silica, promotes quick formation of a solidified metal layer and helps in producing castings with a fine grained structure. Its higher density than that of silica prevents metal penetration.

Graphite refractory materials are most commonly used for coatings in iron foundries and for non-ferrous castings. Molten metal does not wet graphite and sand grains coated with graphite coatings resist metal penetration. This is the reason why graphite, Plumbago and carbon are usually used in mould and core coatings except those for steel. Mould and core coatings containing carbonaceous ingredients are not used for steel, particularly low-carbon steels. The reason for this is because steel is sensitive to the carbon content and if there is carbon pick-up, the properties of the steel will change.

Graphite Nanoparticles and Nanopowder: Due to its high temperature stability and chemical inertness graphite is a good candidate for a refractory material. It is used in the production of refractory bricks and in the production of “Mag-carbon” refractory bricks (Mg-C.) Graphite is also used to manufacture crucibles, ladles and moulds for containing molten metals. Additionally, graphite is one of the most common materials used in the production of functional refractories for the continuous casting of steel. In this application graphite flake is mixed with alumina and zirconia and then isostatically pressed to form components such as stopper rods, subentry nozzles and ladle shrouds used in both regulating flow of molten steel and protecting against oxidation. This type of material may also be used as shielding for pyrometers. In the production of iron, graphite blocks are used to form part of the lining of the blast furnace. Its structural strength

Substitution of Chemical Substances of Potential Concern | 53 Table 9-3: Identification of potential alternatives for silica flour at temperature, thermal shock resistance, high thermal conductivity, low thermal expansion and good chemical resistance are of paramount importance in this application. Refractory bricks for constructing materials of crucible and furnace are made with high volume impregnation of graphite. Graphite is used in metal casting and in the preparation of electrotype in printing industries.

Foundry grade chromite sands are not only used as casting sands in cores and moulds in steel and iron foundries, but also as base material in sliding gate mixes or plugging sands in ladles at steelworks. The merits of chromite foundry sands include high refractoriness, good chemical stability, low thermal expansion – which means the mould retains a stable size – and high density and thermal conductivity (which promote rapid solidification of the casting).

Olivine is orthosilicate of magnesium and iron (MgFe)O·SiO2 and it occurs as forsterite and fayalite. Its density, conductivity and refractoriness are higher than those of silica. Its fusion point is high (about 1800 °C) and as such it is favoured for heavy sections of alloy steel casting. Its resistance to slag reaction makes it suitable for the casting of high manganese steels. Olivine refractory material can also be used for the casting of non-ferrous castings of intricate nature. Olivine is used in preference to silica sand to overcome the silicosis hazard.

Talc is a hydrous magnesium silicate mineral with the chemical formula (Mg3Si4O10·(OH)2) and the softest mineral on Mohr’s scale of hardness. Talc is widely used as a filler material and as a parting compound.

Mica can be used as refractory filler in foundry core and mould coatings to eliminate or reduce finning defect in castings because of its lamellar plate-like nature Application 6 Filtration Name/description of alternative Potential alternatives include: - Activated coal - Anthracite coal - Pumice - Calcium carbonate - Dolomite - Garnet - Manganese dioxide - Zeolites - Expanded clays - Filter glass - Polymer beads (microspheres) Identifiers (if chemical substance) Substance name EC Number CAS Number

Substitution of Chemical Substances of Potential Concern | 54 Table 9-3: Identification of potential alternatives for silica flour Activated coal - - Anthracite coal - - Lignite coke - - Pumice 603-719-3 1332-09-8 Calcium carbonate 207-439-9 471-34-1, 7440-70-2 Dolomite 240-440-2 16389-88-1 Garnet - - Manganese dioxide 215-202-6 1313-13-9 Zeolites 215-283-8 1318-02-1 Expanded clays - - Description of applicability of A short overview of the applicability of the identified alternatives is as follows: alternatives - Activated coal is pure carbon with a residual ash content; it is used as an absorber for non-polar, especially organic, compounds that contaminate the water in very low concentrations - Anthracite coal is used in the mechanical filtration of solids in multilayer filters - Lignite coke is used in the mechanical filtration of solids in multi-layer filters with adsorptive properties - Expanded clays (aluminium silicates) are used in the mechanical filtration of solids in multilayer filters - Pumice (porous rock of volcanic origin) is used in mechanical filtration and for large surface areas for biological processes - Calcium carbonate (limestone) is used in the mechanical filtration of solids in multilayer filters and deacidification - Dolomite (calcium magnesium carbonate) is used in mechanical filtration, deferrisation, demanganisation and for part- deacidification - Garnet (iron-aluminium silicate) is used in mechanical filtration and has support layer properties - Manganese dioxide is used in demanganisation - Zeolites can be used as a sand replacement in recreational water, drinking water, and industrial applications. Zeolites can be used in pool filters - Filter glass can also be used in pool filters and is compatible with all sanitizers, clarifiers, and metal removals - Polyester balls (microbeads) can also be used in filters (e.g. for pool water) Application 7 Construction Applications, Specialities and Commodities Name/description of alternative Fillers used on construction materials such as concrete include: - Chalk (calcium carbonate) - Gravel - Limestone - Crushed stone - Clay - Granite

Substitution of Chemical Substances of Potential Concern | 55 Table 9-3: Identification of potential alternatives for silica flour - Expanded glass - Metallic fillers Identifiers (if chemical substance) Substance name EC Number CAS Number Calcium carbonate 207-439-9 471-34-1, 7440-70-2 Description of applicability of All the above can be used in polymer concrete and other applications where an inert filler is required alternatives Application 8 Cosmetics Name/description of alternative Abrasive fillers may include: - Calcium carbonate - Sodium bicarbonate - Dicalcium phosphate - Sodium metaphosphate - Amorphous diatomite - Kaolin clay Identifiers (if chemical substance) Substance name EC Number CAS Number Calcium carbonate 207-439-9 471-34-1, 7440-70-2 Sodium bicarbonate 205-633-8 144-55-8 Dicalcium phosphate 231-826-1 7757-93-9 Sodium metaphosphate 233-343-1 10124-56-8 Amorphous diatomite 612-383-7 61790-53-2 Kaolin clay 266-340-9 66402-68-4 Description of applicability of All these fillers can be used as abrasive fillers that support the polishing action of toothpastes alternatives Application 9 Cleaning, polishing, scouring and metal finishing Name/description of alternative Fillers that find applications in cleaning products and scouring powders include: - Marble dust - Diatomine (kieselguhr) - Bentonite - Feldspar - Pumice Identifiers (if chemical substance) Substance name EC Number CAS Number Marble dust - - Diatomite (kieselguhr) 272-489-0 68855-54-9 Bentonite 215-108-5 1302-78-9

Substitution of Chemical Substances of Potential Concern | 56 Table 9-3: Identification of potential alternatives for silica flour Feldspar (group minerals) 270-666-7 37244-96-5, 68476-25- 5 Pumice 603-719-3 1332-09-8 Description of applicability of These minerals can demonstrate an abrasive action which is useful in cleaning products such as scouring powders and abrasive soaps alternatives and pastes. Bentonite in particular can swell in the presence of water, emulsify oily materials and peptise fine particles of soil keeping them in suspension. It can also soften the water; as such bentonite could also find uses as a low-cost builder in detergent compounds Application 10 Pharmaceuticals Name/description of alternative Fillers and diluents in pharmaceuticals add bulk to products making very small active components easy for consumer to take. Example fillers include: - Lactose - Sucrose - Magnesium stearate - Glucose - Plant cellulose - Calcium carbonate - Dibasic calcium phosphate Identifiers (if chemical substance) Substance name EC Number CAS Number Lactose 200-559-2 63-42-3 Sucrose 200-334-9 57-50-1 Magnesium stearate 209-150-3 557-04-0 Glucose 200-075-1 50-99-7 Plant cellulose - - Calcium carbonate 207-439-9 471-34-1, 7440-70-2 Dibasic calcium phosphate 231-826-1 7757-93-9 Description of applicability of A good filler should typically be inert, compatible with the other components of the formulation, non-hygroscopic, relatively cheap, alternatives compactible, and preferably tasteless or pleasant tasting Application 11 Food additive Name/description of alternative Following is the list of anti-caking agents commonly used in foods and drinks. - E341 (iii) Tricalcium phosphate - E343 Magnesium phosphates (i) monomagnesium phosphate (ii) Dimagnesium phosphate - E421 Mannitol - E552 Calcium silicate - E553a (i) Magnesium silicate (ii) Magnesium trisilicate - E553b Talc

Substitution of Chemical Substances of Potential Concern | 57 Table 9-3: Identification of potential alternatives for silica flour Identifiers (if chemical substance) Substance name EC Number CAS Number Tricalcium phosphate 231-840-8 7758-87-4 Monomagnesium phosphate 236-004-6 13092-66-5 Dimagnesium phosphate 231-823-5 7757-86-0 Mannitol 200-711-8 69-65-8 Calcium silicate 233-250-6 10101-39-0 Magnesium silicate 237-413-2 13776-74-4 Magnesium trisilicate 239-076-7 14987-04-3 Talc (Mg3H2(SiO3)4) 238-877-9 14807-96-6 Description of applicability of The anti-caking agents most compatible with the applications of E551 are phosphates and particularly silicates and talc alternatives Application 12 Oilfield chemicals Name/description of alternative There are no known non-silica alternatives. Silica fume is another form of silica that may be used. Also, silica flour in the form of a slurry may be considered Identifiers (if chemical substance) Substance name EC Number CAS Number Fumes, silica 273-761-1 69012-64-2 Description of applicability of Silica fume is a by-product of producing silicon metal or ferrosilicon alloys. It consists of amorphous silicon dioxide particles from the alternatives volatilisation and vaporisation of furnace feed materials in the manufacture of ferrosilicon and silicon. One of the most beneficial uses for silica fume is in concrete. Because of its chemical and physical properties, it is a very reactive pozzolan. Concrete containing silica fume can have very high strength and can be very durable.

Substitution of silica flour with varying proportions of silica fume affects the permeability of hardened cements. The positive effect on the strength regression at increased temperatures is due to a greater rate of carbonation of the set cement. Carbonation is controlled not by permeability but by the calcium hydroxide content at 150 °C. The use of silica fume has been found to decrease the permeability slightly.

A technical alternative is the use of a slurryfied silica flour product. Once such product has been designed to provide an alternative to dry-blended silica flour for high temperature cementing. It contains amorphous, spherical microsilica slurrified with silica flour. This has been claimed to offer: - Gas-migration control - Zero free water - Low fluid loss - Low viscosity - Early strength development enhancer

Substitution of Chemical Substances of Potential Concern | 58 Table 9-3: Identification of potential alternatives for silica flour - Improved bonding - Stable cement slurry - Corrosion resistance Sources: CEES website, http://www.cees-silicates.org/manufacture.html (accessed on 4 August 2017) Wallenberger FT, www.springer.com/cda/content/document/cda_downloaddocument/9781441907356-c1.pdf?SGWID=0-0-45-837960-p173908106 (accessed on 7 August 2017) Laser Components website, http://www.lasercomponents.com/uk/product/sapphire-fibers/ (accessed on 7 August 2017) Quarzwerke website, http://www.quarzwerke.com/en/sales/overview-of-industries/plastics-elastomers/thermosets (accessed on 4 August 2017) Boud Minerals website, http://www.boud.com/products/feldspar (accessed on 4 August 2017) Sarkar AD, https://books.google.co.uk/books?id=9rYgBQAAQBAJ (accessed on 4 August 2017) Nwaogu & Tiedje, http://file.scirp.org/pdf/MSA20110800028_74577735.pdf (accessed on 4 August 2017) Kogel JE, https://books.google.co.uk/books?id=zNicdkuulE4C (accessed on 4 August 2017) Euroquarz website, https://www.euroquarz.com/wissen-ueber-quarzsand-quarzkies/wasserwissen/trinkwasser/filter-products/ (accessed on 4 August 2017) Inyopools website, http://www.inyopools.com/Blog/pool-filter-sand-alternatives/ (accessed on 4 August 2017) UK Essays website, https://www.ukessays.com/essays/construction/natural-vs-synthetic-fiber-reinforced-polymer-construction-essay.php (accessed on 4 August 2017) Silverson website, http://www.silverson.co.uk/en/resource-library/application-reports/manufacture-of-toothpaste-uk (accessed on 4 August 2017) PMS website, http://www.pms.nl/en/chromite-foundry-grade/ (accessed on 11 August 2017) ICDA website, http://icdacr.com/index.php?option=com_content&view=article&id=140&Itemid=346&lang=en (accessed on 11 August 2017) Ash M, https://books.google.co.uk/books?id=C4Cr8dHupVsC (accessed on 4 August 2017) OraWellness website, https://www.orawellness.com/whats-the-safest-and-most-effective-abrasive-for-naturally-whiter-teeth/ (accessed on 4 August 2017) US patent 77907847A, http://www.freepatentsonline.com/2489848.html (accessed on 4 August 2017) NIIR Board of Consultants Engineers, https://books.google.co.uk/books?id=qgC_CwAAQBAJ (accessed on 4 August 2017) ND Health Facts website, http://www.ndhealthfacts.org/wiki/Excipients_and_Fillers (accessed on 4 August 2017) Nahid H, https://www.slideshare.net/nahidhasan7921/pharmaceutical-excipients (accessed on 4 August 2017) Breaking the Vicious Cycle website, http://www.breakingtheviciouscycle.info/knowledge_base/detail/e-codes-for-food-additives-in-europe/ (accessed on 7 August 2017) Venderbilt Chemicals website, https://www.rtvanderbilt.com/FillersIntroWeb.pdf (accessed on 4 August 2017) Rothon RN, http://www.polymerjournals.com/pdfdownload/844670.pdf (accessed on 4 August 2017) Fink J, https://books.google.co.uk/books?id=lT9uQBIc4_8C (accessed on 4 August 2017) Silica Fume Association website, http://silicafume.org/general-silicafume.html (accessed on 7 August 2017) Elkem website, https://www.elkem.com/documents/esm/oilfield/microblock-ht-general-presentation-technical-product-information.pdf (accessed on 4 August 2017)

A1.1.4 Assessment of feasibility of potential alternatives

Substitution of Chemical Substances of Potential Concern | 59 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Silica sand 1 Silica sand is effectively the same Price: for 2016 No harmonised classification but Abundant mineral (quartz) substance but only in coarser The price of as-grown cultured an intention to propose a Carc form quartz was estimated to be classification (France). Most €250 per kilogram in 2016. notifiers do not classify the Lumbered quartz, which is as- substance but impurities may grown cultured quartz that has warrant a STOT RE 1 H372 (lung) been processed by sawing and (Inhalation) classification grinding, was estimated to be €145 per kilogram in 2016, but the price can range from €18-900 per kilogram, depending on the application

Aluminium (III) 2 Suitable for glass fibre Price: for 2016 Not classified for hazards Registered at 10,000,000+ tonnes oxide (Sapphire) manufacture and niche Fused aluminium oxide, regular, per annum applications €400 per ton Sapphire does not require Fused aluminium oxide, high- registration as a natural mineral purity: €1,300 per ton Yttria-alumina- 2 Can be used as an alternative to No data No data Synthetic crystalline material; garnet (Y3Al5O12) sapphire as an optical material unlikely to be available in very and thus suitable for niche large quantities applications only Calcium 3, 6, 7, 8, Widely used filler, available as Price: for 2016 No harmonised classification. Registered at carbonate 10 ground natural carbonate (GCC) Average €10 per tonne Not classified according to lead 1,000,000 – 10,000 000 tonnes and precipitated carbonate, the registrant per annum latter having better qualities and compatibility with polymers. It is also used in the mechanical filtration of solids in multilayer filters and deacidification Kaolin 3, 8, 11 Widely used general filler Price: for 2016 No harmonised classification. Natural mineral. Ex-works, average, €120 per ton Not classified according to lead Registered at 10,000 – registrant 100,000 tonnes per annum

Substitution of Chemical Substances of Potential Concern | 60 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Talc 3, 5, 11 Widely used general filler and Price: for 2016 Environmental Hazards Abundant natural mineral. parting compound. Average, milled, €160 per tonne No harmonised classification. Registered at 10 - 100 tonnes per E553b approved food additive (industrial grade). Up to €250 per annum with application range similar to tonne for food applications Human Health Hazards that of silica No harmonised classification.

Not classified according to lead registrant Wollastonite 3 Wollastonite can be used in Price: for 2016 Environmental Hazards Abundant natural mineral. polymer applications vulnerable Ex-works price for US No harmonised classification. Not registered to cracks/tears wollastonite, €210-440 per ton, Free-on-board price for Chinese Human Health Hazards wollastonite (minimally refined), No harmonised classification. €70-95 per ton Not classified by majority of notifiers Mica 3, 5 Widely used filler. It can be used Price: for 2016 Environmental Hazards Abundant natural mineral. as refractory filler in foundry core Average, scrap and flake, €120 No harmonised classification. Not registered and mould coatings to eliminate per tonne or reduce finning defect in Average, ground dry, €260 per Human Health Hazards castings tonne No harmonised classification. Average, ground wet, €340 per tonne Not classified by majority of notifiers Baryte (barium 3 Suitable for polymer applications Price: for 2016 Environmental Hazards Registered at 10, 000 – sulphate) where high brightness is Average, ground free-on-board No harmonised classification. 100,000 tonnes per annum required; widely used pigment mill, €1,300 per ton Human Health Hazards No harmonised classification.

Not classified according to lead registrant

Substitution of Chemical Substances of Potential Concern | 61 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Diatomite 3, 8, 9 Coarse fractions are sold for Price: for 2016 Environmental Hazards Registered at 100,000 – (kieselguhr) filtration uses and fine fractions Average, free-on-board plant, No harmonised classification. 1,000,000 tonnes per annum as white fillers. It can also be €265 per ton used in scouring powders Human Health Hazards No harmonised classification.

Not classified according to lead registrant Feldspar (group 3, 9 Some limited use as a polymer Price: for 2016 Environmental Hazards Abundant mineral minerals) filler. Nepheline syenite are Average, marketable production, No harmonised classification. Not registered similar, the latter is more often €65 per tonne used because it is available in a Human Health Hazards broader range of fine grinds (325 No harmonised classification. mesh to 1250 mesh) and it has Majority of notifiers classified as generally higher brightness. The Eye Irrit. 2 (H319) and STOT SE 3 main application for Feldspar is as (H335) general filler in self-levelling floor screeds, paints, polymers, adhesives, polishes and rubbing compounds. It is primarily used as an alternative to silica flour because it has good opacity Nepheline syenite 3 See Feldspar Price: see price for feldspar Environmental Hazards Natural mineral. above No harmonised classification. Not registered

Human Health Hazards No harmonised classification.

Not classified by majority of notifiers Dolomite (marble 3, 6, 9 Natural product with several filler Price: €8 per tonne (current) Environmental Hazards Natural mineral. flour) uses. It is also used in mechanical No harmonised classification. Not registered filtration, deferrisation,

Substitution of Chemical Substances of Potential Concern | 62 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability demanganisation and for part- Human Health Hazards deacidification. It can also be No harmonised classification. used in scouring powders Not classified by majority of notifiers Carbon black 3 Widely used polymer filler Price: for end of 2011 Environmental Hazards Registered at 1,000,000 – Market price of dry N220 hard No harmonised classification. 10,000,000 tonnes per annum carbon black, €775 per ton Market price of wet N220 hard Human Health Hazards carbon black, €840 per ton No harmonised classification. Market price of N330 hard carbon black, €730 per ton Not classified according to lead Market price of N660 soft carbon registrant black, €720 per ton Calcium sulphate 3 Synthetic product with some uses Price: for 2016 Environmental Hazards Registered at 10,000+ tonnes per (gypsum) in polymer filler applications Average crude, free-on-board No harmonised classification. annum mine, €8 per tonne Average calcined, free-on-board Human Health Hazards plant, €28 per tonne No harmonised classification.

Not classified according to lead registrant Aluminium 3 Synthetic product with some uses Price: for 1999 Environmental Hazards Registered at 1,000,000 – hydroxide in polymer filler applications €620 per tonne No harmonised classification. 10,000,000 tonnes per annum (Alumina Trihydrate) Human Health Hazards No harmonised classification.

Not classified according to lead registrant Magnesium 3 Synthetic product with some uses Price: for 2015 Environmental Hazards Registered at 100,000 – hydroxide in polymer filler applications €685 per tonne No harmonised classification. 1,000,000 tonnes per annum

Substitution of Chemical Substances of Potential Concern | 63 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Human Health Hazards No harmonised classification.

Not classified according to lead registrant Zircon 5 Highly refractory material and is Price: for 2016 Environmental Hazards Natural mineral. primarily used for coatings in €900 per tonne (gross weight) No harmonised classification. Not registered steel foundries. Its high heat conductivity, about double that Human Health Hazards of silica, promotes quick No harmonised classification. formation of a solidified metal layer and helps in producing Not classified by majority of castings with a fine-grained notifiers structure. Its higher density than that of silica prevents metal penetration Graphite 5 Graphite refractory materials are Price: for 2016 Environmental Hazards Registered at 100,000 – most commonly used for coatings Fine flake: Fine flake (-100 mesh) No harmonised classification. 1,000,000 tonnes per annum in iron foundries and for non- €585 per tonne ferrous castings. Molten metal Human Health Hazards does not wet graphite and sand No harmonised classification. grains coated with graphite coatings resist metal penetration. Not classified according to lead This is the reason why graphite, is registrant used in mould and core coatings except those for steel Chromite 5 Used as casting sand in cores and Price: for 2008 Environmental Hazards Natural mineral. moulds in steel and iron €400 per ton; typically a multiple No harmonised classification. Not registered foundries, particularly in the of the raw chromite ore price automotive, shipbuilding and (US$200 in 2017) Human Health Hazards heavy-engineering sectors No harmonised classification.

Not classified by majority of

Substitution of Chemical Substances of Potential Concern | 64 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability notifiers Olivine 5 Its resistance to slag reaction Price: for 2001 Environmental Hazards Natural mineral. makes it suitable for the casting €55-110 per ton No harmonised classification. Not registered of high manganese steels. Olivine refractory material can also be Human Health Hazards used for the casting of non- No harmonised classification. ferrous castings of intricate Majority of notifiers classified as nature. Olivine is used in Eye Irrit. 2 (H319) when in bulk preference to silica sand to form overcome the silicosis hazard Activated coal 6 Used in filtration as an absorber Price: for 2017 - Abundant for non-polar - especially organic €1290 per ton compounds that contaminate the water in very low concentrations Anthracite coal 6 It is used in the mechanical Price: for 2012 - Abundant filtration of solids in multilayer €100-160 per ton filters Lignite coke 6 It is used in the mechanical Price: for 2015 - Abundant filtration of solids in multi-layer Price at the mine, €20 per ton filters with adsorptive properties Pumice 6, 9 It is used in mechanical filtration Price: for 2016 Environmental Hazards Natural mineral. and for large surface areas for Average, free-on-board mine or No harmonised classification. Not registered biological processes. It can also mill, €30 per ton be used in scouring powders Human Health Hazards No harmonised classification.

Not classified by majority of notifiers Garnet 6 It is used in mechanical filtration Price: for 2016 Not classified Natural mineral and has support layer properties Price varies depending on the amount of processing and refining, degree of fracturing, garnet mineral type, quality, and

Substitution of Chemical Substances of Potential Concern | 65 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability quantity purchased. Most crude garnet concentrate was priced at €90-200 per ton, and most refined material priced at €90- 360 per ton Manganese 6 It is used in demanganisation No data available Environmental Hazards Registered at 10,000 – dioxide No harmonised classification. 100,000 tonnes per annum

Human Health Hazards Harmonised classification: Acute Tox. 4 (H302, H332) Zeolites 6 They can be used as a sand Price: for 2016 Environmental Hazards Natural mineral. replacement in recreational Prices vary with the percentage of No harmonised classification. Not registered water, drinking water, pool filters zeolite present in the product, and industrial applications the chemical and physical Human Health Hazards properties of the zeolite No harmonised classification. mineral(s), particle size, surface modification and (or) Not classified by majority of activation, and end use notifiers Range of values: €90-850 per tonne Sodium 8 It can be used as an abrasive filler Price: for 2002 Environmental Hazards Registered at 1,000,000 – bicarbonate that supports the polishing action USP powder, regular grade, No harmonised classification. 10,000,000 tonnes per annum of toothpastes carload, bags, freight equalised, €420 per tonne Human Health Hazards No harmonised classification.

Not classified according to lead registrant Dicalcium 8, 10 It can be used as an abrasive filler Price: for 2015 Environmental Hazards Registered at 100,000 – phosphate that supports the polishing action Fertiliser grade, free-on-board, No harmonised classification. 1,000,000 tonnes per annum of toothpastes USA, €450 per tonne Human Health Hazards

Substitution of Chemical Substances of Potential Concern | 66 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability No harmonised classification.

Not classified according to lead registrant Sodium 8 It can be used as an abrasive filler Price: for 2000 Environmental Hazards Registered at 1,000 – 10,000 metaphosphate that supports the polishing action Food grade bags, free-on-board, No harmonised classification. tonnes per annum of toothpastes €1,950 per tonne Human Health Hazards No harmonised classification.

Not classified according to lead registrant Bentonite 9 It can be used in scouring Price: for 2016 Environmental Hazards Natural mineral. powders where it can swell in the Ex-works, average, €67 per ton No harmonised classification. Not registered presence of water, emulsify oily materials and peptise fine Human Health Hazards particles of soil keeping them in No harmonised classification. suspension. It can also soften the water; as such bentonite could Not classified by majority of also find uses as a low-cost notifiers builder in detergent compounds Lactose 10 Lactose is widely used as a filler or Price: €4,200 – 12,700 per tonne, Approved pharmaceutical Natural product. filler-binder in the manufacture pharma grade excipient. Not registered of pharmaceutical tablets and capsules Environmental Hazards No harmonised classification.

Human Health Hazards No harmonised classification.

Not classified by majority of notifiers Sucrose 10 Used in syrups and tablets diluent Price: unclear, €935 – 1,400 per Approved pharmaceutical Natural product.

Substitution of Chemical Substances of Potential Concern | 67 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability or binder tonne, pharma grade excipient. Not registered

Environmental Hazards No harmonised classification.

Human Health Hazards No harmonised classification.

Not classified by majority of notifiers Magnesium 10 Used as a diluent for the Price: €1,400 – 4,200 per tonne, Approved pharmaceutical Food additive. stearate manufacture of tablet, capsule, pharma grade excipient. Not registered and powder dosage forms Environmental Hazards No harmonised classification.

Human Health Hazards No harmonised classification.

Not classified by majority of notifiers Glucose 10 Used as an excipient, binder and Price: €340 – 510 per tonne, Approved pharmaceutical Natural product. in direct compression tabletting pharma grade excipient. Not registered

Environmental Hazards No harmonised classification.

Human Health Hazards No harmonised classification.

Not classified by majority of notifiers Plant cellulose 10 Cellulose and its derivatives No data available Approved pharmaceutical Natural product

Substitution of Chemical Substances of Potential Concern | 68 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability (ether and ester) are among the excipient. excipients most frequently used in pharmaceuticals. Among their Environmental Hazards uses, the most frequently No harmonised classification. reported are as suspending agents in oral liquid Human Health Hazards extemporaneous preparation No harmonised classification. and as viscosity increasing agents in topical formulations. Not classified by majority of Particularly, in oral solid dosage notifiers forms, cellulose and its derivatives (also known as cellulosics) can render distinct drug delivery property patterns: immediate, controlled/sustained or delayed release. In addition, cellulosics show several interesting characteristics such as low cost, reproducibility, biocompatibility, and recyclability. Microcrystalline cellulose has excellent compressibility properties and is used in solid dose forms, such as tablets. Tablets can be formed that are hard, but dissolve quickly Tricalcium 11 E341(iii) approved food additive. Price: €610 – 720 per tonne Approved food additive. Registered at 1,000 – 10,000 phosphate Used among others in table-top tonnes per annum sweeteners in powder form, Environmental Hazards processed cereal-based foods No harmonised classification. and baby foods for infants and young children, dietary foods for Human Health Hazards infants for special medical No harmonised classification. purposes and special formulae

Substitution of Chemical Substances of Potential Concern | 69 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability for infants, Vegetable oil pan Not classified according to lead spray registrant Monomagnesium 11 E343(i) approved food additive. Price: unclear, ca. €1250 – Approved food additive. Registered at 100 – 1,000 tonnes phosphate Used among others in table-top 1300 per tonne per annum sweeteners in powder form, Environmental Hazards processed cereal-based foods No harmonised classification. and baby foods for infants and young children, dietary foods for Human Health Hazards infants for special medical No harmonised classification. purposes and special formulae for infants, Vegetable oil pan Not classified according to lead spray registrant Dimagnesium 11 E343(ii) approved food additive. Price: unclear, ca. €1250 – Approved food additive. Registered at 10,000 – phosphate Used among others in table-top 1300 per tonne 100,000 tonnes per annum sweeteners in powder form, Environmental Hazards processed cereal-based foods No harmonised classification. and baby foods for infants and young children, dietary foods for Human Health Hazards infants for special medical No harmonised classification. purposes and special formulae for infants, Vegetable oil pan Not classified according to lead spray registrant Mannitol 11 E421 approved food additive, Price: unclear, ca. €2,500 – 4,300 Approved food additive. Not registered mainly used as a sweetener in, per tonne among others, confectionery Environmental Hazards including breath freshening No harmonised classification. microsweets Human Health Hazards No harmonised classification.

Not classified according to lead registrant Calcium silicate 11 E552 approved food additive with No data available Approved food additive. Not registered

Substitution of Chemical Substances of Potential Concern | 70 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability application range similar to that of silica Environmental Hazards No harmonised classification.

Human Health Hazards No harmonised classification.

Not classified according to lead registrant Magnesium 11 E553a(i) approved food additive Price: unclear, ca. €340 – 1,275 Approved food additive. Not registered silicate with application range similar to per tonne that of silica Environmental Hazards No harmonised classification.

Human Health Hazards No harmonised classification.

Not classified according to lead registrant Magnesium 11 E553a(ii) approved food additive No data available Approved food additive. Not registered trisilicate with application range similar to that of silica Environmental Hazards No harmonised classification.

Human Health Hazards No harmonised classification.

Majority of notifiers provide hazard statement code H413 when in bulk form Fumes, silica 12 Can be used as an alternative Price: US$300-800 (€270-720) Environmental Hazards Registered at 100,000 – silica form in oil well cement per ton No harmonised classification. 1,000,000 tonnes per annum formulations

Substitution of Chemical Substances of Potential Concern | 71 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Human Health Hazards No harmonised classification.

Not classified according to lead registrant Sources: Northrop Grumman website, http://www.northropgrumman.com/BusinessVentures/SYNOPTICS/Products/SpecialtyCrystals/pages/UndopedYAG.aspx (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/abrasives/mcs-2017-abras.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/barite/mcs-2017-barit.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/clays/mcs-2017-clays.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/stone_crushed/mcs-2017-stonc.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/diatomite/mcs-2017-diato.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/feldspar/mcs-2017-felds.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/garnet/mcs-2017-garne.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/mica/mcs-2017-mica.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/pumice/mcs-2017-pumic.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/talc/mcs-2017-talc.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/silica/mcs-2017-quart.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/wollastonite/mcs-2017-wolla.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/zeolites/mcs-2017-zeoli.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/zirconium/mcs-2017-zirco.pdf (accessed on 9 August 2017) Skalda website, http://skalda.lt/en/dolomite-powder (accessed on 9 August 2017) Asia Carbon Industries, http://edg1.precisionir.com/companyspotlight/NA019330/AsiaCarbonCorporateProfile.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/gypsum/mcs-2017-gypsu.pdf (accessed on 9 August 2017) USGS website, https://minerals.usgs.gov/minerals/pubs/commodity/magnesium/myb1-2015-mgcom.pdf (accessed on 9 August 2017) ICIS website, https://www.icis.com/resources/news/2003/11/28/538335/supply-balanced-and-prices-firm-for-sodium-bicarbonate/ (accessed on 9 August 2017) Cement Americas website, http://www.cementamericas.com/cement-newsline/244-technology-shears-cost-of-processing-fly-ash-to-match-silica-fume-performance.html (accessed on 9 August 2017) The Globe and Mail website, https://www.theglobeandmail.com/report-on-business/small-business/sb-growth/building-with-a-more-durable-greener-concrete/article4301342/ (accessed on 9 August 2017) CRU website, https://events.crugroup.com/phosphates/uploads/fertilizer-international-phosphatesconference-may_17.pdf (accessed on 9 August 2017) Cronan DS, https://books.google.co.uk/books?id=MZ7L0ZGZpJQC (accessed on 9 August 2017) Geovic Mining Corp website, http://www.geovic.net/userfiles/file/Chromite_Market_Summary (accessed on 11 August 2017)

Substitution of Chemical Substances of Potential Concern | 72 Table 9-4: Assessment of potential alternatives for silica flour Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Mining Markets website, http://www.miningmarkets.ca/news/a-market-for-chromite/ (accessed on 11 August 2017) Kramer DA, https://www.netl.doe.gov/publications/proceedings/01/minecarb/kramer.pdf (accessed on 11 August 2017) IBIS World website, https://www.ibisworld.com/procurement-research-reports/chemicals-fuels-wood-products/activated-carbon.html (accessed on 11 August 2017) Atlantic Coal website, http://www.atlanticcoal.com/Investors/Docs/Atlantic%20Coal%20Anthracite%20Fact%20Sheet%20(1).pdf (accessed on 11 August 2017) US Energy Information Administration website, https://www.eia.gov/energyexplained/index.cfm?page=coal_prices (accessed on 11 August 2017) ICIS website, https://www.icis.com/resources/news/2000/05/15/114502/chemical-prices-sa/ (accessed on 11 August 2017) Ash M, https://books.google.co.uk/books?id=C4Cr8dHupVsC (accessed on 11 August 2017) Drugs.com website, https://www.drugs.com/inactive/cellulose-164.html (accessed on 11 August 2017) Marques-Marinho & Vianna-Soares, http://cdn.intechopen.com/pdfs/45627/InTech-Cellulose_and_its_derivatives_use_in_the_pharmaceutical_compounding_practice.pdf (accessed on 11 August 2017) Prices for some alternatives sourced from Alibaba.com

A1.2 Substance 2: Chromium trioxide

A1.2.1 Identity of the substance

Table 9-5: Identity of chromium trioxide Name of substance Chromium trioxide Synonyms trioxochromium EC Number 215-607-8 CAS Number 1333-82-0 Molecular formula CrO3

Substitution of Chemical Substances of Potential Concern | 73 Table 9-5: Identity of chromium trioxide

REACH Registration tonnage band 10,000 – 100,000 tonnes per annum Sources: https://echa.europa.eu/registration-dossier/-/registered-dossier/15927

A1.2.2 Functionality and applications

Table 9-6: Functionality and applciations for chromium trioxide General description of functionality and The main uses of chromium trioxide are metal finishing, manufacture of wood preservation products, catalyst manufacture, key physico-chemical parameters1 chromium dioxide manufacture and pigment manufacture.

Physico-chemical properties: Boiling point: N/A decomposes at ~250°C to Cr2O3 and O2 Melting point: 196°C Density: 0.72kg/m3 Vapour pressure: N/A inorganic ionic compound Partition coefficient (log Pow): N/A inorganic ionic compound Water solubility : ~1.667g/l

CLH2: Acute Tox. 3 – H301, H311 Acute Tox. 2 – H330 Skin Corr. 1A – H314 Skin Sens. 1 – H317 STOT RE 1 – H372 Resp. Sens. 1 – H334 Muta 1B – H340 Carc. 1A – H350

Substitution of Chemical Substances of Potential Concern | 74 Table 9-6: Functionality and applciations for chromium trioxide Repr 2 – H361f Aquatic Acute 1 – H400 Aquatic Chronic 2 – H411

Average cost per tonne = €2915.40 Family the substance belongs to Chromium (VI) compounds Electropolishing3 Sector of Use SU 15: manufacture of fabricated metal products, except machinery and equipment Product category PC14: metal surface treatment products, including galvanic and electroplating products Industrial/Professional/ Consumer Industrial users: PROC 2: Use in closed, continuous process with occasional controlled exposure. PROC 8b: transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities. PROC 9: transfer of substance or preparation into small containers (dedicated filling line, including weighing) PROC 10: roller application or brushing. Description Chromium trioxide is used as an electrolyte for electropolishing aluminium in order to smooth the surface. Use in a catalyst4 Sector of Use SU 8: Manufacture of bulk, large scale chemicals (including petroleum products) Product category PC 20: Products such as ph-regulators, flocculants, precipitants, neutralisation agents Industrial/Professional/ Consumer PROC 1: Use in closed process, no likelihood of exposure PROC 15: Use as laboratory reagent PROC 26: Handling of solid inorganic substances at ambient temperature PROC 28: Manual maintenance (cleaning and repair) of machinery Description Use of chromium trioxide in a catalyst for the dehydrogenation of propane to propene. Catalyst consists of an alumina carrier that is surface treated with chromium reagents. The industrial process is characterised by a high level of automation where the propene production is undertaken in a closed reactor without human intervention. Key functional requirements of the catalyst: • To be used in a fixed bed reactor • High selectivity for the desired product, low amount of unwanted by- products • High conversion rate, resulting in a more efficient process with lower energy cost and higher production volume

Substitution of Chemical Substances of Potential Concern | 75 Table 9-6: Functionality and applciations for chromium trioxide • Long life cycle of the catalyst • Mechanical strength of the catalyst: to avoid attrition caused by pressure changes and during loading of the reactor • Thermal conductivity and heat capacity: the potential to store and release heat during the dehydrogenation cycle

Sources: 1 https://echa.europa.eu/documents/10162/f5f958a9-8ec8-45ba-b30a-0d7a143b6a12 2 https://echa.europa.eu/information-on-chemicals/cl-inventory-database/-/discli/details/14356 3 https://echa.europa.eu/registration-dossier/-/registered-dossier/15927/3/1/4 4 https://echa.europa.eu/addressing-chemicals-of-concern/authorisation/applications-for-authorisation-previous-consultations/-/substance- rev/15316/term?_viewsubstances_WAR_echarevsubstanceportlet_SEARCH_CRITERIA_EC_NUMBER=215-607-8&_viewsubstances_WAR_echarevsubstanceportlet_DISS=true

A1.2.3 Potential alternatives

Table 9-7: Identification of potential alternatives for chromium trioxide Application 1 Electropolishing of aluminium Name/description of Alternative electrolytes that replace the need for chromium trioxide: alternative5 • Phosphoric acid • Sulphuric acid • Nitric acid • Sulfonitroferric acid (mixture of sulphuric acid, nitric acid and ferric ions) Identifiers (if chemical Substance name EC Number CAS Number substance)5 Phosphoric acid 231-633-2 7664-38-2 Sulphuric acid 231-633-2 7664-93-9 Nitric acid 231-714-2 7697-37-2 Sulfonitroferric acid (mixture of sulphuric acid, nitric acid and N/A N/A ferric ions)

Description of Phosphoric acid applicability of Use is at a developmental stage. It is more aggressive than Cr(VI)-based solutions for oxide removal and can cause higher degrees of end grain pitting alternatives5 and intergranular attacks. Does not yet prepare the surface equivalently to chromium trioxide-based solutions. Sulphuric acid

Substitution of Chemical Substances of Potential Concern | 76 Table 9-7: Identification of potential alternatives for chromium trioxide Use is at a developmental stage. It is more aggressive than Cr(VI)-based solutions for oxide removal and can cause higher degrees of end grain pitting and intergranular attacks. Does not yet prepare the surface equivalently to chromium trioxide-based solutions. Nitric acid Use is at a developmental stage. It is more aggressive than Cr(VI)-based solutions for oxide removal and can cause higher degrees of end grain pitting and intergranular attacks. Does not yet prepare the surface equivalently to chromium trioxide-based solutions. Sulfonitroferric acid Already qualified and implemented for surface preparation on aluminium alloys for some specific applications in the aerospace industry. Application 2 Use in a catalyst Name/description of Alternative process alternative Oleflex process using a platinium catalyst Krupps-Uhde STAR process using a platinum/tin catalyst Identifiers (if chemical Substance name EC Number CAS Number substance) Platinum 231-116-1 7440-06-4 Tin 231-141-8 7440-31-5 Description of Oleflex process applicability of Catalytic dehydrogenation of propane to propene, independent of a steam cracker of FCC unit, using a moving bed reactor. alternatives6 Krupps-Uhde STAR process Combination of catalytic dehydrogenation and oxydehydrogenation of propane to propene using steam. Sources: 5 https://echa.europa.eu/documents/10162/abfeff08-5b9e-4e89-8296-8d8f08c1aac7 6 https://echa.europa.eu/addressing-chemicals-of-concern/authorisation/applications-for-authorisation-previous-consultations/-/substance- rev/15316/term?_viewsubstances_WAR_echarevsubstanceportlet_SEARCH_CRITERIA_EC_NUMBER=215-607-8&_viewsubstances_WAR_echarevsubstanceportlet_DISS=true

A1.2.4 Assessment of feasibility of potential alternatives

Table 9-8: Assessment of potential alternatives for chromium trioxide Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Phosphoric acid7 1 At the developmental stage and requires more research to Average cost per Environmental Hazards Registered 100,000 – ascertain whether or not it can be a suitable alternative. It tonne = €609.10 No CLH, no PBT properties. 10,000,000 tonnes currently does not produce the same level of effectiveness as chromium trioxide electrolytes. The use of this would Readily available. Human Health Hazards

Substitution of Chemical Substances of Potential Concern | 77 Table 9-8: Assessment of potential alternatives for chromium trioxide Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability mean that further steps in the treatment of aluminium CLH for Skin Corrosion 1B would need to change as the effectiveness of this (H314). alternative is not as high as chromium trioxide solutions. Depending on the Can be used in combination with sulphuric acid. Process8: concentration, phosphoric Sulphuric acid 4-45% acid entails acute toxicity Phosphoric acid 40-80% issues. In addition, contact Voltage 7-15V with strong bases, Current density 2.7-100 A/dm2 oxidisers and certain Temperature 70-95°C metals can lead to violent Operation time 20 minutes. reactions or explosions.

Process 29: Current density 5-15 A/d m2 Temperature 64-67 °C Operation time 2-10 minutes

Process 3: Phosphoric acid Ethanol 95% Water Voltage 25-30 V Operation time 4-6 minutes Michael Bauccio (1993) ASM Metals Reference Book. ASM International. 3rd edition Sulphuric acid7 1 At the developmental stage and requires more research to Average cost per Environmental Hazards Registered 10,000,000 – ascertain whether or not it can be a suitable alternative. It tonne = €196.70 No CLH, no PBT properties. 100,000,000 tonnes and currently does not produce the same level of effectiveness 10-100 tonnes. as chromium trioxide electrolytes. The use of this would Readily available. Human Health Hazards mean that further steps in the treatment of aluminium CLH for Skin Corrosion 1A would need to change as the effectiveness of this (H314). alternative is not as high as chromium trioxide solutions. Sulphuric acid is a highly Can be used in combination with sulphuric acid. Process8: corrosive element that, in

Substitution of Chemical Substances of Potential Concern | 78 Table 9-8: Assessment of potential alternatives for chromium trioxide Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Sulphuric acid 4-45% contact with metals may Phosphoric acid 40-80% lead to the formation of Voltage 7-15V hydrogen gas and Current density 2.7-100 A/dm2 therefore to combustion Temperature 70-95°C or explosion. Operation time 20 minutes.

Process 29: Current density 5-15 A/d m2 Temperature 64-67 °C Operation time 2-10 minutes

Can also be used in combination with nitric acid and ferric ions. Nitric acid7 1 At the developmental stage and requires more research to Average cost per Environmental Hazards Registered 10,000,000 – ascertain whether or not it can be a suitable alternative. It tonne = €343.40. No CLH, no PBT properties. 100,000,000 tonnes currently does not produce the same level of effectiveness as chromium trioxide electrolytes. The use of this would Readily available. Human Health Hazards mean that further steps in the treatment of aluminium CLH for Skin Corrosion 1A would need to change as the effectiveness of this (H314) alternative is not as high as chromium trioxide solutions. Nitric acid is a highly corrosive element and a powerful oxidising agent. In contact with other compounds may lead to violent reactions such as explosions. Sulfonitroferric 1 This mixture is commercially available for some Cannot determine Environmental and human Not registered. acid7 applications. The use of this would mean that further steps cost. health hazards will depend in the treatment of aluminium would need to change as on the concentration of the effectiveness of this alternative is not as high as each substance within the chromium trioxide solutions. mixture. A standard composition has not been

Substitution of Chemical Substances of Potential Concern | 79 Table 9-8: Assessment of potential alternatives for chromium trioxide Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability given in the literature. Oleflex process 2 Uses a platinum catalyst in a moving bed reactor as Would require the Environmental Hazards Platinum registered 10- with platinum opposed to a fixed bed reactor. Has similar overall industrial site to be Use of platinum in this 100 tonnes. (registered for based catalyst10 performance to Cr catalyst Catofin process. reconstructed as process has self catalyst use) Commercialised for propane dehydrogenation in the process is different. classifications for Harmful 1990s. Cannot use the platinum catalyst currently in use in to the aquatic this process in a Lummus process fixed-bed reactor Approximate cost to environment 4 (chronic because of the catalyst size and shape. The difference in build Oleflex plant: (H413)). pressure drop and equal distribution of gas over the 250kt capacity = catalyst bed is defined by the catalyst shape and size. €350m Human Health Hazards (costs are not Use of platinum in this The platinum catalyst is smaller and spherical whilst the Cr entirely comparable) process has self catalyst is cylindrical. Therefore the pressure drop when classifications for Skin using the platinum catalyst would be too high, reducing the Sensitisation 1 (H317). propane conversion rate.

Licensing conditions could be an issue. Krupps-Uhde STAR 2 The first production unit was awarded in 2006 and atarted Would require the Environmental Hazards Platinum registered 10- process using in 2010. industrial site to be Use of platinum in this 100 tonnes. (registered for platinum/tin reconstructed as process has self catalyst use) based catalyst10 Uses high pressure, reaction in the presence of steam, process is different. classifications for Harmful catalysts in tubes, external heating of tubes which are to the aquatic Tin registered 10,000- placed in afurnace. Approximate cost to environment 4 (chronic 100,000 tonnes (not build a STAR plant: (H413)). Use of tin in this registered for catalyst use) Licensing conditions could be an issue. 250kt plant = €450m process has no classification.

Human Health Hazards Use of platinum in this case has self classifications for Skin Sensitisation 1 (H317). Use of tin in this process has a classification for Eye Irritation 2 (H319)

Substitution of Chemical Substances of Potential Concern | 80 Table 9-8: Assessment of potential alternatives for chromium trioxide Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability 7 https://echa.europa.eu/documents/10162/abfeff08-5b9e-4e89-8296-8d8f08c1aac7 8 http://core.materials.ac.uk/repository/eaa/talat/5201.pdf 9 http://foster-chemicals.de/en/portfolio-items/electropolishing-steel-aluminum/?portfolioID=11682 10 https://echa.europa.eu/addressing-chemicals-of-concern/authorisation/applications-for-authorisation-previous-consultations/-/substance- rev/15316/term?_viewsubstances_WAR_echarevsubstanceportlet_SEARCH_CRITERIA_EC_NUMBER=215-607-8&_viewsubstances_WAR_echarevsubstanceportlet_DISS=true

Substitution of Chemical Substances of Potential Concern | 81 A1.3 Substance 3: Glutaraldehyde

A1.3.1 Identity of the substance

Table 9-9: Identity of Glutaraldehyde Name of substance Glutaraldehyde Synonyms 1,5-Pentanedial Glutaral Glutardialdehyde Glutaric dialdehyde EC Number 203-856-5 CAS Number 111-30-8 Molecular formula C5H8O2

REACH Registration tonnage band 1000+ tonnes per annum Sources: http://dissemination.echa.europa.eu/Biocides/ActiveSubstances/1310-02/1310-02_Assessment_Report.pdf

A1.3.2 Functionality and applications

Table 9-10: Functionality and applications for Glutaraldehyde General description of functionality and This substance has biocidal properties and is approved as an active substance for use in the product types1: key physico-chemical parameters 2 - Disinfectants and algaecides not intended for direct application to humans or animals 3 - Veterinary hygiene

Substitution of Chemical Substances of Potential Concern | 82 Table 9-10: Functionality and applications for Glutaraldehyde 4 – Food and feed area 6 – Preservatives for products during storage 11 – Preservatives for liquid-cooling and processing systems 12 – Slimicides.

It has biocidal effects against fungi, bacteria and certain viruses. It is usually sold commercially in 45% or 50% aqueous solutions. There are a number of suggested uses for glutaraldehyde but not all of these are registered within the EU. It can be used as a cold disinfectant in the health care industry for the sterilisation of clinical instruments, in the form of 1% or 2% aqueous solution activated by an alkaline buffer; a hardener (cross-linker) in x-ray film processing; treatment of water in cooling towers, air washers and water recirculation systems in the form of aqueous solutions of 15-50%; biocide in the pulp and paper industry to inhibit micro-organism growth in pulp slurries in the form of 10-50% aqueous solutions; a preservative in cleaning agents at varying concentrations; biocide in the petroleum industry; disinfection of animal and bird houses at varying concentrations depending on the form of application; softening leathers and improving their resistance to water, alkalis or mould in the form of 0.5-2% solutions; tissue fixative in histology and electron and light microscopy in the form of 1.5-6% aqueous solution; control of viruses and other micro-organisms in fish farming; preservative in cosmetics up to a concentration of 0.1%.

Average cost per tonne = €1546

Physico-chemical properties2: Boiling point: 188°C (at 1002 hPa) Melting point: -14°C Density: 0.72kg/m3 Vapour pressure: 60 Pa at 20°C Partition coefficient (log Pow): -0.01 Water solubility : miscible pH : mildly acidic (50% solution)

CLH3: Acute Tox. 3 – H301 Acute Tox. 2 – H330 Skin Corr. 1B – H314 Skin Sens. 1A – H317 STOT SE 3 – H335 Resp. Sens. 1 – H334 Aquatic Acute 1 – H400

Substitution of Chemical Substances of Potential Concern | 83 Table 9-10: Functionality and applications for Glutaraldehyde Aquatic Chronic 2 – H411 Family the substance belongs to Aldehydes Health services cleaning Sector of Use SU 20 Health services4 Product category PC8 biocidal products4 Industrial/Professional/ Consumer Professional users – PROC 19 – hand-mixing with intimate contact. Exposure of hands and forearms can be expected; no dedicated tools or specific exposure controls other than PPE can be put in place4. Consumers – direct exposure if rinsing is inadequate2 Description Biocidal product Hard surface disinfection in hospitals and disinfection of medical equipment. Target organisms: bacteria, mycobacteria, bacterial spores. Fungi, virus, algae, biofilms5. Used in the form of 1% or 2% aqueous solution which has to be activated by an alkaline buffer, e.g. sodium bicarbonate. Cosmetic products Sector of Use Not provided in Registration dossier Product category PC 39 Cosmetics, personal care products4 Industrial/Professional/ Consumer Professional and Consumer. Exposure linked to cosmetic use. Mean total estimate for consumer exposure to glutaraldehyde 0.037mg/kg/day2 Description Use as a preservative in cosmetics below 0.1%, it is not allowed in aerosols or sprays6. Leather tanning Sector of Use SU 5 Manufacture of textiles, leather, fur Product category PC 23 leather tanning, dye. Finishing, impregnation and care products Industrial/ Professional/ Consumer Limited occupational exposure2. Description Used to soften leather and improve their resistance to water, alkalis and mould2. Leathers are typically soaked in a solution containing 0.5-2% glutaraldehyde2. Sources: 1https://echa.europa.eu/information-on-chemicals/biocidal-active- substances?p_p_id=echarevbiocides_WAR_echarevbiocidesportlet&p_p_lifecycle=1&p_p_state=normal&p_p_mode=view&p_p_col_id=column- 1&p_p_col_pos=1&p_p_col_count=2&_echarevbiocides_WAR_echarevbiocidesportlet_javax.portlet.action=searchBiocidesAction 2 http://www.inchem.org/documents/sids/sids/111308.pdf 3 https://echa.europa.eu/information-on-chemicals/cl-inventory-database/-/discli/details/115859 4 https://echa.europa.eu/registration-dossier/-/registered-dossier/1930/3/1/5 5http://dissemination.echa.europa.eu/Biocides/ActiveSubstances/1310-02/1310-02_Assessment_Report.pdf 6 http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2009:342:0059:0209:en:PDF

Substitution of Chemical Substances of Potential Concern | 84 A1.3.3 Potential alternatives

Table 9-11: Identification of potential alternatives for glutaraldehyde Application 1 Health service cleaning (PT2) Name/description of Peracetic acid alternative 5-Chloro-2-(4-chlorophenoxy)-phenol (DCPP) Ampholyt Propan-2-ol Identifiers (if chemical Substance name EC Number CAS Number substance) Peracetic acid 201-186-8 79-21-0 5-Chloro-2-(4-chlorophenoxy)-phenol (DCPP) 429-290-0 3380-30-1 Ampholyt Propan-2-ol 139734-65-9 200-667-7 67-63-0 Description of applicability of • Paracetic acid7 – can be used for the disinfection of surfaces in health care areas through wiping with flat mops or cleaning cloths. 20ml alternatives of solution is needed per m2 of surface treated. The likely concentration is 1500ppm. Requires the use of PPE. This substance exerts toxic effects on target organisms including bactericidal, fungicidal and sporicidal activity within PT2. It has harmonised classifications for Acute Tox (H302, H312, H332); Skin Corr 1A (H314); Aquatic Acute 1 (H400). Expiry date of active substance approval is 01/10/2027. • 5-Chloro-2-(4-chlorophenoxy)-phenol 8 – is used as a bactericide in hospitals. The final solution used for disinfection tends to be 0.004% w/w and is used in mopping or wiping with a cloth. Typically 0.8g is required per m2 (equivalent of 40ml in 1:50 diluted cleaning solution). Maximum concentration of DCPP in a biocidal product is 0.2%w/w. harmonised classifications for DCPP include Eye Dam 1 (H318); Aquatic Acute 1(H400); Aquatic Chronic 1 (H410). Expiry of active substance approval is 01/12/2026. • Ampholyt 9 – can be used as a disinfectant for hard surfaces in health care areas. The spectrum of antimicrobial activity is focused on the destruction of gram-positive and gram-negative bacteria, yeasts and has limited virucidal activity against enveloped viruses and non-enveloped adenovirus. The concentration range tends to be 20% w/w. it can be used for low pressure spraying, mopping, wiping and ready-to-use trigger sprays. This substance does not appear in the CLI. Proposed classifications are Acute Tox 4 (H302); Skin Corr 1 (H314); Repro 2 (H361f); STOT RE 1 (H372); Aquatic Acute 1 (H400); Aquatic Chronic 1 (H410). The expiry date for active substance approval is 01/01/2028. • Propan-2-ol 10 – this substance is used in ready-to-use products for the health care industry. These products tend to be sprayed or wiped over the surface. The target organisms are obligate or facultative pathogenic bacteria such as mycobacteria; fungi and viruses. The concentration of the active substance in the solution tends to be 70%. Propan-2-ol has harmonised classifications for Eye Irrit 2 (H319) and STOT SE 3 (H336). Application 2 Cosmetic products Name/description of Alternative substances: alternative Parabens: e.g. methylparaben, ethylparaben, propylparaben, butylparaben.

Substitution of Chemical Substances of Potential Concern | 85 Table 9-11: Identification of potential alternatives for glutaraldehyde 2-methyl-2H-isothiazol-3-one (methylisothiazolinone (MIT)) 2-phenoxyethanol Identifiers (if chemical Substance name EC Number CAS Number substance) methylparaben 202-785-7 99-76-3 ethylparaben 204-399-4 120-47-8 propylparaben 202-307-7 94-13-3 butylparaben 202-318-7 94-26-8 2-methyl-2H-isothiazol-3-one (methylisothiazolinone (MIT)) 220-239-6 2682-20-4 2-phenoxyethanol 204-589-7 122-99-6 Description of applicability of Chemical alternatives alternatives • Parabens (methyl - butyl) are widely used preservatives that are suitable for the preservation of cosmetic products against a number of microorganisms including fungi and gram positive bacteria. They are currently allowed for both rinse-off and leave-on cosmetic products meaning that there is a possibility that they could span a similar range of products as glutaraldehyde. None of the selected parabens have a harmonised classification and the self-classifications that have been reported are Skin Irrit. 2, Eye Irrit. 2, STOT SE 3, meaning that they have a lower hazard profile than glutaraldehyde. Methyl and ethylparabens may be used in concentrations up to 0.4% for single ester and 0.8% for mixtures of esters. Butyl and propyl parabens can be used at concentrations up to 0.14% for the sum of individual concentrations and 0.8% for mixtures of substances in entry 12 and 12a of Annex V of the Cosmetic Products Regulation, where the individual concentrations of butyl or propyl paraben does not exceed 0.14%. Butyl and propyl parabens cannot be used in leave-on cosmetics for application to the nappy area of children under 3 years of age. • 2-methyl-2H-isothiazol-3-one is preservative approved for use in rinse-off cosmetic products up to a concentration of 0.01%. It is banned for use in leave-on cosmetic products due to the risk of skin sensitisation. MIT does not currently have a CLH, although a CLH proposal was submitted by Slovenia for Acute Tox. 3, H301 Acute Tox. 3, H311 Acute Tox. 1, H330 Skin Corr. 1B, H314 Skin Sens. 1A, H317 STOT SE 3, H335 Aquatic Acute 1, H400 Aquatic Acute 1. The 18 month deadline for opinion adoption has passed but this opinion does not appear to have been adopted. The self-classifications listed are Acute Tox. 2-4; Skin Corr. 1B/1C; Skin Sens. 1/1A; STOT SE 3; STOT RE 2; Eye Dam. 1; Aquatic Acute 1; Aquatic Chron. 1. • 2-phenoxyethanol is authorised for use in cosmetic products up to a concentration of 1.0%. 2-phenoxyethanol has harmonised classifications for Acute Tox. 4 (H302) and Eye Irrit. 2 (H319). 2-phenoxyethanol is susceptible to sublimation and evaporation during manufacture and product lifecycle as it is relatively volatile, it can also be adsorbed by PVC and cellulose-based excipients11. Application 3 Leather tanning Name/description of Alternative substances: oxazolidines (4,4-dimethyloxazolidine; 7a-ethyldihydro-1H,3H,5H – oxazolo[3,4-c]oxazole; 1H,3H,5H-oxazolo[3,4- alternative c]oxazole-7a(7H)-methanol), vegetable tanning agents (hydrolysable pyrogallol (myrobalan, oak, sumac, chestnut etc.) or condensed, catechol based tannins (mimosa, quebracho)) Identifiers (if chemical Substance name EC Number CAS Number substance) Oxazolidines:

Substitution of Chemical Substances of Potential Concern | 86 Table 9-11: Identification of potential alternatives for glutaraldehyde 4,4-dimethyloxazolidine 257-048-2 51200-87-4 7a-ethyldihydro-1H,3H,5H-oxazolo[3,4-c]oxazole 231-810-4 7747-35-5 1H,3H,5H-oxazolo[3,4-c]oxazole-7a(7H)-methanol 229-457-6 6542-37-6 Description of applicability of • There are three oxazolidines that could be used as alternatives to glutaraldehyde in leather tanning. There is a need to combine these alternatives substances with a synthetic (syntan) or vegetable tanning agent in order to raise the shrinkage temperature to around 80°C. The syntan or vegetable tanning agent chosen depends on the individual case with syntans being suitable for lighter colours and high light-fastness; and vegetable tanning agents for darker colours with no light-fastness required. There is a need to remove free-formaldehyde from the leather after tanning which can be done through intensification of skin washing or prevention or use of formaldehyde-free syntans and vegetable tanning agents. The use of oxazolidines meets the requirement s for hazardous substance content limits according to the EU ecolabel criteria. Only a 3% concentration is required for the tanning solution.15 None of the oxazolidines have harmonised classifications. • Vegetable tanning agents – the type of vegetable tanning agent used will depend on the type of leather that is required. Human health concerns associated with vegetable tanning agents are limited, but environmental concerns do exist. Vegetable tanning agents have low biodegradability, as such they have very high chemical oxygen demand (COD)12. This will decrease the amount of oxygen available for aquatic organisms and can increase algal blooms. Tanning using vegetable tanning agents can take longer than chemical treatment (weeks rather than days). Sources: 7 http://dissemination.echa.europa.eu/Biocides/ActiveSubstances/1340-02/1340-02_Assessment_Report.pdf 8 http://dissemination.echa.europa.eu/Biocides/ActiveSubstances/1232-02/1232-02_Assessment_Report.pdf 9 http://dissemination.echa.europa.eu/Biocides/ActiveSubstances/1240-02/1240-02_Assessment_Report.pdf 10 http://dissemination.echa.europa.eu/Biocides/ActiveSubstances/1355-02/1355-02_Assessment_Report.pdf

A1.3.4 Assessment of feasibility of potential alternatives

Table 9-12: Assessment of potential alternatives for glutaraldehyde Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Peracetic acid 1 Unable to quantify how many biocidal Available in aqueous solution or in Environmental hazards: Registered at 1000 – products it is currently used in as not powder form. Peracetic acid has a 10,000 tonnes. present in R4BP3 database. harmonised classification Average cost per tonne = €547.71 for harmful to the aquatic Number of Article 95 list suppliers (as environment (acute 1,

Substitution of Chemical Substances of Potential Concern | 87 Table 9-12: Assessment of potential alternatives for glutaraldehyde of 2017) = 28. High cost compare with H400). It is not a PBT glutaraldehyde. substance based on its Target organisms are spores, bacteria, intrinsic properties. viruses and fungi. Human Health hazards: Disinfection time from 10 minutes and Peracetic acid has stable between 1 and 30 days. A harmonised classifications concentration of 0.2% is active against for Acute Toxicity 4 (H302, microorganisms. H312, H332) and Skin Corrosion 1A Less harmful decomposition products: acetic acid and water. 5-Chloro-2-(4- 1 Unable to quantify how many biocidal Unable to establish cost. Does not Environmental hazards: Full registration at 0 chlorophenoxy)-phenol products it is currently used in as not appear in the product list of the Article Harmonised classification – 10 tonnes. (DCPP) present in R4BP3 database. 95 supplier. for harmful to the aquatic NONS registration environment (acute H400 Number of Article 95 list suppliers (as and chronic H410). It is not of 2017) = 1. a PBT substance based on its intrinsic properties. Target organisms: bacteria Human Health hazards: Harmonised classification for Eye Damage 1 (H318) Ampholyt 1 Unable to quantify how many biocidal The only Article 95 supplier no longer Environmental hazards: No registration but products it is currently used in as not has this product in their portfolio. No entry in CLI. It is not a approved for use as present in R4BP3 database. PBT substance based on its an active substance intrinsic properties. under BPR. Number of Article 95 list suppliers (as of 2017) = 1 Human Health hazards: Target organisms: gram-positive and No entry in CLI. It is not a gram-negative bacteria, yeasts and has PBT substance based on its limited virucidal activity against intrinsic properties. enveloped viruses and non-enveloped adenovirus

Substitution of Chemical Substances of Potential Concern | 88 Table 9-12: Assessment of potential alternatives for glutaraldehyde Propan-2-ol 1 Unable to quantify how many biocidal Average price per tonne = €898.25 Environmental hazards: Registered 100,000 products it is currently used in as not No CLH, It is not a PBT – 1,000,000 tonnes present in R4BP3 database. substance based on its Registered 0 – 10 intrinsic properties. tonnes Number of Article 95 list suppliers (as of 2017) = 41. Human Health hazards: Harmonised classification Target organisms: obligate or for Eye Irritation 2 (H319) facultative pathogenic bacteria such as and STOT SE 3 (H336). mycobacteria; fungi and viruses. Parabens: 2 The pH range for parabens is between - methylparaben 4-8, they may be susceptible to Average price per kg €4.51. Likely to be Environmental hazards: Registered 1000 – sublimation or evaporation during sold in small quantities to smaller NO CLH. Self classifications 10,000 tonnes and manufacture of during product life manufacturers of cosmetics. The price for Harmful to the aquatic for intermediate cycle and may adsorb to ion exchange for sale to larger companies like environment (chronic 3, use only. resins and some plastics. Parabens may L’Oréal is likely to be in tonnes rather H412). It is not a PBT need to be combined with other than kg. substance based on its Appears on CoRAP preservatives (EDTA or intrinsic properties. list. phenoxyethanol) in order to preserve against gram negative bacteria. 11 Human Health hazards: No CLH. Self classifications for Skin Irritant 2 (H315), Eye Irritant 2 (H319), STOT SE 3 (H335 – respiratory tract), mutagen 2 (H341) (only appears once), Acute Tox 4 (H302), Respiratory sensitiser 1 (H334) (only appears once), Skin sensitiser 1 (H317). - ethylparaben Average price per kg €4.85. Likely to be Environmental hazards: Registered 100 – sold in small quantities to smaller No CLH or self 100 tonnes. manufacturers of cosmetics. The price classifications. It is not a for sale to larger companies like PBT substance based on its Appears on CoRAP L’Oréal is likely to be in tonnes rather intrinsic properties. list

Substitution of Chemical Substances of Potential Concern | 89 Table 9-12: Assessment of potential alternatives for glutaraldehyde than kg. Human Health hazards: No CLH. Self classifications for Aspiration toxicity 1 (H304), skin irritant 2 (H315), Skin sensitiser 1 (H317), eye irritant 2 (H319), STOT SE 3 (H335 respiratory system), Acute Toxicity 4 (H302), Respiratory Sensitiser 1 (H334) - propylparaben Average price per kg €6.12. Likely to be Environmental hazards: Registered 100- sold in small quantities to smaller No CLH. Self classifications 1000 tonnes manufacturers of cosmetics. The price for harmful to the aquatic for sale to larger companies like environment (Acute 1 Appears on CoRAP L’Oréal is likely to be in tonnes rather (H400), Chronic 4 (H413)). list than kg. Possible price per tonne It is not a PBT substance €1463.29 based on its intrinsic properties.

Human Health hazards: No CLH. Self classifications for Skin Irritant 2 (H315), Eye Irritant 2 (H319), STOT SE 3 (H335 respiratory tract), Eye Damage 1 (H318), Skin Sensitiser 1 (H317), Respiratory Sensitiser 1 (H334) (only one entry). - butylparaben Likely to be sold in small quantities to Environmental hazards: Not registered smaller manufacturers of cosmetics. No CLH. Self classifications The price for sale to larger companies for harmful to the aquatic like L’Oréal is likely to be in tonnes environment (Chronic 4

Substitution of Chemical Substances of Potential Concern | 90 Table 9-12: Assessment of potential alternatives for glutaraldehyde rather than kg. Possible price per (H413)). It is not a PBT tonne €1463.29 substance based on its intrinsic properties.

Human Health hazards: No CLH. Self classifications for Skin Irritant 2 (H315), Eye Irritant 2 (H319), STOT SE 3 (H335 respiratory tract), Eye Damage 1 (H318), Skin Sensitiser 1 (H317). 2-methyl-2H-isothiazol-3- 2 It has biocidal effects on bacteria, Average cost per tonne €2038.86. Environmental hazards: Not registered. one (methylisothiazolinone viruses, fungi and protozoans. MIT is No CLH. Self classifications PACT list (MIT)) compatible with ingredients within the for harmful to the aquatic pH range of 2-912 and is effective at low environment (acute 1 quantities. 12 (H400)).

Human Health hazards: It is banned for use in leave-on No CLH. Self classifications cosmetics which means that it may not for Acute Toxicity 3 (H301, be able to be used in all cosmetic H311), Skin Corrosion 1B applications that glutaraldehyde is (H314), Skin sensitiser 1 currently used in. (H317), Eye damage 1 (H318), STOT SE 3 (H335 lungs and respiratory tract), Acute Tox 4 (H302, H322), 2-phenoxyethanol 2 It is a broad spectrum preservative, Average cost per tonne = €1744.26 Environmental hazards: Registered 10,000 – acting on gram-positive/ negative No CLH. 100,000 tonnes bacteria, yeast and molds13. Human Health hazards: It can be enhanced in combination with harmonised classification EDTA, caprylyl glycol, sorbic for Acute Toxicity 4 acid/potassium sorbate14. 2- (H302), Eye Irritant 2

Substitution of Chemical Substances of Potential Concern | 91 Table 9-12: Assessment of potential alternatives for glutaraldehyde phenoxyethanol is not pH dependent, (H319) making it suitable for a broad range of cosmetic products.

Oxazolidines: 3 They are water soluble and compatible 4,4-dimethyloxazolidine with most chemicals used in the Only two prices found - €275.48 and Environmental hazards: Not registered tanning of leather. The suitability of €368.15 per gram. It is unclear if this is No CLH. Self classification these substances for the production of representative of the market. for harmful to the aquatic leather used for numerous environment (chronic 3 applications can be tested in part by (H412)) looking at their shrinkage temperature which is around 75°C when used on its Human Health hazards: own. As such there is a need to No CLH. Self classifications combine these substances with a for Acute Toxicity 3 synthetic (syntan) or vegetable tanning (H331), Acute Toxicity 4 agent in order to raise the shrinkage (H302, H312, H322), Skin temperature to around 80°C. The Irritation 2 (H315), Eye syntan or vegetable tanning agent Damage 1 (H318), STOT SE chosen depends on the individual case 3 (H335 respiratory tract), with syntans being suitable for lighter Skin Sensitiser 1 (H317) 7a-ethyldihydro-1H,3H,5H – colours and high light-fastness; and Only two prices found - €159.76 - Environmental hazards: Registered 100 – oxazolo[3,4-c]oxazole vegetable tanning agents for darker €129.86 per kg. It is unclear if this is No CLH. Self classifications 1000 tonnes colours with no light-fastness representative of the market. for harmful to the aquatic required.15, 16 environment (chronic 1, 3 (H412), acute 1 (H400))

Human Health hazards: No CLH. Self classifications for Skin Irritant 2 (H315), Skin Sensitiser 1 (H317), Eye Damage 1 (H318), Acute Toxicity 4 (H312, H332), Eye Irritant 2 (H319), Respiratory Sensitiser 1 (H334), STOT

Substitution of Chemical Substances of Potential Concern | 92 Table 9-12: Assessment of potential alternatives for glutaraldehyde SE 3 (H335 respiratory system, lungs) 1H,3H,5H-oxazolo[3,4- Only one price has been found - Environmental hazards: Not registered c]oxazole-7a(7H)-methanol €482.56 No CLH or self classifications

Human Health hazards: No CLH or self classifications vegetable tanning agents: 3 The shrinkage temperature of Prices vary depending on the tanning Environmental hazards: None are Hydrolysable pyrogallol vegetable tanning agents is in a similar agent being used. Average prices for depends on the tannin but registered. (myrobalan, oak, sumac, range as glutaraldehyde: condensed hydrolysable pyrogallols like no CLH. Self classification: chestnut etc.) tannins - ~84°C, hydrolysable tannins – myrobalan - €33.35 per kg, €570 per Mimosa – harmful to the condensed, catechol based 73 - 75°C17. tonne. Average price for condensed, aquatic environment tannins (mimosa, catechol based tannins such as (chronic 3 (H412)) quebracho) quebracho - €22.86 per kg. Human Health hazards: depends on the tannin but no CLH. Self classification: Oak – Acute Toxicity 3, 4 (H331, H302), Skin Sensitiser 1 (H317), Carcinogen 2 (H351); Chestnut – Eye Irritant (H319); Mimosa – Acute Toxicity 4 (H302, H332). 11 http://www.americanpharmaceuticalreview.com/Featured-Articles/38885-Antimicrobial-Preservatives-Part-Two-Choosing-a-Preservative/ 12 http://www.skininc.com/skinscience/ingredients/17013151.html 13 https://www.in-cosmetics.com/__novadocuments/2426 14 http://microchemlab.com/five_most_common_types_of_preservatives_used_in_cosmetics 15 http://ec.europa.eu/environment/life/project/Projects/index.cfm?fuseaction=home.showFile&rep=file&fil=OXATAN_Manual_Curticion.pdf 16 Covington, Anthony. D. (2009) Tanning Chemistry: The Science of Leather. Royal Society of Chemistry, p304 17 Hassoune, J., Tahiri, S., Aarfane, A., El krati, M. (2017) Removal of Hydrolyzable and Condensed Tannins from Aqueous Solutions by Electrocoagulation Process. Journal of Environmental Engineering. Vol 143, 6. Available at: http://ascelibrary.org/doi/pdf/10.1061/(ASCE)EE.1943-7870.0001196

Substitution of Chemical Substances of Potential Concern | 93 A1.4 Substance 4: Methanol

A1.4.1 Identity of the substance

Table 9-13: Identity of Methanol Name of substance Methanol Synonyms Methyl alcohol Monohydroxymethane EC Number 200-659-6 CAS Number 67-56-1 Molecular formula CH4O

REACH Registration tonnage band 10,000,000 – 100,000,000 tonnes per annum Sources: ECHA website, https://echa.europa.eu/substance-information/-/substanceinfo/100.000.599 (accessed on 11 July 2017)

A1.4.2 Functionality and applications

Table 9-14: Functionality and applications for Methanol General description of functionality and Methanol is a simple alcohol, it is used to produce other chemicals, it is used within fuels, as a solvent, and as an additive in anti- key physico-chemical parameters freeze. Methanol has a low melting/freezing point (around -98°C) meaning that it is an ideal antifreeze, for example it is used to prevent hydrate formation in onshore and offshore oil & gas production operations. Its properties also mean that it can be used for de-icing e.g. car windscreens and airplanes.

Methanol is classified as being a flammable liquid (Flam. Liq. 2 – H225), as being acutely toxic (Acute Tox. 3: – if swallowed – H301, in contact with skin – H311, if inhaled – H331) and having specific target organ toxicity (STOT SE 1 – causes damage to organs – H370). Methanol is also a PACT and CoRAP substance. Family the substance belongs to Alcohols

Substitution of Chemical Substances of Potential Concern | 94 Table 9-14: Functionality and applications for Methanol Application 1 - Chemical manufacturing Sector of Use SU 8: Manufacture of bulk, large scale chemicals (including petroleum products) SU 9: Manufacture of fine chemicals SU 12: Manufacture of plastics products, including compounding and conversion Product category PC 19: Intermediate Industrial/Professional/Consumer Industrial: Manufacture and use as Intermediate and use as solvent, process aid or intermediate in the manufacturing of pharmaceuticals and intermediates Description The main use of methanol is its use in the manufacturing of other chemicals, this includes formaldehyde, methylamines, chloro-methanes, methanol to olefins (MTO) and methanol to propylene (MTP), acetic acid, methyl tert-butyl ether, dimethyl ether, methyl methacrylate (MMA) among others Application 2 - Fuels Sector of Use SU 0: Other: fuel SU 8: Manufacture of bulk, large scale chemicals (including petroleum products) SU 10: Formulation [mixing] of preparations and/or re-packaging (excluding alloys) Product category PC 13: Fuels Industrial/Professional/Consumer Industrial: Use as fuel in industrial settings Professional: Use as fuel in professional settings Consumer: Consumer use of fuels and fuel additives indoors and consumer use of fuels and fuel additives outdoors Description Methanol is used to produce biodiesel through the process known as transesterification. It is also used in petrol/gasoline and diesel blending with the addition of co-solvents and corrosion inhibitors Application 3 - Solvent Sector of Use SU 9: Manufacture of fine chemicals Product category PC 0: Other: solvent PC 29: Pharmaceuticals Industrial/Professional/Consumer Industrial: Use as solvent, process aid or intermediate in the manufacturing of pharmaceuticals and other chemical products Professional: Professional use as a solvent Consumer: Personal care products

Substitution of Chemical Substances of Potential Concern | 95 Table 9-14: Functionality and applications for Methanol Description Methanol is primarily used as an industrial solvent for inks, resins, adhesives to wood items, and dyes. It is also used as a solvent in the manufacture of cholesterol, streptomycin, vitamins, hormones, and other pharmaceuticals Application 4 - Antifreeze/de-icing Sector of Use SU 2b: Offshore industries SU 8: Manufacture of bulk, large scale chemicals (including petroleum products) SU 9: Manufacture of fine chemicals Product category PC 4: Anti-freeze and de-icing products PC 35: Washing and cleaning products (including solvent based products) Industrial/Professional/Consumer Professional: Offshore and onshore mining/ oil & gas operations Consumer: Consumer use of cleaning agents and de-icers (liquid products) Description Methanol is used to prevent the formation of ice and it is used to help melt ice. Methanol is commonly used in windscreen washer fluids to prevent it from freezing, it is also used in de-icers to help melt ice and methanol has also been used to de-ice planes as an alternative to de-icing salts and glycol-based de-icers. Methanol is also used in the oil & gas industry to prevent hydrates from forming, if hydrates from within pipes lines these have the potential to reduce pipeline flow and pressure, hydrate formation may also lead to a pipeline becoming plugged Sources: ECHA website, https://echa.europa.eu/registration-dossier/-/registered-dossier/15569 (accessed on 11 July 2017)

A1.4.3 Potential alternatives

Table 9-15: Identification of potential alternatives for Methanol Application 1 Chemical manufacturing

Substitution of Chemical Substances of Potential Concern | 96 Table 9-15: Identification of potential alternatives for Methanol Name/description of alternative Alternatives: - Formaldehyde: different process and chemicals (e.g. methane, calcium formate) - Methanol-To-Olefins (MTO): different process and chemicals (hydrocarbon cracking, olefin metathesis, Isobutyl alcohol-to- propylene and Hydrogenation of acetic acid) - Methanol-To-Propylene (MTP): (see above) - Methyl tert-butyl ether (MTBE): (methanol may be the only route of production) - Dimethyl ether (DME): (methanol may be the only route of production) - Acetic acid: different processes and chemicals (Acetaldehyde oxidation (Acetaldehyde), ethylene oxidation (ethylene), oxidative fermentation (alcohols – ethanol) and anaerobic fermentation (sugars – glucose)) - Methyl 2-methylpropenoate (MMA): Condensation (ethylene condensed with formaldehyde and then catalysts), carboalkoxylation (ethylene and then condensed with formaldehyde and catalysts) and oxidative dehydrogenation (propene) - Methlamines: hydrolysis of methyl isocyanate and reaction with acetamide and bromine gas - Chloromethanes: heating methane and chlorine Identifiers (if chemical substance) Substance name EC Number CAS Number Methane / calcium formate 200-812-7 / 208-863-7 74-82-8 / 544-17-2 Hydrocarbons / Ethylene and butane / Various / 200-815-3 and 203-448-7 / 201- Various / 74-85-1 and 106-97-8 / 78-83-1 Isobutyl alcohol / Acetic acid and 148-0 / 200-580-7 and 215-605-7 / 64-19-7 and 1333-74-0 hydrogen Acetaldehyde oxidation / ethylene 200-836-8 / 200-815-3 / 200-814-8 / 200- 75-07-0 / 74-85-1 / 74-84-0 / 64-17-5 / 50- oxidation / ethane oxidation / oxidative 578-6 / 200-075-1 99-7 fermentation (alcohols) / anaerobic fermentation (glucose) Ethylene and formaldehyde / propene 200-815-3 and 200-001-8 / 204-062-1 74-85-1 and 50-00-0 / 115-07-1 Methyl isocyanate, acetamide and 210-866-3, 200-473-5 and 231-778-1 624-83-9, 60-35-5 and 7726-95-6 bromine gas. Methane and chlorine 200-812-7 and 231-959-5 74-82-8 and 7782-50-5 Description of applicability of alternatives Methanol is commonly used in the manufacturing process of other chemicals (including formaldehyde, methanol-to-olefins (MTO) and methanol-to-propylene (MTP), methyl tert-butyl ether, dimethyl ether and acetic acid) and some of these processes are very well developed. For some of these alternative methods of production it has been suggested that these methods may not be industrially viable for one reason or another, some alternatives methods do not produce similar high-quality levels of the desired substance, some methods are likely to involve higher costs and some may also involve the use of substances which have higher environmental and human health hazard profiles. However, some alternative methods may be suitable. Application 2 Fuels

Substitution of Chemical Substances of Potential Concern | 97 Table 9-15: Identification of potential alternatives for Methanol Name/description of alternative Methanol itself is an alternative for direct (neat) or mixed use within petrol and diesel fuels. It has lower life cycle greenhouse gas emissions compare to petrol. For example, in Iceland, a methanol plant produces methanol from carbon dioxide. Alternatives to methanol in fuels and methanol as a fuel include: - Dimethyl ether (DME) - Ethanol - Methyl tertiary butyl ether (MTBE) - Ethyl tertiary butyl ether (ETBE) - Fatty acid methyl ester (FAME) - Hydrotreated vegetable oil (HVO) Identifiers (if chemical substance) Substance name EC Number CAS Number Dimethyl ether (DME) 204-065-8 115-10-6 Ethanol 200-578-6 64-17-5 / 97281-11-3 Methyl tertiary butyl ether (MTBE) 216-653-1 1634-04-4 Ethyl tertiary butyl ether (ETBE) 211-309-7 637-92-3 Fatty acid methyl ester (FAME) 273-606-8 / 267-015-4 68990-52-3 / 67762-38-3 (various) (various) Hydrotreated vegetable oil (HVO) - - Description of applicability of alternatives There is a lot of ongoing research into alternative fuel sources, some are aimed at mimicking the current methods of refuelling a vehicle by using a pump at a fuel station, this would enable the current infrastructure to continue to be used and in some cases minimal changes to cars would be required. There are also a range of non-chemical technologies that will affect the amount of methanol in fuels and its potential substitution. For example, an alternative to the use of methanol within fuels is the increasing manufacture and market take up of non-petrol and non-diesel transport, i.e. electric cars. Other alternatives include transported powered by, hydrogen, ethanol, LPG and biofuels.

In the future, the use of methanol within fuels may increase, for example methanol will continue to be used with petrol and diesel fuels (which will be used in petrol, diesel and hybrid vehicles), methanol may still be used within bio-fuels and in some countries methanol is used as an alternative fuel source to petrol- and diesel-powered transport.

National and EU policy is likely to be a major factor affecting the long-term use of methanol within fuels, for example France and the UK have recently signalled an intention to ban the selling of petrol and diesel cars from 2040. Application 3 Solvent

Substitution of Chemical Substances of Potential Concern | 98 Table 9-15: Identification of potential alternatives for Methanol Name/description of alternative Methanol is used as a solvent both in the laboratory and in many industrial settings – a solvent in inks, resins, adhesives and dyes. Alternatives include: - Ethyl Acetate - Petroleum solvents - Iso-propyl alcohol (IPA) - Methyl ethyl ketone (MEK) - tert-Butyl alcohol (TBA) - N-Methyl-2-pyrrolidone (NMP) - Dimethylformamide (DMF) - Dimethylacetamide (DMAc) Identifiers (if chemical substance) Substance name EC Number CAS Number Ethyl Acetate (ink solvent) 205-500-4 141-78-6 Petroleum solvent - Distillates 265-158-7 / 265-156-6 64742-55-8 / 64742-53-6 (petroleum), hydrotreated light (ink solvent) Iso-propyl alcohol (IPA) 200-661-7 67-63-0 Methyl ethyl ketone (MEK) 201-159-0 78-93-3 tert-Butyl alcohol (TBA) 200-889-7 75-65-0 N-Methyl-2-pyrrolidone (NMP) 212-828-1 872-50-4 Dimethylformamide (DMF) 200-679-5 68-12-2 Dimethylacetamide (DMAc) 204-826-4 127-19-5 Description of applicability of alternatives There are a large number of other solvents (non-polar, polar aprotic and polar protic) which exist (some are indicated above), in some situations these could be used as an alternative to methanol. The physical properties of alternative solvents vary, so an alternative may be dependent on a case by case basis for each specific application. Application 4 Antifreeze/de-icing Name/description of alternative Glycols and alcohols: - Monoethylene glycol - Propylene glycol - Diethylene glycol - Triethylene glycol - Iso-propyl alcohol (IPA) Identifiers (if chemical substance) Substance name EC Number CAS Number Monoethylene glycol 203-473-3 107-21-1 Propylene glycol 200-338-0 57-55-6

Substitution of Chemical Substances of Potential Concern | 99 Table 9-15: Identification of potential alternatives for Methanol Diethylene glycol 203-872-2 111-46-6 Triethylene glycol 203-953-2 112-27-6 Iso-propyl alcohol 200-661-7 67-63-0 Description of applicability of alternatives The alternatives, in some situations, are able to successful replace methanol. For example, non-methanol screen washers/de-icing fluids have become more common. However, in this (and other situations) methanol is cheaper than some of the alternative substances.

Products containing ethylene glycol, diethylene glycol and triethylene glycol are all alternatives to methanol to help prevent gas hydrate formation, but, the freezing temperature of methanol is lower than some of these alternatives. However, methanol does have HSE risks due to it flammability, while monoethylene glycol on the other hand is much safer to use on offshore installations.

A1.4.4 Assessment of feasibility of potential alternatives

Substitution of Chemical Substances of Potential Concern | 100 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Alternative 1 Formaldehyde can in principle be Loading: For methane, the Environmental hazards: Methane is registered at 100,000 production of produced by the oxidation of loading required is unknown, methane is not a PBT substance. – 1,000,000 tonnes per annum formaldehyde – methane, but it has been work is ongoing to identify how As calcium formate is an process (methane, suggested that this method of this could be done commercially. inorganic substance, it cannot be Calcium formate is registered at calcium formate) production is not viable on an For calcium formate it is classified a PBT 10,000 – 100,000 tonnes per industrial scale because expected to be used neat and annum formaldehyde is more easily decomposes at high Human health hazards: oxidised than methane. Calcium temperature methane is classified as being an formate, when heated at high extremely flammable gas (H220). temperature can be used to Price: Methane is relatively Calcium formate has been produce formaldehyde. cheap (although its price does suggested by registrants as being Formaldehyde can also be fluctuate) and it may be cheaper a substance that can causes produced by the reaction of as a method to produce serious eye damage (H318) and ethane with ozone in the formaldehyde. Calcium formate eye irritation (H319) presence of a lead catalyst. The costs around €425 per tonne, main industrial method for the this is slightly more than the production of formaldehyde is costs of methanol. by catalytic oxidation of methanol (the temperatures The temperatures required for required to do this are lower the alternatives are higher than than the silver-based catalyst for methanol, therefore the method of production) costs for these methods of production might be higher Alternative 1 Olefins (e.g. ethylene and Loading: In all of these processes Environmental hazards: Hydrocarbons: Not registered production of olefins propylene) are important the main intermediate (MTO & MTP) building blocks used in the component is applied neat or Hydrocarbons are generally Ethylene and butane: Ethylene petrochemical industry, for almost neat with a couple classified or suggested as being registered at 10,000,000+ example, propylene is used to catalysts to produce the desired harmful to aquatic life with long tonnes per annum, butane make polypropylene. olefin lasting effects (H412) but they registered at 1,000,000 – Alternative methods of are not PBT substances 10,000,000 tonnes per annum producing olefins, including Price: The costs of hydrocarbons ethylene and propylene, are: varies and this cost will directly Ethylene and butane: Are not Isobutyl alcohol: Registered at impact the production of olefins PBT substances 10,000 – 100,000 tonnes per Cracking: This has been the main as cracking might be cheaper annum

Substitution of Chemical Substances of Potential Concern | 101 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability method of manufacturing, in this than other methods when the Isobutyl alcohol: Is not a PBT process hydrocarbons are price is low substance Acetic acid and hydrogen: Acetic cracked at a refinery acid registered at 1,000,000 – Ethylene and butane: The price Acetic acid and hydrogen: Are 10,000,000 tonnes per annum, Olefin metathesis: in this process of ethylene is around €940 per not PBT substances hydrogen is not a registered ethylene and normal butene’s tonne and butane is around €205 substance are combined and then per tonne Human health hazards: disproportionated to give propylene Isobutyl alcohol: Isobutyl alcohol Hydrocarbons are generally is around €510-850 per tonne classified as being flammable Isobutyl alcohol-to-propylene: in (H226), may cause cancer this process catalysts and Acetic acid and hydrogen: The (H350), may cause drowsiness or operating conditions are used to price of acetic acid is around dizziness (H336), harmful if allow the conversion of isobutyl €340-425 per tonne and swallowed (H302) alcohol to propylene hydrogen is <€9 per tonne Ethylene and butane: Ethylene Hydrogenation of acetic acid: in substance is an extremely this process catalysts are used to flammable gas (H220) and may promote the conversion of acetic cause drowsiness or dizziness acid and hydrogen to (H336). Butane is extremely manufacture good yields of flammable gas (H220) and propylene contains gas under pressure and may explode if heated

Isobutyl alcohol: is a flammable liquid and vapour (H226), causes serious eye damage (H318), causes skin irritation (H315), may cause respiratory irritation (H335) and may cause drowsiness or dizziness (H336)

Acetic acid and hydrogen: Acetic acid is classified as causing

Substitution of Chemical Substances of Potential Concern | 102 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability severe skin burns and eye damage (H214), and is a flammable liquid and vapour (H226) while hydrogen is an extremely flammable gas (H220) Alternative 1 The process described below are Loading: In all of these processes Environmental hazards: Acetaldehyde: Registered at 0 - production of acetic alternative methods of the main intermediate 10 tonnes per annum (also acid producing forms of acetic acid, component is applied neat or Acetaldehyde: Is not a PBT registered for intermediate use) these processes are unlikely to almost neat with a couple substance involve the direct substitution of catalysts to produce acetic acid Ethylene: Registered at methanol in existing Ethylene: Is not a PBT substance 10,000,000+ tonnes per annum manufacturing techniques Price: The price of acetaldehyde is around €0.9-6 per kg or €0.385 Ethane: Is not a PBT substance Ethane: Registered at 1,000,000 Acetaldehyde oxidation: per lb – 10,000,000 tonnes per annum Acetaldehyde can be used as raw Ethanol: Is not a PBT substance material to produce acetic acid Ethylene: The price of ethylene is Ethanol: Registered at 1,000,000 by oxidation, this takes place in around €940 per tonne Glucose: Is not a PBT substance – 10,000,000 tonnes per annum liquid phase at temperature 60- 70oC with the support of a Ethane: The price of ethane is Human health hazards: Glucose: Not registered (not catalyst relatively cheap; however, its required: naturally occurring price fluctuates based on Acetaldehyde: Is classified as substance) Ethylene oxidation: In this changes in the gas market being an extremely flammable ethylene is prepared into liquid and vapour (H224), causes acetaldehyde or as part of a one- Ethanol: The price of ethanol is serious eye irritation (H319), is step direct oxidation process >€850 per tonne suspected of causing cancer ethylene produces acetic acid (H351) and may cause using a palladium-based Glucose: The price of glucose is respiratory irritation (H335 heteropoly acids catalyst, the around €380 to 425 per tonne oxidation of ethane may be Ethylene: Is classified as being an another such method than could extremely flammable gas (H220) be used to produce acetic acid and may cause drowsiness or dizziness (H336) Oxidative fermentation: In this process alcohols in the presence Ethane: Is classified as being an

Substitution of Chemical Substances of Potential Concern | 103 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability of oxygen and bacteria produce extremely flammable gas (H220) acetic acid Ethanol: Is classified as being a Anaerobic fermentation: In this flammable liquid (H225), the process sugars (glucose) are classification provided by converted into acetic acid companies to ECHA in REACH directly without creating ethanol registrations identifies that this as an intermediate substance is toxic if swallowed (H301), is toxic in contact with skin (H311), is toxic if inhaled (H331), causes damage to organs (H372), causes serious eye damage (H318) and causes skin irritation (H315)

Glucose: Is not classified by any hazards Alternative 1 The process described below are Loading: In all of these processes Environmental hazards: Ethylene is registered at production of alternative methods of the main intermediate 10,000,000+ tonnes per annum. Methyl 2- producing forms of Methyl 2- component is applied neat or Ethylene: Is not a PBT substance methylpropenoate methylpropenoate (MMA): almost neat with a couple Formaldehyde is registered at (MMA) catalysts to produce acetic acid Formaldehyde: Is not a PBT 1,000,000+ tonnes per annum. Condensation: Ethylene is substance hydroformylated to give Price: The price of ethylene is Propene is registered at propanol, it is then condensed around €940 per tonne; the price Propene: Is not a PBT substance 10,000,000+ tonnes per annum. with formaldehyde (and an of formaldehyde is around €300- amine catalyst), air oxidation 340 per tonne Human health hazards: then completes the reaction Producing MMA from methyl Ethylene is classified as being an Ethylene can also undergo propionate (MeP) may be extremely flammable gas (H220) carboalkoxylation to produce cheaper than conventional and may cause drowsiness or methyl propionate (MeP). MeP systems and it produces dizziness (H336) is then condensed with significantly less waste formaldehyde in a single Formaldehyde is classified as

Substitution of Chemical Substances of Potential Concern | 104 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability heterogeneous reaction step Propene: The price of propane is being toxic if swallowed (H301), (with a catalyst) to form MMA around €340 to 495 is toxic in contact with skin (H311), causes severe skin burns Oxidative dehydrogenation: and eye damage (H314), is toxic Propene undergoes if inhaled (H331), may cause hydrocarboxylation to produce cancer (350), is suspected of isobutyric acid. Oxidative causing genetic defects (H341) dehydrogenation of the and may cause an allergic skin isobutyric (using a catalyst) reaction (H317) produces methyl 2- methylpropenoate Formaldehyde is also a CoRAP substance

Propene: is classified as being an extremely flammable gas (H220) Alternative 1 Methylamine has been produced Loading: In this process, the Environmental hazards: Methyl isocyanate: Not production of in the laboratory by the main intermediate component registered methylamines hydrolysis of methyl isocyanate (methyl isocyanate) is applied Methyl isocyanate: Is not a PBT and reaction with acetamide and almost neat with a couple substance Acetamide is registered at 10 – bromine gas. However, the reactants to produce 100 tonnes per annum production of methylamines in methylamines Acetamide: Is not a PBT this way has been conducted at substance Bromine: is registered at 10,000 laboratory level rather than on Price: The price of methyl – 100,000 tonnes per annum an industrial scale isocyanate is unclear Bromine: Is classified as being very toxic to aquatic life (H400) Acetamide: The price is around €4.20-7.80 per kilogram Human health hazards:

Bromine: The price of liquid Methyl isocyanate is classified as bromine is around €19-22 per being fatal if inhaled (H330), is kilogram toxic if swallowed (H301), is toxic in contact with skin (H311), is a highly flammable liquid and vapour (H225), causes serious

Substitution of Chemical Substances of Potential Concern | 105 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability eye damage (H318), is suspected of damaging the unborn child (H361d), causes skin irritation (H315), may cause an allergic skin reaction (H317), may cause allergy or asthma symptoms or breathing difficulties if inhaled (H334) and may cause respiratory irritation (H335)

Acetamide: is classified as being a substance that is suspected of causing cancer (H351) (Carc. Cat. 2)

Bromine: is classified as being fatal if inhaled (H330), causes severe skin burns and eye damage (H314) Alternative 1 By heating a mixture of methane Loading: In this process, a Environmental hazards: Methane is registered at 100,000 production of and chlorine together it is mixture of methane and chlorine methane is not a PBT substance. – 1,000,000 tonnes per annum chloromethane possible to produce is heated together As calcium formate is an chloromethane. This method inorganic substance, it cannot be Calcium formate is registered at has historically been used, Price: Methane is relatively classified a PBT 10,000 – 100,000 tonnes per however, this process produces cheap (although its price does annum less chloromethane and more fluctuate) and may be cheaper to Human health hazards: highly chlorinated compounds produce chloromethane. methane is classified as being an compared to the methanol and Chlorine costs around €510-675 extremely flammable gas (H220), hydrogen chloride process per tonne calcium formate has been suggested as a substance that The temperatures required for can causes serious eye damage the alternatives are around 400 (H318) and eye irritation (H319) °C, this is higher than the temperatures need for methanol

Substitution of Chemical Substances of Potential Concern | 106 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability which are around 350 °C Dimethyl ether 2 DME is a volatile organic Loading: DME is potential a Environmental hazards: DME is Registered at 10,000 – 100,000 (DME) compound that can be used in replacement for diesel fuel, DME not a PBT substance tonnes per annum both diesel and petrol engines, would be the major component however it is specifically of the fuel, additional fuel Human health hazards: DME is designed for compression additives would be added to classified as being an extremely ignition diesel engines. Its increase the lubricity of DME and flammable gas (H220) properties are similar to those of enhance other properties liquefied petroleum gases (e.g. The global warming potential of propane and butane). Like other Price: As indicated by DME is comparable to carbon fuel types, only minor Semelsberger et al (2006): NKK dioxide over 20 years, but lower modifications to engines are Corporation, based on their DME over 100 and 500 years needed slurry phase manufacturing scheme, forecasted the cost of A DME fuel would also have DME is reported to have half the DME as a function of natural gas reduced NOx, SOx, and energy density of diesel and so a price, plant scale, and particulate matter bigger taken would be required transportation distance. The for a similar range price was comparable with petrol, diesel whilst being The idea is presently at the cheaper than methanol and research stage but existing ethanol. However, the price of production, infrastructure, and DME will be linked to the price of transportation networks could natural gas which is the primary be used, only relatively small feedstock alterations would be required Ethanol 2, 4 Ethanol is already being used Loading: Various loadings of Environmental hazard: Ethanol Registered at 1,000,000 – within fuels, in North America ethanol have been identified, is not a PBT substance. 10,000,000 tonnes per annum more than 97% of U.S. petrol these range from being a minor contains ethanol, typically E10 component, around 10% up to Human health hazard: Ethanol is (10% ethanol, 90% gasoline), E85 around 100% classified as being a highly (or flex fuel) fuel is also available flammable liquid and vapour and this contains the highest Price: Ethanol: The price of (H225), the classification level of ethanol-gasoline blends ethanol is >€850 per tonne provided by companies to ECHA containing 51%-83% ethanol. In in REACH registrations identifies

Substitution of Chemical Substances of Potential Concern | 107 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Brazil, fuel is available as E100 As indicated by Semelsberger et that this substance is toxic if (with up to 4% water). All petrol al (2006): Ethanol fuels may be swallowed (H301), is toxic in sold in the EU typically contains more expensive than petrol and contact with skin (H311), is toxic up to 5% ethanol. By 2020 the diesel. However, the prices as if inhaled (H331), causes damage EU aims to have 10% of the indicated by the Alternative to organs (H370), causes serious transport fuel of every EU Fuels Data Center are that eye damage (H318) and causes country come from renewable ethanol is cheaper than petrol skin irritation (H315) sources such as biofuels and diesel – however due to its Energy-Equivalent Basis it works Existing production, out being more expensive (i.e. infrastructure, and more fuel is required to produce transportation networks could the same energy – more fuel is be used, only small alterations required to cover the same would be required range)

Ethanol can be used as an alternative to methanol in screen washers/de-icers Methyl tertiary butyl 2 MTBE is a currently used as a fuel Loading: The content of EU fuels Environmental hazard: MTBE is Registered at 1,000,000 – ether (MTBE) additive, it is used as an is allowed to contain up to 15% not a PBT substance 10,000,000 tonnes per annum oxygenate to raise the octane of MTBE number. Up to 15% content is Human health hazard: MTBE is allowed in the EU Price: MTBE is already used in classified as being a highly fuels. Costing around €280-285 flammable liquid and vapour MTBE can be easily blended with a tonne. MTBE, made from (H225) and causes skin irritation fuels; however, it is unlikely to be methanol is cheaper than ETBE, (H315) suitable as a fuel to be used neat made from ethanol MTBE also gives water an MTBE is already used in fuels and unpleasant taste at very low existing production, concentrations, it is also poorly infrastructure, and biodegradable transportation networks are being used Some people have complained of symptoms such as nausea,

Substitution of Chemical Substances of Potential Concern | 108 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability dizziness, light-headedness, headaches, and nose and throat irritation after breathing vapours from gas containing MTBE. But it's not clear if these symptoms are caused by MTBE or other components of petrol

MTBE can lead to a reduction in emissions of exhaust pollutants such as volatile organic compounds (VOCs) and particulates (PM) Ethyl tertiary butyl 2 ETBE is a currently used as a fuel Loading: In the EU, the maximum Environmental hazard: ETBE is Registered at 1,000,000 – ether (ETBE) additive, it is used as an blending level specification for not a PBT substance 10,000,000 tonnes per annum. oxygenate to raise the octane ETBE is 22% in E10 gasoline and number. ETBE was developed as 17.24% mass in E5 Human health hazard: ETBE is an alternative to MTBE not classified under CLP, Price: The price of ETBE is linked however it has been suggested ETBE is normally blended in fuels to the price of ethanol, presently by registrants as being a highly at higher percentage volume ETBE is one of the more flammable liquid and vapour than MTBE and methanol expensive fuel additives, it is (H225) and it may cause more expensive than MTBE, drowsiness or dizziness (H336) ETBE offers advantageous methanol and ethanol physical and chemical It is inherently biodegradable characteristics over ethanol, and under certain conditions in other benefits when co-blended aerobic environment, otherwise with ethanol it is not thought to pose a significant hazard to human ETBE is already used in fuels and health or the environment existing production, infrastructure, and ETBE can lead to a reduction in transportation networks are emissions of exhaust pollutants being used such as VOCs and PM

Substitution of Chemical Substances of Potential Concern | 109 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Fatty acid methyl 2 FAME is being developed as a Loading: Various loadings of Environmental hazard: FAME is Registered at 1,000,000 – ester (FAME) biodiesel, an alternative to diesel FAME have been identified and not a PBT substance 10,000,000 tonnes per annum tested, these range from being a Test have been performed in the minor component, around 5% of Human health hazard: FAME is EU with blends of FAME with the fuel up to around 100% of not classified under CLP; diesel oil up to 5-10%, or at the fuel however, FAME might be a skin 25-30% and 100% pure irritant (H315) and eye irritant Price: The main feedstocks of (H319) Modifications (seals, piping) are FAME are oil seeds (rape, required for use at 100% pure, sunflower, soy, palm), used Esters tend to lead to a reduction but presently up to 7% of diesel cooking oil, waste animal fat. in emissions of exhaust can be made of biodiesel pollutants such as VOCs and PM Production is relatively simple Presently up to 7% of diesel can and also allows for small be made of biodiesel, this means decentralised production units that existing production, without excessive extra costs. infrastructure, and Methanol, may be one of transportation networks could substances used in the be used production process Hydrotreated 2 HVO biodiesel (Hydrotreated Loading: HVO biodiesel has been Environmental hazard: HVO is Not registered under REACH vegetable oil (HVO) Vegetable Oil) is a form of loaded up to 50% within fuel not expected to be a PBT (hydrogenated vegetable oil is renewable diesel that has been sold. European diesel standards substance REACH registered at 100,000 – produced from vegetable fats limit the HVO blend due to 1,000,000 tonnes per annum) and oils. Unlike regular density limits and the use of Human health hazard: it is biodiesel, hydrogen is used as a 100% HVO must be approved by expected that HVO may be fatal catalyst in the creation process the vehicle manufacturer if swallowed and enters the instead of methanol airways (H304) Price: The main feedstocks are HVO is more stable that biodiesel vegetable fats and oils. HVO fuel shows tendencies of and it may offer other beneficial However, the hydrotreating reducing the regulated emissions characteristics over FAME and process incurs large capital costs and causing weaker toxic effects regular diesel and therefore requires large- compared to fossil diesel. PM scale production but the and NOx emissions can be HVO is allowed in fuels without produce fuel will be more stable. reduced after optimization of

Substitution of Chemical Substances of Potential Concern | 110 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability any limits and without specific The price of HVO may be the engine labelling requirements. Up to comparable but slightly higher 50% renewable diesel (HVO) than FAME The land requirements to grow blends have been sold since and compete with food 2007. The fuel can be used all production may result in some year round including severe environmental impacts winters. It is being sold as thousands of service stations and no modifications to fuel delivery logistics or service station pump requirements are required. Also, no modifications to vehicles are needed Ethyl Acetate (ink 3 Ethyl Acetate is already used as a Loading: The content/loading of Environmental hazard: Ethyl Registered at 100,000 – solvent) solvent in inks and paints the solvent will depend on the Acetate is not a PBT substance 1,000,000 tonnes per annum specific application. The overall content of all solvents within Human health hazard: Ethyl some inks can exceed 80%. Acetate is classified as being highly flammable liquid and Price: Ethyl Acetate is widely vapour (H225), causes serious available and reasonably cheap eye irritation (H319) and may at around €595 – 765 per tonne. cause drowsiness or dizziness (H336) Distillates 3 Distillates (petroleum) and Loading: The content/loading of Environmental hazard: Registered at 1,000,000 – (petroleum), hydrotreated light are two such the petroleum solvent will Distillates are not expected to be 10,000,000 tonnes per annum hydrotreated light petroleum solvents that are depend on the specific PBT substances paraffinic/ already used in printing inks, application. The overall content naphthenic however, efforts have been of all petroleum solvents within Human health hazard: the made to move away for some inks can be between 10- hazards from petroleum hydrocarbon inks 70% distillates and related substances are likely to be high. Price: Petroleum distillates are Petroleum distillates may be widely available and reasonably fatal if swallowed and enters cheap airways (H304), causes damage

Substitution of Chemical Substances of Potential Concern | 111 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability to organs through prolonged or repeated exposure (H372), being a highly flammable liquid and vapour (H225) and is suspected of damaging fertility or the unborn child (H361) Iso-propyl alcohol 3,4 Isopropyl alcohol is an Loading: Isopropyl alcohol is Environmental hazard: Iso- Registered at 100,000 – (IPA) alternative to methanol in de- typically loaded in windscreen propyl alcohol does not have any 1,000,000 tonnes per annum icers and it is an alternative washer fluids at between 0-10%, environmental classifications solvent as a solvent the loading will vary and is not a PBT substance based on the application Human health hazard: Isopropyl Price: Isopropyl alcohol costs alcohol is classified as being a around €995 euro a tonne, this is highly flammable liquid and more than double the price of vapour (H225), it causes serious methanol (around €415). As a eye irritation (H319) and may complete substitute, higher cause drowsiness or dizziness concentrations might be (H336) required, as a mixture contain methanol and other alternatives lower concentrations might be required Methyl ethyl ketone 3 Methyl ethyl ketone is an Loading: Methyl ethyl ketone is Environmental hazard: Methyl Registered at 100,000 – (MEK) alternative solvent loaded in windscreen washer ethyl ketone does not have any 1,000,000 tonnes per annum fluids at <2%, As a complete environmental classifications substitute, higher and is not a PBT substance concentrations might be required, as a mixture contain Human health hazard: Methyl methanol and other alternatives ethyl ketone is classified as being lower concentrations might be a highly flammable liquid and required vapour (H225), it causes serious eye irritation (H319) and may Price: Methyl ethyl ketone is cause drowsiness or dizziness around three and a half times (H336)

Substitution of Chemical Substances of Potential Concern | 112 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability the price of methanol tert-Butyl alcohol 3 tert-Butyl alcohol is an Loading: As a solvent, the Environmental hazard: tert- Registered at 1,000,000 – (TBA) alternative solvent loading will vary based on the Butyl alcohol is not a PBT 10,000,000 tonnes per annum application substance

Price: The price is expected to be Human health hazard: tert-Butyl higher than the price of alcohol is classified as being a methanol. As a complete highly flammable liquid and substitute, higher vapour (H22), causes serious eye concentrations might be irritation (H319), is harmful if required, as a mixture contain inhaled (H332) and may cause methanol and other alternatives respiratory irritation (H335) lower concentrations might be required N-Methyl-2- 3 N-Methyl-2-pyrrolidone is a non- Loading: As a solvent, the Environmental hazard: N- Registered at 10,000 – 100,000 pyrrolidone (NMP) volatile aprotic solvent. Its loading will vary based on the Methyl-2-pyrrolidone does not tonnes per annum properties have led to it being application have any environmental used as an extraction solvent, classifications and it is not a PBT dissolving polymers and Price: N-Methyl-2-pyrrolidone substance pharmaceutical uses. Its costs around €1695 – 2545 per properties may allow for it to be tonne Human health hazard: N- used more widely as a solvent Methyl-2-pyrrolidone is classified as being a substance that may damage the unborn child (Repr. Cat. 1B) (H360D), causes serious eye irritation (H319), causes skin irritation (H315) and may cause respiratory irritation (H335)

Due to N-Methyl-2-pyrrolidone being classified as Repr. Cat. 1B it has been identified as an SVHC

Substitution of Chemical Substances of Potential Concern | 113 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Dimethylformamide 3 Dimethylformamide is an aprotic Loading: As a solvent, the Environmental hazard: Registered at 10,000 – 100,000 (DMF) solvent. Its properties have lead loading will vary based on the Dimethylformamide does not tonnes per annum and as an it to be used as a low application have any environmental intermediate evaporation rate solvent. It has classifications and it is not a PBT been used in the production of Price: Dimethylformamide costs substance plastics, adhesives, surface around €600 – 760 per tonne coatings, films and in Human health hazard: pharmaceuticals Dimethylformamide is classified as being a substance that may damage the unborn child (Repr. Cat. 1B) (H360D), is harmful in contact with skin (H312), is harmful if inhaled (H332) and causes serious eye irritation (H319)

Due to dimethylformamide being classified as Repr. Cat. 1B it has been identified as an SVHC Dimethylacetamide 3 Dimethylacetamide is miscible Loading: As a solvent, the Environmental hazard: Registered at 10,000 – 100,000 (DMAc) with most other solvents and has loading will vary based on the Dimethylacetamide does not tonnes per annum been used in the production of application have any environmental pharmaceuticals and plasticizers classifications and it is not a PBT Price: Dimethylformamide costs substance around €850 per tonne Human health hazard: Dimethylacetamide is classified as being a substance that may damage the unborn child (Repr. Cat. 1B) (H360D), is harmful in contact with skin (H312) and is harmful if inhaled (H332)

Due to dimethylacetamide being

Substitution of Chemical Substances of Potential Concern | 114 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability classified as Repr. Cat. 1B it has been identified as an SVHC Monoethylene 4 Monoethylene glycol has already Loading: Monoethylene glycol is Environmental hazard: Registered at 1,000,000 – glycol (MEG) been used as a substitute to typically loaded in windscreen Monoethylene glycol is not a PBT 10,000,000 tonnes per annum methanol in de-icers. It is also washer fluids at between 0-20%, substance registered for use in the offshore monoethylene glycol gas hydrate oil and gas industry to be used as inhibitors may contain up to Human health hazard: a gas hydrate inhibitor. In some 100% monoethylene glycol, Monoethylene glycol is classified situations, the surrounding when applied the oil/gas process as being harmful if swallowed physical conditions and both system it will be diluted in the (H302). It has been suggested by reservoir and production process stream registrants that it may cause chemistry might mean that the damage to organs through other products being used Price: Monoethylene glycol is prolonged or repeated exposure (demsulifier, corrosion inhibitor, more than double the price of (H373) scale inhibitor etc.) are more methanol, at around €875 per compatible with methanol. For tonne. As a complete substitute, example, the freezing point of higher concentrations might be methanol is around -97.6 °C required, as a mixture contain compared to -12.9 °C of methanol and other alternatives monoethyelene glycol lower concentrations might be required Diethylene glycol 4 Diethylene glycol is registered Loading: Diethylene glycol gas Environmental hazard: Registered at 100,000 – (DEG) for use in the offshore oil and hydrate inhibitors may contain Diethylene glycol is not a PBT 1,000,000 tonnes per annum gas industry to be used as a gas up to 100% diethylene glycol, substance hydrate inhibitor. In some when applied the oil/gas process situations, the surrounding system it will be diluted in the Human health hazard: physical conditions and both process stream Diethylene glycol is classified as reservoir and production being harmful if swallowed chemistry might mean that the Price: The price is expected to be (H302). It has been suggested by other products being used higher than the price of registrants that it may cause (demsulifier, corrosion inhibitor, methanol. As a complete damage to organs through scale inhibitor etc.) are more substitute, higher prolonged or repeated exposure compatible with methanol. For concentrations might be (H373) example, the freezing point of required, as a mixture contain

Substitution of Chemical Substances of Potential Concern | 115 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability methanol is around -97.6 °C methanol and other alternatives compared to -10 °C of lower concentrations might be diethylene glycol required Triethylene glycol 4 Triethylene glycol is registered Loading: Triethylene glycol gas Environmental hazard: Registered at 10,000 – 100,000 (TEG) for use in the offshore oil and hydrate inhibitors may contain Triethylene glycol is not a PBT tonnes per annum gas industry to be used as a gas up to 100% triethylene glycol, substance hydrate inhibitor. In some when applied the oil/gas process situations, the surrounding system it will be diluted in the Human health hazard: physical conditions and both process stream Triethylene glycol is not reservoir and production classified under CLP. It is chemistry might mean that the Price: The price is expected to be expected to be less hazardous other products being used higher than the price of than methanol (demsulifier, corrosion inhibitor, methanol. As a complete scale inhibitor etc.) are more substitute, higher compatible with methanol. For concentrations might be example, the freezing point of required, as a mixture contain methanol is around -97.6 °C methanol and other alternatives compared to -7 °C of triethylene lower concentrations might be glycol required Propylene glycol 4 Propylene glycol has already Loading: Propylene glycol gas Environmental hazard: Registered at 100,000+ tonnes been used as a substitute to hydrate inhibitors may contain Propylene glycol is not a PBT per annum methanol in de-icers. The up to 100% propylene glycol, substance freezing point of methanol is when applied the oil/gas process around -97.6 °C compared to - system it will be diluted in the Human health hazard: 59 °C of propylene glycol. process stream. In de-icing Propylene glycol is not classified fluids for aircraft up to 80% of under CLP Propylene glycol has also been the product might be made up of used in de-icing fluids, in propylene glycol particular de-icing fluids for aircraft Price: Propylene glycol is more than double the price of methanol. As a complete substitute, higher concentrations might be

Substitution of Chemical Substances of Potential Concern | 116 Table 9-16: Assessment of potential alternatives for Methanol Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability required, as a mixture contain methanol and other alternatives lower concentrations might be required Sources: Economics of Acetic Acid Production by Partial Oxidation of Ethane, Soliman, M., et al, http://ac.els-cdn.com/S2212670812001418/1-s2.0-S2212670812001418- main.pdf?_tid=c55808ea-7d01-11e7-ac55-00000aab0f27&acdnat=1502283401_5672a40e9ba99d59cbeddffdd60aefcb (accessed 20 July 2017) Methanol to Olefins (MTO): From Fundamentals to Commercialization http://pubs.acs.org/doi/abs/10.1021/acscatal.5b00007 (accessed 20 July 2017) Dimethyl ether (DME) as an alternative fuel, Semelsberger T.A., et al, http://www.sciencedirect.com/science/article/pii/S0378775305007846 (accessed 24 July 2017) Renewable Methanol fuel for Europe, https://www.innovatum.se/wp-content/uploads/2017/03/cribenedikt-stefanssonliquid-wind.pdf (accessed 24 July 2017) Will politics push the gas or brakes on methanol fuels, http://studylib.net/doc/13578894/will-politics-push-the-gas-or-brakes-on-methanol-fuels-gr... (accessed 24 July 2017) FAME Fact Sheet, http://www.etipbioenergy.eu/images/fame-fact-sheet.pdf (accessed 24 July 2017) Neste Renewable Diesel Handbook, https://www.neste.com/sites/default/files/attachments/neste_renewable_diesel_handbook.pdf (accessed 24 July 2017) ECHA website for substance classifications, https://echa.europa.eu/

Substitution of Chemical Substances of Potential Concern | 117 A1.5 Substance 5: Bisphenol A (BPA)

A1.5.1 Identity of the substance

Table 9-17: Identity of Bisphenol A Name of substance 4,4'-isopropylidenediphenol Synonyms Bisphenol A (BPA) EC Number 201-245-8 CAS Number 80-05-7 Molecular formula C15H16O2

REACH Registration tonnage band 1000000 - 10000000 tonnes per annum Sources: ECHA website, https://echa.europa.eu/substance-information/-/substanceinfo/100.001.133

A1.5.2 Functionality and applications

Table 9-18: Functionality and applications for Bisphenol A General description of functionality and Bisphenol A has a wide range of applications. It is used to make polycarbonate, a hard, clear plastic, which is used in many consumer key physico-chemical parameters products such as re-usable plastic tableware and bottles for drinks, sports equipment, CDs, and DVDs. BPA is also found in epoxy resins, which act as a protective lining on the inside of some metal-based food and beverage cans and is used in adhesives and sealants, toys, paints and coatings and electrical and electronic products. BPA is also used to develop dye in thermal paper, which is used for shop sales receipts, and public transport and parking tickets. As of 2015, polycarbonates accounted for nearly 64% of world bisphenol A demand, while epoxy resins, the second-largest end use, accounted for 34% Family the substance belongs to Bisphenols

Substitution of Chemical Substances of Potential Concern | 118 Table 9-18: Functionality and applications for Bisphenol A Polycarbonates Sector of Use SU 12: Manufacture of plastic products, including compounding and conversion SU 16: Manufacture of computer, electronic and optical products, electrical equipment SU 17: General manufacturing, e.g. machinery, equipment, vehicles, other transport equipment SU 19: Building and construction work Product category PC 32: Polymer preparations and compounds Industrial/Professional/ Consumer Industrial: used at industrial sites and in manufacturing Professional: in formulation or re-packing Consumer: used by consumers in articles Description There are two types of polycarbonates depending on the reagents and synthesis processes: thermoset and thermoplastic. The bisphenol A polycarbonate belongs to the second family: thermoplastics. These polymers are clear, and display heat and impact resistance. It is used in CDs/DVDs, electrical equipment (such as sockets), computers, domestic appliances, covers for solar panels, items for motor vehicles, food containers, reusable water bottles, optical equipment (such as eyeglasses) and medical equipment (such as catheters) Epoxy resins Sector of Use SU 10: Formulation [mixing] of preparations and/or re-packaging (excluding alloys) SU 12: Manufacture of plastics products, including compounding and conversion SU 17: General manufacturing, e.g. machinery, equipment, vehicles, other transport equipment SU19: Building and construction work Product category PC 9a: Coatings and paints, thinners, paint removers PC 19: Intermediate PC 32: Polymer preparations and compounds Industrial/Professional/ Consumer Industrial: used at industrial sites and in manufacturing Professional: in formulation or re-packing Consumer: used by consumers in articles Description Bisphenol A diglycidyl ether (BADGE) is the most widely used epoxy resin (95% of world tonnage for epoxy resins). It is synthesised from bisphenol A and epichlorhydrin. Epoxy resins are used for their ability to protect against corrosion and their thermal stability. These resins are used as protective coatings, composites and laminates, in electrical and electronic applications, in the construction industry and in the manufacture of adhesives

Substitution of Chemical Substances of Potential Concern | 119 Table 9-18: Functionality and applications for Bisphenol A Flame retardants Sector of Use SU 16: Manufacture of computer, electronic and optical products, electrical equipment Product category PC 19: Intermediate Industrial/Professional/ Consumer Industrial: used at industrial sites and in manufacturing Professional: in formulation or re-packing Consumer: used by consumers in articles Description - Tetrabromobisphenol A - bisphenol A is used in the production of tetrabromobisphenol A (TBBPA), which can be utilised as a monomer in the manufacture of flame retardants for printed circuit boards. TBBPA can be found in consumer products such as computers, televisions and dishwashers - Tetrachlorobisphenol A - BPA is also used in the production of a second flame retardant, tetrachlorobisphenol A, employed as an additive in polymers, epoxy resins, phenolic resins and adhesives Bisphenol A-bis (diphenyl phosphate) - a flame retardant derived from BPA, but much less frequently used than TBBPA Thermal paper Sector of Use SU6b: Manufacture of pulp, paper and paper products Product category Industrial/Professional/ Consumer Industrial: use at industrial sites and in manufacturing Professional: in formulation or re-packing Consumer: used by consumers in articles Description BPA is an additive in the coating applied to thermal paper and is therefore used as a substance for this application. It is used as a developing agent, which causes a chemical reaction when the paper is heated, resulting in colour being produced when using the paper Manufacture of chemicals Sector of Use SU 8: Manufacture of bulk, large scale chemicals (including petroleum products) SU9: Manufacture of fine chemicals Product category PC 19: Intermediate Industrial/Professional/ Consumer Industrial: used at industrial sites and in manufacturing Professional: in formulation or re-packing Consumer: no direct contact Description BPA is used in the manufacture of other chemicals

Substitution of Chemical Substances of Potential Concern | 120 Table 9-18: Functionality and applications for Bisphenol A Sources: FDA website: Bisphenol A (BPA): Use in Food Contact Application, https://www.fda.gov/NewsEvents/PublicHealthFocus/ucm064437.htm ECHA website, https://echa.europa.eu/addressing-chemicals-of-concern/substances-of-potential-concern/pact?diss=true&search_criteria_ecnumber=201-245- 8&search_criteria_casnumber=80-05-7&search_criteria_name=4%2C4%27-isopropylidenediphenol

ECHA website, https://echa.europa.eu/chemicals-in-our-life/hot-topics/bisphenol-a Chemical Economics Handbook: Bisphenol A, https://www.ihs.com/products/bisphenol-chemical-economics-handbook.html ECHA website, https://echa.europa.eu/substance-information/-/substanceinfo/100.001.133 Bisphenol A Registration dossier, https://echa.europa.eu/registration-dossier/-/registered-dossier/15752/3/1/5

A1.5.3 Potential alternatives

Table 9-19: Identification of potential alternatives for Bisphenol A Application 1 Polycarbonate reusable food and beverage containers (e.g. sippy cups, baby bottles, reusable water bottles, reusable food storage containers) Name/description of Alternative to polycarbonate: other polymers: alternative - Tritan Copolyester ™ (Eastman Chemical) – is one of the newest polycarbonate alternatives released on the market and is now used in many products including Nalgene bottles, Weil-Baby bottles and Camelback, as an alternative to BPA-polycarbonate - High Density Polyethylene (HDPE) – primarily used for non-reusable containers that hold milk, juice, water and other beverages - Polypropylene Homopolymer (PP) – used in food containers and reusable water bottles - Polyethersulfone (PES) and Polyphenylsulfone (PPS) – thermoplastic polymers that are increasingly being utilised as alternatives to polycarbonate baby bottles - Polyethylene Terephthalate (PET) – used in single-use soda and water bottles - Isosorbide material (polyester and polycarbonate) – containers used in the microwave, sports bottles, food containers - Polyetherimide – containers used in the microwave - Poly lactic acid (PLA) – food packaging, bottles - Topas® IT X1 – medical devices, food applications - Melamine material – tableware, kitchen utensils, meal trays - Acrylonitrile-butadience-styrene (ABS) – tableware, kitchen utensils, electric kettles - Methyl methacrylate polystyrene – perfect for thick parts - Styrene butadiene copolymer – blister packs, tests on baby bottles - Styrene butadiene methacrylate – cosmetic and food contact packaging - Methyl polymethacrylate – dialysis cassette - Glycol polyethylene terephthalate – blister packs

Substitution of Chemical Substances of Potential Concern | 121 Table 9-19: Identification of potential alternatives for Bisphenol A

Alternative to polycarbonate: other materials: - Glass - material has been safely used for years - so stable that individuals can heat and cook food or beverages safely without any health concerns - Stainless steel - can heat and cook food or beverages safely without any health concerns - Ceramic – tableware, kitchen utensils - Silicon – baby bottles Identifiers (if chemical Substance name EC Number CAS Number substance) Tritan Copolyester ™ DMT, 204-411-8 DMT, 120-61-6 CHDM, 105- Consists of 3 monomers dimethyl terephthalate (DMT), 1,4 CHDM, 203-268-9 08-8 TMCD, 3010-96-6 cyclohexanedimethanol (CHDM) and 2,2,4,4-tetramethyl-1,3-cyclobutanediol TMCD, 221-140-0 (TMCD) HDPE 919-651-5 Polypropylene (PP) 618-352-4 9003-07-0 Polyethylene terephthalate (PET) 607-507-1 25038-59-9 Polyetherimide 612-092-5 61128-46-9 Melamine 203-615-4 108-78-1 Acrylonitrile-butadience-styrene (ABS) 618-371-8 9003-56-9 Styrene butadiene copolymer 618-370-2 9003-55-8 Methyl polymethacrylate 618-466-4 9011-14-7 Description of applicability of Few studies have been conducted on the substitution of polycarbonate because alternatives are already in use for the major applications: baby alternatives bottles made from polypropylene were already manufactured before the ban of BPA, and containers, packaging and utensils used for food contact, are already manufactured with a copolyester to replace polycarbonate. Also alternatives to polycarbonate food and beverage containers such as glass and stainless steel are safe and have been used widely for years Application 2 Epoxy resins which act as a protective lining on the inside of some metal-based food and beverage cans Name/description of Alternatives to epoxy resins: other resins: alternative - Polyester coatings (DAREX Polyester, PET Film) - polyester coatings can be used in place of BPA liners or as an overlay on an epoxy undercoating, which reduces leaching capabilities of BPA by up to 95% into food and beverages. - Carbonate polypropylene – food packaging, internal coating of beer and soda cans - Baked-on resins (Oleoresin) - oleoresin is a natural mixture of an oil and a resin extracted from various plants, such as pine or balsam fir - Tanin resin – cans, aeronautic - Biolignine™ - adhesives - Polyurethane – wastewater, industrial water, sea water pipes

Substitution of Chemical Substances of Potential Concern | 122 Table 9-19: Identification of potential alternatives for Bisphenol A - Verdanol – coating of flexible packaging - Resin UVL-Eco resin – sailing applications - Resin SPR – electrical cables encapsulation - Isosorbid resin – internal coating of cans - Polyacrylate – floor coatings - Acrylic – cans - Vinyl (synthesised from vinyl chloride and vinyl acetate) - cans

Alternative to epoxy resins: other materials: - Glass - bottle, jar, food packaging - Tetrapack® - carton packaging - Doypack® - flexible bag

Other processes: - Decrease BPA migration in food containers Identifiers (if chemical Substance name EC Number CAS Number substance) PET film 607-507-1 25038-59-9 Description of applicability of No single alternative exists to substitute BPA in epoxy resin for all food contact applications. Indeed, it is difficult to find an alternative that is alternatives adequate for both acid and non-acid food. SNFBM notes that the work on substitution is ongoing to improve the quality of alternatives (cost and use by date) Application 3 Thermal paper Name/description of A large range of alternatives have been identified, four listed below are bisphenol A derivative, but a more comprehensive group of substances alternative is listed in the next section

- 4,4’-methylenediphenol (Bisphenol F - para) - 2,2’methylenediphenol (Bisphenol F – ortho) - 4,4'-sulphonyldiphenol (Bisphenol S) - 1,1-bis(4-hydroxyphenyl)-1-phenylethane(Bisphenol AP)

- Adopting another printing technique, still based on paper but not using thermal paper. On the other hand, a more radical approach would be to switch to paper-free techniques, based on electronic and IT technologies Identifiers (if chemical Substance name EC Number CAS Number substance) 4,4’-methylenediphenol (Bisphenol F - para) 210-658-2 620-92-8 2,2’methylenediphenol (Bisphenol F – ortho) 219-578-2 2467-02-9

Substitution of Chemical Substances of Potential Concern | 123 Table 9-19: Identification of potential alternatives for Bisphenol A 4,4'-sulphonyldiphenol (Bisphenol S) 201-250-5 80-09-1 1,1-bis(4-hydroxyphenyl)-1-phenylethane (Bisphenol AP) 433-130-5 1571-75-1 2,2’-diallyl-4,4’-sulfonyldiphenol (TGSA) 411-570-9 41481-66-7 4-(4-isopropoxyphenylsulfonyl)phenol (D8) 95235-30-6 95235-30-6 4-[[4-(2-Propenyloxy)phenyl]sulfonyl]phenol (BPS-MAE) 479-880-7 97042-18-7 4-4’-methylenebis(oxyethylenethio)diphenol 407-480-4 93589-69-6 Phenol, 4,4’-sulfonylbis-,polymer with 1,1’-oxybis[2-chloroethane] (D90) 191680-83-8 biphenyl-4-ol 202-179-2 92-69-3 4,4’-thiobisphenol 220-197-9 2664-63-3 4-tert-butylphenol 202-679-0 98-54-4 benzyl 4-hydroxybenzoate 202-311-9 94-18-8 dimethyl 4-hydroxyphthalate 204-399-4 120-47-8 dimethyl 4-hydroxyphthalate (DMP-OH) 245-023-9 22479-95-4 3,5-bis-tert-butylsalicylic acid 243-246-6 19715-19-6 zinc 3,5-bis(α-methylbenzyl)salicylate 258-753-8 53770-52-8 Benzenesulfonamide, 4-methyl-N-[[[3- 432-520-2 232938-43-1 [[(4methylphenyl)sulfonyl]oxy]phenyl]amino]car bonyl]- (Pergafast (DP 201)) p-[[p-benzyloxyphenyl]sulfonyl]phenol 263-920-3 63134-33-8 Urea-urethane Compound (UU) 321860-75-7 4,4’-bis(N-carbamoyl-4-methylbenzenesulfonamide)diphenylmethane 418-770-5 151882-81-4 o-[(4-hydroxyphenyl) sulfony]phenol 226-421-1 5397-34-2 4,4’-isopropylidenedi-o-cresol 201-240-0 79-97-0 methyl bis(4-hydroxyphenyl)acetate (MBHA) 225-870-0 5129-00-0 4,4’-isopropyllidenebis (2-phenylphenol) 678-197-3 24038-68-4 6,6’-di-tert-butyl-4,4’-butylidenedi-m-cresol 201-618-5 85-60-9 2,6-di-tert-butyl-p-cresol 204-881-4 128-37-0 octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate 218-216-0 2082-79-3 pentaerythritol tetrakis(3-(3,5-di-tertbutyl-4-hydroxyphenyl)propionate) 687-966-2 6683-19-8 4,4’,4’’-(1-methylpropanyl-3-ylidene) tris [6-tert-butyl-m-cresol] 217-420-7 1843-03-4 1,2-diphenoxyethane 203-224-9 104-66-5 Description of applicability of Bisphenol S and F are already used as alternatives to bisphenol A in thermal paper. However, bisphenol S appears to have endocrine-disrupting alternatives properties akin to bisphenol A and some studies have shown that bisphenol F may also have endocrine-disrupting effects. Sources:

Substitution of Chemical Substances of Potential Concern | 124 Table 9-19: Identification of potential alternatives for Bisphenol A Annex XV report: Proposal For Identification Of A Substance Of Very High Concern On The Basis Of The Criteria Set Out In Reach Article 57, https://echa.europa.eu/documents/10162/1434e531-b7e2-45b3-92ee-67fc59dc593d ANNEX XV RESTRICTION REPORT PROPOSAL FOR A RESTRICTION, https://echa.europa.eu/documents/10162/c6a8003c-81f3-4df6-b7e8-15a3a36baf76 Food Packaging Forum: Can coatings, http://www.foodpackagingforum.org/food-packaging-health/can-coatings Safer Alternatives to Bisphenol A (BPA) (2010) - California WIC Association, www.calwic.org/storage/documents/state/2010/bpa_alternatives.pdf OPINION of the French Agency for Food, Environmental and Occupational Health & Safety on the assessment of the risks associated with bisphenol A for human health, and on toxicological data and data on the use of bisphenols S, F, M, B, AP, AF and BADGE, https://www.anses.fr/en/system/files/CHIM2009sa0331Ra-0EN.PDF WRAP website, http://www.wrap.org.uk/

A1.5.4 Assessment of feasibility of potential alternatives

Substitution of Chemical Substances of Potential Concern | 125 Table 9-20: Assessment of potential alternatives for Bisphenol A Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Tritan 1 Containers, packaging and Used in many products, including Toxicological studies conducted by DMT, Registered 100,000 – Copolyester ™ utensils used for food Nalgene bottles, Weil-Baby Bottles and Eastman Chemical state copolyester 1,000,000 tonnes per year (made of 3 contact, are already Camelback, so must be affordable is not carcinogenic and that the CHDM, Registered 10 000 - 100 monomers) manufactured with a monomers used in Tritan do not 000 tonnes per year copolyester to replace demonstrate an affinity to bind to TMCD, Registered 100 - 1000 polycarbonate hormone receptors, nor a potential to tonnes per year cause endocrine disruptive effects

High density 1 Widely available for years €130-200 per tonne (source: HDPE is not known to release any HDPE is manufactured in over polyethylene and is commonly used for https://www.icis.com/resources/news hazardous substances 30 million tonnes per year (HDPE) milk bottles, reusable juice /2007/11/06/9076151/polyethylene- bottles, packaging of milk high-density-hdpe-prices-and-pricing- and dairy products information/) Polypropylene 1 Polypropylene products Around €700/tonne It appears to be safer for human Polypropylene is manufactured (PP) have been widely available PP will remain expensive because of health and the environment than BPA in the EU28 in quantities over for years and is used in food the shortage of propylene polycarbonate plastics 10,000,000 tonnes per year containers and reusable feedstock water bottles. Baby bottles Eurostat PRODCOM made from this material https://www.platts.com/news- were already manufactured feature/2014/petrochemicals/pgpi/pr before the ban of BPA opylene Few studies have been conducted on the substitution of polycarbonate because alternatives are already in use for the major applications: baby bottles made from polypropylene were already manufactured before the ban of BPA, and containers, packaging and

Substitution of Chemical Substances of Potential Concern | 126 Table 9-20: Assessment of potential alternatives for Bisphenol A Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability utensils used for food contact, are already manufactured with a copolyester to replace polycarbonate. Polyethylene 2 PET coatings are used to Virgin PET prices have remained over PET is biologically inert if ingested, is PET is manufactured in the terephthalate laminate beverage cans, £1,000 per tonne since January 2017. dermally safe during handling and is EU28 in quantities over (PET) but adhesives are needed While PET plastics are cost competitive not a hazard if inhaled. No evidence 3,000,000 tonnes per year to bind the PET onto the with other BPA-free alternatives, they of toxicity has been detected in metal. do not perform as well under high feeding studies using animals Eurostat PRODCOM temperatures and multiple uses Polyester 2 In France epoxy resins have No specific information, but products IPA, Registered 100,000 –1000 (made of 2 been replaced by three containing this substance instead of 000 tonnes per year monomers) types of resin (polyester, BPA are already on the market in TPA, Registered 1,000,000 – acrylic and vinyl) in internal France 10,000,000 tonnes per year coatings of containers dependant on acidity of Polyester is manufactured in food. Isophthalic acid (IPA) the EU28 in quantities over and terephthalic acid (TPA) 1,400,000 tonnes per year are the main carboxylic acids used in polyester Eurostat PRODCOM coatings. Polyester resins are easy to handle during the production process and adhere well to the metal surface, but they are usually not stable under acidic conditions and have a poor corrosion resistance. Acrylic resin 2 Acrylic resins derived from No specific information, but products No CAS registry number therefore no No CAS registry number butyl acrylate, styrene, containing this substance instead of harmonised classification methacrylic acid, ethyl BPA are already on the market in acrylate, glycidyl France

Substitution of Chemical Substances of Potential Concern | 127 Table 9-20: Assessment of potential alternatives for Bisphenol A Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability methacrylate, and hydroxypropyl methacrylate, cross-linked with pehenolic resins. They have a clean appearance and display corrosion and sulfide stain resistance, but they are brittle and may change the taste and odour of foods. One of the three types of resin used to replace epoxy resin in France. They are used for can linings Vinyl resin 2 Synthesised from vinyl No specific information, but products According to the classification Not registered (made of 2 chloride and vinyl acetate. containing this substance instead of provided by companies to ECHA in monomers) One of the three types of BPA are already on the market in CLP notifications this substance is resin used to replace epoxy France harmful to aquatic life and may cause resin in France cancer Polyetherimide 1 Polyetherimide is used in $8.80 per pound for less that truckload No harmonised classification Not registered microwaveable containers quantities (2,000 to 4,000 pounds) Acrylonitrile- 1 Acrylonitrile-butadiene- ABS is relatively inexpensive (prices, According to the classification Not registered butadiene- styrene is used in currently around $1.50 per pound, provided by companies to ECHA in styrene (ABS) tableware, kitchen utensils typically fall somewhere between CLP notifications this substance is and electric kettles those of polypropylene and harmful if swallowed, causes serious polycarbonate eye irritation, causes skin irritation and may cause respiratory irritation. Styrene 1 Styrene butadiene No specific information According to the classification Not registered butadiene copolymer is technically provided by companies to ECHA in copolymer feasible and used in blister CLP notifications this substance is packs and tests on baby harmful to aquatic life with long bottles lasting effects and may cause an allergic skin reaction. Listed as

Substitution of Chemical Substances of Potential Concern | 128 Table 9-20: Assessment of potential alternatives for Bisphenol A Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability carcinogenic, mutagenic and skin sensitiser Melamine 1 Melamine is technically No specific information but is According to the notifications Registered 100,000 – 1,000,000 feasible and is used in economically feasible as melamine provided by companies to ECHA in tonnes per year tableware, kitchen utensils products are widely used REACH registrations no hazards have and meal trays been classified Bisphenol S (BPS) 3 BPS is the first alternative According to INERIS, 2013, BPS price Oestrogenic properties, anti- Registered 1000 – 10,000 used in thermal paper - it ranges from 2,920€/t to 4,200€/t with androgenic activity, uterotrophic tonnes per year has more or less similar an average price of 3,583€/t. It is thus effect, effects on the reproduction properties as BPA. It raises higher than BPA price and the development at maternal the same questions about toxic doses (300 mg/kg/d), potential harmful impacts discrepancies between genotoxicity on health, and even less studies. (ANSES; study report on the studies than for BPA are bisphenol family compounds, 2012) available. BPS is currently used in Japan and USA instead of BPA. So this alternative is the most likely to be widely used instead of BPA in the case of a regulation. Thermal paper containing BPS as developer seems to have a longer persistence compared to BPA-based paper – the print will last at least 10 years. There seems to be no problem to adjust production, using BPS instead of BPA. Overall, BPS is claimed to be efficient and technically feasible by industry

Substitution of Chemical Substances of Potential Concern | 129 Table 9-20: Assessment of potential alternatives for Bisphenol A Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Bisphenol F (BPF) 3 It is unknown whether BPF Impossible to conclude since no data Difficult to state on the reprotoxicity Not registered – unsure of is actually used in thermal could be found on its price for the organs of the reproduction; availability paper but there is no Activity of endocrine disruption via indication that it is not. As the estrogens receptors; Direct BPF has similar properties genotoxic effect by break of the DNA. to BPA, it can be (ANSES; study report on the considered as theoretically bisphenol family compounds, 2012) usable as a dye developer in thermal paper and thus technically feasible Bisphenol AP 3 It is unknown whether Impossible to conclude since no data Oestrogenic activity, Not possible to Not registered – unsure of (BPAP) bisphenol AP is actually could be found on its price. conclude on the activity of endocrine availability used in thermal paper but disruption. No toxicokinetic data, no there is no indication that it data on toxicity for the organ of is not. As it has similar reproduction. (ANSES; study report properties to BPA, it can be on the bisphenol family compounds, considered as theoretically 2012) usable as a dye developer in thermal paper and thus technically feasible TGSA 3 It is unknown whether Impossible to conclude since no data Skin Sens 1 Registered –tonnage data TGSA is actually used in could be found on its price Aquatic chronic 2 confidential thermal paper, so it is difficult to conclude on its technical feasibility D8 3 Some special applications Around 5 times higher than BPA's cost Aquatic chronic 2 Registered – tonnage data of thermal papers required at 11,390-15,104€/t confidential the use of D8 which is currently used in applications requiring highly sensitive paper (e.g. mobile printers needing less energy when the paper

Substitution of Chemical Substances of Potential Concern | 130 Table 9-20: Assessment of potential alternatives for Bisphenol A Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability is more sensitive). It is difficult to conclude the availability of D8 1,2- 3 1,2-diphenoxyethane Impossible to conclude since no data Aquatic Chronic 2 Registered 100 – 1000 tonnes diphenoxyethane seems to be used in could be found on its price per year thermal paper – it can be deemed as technically feasible Pergafast 3 Pergafast is already used in Around 10 times higher than BPA's cost Aquatic Chronic 2 Registered – tonnage data (DP 201) thermal paper. The large at 15,000€-30,000€/t confidential retailer Carrefour in France phased out BPA and now uses thermal tickets containing Pergafast. However, to what exact extent Pergafast is generally used is unknown D90 3 There is indication it is used Impossible to conclude since no data No harmonised classification Not registered thermal paper so can be could be found on its price considered technically feasible

UU 3 It is unknown to what Impossible to conclude since no data No harmonised classification Not registered extent UU is actually used in could be found on its price thermal paper but there is indication that it is – so in principle technically feasible

Substitution of Chemical Substances of Potential Concern | 131 A1.6 Substance 6: Hydrazine

A1.6.1 Identity of the substance

Table 9-21: Identity of Hydrazine Name of substance Hydrazine

Synonyms -

EC Number 206-114-9

CAS Number 302-01-2, 7803-57-8

Molecular formula H4N2

REACH Registration tonnage band 1 000 - 10 000 tonnes per annum

Sources: https://echa.europa.eu/substance-information/-/substanceinfo/100.005.560

A1.6.2 Functionality and applications

Table 9-22: Functionality and applications for Hydrazine General description of functionality Hydrazine is used in a variety of applications. The most common use is in the production of foaming agents (as a chemical or physical and key physico-chemical blowing agent), such as azodicarbonamide which is used for disposable cups and packaging, insulation panels and spandex. Hydrazine is parameters also used in the production of pesticides and pharmaceuticals. Hydrazine is a powerful reducing agent and this property allows hydrazine to be used as an oxygen scavenger with applications in fossil fuels and nuclear power stations (corrosion agent). Hydrazine is used in the production of sodium azide. Hydrazine has also been used as a rocket fuel propellant and can be used as a fuel for hydrogen fuel cells. Family the substance belongs to Azane compounds

Substitution of Chemical Substances of Potential Concern | 132 Table 9-22: Functionality and applications for Hydrazine Application as a propellant/fuel Sector of Use SU 0: Other: NACE-Code H51 2.2 Space Transport SU 17: General manufacturing, e.g. machinery, equipment, vehicles, other transport equipment Product category PC 13: Fuels Industrial/Professional/ Consumer Industrial: used in a closed process Professional: Formulation use as propellant Consumer: N/A Description Hydrazine is used as a propellent for on board space vehicles. Hydrazine is mixed with dinitrogen tetroxide (N2O4) to create a hypergolic mixture which doesn’t require ignition. The mixture decomposes to nitrogen, hydrogen and ammonia. The ammonia decomposes with the nitrogen and hydrogen emitted to generate thrust Application as a reducing agent Sector of Use SU 8: Manufacture of bulk, large scale chemicals (including petroleum products) SU 9: Manufacture of fine chemicals SU 14: Manufacture of basic metals, including alloys Product category PC 0: Other: UCN R0500/R05100 (reduction agents) Industrial/Professional/ Consumer Industrial: no inclusion onto articles Professional: used in manufacturing processes Consumer: no uses Description Hydrazine is used as a reducing agent. It uses as a reducing agent include in electro less plating and the recovery of precious metals Azodicarbonamide Sector of Use SU 10: Formulation (mixing) of preparations and/or repackaging (excluding alloys) SU 11: Manufacture of rubber products SU 12: Manufacture of plastic products, including compounding and conversion Product category PC 21: Laboratory chemicals PC 32:Polymer preparations and compounds PC 13: Fuels Industrial/Professional/ Consumer Industrial: Used in mixing/blending and transfer Professional: Applications i.e. production of articles Consumer: used by consumers in articles Description Azodicarbonamide is used for disposable cups and packaging, insulation panels and spandex. Azodicarbonamide is also used in the manufacture of construction products and is used as an oxidising agent in cereal flours.

Substitution of Chemical Substances of Potential Concern | 133 Table 9-22: Functionality and applications for Hydrazine Corrosion Inhibitor Sector of Use SU 23: Electricity, steam, gas water supply and sewage treatment Product category PC 37: Water treatment chemicals Industrial/Professional/Consumer Industrial: used as a functional fluid Professional: used as a water treatment reagent Consumer: no consumer uses Description Hydrazine is used as a corrosion inhibitor for metals (such as steel) and also for applications involving water. Sources: American Chemical Society, Azodicarbonamide, https://www.acs.org/content/acs/en/molecule-of-the-week/archive/a/azodicarbonamide.html (accessed on 27th July 2017) ECHA website, https://echa.europa.eu/substance-information/-/substanceinfo/100.001.133 (accessed on 27th July 2017) ECHA Annex XV Dossier- Hydrazine, https://echa.europa.eu/documents/10162/2f29c6b2-e043-4a13-927e-c25a04cd4abe (accessed on 27th July 2017) Royal Society of Chemistry, Hydrazine, https://eic.rsc.org/magnificent-molecules/hydrazine/2000023.article (accessed on 27th July 2017)

A1.6.3 Potential alternatives

Table 9-23: Identification of potential alternatives for hydrazine Application 1 Application as Propellent/fuel Name/description of alternative Ammonium dinitramide- Alternatives based on ammonium dinitroamide have been the subject of interest. hydroxyl ammonium nitrate (such as AF-M315E)- Alternatives based on hydroxyl ammonium nitrate have been researched, with AF- M315E subject to demonstration Hydrogen peroxide- Alternatives based on hydrogen peroxide and prototypes have been tested Hydrazinium nitroformate- Alternatives based on hydrazinium nitroformate have been identified and has been marketed by a Dutch company Identifiers (if chemical substance) Substance name EC Number CAS Number Ammonium dinitramide 604-184-9 140456-78-6 AF-M315E (hydroxyl ammonium nitrate) 236-691-2 13465-08-2 Hydrogen peroxide 231-765-0 7722-84-1 Hydrazinium nitroformate 20773–28–8 Description of applicability of Replacement of hydrazine as a propellant fuel is currently in the development phase. AF-M315E is scheduled to be used in a Green alternatives Propellent Infusion Mission (GPIM) by NASA to show its capability. Application 2 Application as a reducing agent

Substitution of Chemical Substances of Potential Concern | 134 Table 9-23: Identification of potential alternatives for hydrazine Name/description of alternative For reduction in gold refining Aqua Regia Process the following have been used as alternatives to hydrazine: Ferrous sulphate, Sodium bisulphite, Sulphur dioxide, Oxalic acid, Hydroquinone and certain salts For metal precipitation from salt solutions: formic acid and formulates, sodium borohydride and thioform and zinc have been identified as alternatives. Smopex®fibres- can be used for the recovery of platinum group metal and consist of either a polypropylene or a viscose backbone with specific functional groups dependent on the application

Identifiers (if chemical substance) Substance name EC Number CAS Number Ferrous sulphate 231-753-5 7720-78-7, 7782-63-0, 13463-43-9 Sodium bisulphite 231-548-0 7631-90-5 Sulphur dioxide 231-195-2 7446-09-5 Oxalic acid 205-634-3 144-62-7, 6153-56-6 Hydroquinone 204-617-8 123-31-9 Formic acid 200-579-1 64-18-6 sodium borohydride 241-004-4 16940-66-2 Thioform and zinc 231-175-3 (zinc) 7440-66-6 (zinc) Description of applicability of Alternatives to hydrazine as a metal reduction agent are currently in used dependent on the application. The ECHA Annex XV dossier alternatives discusses alternatives for two companies, where for the precipitation of basic metals formulate does not achieve the metal purity and sodium borohydride has worked well in the laboratory. Application 3 azodicarbonamide Name/description of alternative Chemical blowing agents: SAFOAM® HT- High temperature endothermic chemical blowing agent which has been developed as alternative to azodicarbonamide p,p’-oxybisbenzenesulfonylhydrazide (OBSH): Sulfonyl hydrazide which is a low temperature blowing agent and is used in rubber foams p-toluenesulfonylsemicarbazide: Semicarbazide which is an intermediate high temperature blowing agent and is used for ABS and PP moulding applications 5-phenyltetrazole: Tetrazole which is an high temperature agent and is used in polycarbonates Toluenesulfonylhydrazide (TSH): Sulfonyl hydrazide which is a low temperature blowing agent Sodium bicarbonate: Chemical blowing agent which is a coarse foam Sodium bicarbonate/ citric acid mixture: Chemical blowing agent which produces a fine foam Physical blowing agent: Nitrogen, Pentane and Supercritical carbon dioxide: Soluble in molten polymers and has been used in extrusion and pressure moulding processes

Identifiers (if chemical substance) Substance name EC Number CAS number

Substitution of Chemical Substances of Potential Concern | 135 Table 9-23: Identification of potential alternatives for hydrazine OBSH 201-286-1 80-51-3 p-toluenesulfonylsemicarbazide 233-857-6 10396-10-8 5-phenyltetrazole 241-950-8 18039-42-4 Toluenesulfonylhydrazide 216-407-3 1576-35-8 Sodium bicarbonate 205-633-8 144-55-8 Nitrogen 231-783-9 7727-37-9 Pentane 203-692-4 109-66-0 Carbon dioxide 204-696-9 124-38-9 Description of applicability of A commercially available alternative to azodicarbonamide as a chemical blowing agent is available. There are other alternatives alternatives available for specific applications (such as for extrusion and moulding processes) Application 4 Corrosion Inhibitor (including water boiler treatment) Name/description of alternative Alternatives to hydrazine as a corrosion inhibitor include: Sodium sulphite Sodium dithionite Carbohydrazide, such as Accepta 2565 Diethyl hydroxylamine (DEHA) Methyl ethyl ketoxime (MEKO) Hydroquinone Tannic acid Filming amines: isopropyl hydroxylamine (IPHA), octadecylamine (ODA), 1-amino-4-methylpiperazine and 8-azaguanin Ascorbic acid derivatives: sodium erythorbate and ascorbic acid Oxalates: ammonium oxalate and ascorbic acid Formic acid Hydrogen Alternative techniques include vacuum with pressure thermal deaeration, catalytic reduction and treatment by the addition of other chemicals apart from hydrazine

Identifiers (if chemical substance) Substance Name EC Number CAS Number Sodium sulphite 231-821-4 7757-83-7 Sodium dithionite 231-890-0 7775-14-6 Carbohydrazide 207-837-2 497-18-7 Diethyl hydroxylamine Methyl ethyl ketoxime 202-496-6 96-29-7 Hydroquinone 204-617-8 123-31-9

Substitution of Chemical Substances of Potential Concern | 136 Table 9-23: Identification of potential alternatives for hydrazine Tannic acid 215-753-2 1404-55-4 Description of applicability of There are a number of identified alternatives for hydrazine as a corrosion inhibitor (oxygen scavenger) in the literature. Literature alternatives review and consultation performed by ECHA for the Annex XV dossier has suggested that there are issues with a number of the alternatives including the build-up of organic salts which is discussed in the following table Sources: Accepta (2017): Boiler Water Oxygen Scavenger (Hydrazine Replacement), https://accepta.com/water-treatment-chemicals-wastewater-effluent-treatment-products/boiler- water-treatment-chemicals/oxygen-scavengers-boiler-water-treatment-chemicals/189-boiler-water-oxygen-scavenger-hydrazine-replacement-2565 (accessed 3rd August 2017) ECHA (2011): Annex XV dossier, Hydrazine, https://echa.europa.eu/documents/10162/2f29c6b2-e043-4a13-927e-c25a04cd4abe (accessed 3rd August 2017) ECHA (undated): Annex XV dossier, ADCA,https://www.echa.europa.eu/documents/10162/d9e11c88-481a-47a9-8fff-915b48086ddb (accessed 3rd August 2017) Frankham J (2010): The Use of Metal Scavengers for Recovery of Precious, Base and Heavy Metals from Waste Streams, Platinum Metals Rev., 54(3), 200, http://www.technology.matthey.com/article/54/3/200-202/ (accessed 3rd August 2017) Larsson A and Wingborg N (2011): Advances in Spacecraft Technologies, http://cdn.intechweb.org/pdfs/13473.pdf (accessed 3rd August 2017) NASA (2017): Green Propellant Infusion Mission Overview, https://www.nasa.gov/mission_pages/tdm/green/overview.html (accessed 3rd August 2017) Witze A (2013): Green fuels blast off, Nature, http://www.nature.com/news/green-fuels-blast-off-1.13603 (accessed 3rd August 2017)

A1.6.4 Assessment of feasibility of potential alternatives

Substitution of Chemical Substances of Potential Concern | 137 Table 9-24: Assessment of potential alternatives for hydrazine Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Ammonium dinitramide 1 High solubility which is a - Ammonium dinitramide has Not registered requirement for a propellant acute toxicity properties. oxidiser. Has been the subject Dust inhalation may cause of further investigation for its respiratory irritation and technical feasibility. long-term exposure can result Promising alternative in dizziness, sleeping issues according to hydrazine and indisposition (Larsson, 2011) Hydroxyl ammonium nitrate 1 Highly soluble in water. Also - Not registered comparable to propellants in boosters and missiles Hydrogen peroxide 1 Decomposes exothermically - Has been registered on CLP as Registered 1,000,000 – to oxygen and water. Has a an Acute Tox. 4 and Skin Corr. 10,000,000 tonnes per year propulsive performance 20% 1A lower than hydrazine, however has a high density Hydrazinium nitroformate 1 Has a high density and specific - Data from Maree et al (ECHA Not registered impulse Annex XV dossier) suggests there is no indication of danger from inhalation, while it could be harmful to skin, its oral toxicity is lower than hydrazine however long term effects need to be investigated Ferrous sulphate 2 Is a possible alternative to - From classifications given to Registered 1,000,000 – hydrazine in the aqua regia ECHA, the substances causes 10,000,000 tonnes per year process for gold refining serious eye irritation, causes skin irritation, can cause an allergic skin reaction and is harmful if swallowed Sodium bisulphite 2 Is a possible alternative to - From classifications given to Registered 100,000 – hydrazine in the aqua regia ECHA, the substance is 1,000,000 tonnes per year

Substitution of Chemical Substances of Potential Concern | 138 Table 9-24: Assessment of potential alternatives for hydrazine Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability process for gold refining harmful if swallowed

Sulphur dioxide 2 Is a possible alternative to - From CLP classifications, the Registered 100,000 – hydrazine in the aqua regia substance is toxic if inhaled, 1,000,000 tonnes per year process for gold refining causes severe skin burns and eye damage Oxalic acid 2 Is a possible alternative to - From classifications given to Registered 10,000 – 100,000 hydrazine in the aqua regia ECHA, the substance is tonnes per year process for gold refining harmful if swallowed, harmful with skin contact and can cause serious eye damage

Hydroquinone 2 Is a possible alternative to - The substance is suspected to Registered 10,000 – 100,000 hydrazine in the aqua regia cause cancer, serious eye tonnes per year process for gold refining damage, is suspected of causing genetic damage and may also cause an allergic skin reaction (ECHA) Formic acid 2 Testing has been undertaken - The substance is classified as Registered 100,000 – for their technical suitability being a skin and eye irritant 1,000,000 tonnes per year but no results are available Sodium borohydride 2 Registered 1,000 – 10,000 tonnes per year Thioform and zinc 2 It has been suggested by Effluent disposal can be costly - - Philips (ECHA) that thioform and zinc could be a replacement for hydrazine Smopex®fibres 2 Smopex®fibres can be used to - - - scavenge residual platinum and can also be used for base and heavy metals in water. They can be used up to a temperature of 120 oC

Substitution of Chemical Substances of Potential Concern | 139 Table 9-24: Assessment of potential alternatives for hydrazine Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability (Johnson Matthey) p,p’- 3 Low temperature blowing - From REACH notifications, the Registered 1,000 – 10,000 oxybisbenzenesulfonylhydrazide agent which shouldn’t substance has been notified tonnes per year (OBSH) operate above 177oC. Used to be harmful if swallowed, mostly in PVC and rubber can cause serious eye irritation, may cause organ damage, may cause allergic skin reactions, can cause skin irritations and is also suspected of genetic damage 5-phenyltetrazole 3 High temperature chemical - Commercially available blowing agent. Decomposes between 240-250oC with generation of nitrogen Toluenesulfonylhydrazide 3 Low temperature agent. Classed in the CLP as Acute Not registered Used mostly in rubber. Tox. 3, Skin Irrit. 2, Eye Irrit. 2 Hydrazine based and Muta. 2 Sodium bicarbonate 3 Endothermic chemical Cheap material No hazards have been Registered 1,000,000 – blowing agent. Decomposes classified on the CLP 10,000,000 tonnes per year around 140 oC and is coarse foam. Bicarbonates are used in injection moulding of foam Nitrogen 3 Been used in extrusion and - No classification Not registered pressure holding processes. Pentane 3 Been used in extrusion and - Highly flammable. Classed as Registered 100,000 – pressure moulding processes. possibly causing dizziness or 1,000,000 tonnes per year Flammable drowsiness and can be fatal if inhaled and enters airways Carbon dioxide 3 Supercritical carbon dioxide is - Self-classified as Acute Tox. 4 Not registered used. Been used in extrusion and STOT SE 3 and pressure moulding processes. The supercritical

Substitution of Chemical Substances of Potential Concern | 140 Table 9-24: Assessment of potential alternatives for hydrazine Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability carbon dioxide acts as a plasticiser and is a relatively new technology Sodium sulphite 4 Reacts with oxygen to form Cheapest oxygen scavenger Not hazardous Registered 10,000 – 100,000 sodium sulphate. Not used tonnes per year for high pressure applications and can’t protect the condensate loop (not volatile enough) and sulphate salts build up in the boiler. Theoretical dosage of 8:1 Sodium dithionite 4 Mentioned by a report by - The substance has been Registered 100,000 – BuuA (1991) but there is no notified as causing serious eye 1,000,000 tonnes per year further information irritation Carbohydrazide 4 Hydrazine replacement. The High cost The substance has been Registered 100 - 1000 tonnes substance doesn’t contribute notified as may cause an per year to boiler salts, however allergic skin reaction produces carbon dioxide (with possible carbonic acid formation). Can be used in boilers at a wide variety of pressures, however at temperatures over 180 oC it can break down to form hydrazine. Theoretical dosage of 1.4:1 Diethyl hydroxylamine 4 Arkema (2003) from the ECHA - Not registered REACH Annex XV report states the substance has good passivation, low toxicity ((some decomposition of ammonia does not occur until 280 oC which is a higher

Substitution of Chemical Substances of Potential Concern | 141 Table 9-24: Assessment of potential alternatives for hydrazine Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability temperature than hydrazine), high volatility and good thermal stability. Slow kinetics of oxygen scavenging at low temperatures. Theoretical dosage of 1.2:1 Methyl ethyl ketoxime 4 Volatile oxygen scavenger. Substance has been notified Registered 1000 – 10,000 Compared to hydrazine, the under CLH as being suspected tonnes per year substance does not have the of causing cancer, causing same passivation. The serious eye damage, being theoretical dosage is 5.4:1 harmful when in contact with skin and can cause an allergic skin reaction Hydroquinone 4 The substance has a quick Substance has been notified Registered 10,000 – 100,000 reaction rate. The theoretical under CLH as being suspected tonnes per year dosage is 6.9:1 of causing cancer, is suspected of causing genetic defaults, causing serious eye damage, being harmful when in contact with skin, can cause an allergic skin reaction and is toxic to aquatic life Tannic acid 4 Tannins are used in blend and This substance can have Not registered have been suggested as an lasting effects to aquatic life alternative, however no and can cause serious eye further information is irritation (CLH) available

Substitution of Chemical Substances of Potential Concern | 142 A1.7 Substance 7: N-Methyl-2-pyrrolidone (NMP)

A1.7.1 Identity of the substance

Table 9-25: Identity of NMP Name of substance N-Methyl-2-pyrrolidone Synonyms 1-methylpyrrolidin-2-one 1-mehyl-2-pyrrolodone 1-Methyl 2-pyrrolidone 1-Methyl-2-pyrrolidinone 1-methyl-2-pyrrolidon 1-Methyl-2-Pyrrolidone 2-Pyrrolidinone, 1-methyl- 2-Pyrrolidone, 1-methyl NMP EC Number 212-828-1 CAS Number 872-50-4 Molecular formula C5H9NO

REACH Registration tonnage band 10,000 – 100,000 tonnes per annum Sources: ECHA website, https://echa.europa.eu/substance-information/-/substanceinfo/100.011.662 (accessed on 31 July 2017)

A1.7.2 Functionality and applications

Table 9-26: Functionality and applications for NMP General description of functionality NMP is an organic compound consisting of a 5-membered lactam. It belongs to the class of dipolar aprotic solvents such as dimethyl and key physico-chemical parameters formamide and dimethyl sulfoxide. It is used in the petrochemical and plastics industries as a solvent, exploiting its non-volatility and ability to dissolve diverse materials

Substitution of Chemical Substances of Potential Concern | 143 Table 9-26: Functionality and applications for NMP Family the substance belongs to Nitrogen containing heterocycles. Dipolar aprotic solvents Polymers Sector of Use SU12: Manufacture of plastics products, including compounding and conversion Product category PC32: Polymer preparations and compound Industrial/Professional/ Consumer Industrial Description NMP has been widely used in the preparation of various types of polymers: polyurethane (PU), polyaniline (PANI), polyamideimide (PAI), polyimide (PI), polyvinylidene fluoride (PVDF), polysulphone (PFS) and polyethersulphone (PES), but also in the preparation of poly para- phenyleneterephtalamide (PPTA), polyphenylene sulphide (PPS) and other high performance thermoplastics (HPTP). These polymers are applied in a wide range of applications: - PU is often used in coatings - PANI is used for high electrical conductivity thin films to be used in electronics and semiconductor industries - PAI is used for coatings and wire coatings - PVDF is used as of high quality coatings, in wire coatings, as binder for cathodes (battery industries), and in the production of membranes - PI in used for wire coatings, membranes and electronics and semiconductor industries - PFS and PES are used for membranes - PPTA is used to produce the para-aramids Twaron and Kevlar - PPTA is used to produce the para-aramids PPS is used for membranes and high performance thermoplastics Petrochemicals Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU9: Manufacture of fine chemicals Product category PC20: Processing aids such as pH-regulators, flocculants, precipitants, neutralization agents PC24: Lubricants, greases, release products PC40: Extraction agents PC41: Oil and gas exploration or production products Industrial/Professional/ Consumer Industrial Description NMP is used in the large-scale recovery of hydrocarbons by extractive distillation. NMP is used by some petroleum refineries (i.e. industrial facilities) as an extraction solvent in the production of lubricant base oils to remove aromatic hydrocarbons (e.g. PAHs) and other polar components. This extraction process generates lubricating oils with lower impact to human

Substitution of Chemical Substances of Potential Concern | 144 Table 9-26: Functionality and applications for NMP health and the environment. Furthermore, NMP is used in the desulphurisation of oil products, the removal of CO2, COS and H2S from gas streams and in butadiene production Coatings Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU9: Manufacture of fine chemicals SU12: Manufacture of plastics products, including compounding and conversion Product category PC9a: Coatings and paints, thinners, paint removes PC9b: Fillers, putties, plasters, modelling clay PC18: Ink and toners PC23: Leather treatment products PC32: Polymer preparations and compounds Industrial/Professional/ Consumer Industrial/Professional/Consumer Description NMP is used as a solvent in a wide range of different coating products. NMP is often used in polymer based coatings, such as wire coatings. NMP is mainly used in the wire coatings made from the most solvent resistant polymers: polyamideimides (PAI) and polyimides (PI). Polymers such as polyurethanes (PUs) and polyvinylidene fluorides (PVDFs) are also used as important ingredients in high-quality coatings for metal and other materials. These polymers are used as binder and are often dissolved in NMP as a solvent. NMP is especially used in the production of magnetic wire coatings that require a high quality coating. The wire end products are assumed not to contain any remaining NMP. Magnetic wires are used in the manufacturing of e.g. motors, generators and transformers. The non-wire coaters include sectors that deal with the use of coatings for many purposes; a very large relevant sector is the automotive industry. Besides that uses in films and medical images and in the textile and leather industry, have been mentioned. Example include: - Production of enamelled wire - Coalescing solvent in waterborne paints - Thinner to aid coating spray application - Specialist coatings - Solvent-based high temperature coatings (solvent and water-based and diluent/cleaner) - Solvent for paint resins - Co-solvent (at c. 5 %) in screen printing inks and thinner - Automotive waterborne paint - Coalescing solvent in automotive paints

Substitution of Chemical Substances of Potential Concern | 145 Table 9-26: Functionality and applications for NMP - Additive for coating esp. technical textiles (solvent for thixotropic agent) - Component in screen inks and printing inks - Waterborne paint for steel/automotive components - Wood impregnation product (co-solvent for fungicide) - Use in industrial continuous inkjet mixtures (ink) - Metal coating for hot environments (prevent corrosion/chemical attack) - Waterborne parquet varnish - Binder in waterborne PU wood paint - Binder in waterborne PU top coat - Epoxy paints - Artists colours (acrylics) NMP may also be used in the production of coatings used in the production of food contact material/bakeware Cleaning products (excluding Sector of Use SU17: General manufacturing, e.g. machinery, equipment, vehicles, other transport electronics) equipment SU0: Other Product category PC9a: Coatings and paints, thinners, paint removers PC35: Washing and cleaning products Industrial/Professional/ Consumer Industrial/Professional/Consumer Description NMP is a powerful solvent and has a high solvating power for plastics, resins, oil and grease. NMP is used as an ingredient in paint removers, cleaners and as or in degreasers. It can be used in pure form or in mixtures for removal of oil, carbon deposits and other tarry polymeric residues from metal chambers, pistons and cylinders, as well as for wet cleaning of combustion engines and in the optics industry Electronics Sector of Use SU16: Manufacture of computer, electronic and optical products, electrical equipment Product category PC35: Washing and cleaning products Industrial/Professional/ Consumer Industrial Description NMP is being used within the European semiconductor industry: - In wafer cleaning and stripping to remove organic contamination and organic layers - As a solvent in dedicated formulations (i.e. precursor solutions for wafer coatings such as polyimides and anti-reflective coatings). Polyimides are applied as a protection layer in a wide range of semiconductor products In other electronics, NMP is used as:

Substitution of Chemical Substances of Potential Concern | 146 Table 9-26: Functionality and applications for NMP - A processing aid in pure form or in mixture with other substances (photoresist, BARC and TARC) - A surface cleaner in clean rooms (tabletop and mat cleaner and electrostatic charge neutralising agent) - Agent for failure analysis (cleaning/stripping) Batteries Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU12: Manufacture of plastics products, including compounding and conversion SU16: Manufacture of computer, electronic and optical products, electrical equipment Product category PC9a: Coatings and paints, thinners, paint removes PC32: Polymer preparations and compounds PC0: Other Industrial/Professional/ Consumer Industrial Description NMP is used both in lithium ion batteries as in other hybrid batteries using nickel, magnesium, or cobalt. In lithium battery production it is applied as a solvent for the binder resins for both the carbon anode and the lithium cobalt oxide cathode, it may be used in gel-polymer lithium ion battery separators/electrolytes, and it may be used in coatings on the outside of the batteries. Also for other hybrid batteries using nickel, magnesium, or cobalt NMP is used in the slurry to bind the active material to the electrodes Membrane manufacture Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU12: Manufacture of plastics products, including compounding and conversion Product category PC32: Polymer preparations and compounds PC0: Other Industrial/Professional/ Consumer Industrial Description NMP is used as a processing aid in the production of polymer based membranes. Various polymers can be used in membrane production such as polysulphone (PFS or PSU), polyethersulphones (PES or PESU), polyimide (PI), polyvinylidene fluoride (PVDF) and polycarbonate as well as polyacrylonitrile (PAN), poly (vinyl alcohol) (PVA), polymethylmethacrylate (PMMA), and ethylene vinyl alcohol (EVAL). The membranes are applied in a variety of (industrial) processes such as gas separation, nanofiltration, ultrafiltration and desalination and as such different types of membranes exist. Membranes produced with NMP are used in a variety of applications, e.g. water filtration, beer/wine filtration, blood filtration and vapour permeation Agrochemicals Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products)

Substitution of Chemical Substances of Potential Concern | 147 Table 9-26: Functionality and applications for NMP Product category PC27: Plant protection products Industrial/Professional/ Consumer Industrial: synthesis Professional: co-solvent Description NMP is both used in the synthesis of active ingredients and as a co-solvent in the formulation of various agrochemicals (it is used in insecticides, fungicides, herbicides, seed treatment products and bio regulators). Besides the function of solvent for the active ingredients NMP, may have been used in these formulations as an adjuvant enhancing the uptake and downward transport of the active ingredient from apex towards the base of a shoot or a stem (basipetal translocation). Now banned under EU Regulation 1107/2009 Pharmaceuticals Sector of Use SU9: Manufacture of fine chemicals SU20: Health services Product category PC29: Pharmaceuticals Industrial/Professional/ Consumer Industrial/Professional/Consumer Description NMP finds variable uses in the pharmaceuticals industry: - NMP is an important solvent used in the extraction, purification, and crystallisation of pharmaceuticals. - NMP (low in free amines) is used for the solid-phase synthesis of therapeutic peptides - NMP may function as a reaction medium in the chemical synthesis of antibiotics for human, animal and agro purposes (e.g. Ertapenem) - NMP is used as a solvent for difficult to dissolve drugs, but it has also a function as an enhancer for the transdermal delivery of drugs from the aqueous phase - NMP is also used in parenteral formulations for human and veterinary drugs where a standard biodegradable polymer or copolymer is dissolved in a solvent, to be used in a parenteral controlled released delivery systems Laboratory use Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU9: Manufacture of fine chemicals SU12: Manufacture of plastics products, including compounding and conversion SU16: Manufacture of computer, electronic and optical products, electrical equipment SU24: Scientific research and development Product category PC21: Laboratory chemicals Industrial/Professional/ Consumer Industrial/Professional Description NMP is used in laboratories during research and development of petrochemicals, pharmaceuticals, all sorts of formulations and functional fluids and as a ‘traditional solvent’

Substitution of Chemical Substances of Potential Concern | 148 Table 9-26: Functionality and applications for NMP for laboratories Functional fluids Sector of Use SU0: Other Product category PC16: Heat transfer fluids PC17: Hydraulic fluids PC24: Lubricants, greases, release products PC0: Other Industrial/Professional/ Consumer Industrial/Professional Description NMP is used in functional fluids, for example in cable oils, transfer oils, coolants, insulators, refrigerants, hydraulic fluids in industrial equipment including maintenance and related material transfers Construction chemicals Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU12: Manufacture of plastics products, including compounding and conversion Product category PC1: Adhesives, sealants PC32: Polymer preparations and compounds Industrial/Professional/ Consumer Industrial/Professional Description From literature, the uses of polymer dispersions, powders and solutions are often classified under the construction chemicals. They may be produced on the basis of acrylates, styrene, butadiene and polyurethane and may be applied as filling compounds, roof coatings, sealants and flooring adhesives. There are reports on the use of NMP in adhesives, binders and anti- corrosion or waterproofing coatings Sources: ECHA website, https://echa.europa.eu/documents/10162/ee4c88a9-d26f-4872-98fd-fb41646cc9e1 (accessed on 31 July 2017) ECHA website, https://echa.europa.eu/documents/10162/a3e8fb17-d794-493c-a5ac-8cce41def0c7 (accessed on 1 August 2017)

A1.7.3 Potential alternatives

Table 9-27: Identification of potential alternatives for NMP Application 1 Polymers Name/description of alternative See specific applications below; for high performance polymers, substitution prospects are poor. A range of alternative solvents can be found in the literature and are presented below Identifiers (if chemical substance) Substance name EC Number CAS Number N-ethyl pyrrolidone (NEP) 220-250-6 2687-91-4

Substitution of Chemical Substances of Potential Concern | 149 Table 9-27: Identification of potential alternatives for NMP Dimethyl formamide (DMF) 200-679-5 68-12-2 Dimethyl acetamide (DMAc) 204-826-4 127-19-5 Dimethyl sulphoxide (DMSO) 200-664-3 67-68-5 Acetone 200-662-2 67-64-1 Triethyl phosphate (TEP) 201-114-5 78-40-0 Methyl ethyl ketone (MEK) 201-159-0 78-93-3 Hexamethylphosphoramide (HMPA) (high performance polymers) 211-653-8 680-31-9 Description of applicability of Besides NMP, DMF, DMAc and DMSO are all good solvents for many polymers. Often one of these solvents are used in preparing polymer alternatives solutions. Sometimes acetone, MEK or triethylphosphate (TEP) are used. However, finding alternatives for the use of NMP (with CaCl2) in high performance polymer manufacturing is a more challenging task Application 2 Petrochemicals Name/description of alternative Some possibilities are available. A range of alternative solvents are known to be used in the petrochemicals industry but these are typically implemented within different production technologies and equipment, thus they cannot act as drop-in substitutes Identifiers (if chemical substance) Substance name EC Number CAS Number Dimethyl formamide (DMF) 200-679-5 68-12-2 Dimethyl sulphoxide (DMSO) 200-664-3 67-68-5 Methanol (MeOH) 200-659-6 67-56-1 Acetylene 200-816-9 74-86-2 Furfural 202-627-7 98-01-1 Phenol 203-632-7 108-95-2 Sulphur oxide 231-195-2 7446-09-5 Acetonitrile 200-835-2 75-05-8 Acrylonitrile 203-466-5 107-13-1 N-formyl morpholine 224-518-3 4394-85-8 Trimethyl glycol dimethyl ether (triglyme) (TEGDME) 203-977-3 112-49-2 Ethylene glycol 203-473-3 107-21-1 Diethylene glycol 203-872-2 111-46-6 Tetraethylene glycol (Tetra EG) 203-989-9 112-60-7 Propylene carbonate (PC) 203-572-1 108-32-7 Sulpholane (tetramethylene sulphone) 204-783-1 126-33-0 2-(2-aminoethoxy)ethanol (diethylene glycolamine) 213-195-4 929-06-6

Substitution of Chemical Substances of Potential Concern | 150 Table 9-27: Identification of potential alternatives for NMP Description of applicability of A range of different applications can be considered: alternatives - Extraction of aromatic compounds from lube feed stock after distillation and deasphalting: furfural and phenol are referred to in literature as possible solutions. The Reference Document on Best Available Techniques (BREF) for Mineral Oil and Gas Refineries from 2003 recommends the use of NMP as solvent in the aromatic extraction of base oils but the switch from furfural to NMP may not be justified environmentally or technically especially when producing lower boiling point base oils (e.g. transformer oil distillates). Further alternative solvents mentioned in the BREF for aromatic extraction are phenol and liquid sulphur dioxide. However, changing the process from one solvent to another requires major modifications in the extraction process, which is accompanied by high costs - Aromatic extraction from the light steam cracking effluents: literature describes the use of diethylene glycol, tetraethylene glycol, sulpholane, DMSO and N-formyl morpholine (NFM). Six extraction processes applying different solvents have been described extensively in the literature: the UDEX process using diethylene glycol (DEG), the Sulpholane process using sulpholane, the Arosolvan process using NMP, the Tetra process using tetra ethylene glycol, the Morphylex process using NFM and the DMSO process using DMSO and butane. Although alternatives are available, the process using NMP cannot simply be replaced by one of the other processes as it needs other chemicals and other process conditions. It is also clear that changes in the downstream use and market of products affect the whole chain - Butadiene production: butadiene can be produced by four different processes, one of which uses aqueous NMP as a solvent in extractive distillation (BASF/Lurgi), another uses non-aqueous solvent extraction with dimethylformamide (DMF) (ZEON Corp) and another two, less applied, use acetylene hydrogenation and acetonitrile extraction. As above, shifting to an alternative process might be accompanied by high costs - Desulphurisation of oil products: in oxidative desulphurisation polar solvents such as DMF, DMSO and methanol (MeOH) can be used. In contrast to hydrosulphurisation, which is relatively costly, oxidative sulphurisation can run at lower production costs. However, it is not known whether the alternatives can be used within the same process or whether process changes are required to shift to alternative substances - Removal of CO2, COS and H2S from gas streams: various solvents such as sulpholane, NFM, triethylene glycol dimethyl ether and 2-(2-aminoethoxy)ethanol are widely applied to remove acidic compounds, such as CO2 , COS and H2S, from high-pressure gas streams Application 3 Coatings Name/description of alternative This application covers a wide range of different end-applications for a variety of polymer materials. Only DMSO would appear to be suitable for both wire and non-wire applications but on a case-by-case basis the solvents shown below might be considered as NMP substitutes. Substitution is more straightforward for non-wire coatings because their technical requirements are not as severe as in the case of wire coatings Identifiers (if chemical substance) Substance name EC Number CAS Number N-ethyl pyrrolidone (NEP) (non-wire) 220-250-6 2687-91-4 Dimethyl formamide (DMF) (wire) 200-679-5 68-12-2

Substitution of Chemical Substances of Potential Concern | 151 Table 9-27: Identification of potential alternatives for NMP Dimethyl acetamide (DMAc) (wire) 204-826-4 127-19-5 Dimethyl sulphoxide (DMSO) (wire & non-wire) 200-664-3 67-68-5 Tetramethyl urea (TMU) (wire) 211-173-9 632-22-4 Acetone (wire & non-wire) 200-662-2 67-64-1 Triethyl phosphate (TEP) 201-114-5 78-40-0 Dipropylene glycol monomethyl ether (DPGME) (non-wire) 252-104-2 34590-94-8 Dipropylene glycol dimethyl ether (non-wire) 601-045-4 111109-77-4 Dichloromethane (DCM) (non-wire) 200-838-9 75-09-2 Ethyl acetate (non-wire) 205-500-4 141-78-6 Propyl acetate (non-wire) 203-686-1 109-60-4 Xylene (various CAS Nos.) (non-wire) 215-535-7 1330-20-7 Sulpholane (tetramethylene sulphone) (wire) 204-783-1 126-33-0 Diphenylmethanediisocyanate, isomers and homologues 618-498-9 9016-87-9 Description of applicability of Non-wire coatings alternatives - Polyurethane coatings: nowadays, NMP has been replaced in a large number of polyurethane dispersions by other solvents, such as acetone, dipropylene glycol dimethyl ether (DPDME) and N-ethyl pyrrolidone (NEP). The development of solvent-free urethane acrylic hybrid polymers for coatings and that of waterborne polyurethane coatings for wood floors have been described in the literature. Diphenylmethanediisocyanate, isomers and homologues also offer a two-component, solvent free, low viscosity, tough elastic, crack-bridging polyurethane resin and can be used for crack bridging, trafficable, slip resistant wearing layers and car park decks, garage floors and bridges. The development of the replacement of NMP-containing waterborne polyurethane binders to NMP-free materials would not lead to total new basecoat developments - Coatings in the automotive industry: NMP can be eliminated form automotive coatings but this would require adaptation of the full coating system both for the industrial and professional uses. Both use the same coatings. At present, there are already NMP-free products for automotive on the market which use NEP and DMSO as alternatives - Coatings in textile and leather: literature suggests the existence of NMP-free polyurethane systems and its replacement would appear to be advanced, but details of the alternatives involved is not readily available - Coatings in films and medical images: NEP has been reported as a potential alternative for NMP in medical imaging. A few years ago a manufacturer of imaging films described a number of technical problems using replacement of NMP by 2- Pyrrolidone, a mixture of propylenecarbonate and ethylene-glycolmonobutylether (EGMBE), ethers of (di) or (tri) propylene

Substitution of Chemical Substances of Potential Concern | 152 Table 9-27: Identification of potential alternatives for NMP glycol and DMSO. These technical problems comprised condensation problems in the drying zone, coating defects, repellences, and levelling problems (cloudy pattern) and increased haziness in the dried coating Wire coatings The solubility of the more thermal and solvent resistant polymers such as PAL, PL and PVDF, make the amount of possible alternatives limited to the ones mentioned above: DMF, DMAc and DMSO for PAL and PL. Solvents for PVDF are dimethyl formamide (DMF), dimethyl acetamide (DMAc), tetramethyl urea, dimethyl sulfoxide (DMSO), triethyl phosphate, and acetone. Wire coating takes place at elevated temperatures, which lead to breakdown of DMSO. This breakdown leads to technical problems within the ovens Application 4 Cleaning products (excluding electronics) Name/description of alternative A wide variety of solvents can be used as cleaning agents. Here, we focus on industrial cleaning and paint stripping/graffiti removal. NMP has been chosen as the preferred alternative for dichloromethane in the 1990s, however, many alternative solutions are currently available on the market Identifiers (if chemical substance) Substance name EC Number CAS Number N-ethyl pyrrolidone (NEP) 220-250-6 2687-91-4 Dimethyl formamide (DMF) 200-679-5 68-12-2 Dimethyl acetamide (DMAc) 204-826-4 127-19-5 Dimethyl sulphoxide (DMSO) 200-664-3 67-68-5 Acetone 200-662-2 67-64-1 Dipropylene glycol monobutyl ether (DEGBE) 249-951-5 29911-28-2 Diethylene glycol monoethyl ether (DEGEE) 203-919-7 111-90-0 Tripropylene glycol ethyl ether (TPM) 247-045-4 25498-49-1 Di-glycol ethers Furfuryl alcohol 202-626-1 98-00-0 Ethylene glycol monobutyl ether (butoxyethanol) (EGBE) 203-905-0 111-76-2 Methyl ethyl ketone (MEK) 201-159-0 78-93-3 Propylene carbonate (PC) 203-572-1 108-32-7 Dibasic esther (DBE) Ethyl 3-ethoxypropionate (EEP) 212-112-9 763-69-9 Dimethyl phthalate (DMP) 201-550-6 84-66-2 Sodium hypochlorite 231-668-3 7681-52-9 Sodium hydroxide 215-185-5 1310-73-2 Potassium hydroxide 215-181-3 1310-58-3 Colza oil ester Formic acid 200-579-1 64-18-6 Monoethanolamine (MEA) 205-483-3 141-43-5

Substitution of Chemical Substances of Potential Concern | 153 Table 9-27: Identification of potential alternatives for NMP Isopropanolamine 201-162-7 78-96-6 Combinations of several substances Gamma butyrolactone (GBL) 202-509-5 96-48-0 Acetophenone 202-708-7 98-86-2 Methanol/toluene/ethylene chloride Benzyl alcohol 202-859-9 100-51-6 Benzyl alcohol/formic acid Dichloromethane (DCM) 200-838-9 75-09-2 Hydrogen peroxide 231-765-0 7722-84-1 Ethyl lactate 202-598-0 97-64-3 Solvent naphtha (various CAS Nos., e.g. 64742-94-5) 265-198-5 64742-94-5 Xylene (various CAS Nos.) 215-535-7 1330-20-7 Description of applicability of Cleaning agents in the industrial setting alternatives In the early nineties NMP replaced dichloromethane as a cleaning agent. The alternatives for dichloromethane should amongst other characteristics, have adequate solvent power, be easy to remove and be safe for man and environment. Six solvents fulfilled the criteria: Du Pont’s dibasic esther solvent (DBE), NMP, ethyl 3-ethoxypropionate (EEP), propylene carbonate (PC), tripropylene glycol ethyl ether (TPM) and dimethyl phthalate (DMP). Finally DBE and TPM were tested and showed better results than dichloromethane. For certain

Substitution of Chemical Substances of Potential Concern | 154 Table 9-27: Identification of potential alternatives for NMP polyurethane adhesives the authors recommended a combination of DBE and NMP. For the optical industry, signals have been received that finding alternatives of NMP in the cleaning process might be problematic. Paint stripping and graffiti removal In the 1970s benzene was applied in paint strippers, but was later replaced by dichloromethane because of the health risks of benzene. Subsequently, dichloromethane was replaced by NMP in the 1990s for the same reason. Alternatives that have been mentioned in the literature for dichloromethane or NMP include: - A combination of ethylene chloride:toluene:methanol (85:10:5) - Acetophenone - Furfuryl alcohol - gamma-butyrolactone - Dibasic esters - Di-glycol-ethers - Solvent naphtha - Hydrogen peroxide - Benzyl alcohol - NEP - DEGEE (diethylene glycol monoethyl ether) - EGBE (ethylene glycol monobutyl ether) - DPBBE (dipropylene glycol monobutyl ether) - Sodium hypochlorite - Sodium hydroxide - Colza oil ester - Formic acid - Monoethanolamine - Potassium hydroxide - 3-butoxypropan-2-ol - Combinations of 3-butoxypropan-2-ol, GBL (butyrolactone) and isopropylamine C10-14 alkyl benzene sulphonate - Soy-based products - Mechanical methods such as wheat starch blasting, infra-red stripping, dry-ice blasting To conclude, alternatives appear to be available for paint stripping and graffiti removal applications. The phase out of NMP in these applications is already ongoing Application 5 Electronics

Substitution of Chemical Substances of Potential Concern | 155 Table 9-27: Identification of potential alternatives for NMP Name/description of alternative Some possibilities are available. No information has been found on the availability of alternatives of NMP in the electronics industry. However, some comparison with alternatives in the semiconductor industry might be possible as some of the use characteristics are assumed to be comparable. For semiconductor cleaning operations a wide range of alternative solvents have been named in the literature, as shown below Identifiers (if chemical substance) Substance name EC Number CAS Number Dimethyl formamide (DMF) (semiconductors) 200-679-5 68-12-2 Dimethyl sulphoxide (DMSO) (semiconductors) 200-664-3 67-68-5 Acetone (semiconductors) 200-662-2 67-64-1 Dipropylene glycol monomethyl ether (DPGME) (semiconductors) 252-104-2 34590-94-8 Propylene glycol (semiconductors) 200-338-0 57-55-6 Ethylene glycol monobutyl ether (butoxyethanol) (EGBE) (semiconductors) 203-905-0 111-76-2 Dipropylene glycol methyl ether acetate (DPMA) (semiconductors) 618-219-0 88917-22-0 Propylene glycol monomethyl acetate (PMA) (semiconductors) 203-603-9 108-65-6 Propylene glycol monomethyl ether (PGME) (semiconductors) 203-539-1 107-98-2 Ethylene glycol phenyl ether (semiconductors) 204-589-7 122-99-6 2-Heptanone (butyl acetone) (semiconductors) 203-767-1 110-43-0 Sodium hydroxide (semiconductors) 215-185-5 1310-73-2 Potassium hydroxide (semiconductors) 215-181-3 1310-58-3 Monoethanolamine (MEA) (semiconductors) 205-483-3 141-43-5 Isopropanolamine (semiconductors) 201-162-7 78-96-6 N-methylethanolamine (semiconductors) 203-710-0 109-83-1 Gamma butyrolactone (GBL) (semiconductors) 202-509-5 96-48-0 Benzyl alcohol (semiconductors) 202-859-9 100-51-6 Peroxysulphuric acid (semiconductors) 231-766-6 7722-86-3 n-butyl acetate (semiconductors) 204-658-1 123-86-4 Ethyl lactate (semiconductors) 202-598-0 97-64-3 Alkaline containing solvents (semiconductors) Phenol (semiconductors) 203-632-7 108-95-2 Xylene (various CAS Nos.) (semiconductors) 215-535-7 1330-20-7 1,3-Dimethyl-2- imidazolidinone (DMI) (semiconductors) 201-304-8 80-73-9 Sulpholane (tetramethylene sulphone) (semiconductors) 204-783-1 126-33-0 o-dichlorobenzene (semiconductors) 202-425-9 95-50-1 Perchlorethylene (PER) (semiconductors) 204-825-9 127-18-4

Substitution of Chemical Substances of Potential Concern | 156 Table 9-27: Identification of potential alternatives for NMP Aromatic hydrocarbon solvent (aromatic naphtha C7 gasoline feedstock) 265-070-9 64741-68-0 (semiconductors) Naphthalene (semiconductors) 202-049-5 91-20-3 2-(2-aminoethoxy)ethanol (diethylene glycolamine) (semiconductors) 213-195-4 929-06-6 Description of applicability of Several methods are technically available to perform stripping of photoresists. In strippers used in wet-stripping of positive photoresists, alternatives a limited number of NMP-free alternatives are available. No specific information on the technical feasibility of these are available or on their costs. There is no blanket replacement currently available that delivers the same required performance that NMP based cleaning solutions deliver today. For niche areas that do not require the same performance, NMP-free or NMP-light products have been invented. For the majority of semiconductor uses, NMP-free or NMP-light products, which deliver equal or at least acceptable performance as NMP based solutions, still need to be invented and subsequently qualified. If an alternative for photostripping is phased in, the whole stripping process needs to be optimised again Application 6 Batteries Name/description of alternative Available options are poor. The development on NMP free lithium ion and other hybrid batteries is ongoing, however, at this moment no alternatives have been proven on a commercial scale Identifiers (if chemical substance) Substance name EC Number CAS Number Water & different binder Description of applicability of Literature describes experiments in which water replaced NMP as a solvent for the PVDF binder of the cathode. As water was used, alternatives another binder was applied. The experiments showed that technically it is possible to replace NMP by water, although the commercial application still has to be proved. There are already commercial binders based on styrene butadiene rubber for application as a binder in lithium batteries that do not need NMP. There are also several other efforts to replace PVDF by water soluble binders to reduce the use of NMP. Also in industry there are steps forward to water soluble binder based techniques. To what extent these alternatives are already available on a commercial scale is not clear from the literature Application 7 Membrane manufacture Name/description of alternative Some possibilities are available. Typical polar aprotic solvents are the most suitable substitutes for NMP in the manufacture of membranes Identifiers (if chemical substance) Substance name EC Number CAS Number Dimethyl formamide (DMF) 200-679-5 68-12-2 Dimethyl acetamide (DMAc) 204-826-4 127-19-5 Dimethyl sulphoxide (DMSO) 200-664-3 67-68-5 Tetrahydrofuran (THF) 203-726-8 109-99-9 Description of applicability of Generally NMP, DMSO, DMF and DMAC are used in membrane preparation as they have a high boiling point, and are miscible with alternatives water. THF may also be applied, but is more volatile. The membranes are applied in a variety of (industrial) processes such as gas separation, nanofiltration, ultrafiltration and desalination and as such different types of membranes exist. The choice of a certain

Substitution of Chemical Substances of Potential Concern | 157 Table 9-27: Identification of potential alternatives for NMP polymer strongly depends on the type of application of the membranes. For certain applications, only PVDF, PSU or PES are possible polymers. The substitution of NMP as a solvent will depend on the type of polymer used. For the relatively solvent resistant polymers such as PAI, PI and PVDF there are less options than for less solvent resistant polymers such as PANI and PU. From the stakeholder consultation it appeared that some research has been carried out by a membrane manufacturer to replace NMP, but at present still without suitable results Application 8 Agrochemicals Name/description of alternative Substitution potential high for formulation (due to regulatory pressures); unknown for synthesis uses. NMP is used in the agrochemical industry both as a solvent in the synthesis of active ingredients and as a co-solvent in the formulation of agrochemicals. Information on alternatives is available only for the use of NMP as co-solvent. Alternatives include other polar aprotic solvents and several other organic compounds, as shown in the table below Identifiers (if chemical substance) Substance name EC Number CAS Number Dimethyl formamide (DMF) 200-679-5 68-12-2 Dimethyl acetamide (DMAc) 204-826-4 127-19-5 Dimethyl sulphoxide (DMSO) 200-664-3 67-68-5 Tetrahydrofurfuryl alcohol 202-625-6 97-99-4 Propylene glycol ethers Organic carbonates Gamma butyrolactone (GBL) 202-509-5 96-48-0 Dimethyl sorbide 226-159-8 5306-85-4 Methyl-, ethyl-, butyl- and ethylhexyl lactates Description of applicability of Specific information on applicability is not available, however, for regulatory reasons the replacement of NMP was planned to be alternatives completed by 2015 Application 9 Pharmaceuticals Name/description of alternative Some possibilities are available. Literature describes efforts being made at developing alternatives for NMP. A list of substances mentioned in literature is given below, however specific information on their technical feasibility is not readily available Identifiers (if chemical substance) Substance name EC Number CAS Number Dimethyl formamide (DMF) 200-679-5 68-12-2 Dimethyl acetamide (DMAc) 204-826-4 127-19-5 Dimethyl sulphoxide (DMSO) 200-664-3 67-68-5 Ethanol (EtOH) 200-578-6 64-17-5 N-formyl morpholine 224-518-3 4394-85-8 Diethylene glycol monoethyl ether (DEGEE) 203-919-7 111-90-0

Substitution of Chemical Substances of Potential Concern | 158 Table 9-27: Identification of potential alternatives for NMP Polyethylene glycol (PEG) 500-038-2 25322-68-3 Tetraglycol (tetraethylene glycol dimethyl ether) 205-594-7 143-24-8 Glycol furol 608-659-1 31692-85-0 Propylene glycol (semiconductors) 200-338-0 57-55-6 Propylene carbonate (PC) 203-572-1 108-32-7 Ethyl lactate 202-598-0 97-64-3 1,3-Dimethyl-2- imidazolidinone (DMI) 201-304-8 80-73-9 D,L-isopropylidene-glycerol 202-888-7 100-79-8 Glycerol 200-289-5 56-81-5 Isopropanol (IPA) 200-661-7 67-63-0 Description of applicability of In 2011 the International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use alternatives published the ICH Tripartite Guideline: Impurities: Guideline for residual solvents. Q3C(R5). The ICH proposed to list NMP as a solvent that should be limited in pharmaceutical products (Class 2 solvents) because of its inherent toxicity and provided a permissible daily exposure (PDE) and a concentration limit from a toxicological point of view. Alternatives should preferably be taken from the Class 3 solvents (solvents with low toxic potential which should be limited by GMP or other quality based requirements) or Class 2 solvents with higher PDE or concentration limit. Among the Class 3 substances are also substances mentioned for the replacement of NMP in other applications such as acetone, DMSO, ethyl acetate, and formic acid Application 10 Laboratory chemicals Name/description of alternative Some possibilities are available. Alternative solvents can be used in diagnostics and quality control, mostly other aprotic solvents Identifiers (if chemical substance) Substance name EC Number CAS Number N-ethyl pyrrolidone (NEP) 220-250-6 2687-91-4 Dimethyl formamide (DMF) 200-679-5 68-12-2 Dimethyl acetamide (DMAc) 204-826-4 127-19-5 Dimethyl sulphoxide (DMSO) 200-664-3 67-68-5 Acetonitrile 200-835-2 75-05-8 Formamide 200-842-0 75-12-7 Toluene 203-625-9 108-88-3 Dichloromethane (DCM) 200-838-9 75-09-2 Description of applicability of NMP belongs to the group of aprotic solvents as NEP, DMF, DMAc, DMSO, acetonitrile, and toluene. Among these there are low polar alternatives solvents (toluene, dichloromethane), medium polar solvents like NMP, NEP, DMF, DMAc, and high polar solvents (DMSO, formamide). The exchangeability of various solvents will differ per actual laboratory use and there might be uses in practice without alternatives Application 11 Functional fluids Name/description of alternative Limited information is available on the availability of alternatives for NMP’s uses in functional fluids

Substitution of Chemical Substances of Potential Concern | 159 Table 9-27: Identification of potential alternatives for NMP Identifiers (if chemical substance) Substance name EC Number CAS Number N-ethyl pyrrolidone (NEP) 220-250-6 2687-91-4 Glycols Description of applicability of Various NMP uses as functional fluids exist (cable oils, transfer oils, coolants, insulators, refrigerants, hydraulic fluids in industrial alternatives equipment including maintenance and related material transfers). No specific information on the replacement of NMP in functional fluids by alternatives is available Application 12 Construction chemicals Name/description of alternative Very limited information is available Identifiers (if chemical substance) Substance name EC Number CAS Number Dipropylene glycol dimethyl ether 601-045-4 111109-77-4 Description of applicability of Theoretically, polyurethane dispersions used in construction chemicals may use dipropylene glycol dimethyl ether or other solvents as alternatives replacement for NMP Sources: ECHA website, https://echa.europa.eu/documents/10162/ee4c88a9-d26f-4872-98fd-fb41646cc9e1 (accessed on 31 July 2017) SubSPORT website, http://www.subsport.eu/case-stories/101-en (accessed on 31 July 2017) SubSPORT website, http://www.subsport.eu/case-stories/152-en (accessed on 31 July 2017) SubSPORT website, http://www.subsport.eu/case-stories/220-en (accessed on 31 July 2017)

A1.7.4 Assessment of feasibility of potential alternatives

There is large number of potential alternatives across the many applications of NMP. Among them, some appear to be relevant to at least three applications and these are considered as the most prominent alternatives. Those substances include:

• N-ethyl pyrrolidone (NEP) • Dimethyl formamide (DMF) • Dimethyl acetamide (DMAc) • Dimethyl sulphoxide (DMSO) • Acetone • Methyl ethyl ketone (MEK) • Propylene carbonate (PC) • Gamma butyrolactone (GBL) • Dichloromethane (DCM)

Substitution of Chemical Substances of Potential Concern | 160 • Ethyl lactate • Xylene • Sulpholane

Taking into account the recent work on the REACH restriction on NMP as well as the harmonised hazard classification of prominent potential alternatives (e.g. other polar aprotic solvents such as NEP, DMF, DMAc), one substance, DMSO, would appear to be the most likely ‘universal’ substitute for NMP and this is the focus of the analysis below.

Substitution of Chemical Substances of Potential Concern | 161 Table 9-28: Assessment of potential alternatives for NMP Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability DMSO General The key technical advantages of DMSO The selling price of DMSO is DMSO has no harmonised DMSO is available in sufficient include: country-specific. The evolution of classification. There is an quantities; it has been - Solving power the price of the two solvents is extensive physico-chemical, registered at a range of 10,000 - High flash point and boiling point favourable to DMSO only in the last environmental and – 100,000 tonnes per annum - Recyclability and biodegradability 4 years, hence limiting the toxicological database - Low door consideration of DMSO as an available on DMSO - Miscibility with most co-solvents economically feasible alternative to demonstrating that DMSO is of - Similar Hansen Solubility NMP before 2010. low concern for the Parameter Data to NMP Prices of DMSO are on average at environment and the human €1.3/kg compared to €2.5/kg for health. DMSO has marginally higher dermal NMP. Prices of DMSO thus appear Despite the low toxicity of penetration than NMP to be significantly lower than NMP; DMSO, its physico-chemical 2 DMSO can be used in the extraction of however, as no information is properties may present aromatic compounds from both the lube available on the replacement ratio hazards by themselves or from feed stock and from the light steam of DMSO versus NMP in the various reactions with other chemicals cracking effluents. For the latter, a process uses, it is not possible to conclude if these are ill-considered. with DMSO and butane has been described upon a change in costs in case DMSO is known for its skin for the extraction of aromatics from C6-C8 DMSO is used as an alternative. penetration enhancement of chains. DMSO has not been mentioned as Furthermore, it is not known other substances. When alternative in the butadiene extraction whether process changes or DMSO is used as alternative 3 Non-wire coaters regulatory validation would be this property of DMSO should DMSO can be substituted 1:1 NMP for liquid required and whether the quality of be carefully considered. On rheology additives for aqueous coatings, the end product would be affected the other hand, in medicines pigment concentrates additives, for this property may be a desired solvent-borne and solvent-free systems. one Laboratory testing has demonstrated that DMSO can also substitute on a 1:1 scale NMP as a coalescing agent and adhesion promoter in waterborne paints for most automotive and industrial uses. However, for waterborne polyurethane dispersion paint without solvents specifically, the high melting point of DMSO and its chemical reactivity lead to breakdown above 150 °C

Substitution of Chemical Substances of Potential Concern | 162 Table 9-28: Assessment of potential alternatives for NMP Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability to sulphur oxides used to be the main technical limitations for this application. In practice a number of DMSO containing non- wire coatings are available, noting that DMSO is not the only alternative being used in practice. Wire coaters As polyamide-imide and polyimide are used, strong solvents have to be used. Although DMSO can be used for dissolving both polymers, there are no data that show it has already been applied in commercial products. The degradation of DMSO at higher temperatures may limit its use in wire coatings 4 Being highly effective, DMSO helps solubilise most organic compounds without affecting the substrates. However, other substances, such as benzyl alcohol, may be more widely used than DMSO in cleaning formulations 5, 6 DMSO is used as a solvent in semiconductor industries and as a, solvent for polymeric battery separators in lithium ion batteries. Specific information indicated that DMSO is a potential alternative for electronics with some technical limitations due to instability of DMSO. High purity electronic grade of DMSO is used as a major component in some photoresist stripping formulations, and as an additive in specialized post-etch cleaning agents and edge bead removers. In these it may appear together with NMP or with

Substitution of Chemical Substances of Potential Concern | 163 Table 9-28: Assessment of potential alternatives for NMP Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability other constituents. DMSO performance can be similar to NMP 7 The use of DMSO is not found suitable for the production of membranes for drinking water filtering purposes, because of technical reasons. Important in the search to alternatives of NMP is that the viscosity of the alternatives needs to be comparable to that of NMP 8 A synthesis solvent for herbicides and pesticides, DMSO is also used as a solvent in water-soluble formulations. Additionally, it helps active substances penetrate through vegetable membranes while minimising risks to the environment thanks to its low- concern ecotoxicological properties. Applicability of DMSO needs to be established on a case-by-case basis 9 Recyclable, DMSO is widely used as a reaction solvent because of its effectiveness and its favourable toxicological properties. It can also be used as an alkylation agent. Its toxicological profile, combined with its solvent characteristics make it an excellent carrier for active substances in certain subcutaneous applications. DMSO is rated as a Class 3 solvent as per EMEA and FDA (ICH). However, for many other applications DMSO has been indicated as a potentially reactive chemical and that thermal instability can be induced by a range of

Substitution of Chemical Substances of Potential Concern | 164 Table 9-28: Assessment of potential alternatives for NMP Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability chemicals / impurities 10 DMSO can be used as alternative for NMP in laboratories as intermediate for chemical synthesis on a case-by-case basis 11 The information on functional fluids is too limited to indicate if DMSO could be used as a feasible alternative for NMP in functional fluids 12 The use of DMSO as construction chemical in industrial use also remains unclear to date Sources: ECHA website, https://echa.europa.eu/documents/10162/a3e8fb17-d794-493c-a5ac-8cce41def0c7 (accessed on 1 August 2017) SubSPORT website, http://www.subsport.eu/wp-content/uploads/2012/05/dimethyl-sulfoxide_dmso-k.pdf (accessed on 1 August 2017) Gaylord Chemical Company website, https://www.gaylordchemical.com/wp-content/uploads/2015/11/NMP-vs-DMSO-brochure.pdf (accessed on 1 August 2017)

A1.8 Substance 8: 4-Nonylphenol, branched and linear, ethoxylated

A1.8.1 Identity of the substance

Table 9-29: Identity of 4-nonylphenol, branched and linear, ethoxylated Name of substance 4-Nonylphenol, branched and linear, ethoxylated Synonyms - EC Number (Non-exhaustive list of relevant numerical identifiers: 230-770-5; 243-816-4; 500-045-0; 248-743-1; 500-315-8) CAS Number (Non-exhaustive list of relevant numerical identifiers: 104-35-8; 7311-27-5; 14409-72-4; 20427-84-3; 26027-38-3; 27942-27-4; 34166-38-6; 37205-87-1; 127087-87-0; 156609-10-8)

Substitution of Chemical Substances of Potential Concern | 165 Table 9-29: Identity of 4-nonylphenol, branched and linear, ethoxylated Molecular formula (C2H4O)n C15H24O, with n≥1

REACH Registration tonnage band Not REACH registered Sources: ECHA website, https://echa.europa.eu/documents/10162/9af34d5f-cd2f-4e63-859c-529bb39da7ae (accessed on 20 July 2017)

A1.8.2 Functionality and applications

Table 9-30: Functionality and applications for 4-nonylphenol, branched and linear, ethoxylated General description of functionality and 4-nonylphenol, branched and linear, ethoxylated (4-NP) is a surface-active substance that is slightly water soluble and soluble in key physico-chemical parameters alcohol. 4-NP has a density of < 1, a low melting point (around -8 to 2°C), a boiling point of >290°C. 4-NP has been formulated and used as floating agent in mining applications, it can also be found in paints; emulsion polymerisation; and potentially as reducing agent in surface treatment. It is moderately bioaccumulative and it is not readily biodegradable.

4-Nonylphenol, branched and linear, ethoxylated is subject to authorisation due to its equivalent level of concern having probable serious effects to environment (Article 57 f). Family the substance belongs to Alkylphenol ethoxylates Application 1 – paints Sector of Use SU 8: Manufacture of bulk chemicals (including petroleum products) Product category PC 9a: Coatings and paints, thinner, colour remover Industrial/Professional/ Consumer Industrial: Manufacture of bulk chemicals (paints) Professional: Professional users of coatings and paints, thinners and colour removers. Consumer: Users of certain paints. Description Paints and Printing Inks: these typically used 4-NP in concentrations of 0.6 to 3% Application 2 – surfactant with various Sector of Use SU 8: Manufacture of bulk chemicals (including petroleum products) applications Product category PC 9a: Coatings and paints, thinners, paint removers PC 18: Ink and toners PC 26: Paper and board treatment products PC 35: Washing and cleaning products PC 41: Oil and gas exploration or production products

Substitution of Chemical Substances of Potential Concern | 166 Table 9-30: Functionality and applications for 4-nonylphenol, branched and linear, ethoxylated Industrial/Professional/ Consumer Industrial: Manufacture of bulk chemicals Professional: Professional use in mining operations and professional users of surfactants Consumer: Consumer uses of some detergents Description The use of 4-NP as a surfactant may include:

Pulp, paper and board industry: NP is used in paper production as a component of phenolic resins used in coatings, e.g. for carbonless copy paper, and other NP-resins used for printing inks.

Adhesive: Nonylphenol ethoxylates are used in water-based adhesives in the textile industry, pulp and paper industry, printing-works, construction industry, and in the plastic products industry.

Metal working fluids and lubricating oils: applied in the metal extraction, refining and processing industries in the formulation and usage of cutting and drilling oils and in the metal working industry as an emulsifiers, degreaser, dispersant and in anti-mist additives. 4-nonylphenol is used in the preparation of lubricating oil additives Sources: ECHA website, https://echa.europa.eu/documents/10162/ec3c30dc-b9c2-40ed-ac63-618981fc29e3 (accessed on 20 July 2017)

A1.8.3 Potential alternatives

Table 9-31: Identification of potential alternatives for 4-nonylphenol, branched and linear, ethoxylated Application 1 Paints (emulsion polymerisation and pigment dispersant) Name/description of alternative Alternative substances: - Fatty alcohol ethoxylates - Esterified linseed oil - Non-ionic tensides - Phosphate esters - Potassium polycarboxylates - Linear and branched alcohol ethoxylates - Glucose-based carbohydrates Identifiers (if chemical substance) Substance name EC Number CAS Number

Substitution of Chemical Substances of Potential Concern | 167 Table 9-31: Identification of potential alternatives for 4-nonylphenol, branched and linear, ethoxylated Fatty alcohol ethoxylates (e.g. Alcohols, - 84133-50-6 / C12-14-secondary, ethoxylate and 69013-19-0 Alcohols, C8-22, ethoxylated) Esterified linseed oil 232-278-6 8001-26-1 Non-ionic tensides (e.g. Dodecan-1-ol, 500-002-6 9002-92-0 ethoxylated) Phosphate esters (e.g. 2-609-691-9 39464-70-5 phenoxyethanol; phosphoric acid) Potassium polycarboxylates - - Linear and branched alcohol ethoxylates 500-446-0 68439-46-3; 160901-09-7 (e.g. Alcohols, C9-11, branched and linear, ethoxylated) Glucose-based carbohydrates such as 500-220-1 68515-73-1 alkylpolyglucoside (e.g. D- Glucopyranose, oligomers, decyl octyl glycosides) Description of applicability of alternatives The selected substances represent a variety of surfactants and ethoxylates. Literature suggests that these types of substances might make good alternatives for emulsion polymerisation and pigment dispersant, primarily due to their surfactant properties. Application 2 Surfactant (various applications) Name/description of alternative Alternative substances: - Octyl Phenol Ethoxylate - Alcohols, C9-11, ethoxylated - Alcohols, C12-15, ethoxylated - Alcohol Ethoxylate Propoxylate - D-Glucopyranose, oligomers, decyl octyl glycosides - Benzenesulfonic acid, C10-13-alkyl derivs., sodium salts - Sodium dodecyl sulphate - Sodium lauryl ether sulfate - Sorbitan stearate Identifiers (if chemical substance) Substance name EC Number CAS Number Octyl Phenol Ethoxylate 618-541-1 9036-19-5 Alcohols, C9-11, ethoxylated 614-482-0 68439-46-3 Alcohols, C12-15, ethoxylated 500-195-7 68131-39-5 Alcohol Ethoxylate Propoxylate 613-582-1 64366-70-7

Substitution of Chemical Substances of Potential Concern | 168 Table 9-31: Identification of potential alternatives for 4-nonylphenol, branched and linear, ethoxylated D-Glucopyranose, oligomers, decyl octyl 500-220-1 68515-73-1 glycosides Benzenesulfonic acid, C10-13-alkyl 270-115-0 68411-30-3 derivs., sodium salts Sodium dodecyl sulphate 205-788-1 151-21-3 Sodium lauryl ether sulfate 618-398-5 9004-82-4 Sorbitan stearate 215-664-9 1338-41-6 Description of applicability of alternatives These alternatives are all based on various surfactant chemistry (ethoxylates, alkyl polyglucose, sulfonates, sulfates and esters); the surfactant properties of these substances may make them good alternatives for various applications. Other factors are likely to have an effect on their ability to be a good substitute, e.g. stability at high temperatures and interaction with other substances within the formulation Source: DfE Alternatives Assessment for Nonylphenol Ethoxylates, https://www.epa.gov/sites/production/files/2014-06/documents/npe_final.pdf (Accessed 27 July 2017)

A1.8.4 Assessment of feasibility of potential alternatives

Substitution of Chemical Substances of Potential Concern | 169 Table 9-32: Assessment of potential alternatives for 4-nonylphenol, branched and linear, ethoxylated Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Fatty alcohol 1 Alcohol ethoxylates, are a large Loadings: The amount required Environmental hazard: Fatty Specific alcohol ethoxylates ethoxylates (e.g. group of chemicals and these is likely to be directly ethoxylates are not PBT might be REACH registered Alcohols, C12-14- have highly been used as comparable with 4-NP, around 1- substances secondary, alternatives. A longer alkyl chain 3% alcohol ethoxylate would be ethoxylate and reduces wetting properties but required Human health hazard: Fatty Alcohols, C8-22, increase emulsifying properties, ethoxylates are not classified ethoxylated). where higher branching Cost: The cost of fatty alcohol under CLP, however it has been increases wetting, decreases ethoxylates can vary, some costs suggested by registrants that foaming and slows may start from around €425 per they cause serious eye damage biodegradation. A medium tonne (H318), is harmful if swallowed ethoxylation gives the best (H302), is harmful in contact with surface active and wetting skin (H312), is harmful if inhaled properties; highly ethoxylated (H332) and causes skin irritation alcohols have very good (H315) dispersing properties Esterified linseed oil 1 Linseed oil paints already exist Loadings: The amount of linseed Environmental hazard: Not registered under REACH and they are an alternative to oil required is considerable more Esterified linseed oil is not a PBT solvent based paints than 4-NP, between 35-55% of substance the content of a linseed paint is made of linseed oil Human health hazard: linseed oil is not classified under CLP; Cost: The cost is around €1.8- however, it has been suggested 2.75 per kilogram by registrants as causing serious eye irritation (H319), harmful if swallowed (H302), is harmful in contact with skin (H312), is harmful if inhaled (H332), may cause an allergic skin reaction (H317), causes skin irritation (H315) and may cause respiratory irritation (H335) Non-ionic tensides 1 Dodecan-1-ol, ethoxylated is a Loadings: The amount required Environmental hazard: data Registered at 100 – 1,000 tonnes (e.g. Dodecan-1-ol, soluble single chain surfactant. might be comparable to level of suggests that non-ionic tensides per annum ethoxylated) It’s degradability and lack of 4-NP, however, loadings are are not expected to be PBT

Substitution of Chemical Substances of Potential Concern | 170 Table 9-32: Assessment of potential alternatives for 4-nonylphenol, branched and linear, ethoxylated Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability branching may limit its likely to be application specific substances compatibility within paints. It is currently used with textiles Cost: The cost is around €1865- Human health hazard: Non-ionic 2200 per tonne tensides might generally be considered as substances which are harmful if swallowed (H302), causes serious eye damage (H318) and causes skin irritation (H315). Phosphate esters 1 Phosphate esters can be used in Loadings: The amount required Environmental hazard: 2- Not registered under REACH (e.g. 2- paints to improve surface might be relatively low (<5% phenoxyethanol; phosphoric phenoxyethanol; wetting and reduce water loading) acid is not expected to be a PBT phosphoric acid) sensitivity in paints substance Cost: Unclear Human health hazard: 2- phenoxyethanol; phosphoric acid is not classified under CLP; however, it has been suggested by registrants as considered to causes serious eye damage (H318) and causes skin irritation (H315) Potassium 1 Polycarboxylates have been used Loadings: The amount required Environmental hazard: Unclear Not registered under REACH polycarboxylates in the dispersion and might be relatively low (1-5% stabilisation of pigment and filler loading) Human health hazard: Unclear particles in waterborne paint formulations Cost: Unclear Linear and branched 1 Alcohol ethoxylates have been Loadings: The amount required Environmental hazard: Alcohols, Registered at 100 – 1,000 tonnes alcohol ethoxylates used in paints as binders, might be relatively low (1-10% C9-11, branched and linear, per annum (e.g. Alcohols, C9- pigments, solvents, water and loading) ethoxylated are not expected to 11, branched and surfactants as stabilisers, be a PBT substance as studies linear, ethoxylated) emulsifiers, wetting agents, Cost: Unclear (perhaps around have shown alcohol ethoxylates dispersants and defoamers €2330 per tonne) to be readily biodegradable.

Substitution of Chemical Substances of Potential Concern | 171 Table 9-32: Assessment of potential alternatives for 4-nonylphenol, branched and linear, ethoxylated Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Linear and branched alcohol ethoxylates does not have any environmental classifications

Human health hazard: Alcohols, C9-11, branched and linear, ethoxylated is not classified under CLP; however, it has been suggested by registrants as considered to cause serious eye damage (H318) Glucose-based 1, 2 It is unclear whether D- Loadings: Unclear, likely to be Environmental hazard: D- Registered at 10,000 – 100,000 carbohydrates such Glucopyranose, oligomers and low loadings in the case of Glucopyranose, oligomers, decyl tonnes per annum as alkylpolyglucoside other alkyl polyglucoses have paints, for other applications the octyl glycosides is not a PBT (e.g. D- been used in paints. They have loading may be higher substance Glucopyranose, however been used in oligomers, decyl household, industrial, and Cost: The cost is around €1100- Human health hazard: D- octyl glycosides) institutional detergent 1185 per tonne Glucopyranose, oligomers, decyl formulations where high, stable octyl glycosides is not classified foam is required, or where there under CLP; however, it has been are likely to be highly alkaline suggested by registrants as concentrations (e.g. considered to cause serious eye formulations containing bleach damage (H318) or ammonia) Octyl Phenol 2 Octyl Phenol Ethoxylate are Loadings: The loadings are Environmental hazard: Octyl Not registered under REACH Ethoxylate surfactants commonly used in anticapted as similar to those of Phenol Ethoxylate is not paints, emulsions and wetting 4-nonylphenol, branched and classified under CLP; however, it agents and are a type of linear, ethoxylated has been suggested by alkylphenol ethoxylate. They registrants as being toxic to can alse be used as: Cost: Unclear aquatic life with long lasting effects (H411). Available data Emulsifiers – in the manufacture suggest it is not a PBT, but the of emulsion polymers and as evidence is inconclusive stabilisers in latex polymers

Substitution of Chemical Substances of Potential Concern | 172 Table 9-32: Assessment of potential alternatives for 4-nonylphenol, branched and linear, ethoxylated Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Human health hazard: Octyl Coatings – for pigment wetting Phenol Ethoxylate is not and stabilisation in coatings classified under CLP; however, it has been suggested by Agriculture – as emulsifiers or registrants as causing serious eye dispersants damage (H318) and is harmful if swallowed (H302) Cleaning products (minor use) – as liquid, paste, or powdered cleaning compounds, and heavy- duty industrial products Alcohols, C9-11, 2 Alcohol ethoxylates are a major Loadings: Unclear, perhaps Environmental hazard: Alcohols, REACH registered only as an ethoxylated class of non-ionic surfactants. comparable or slightly higher C9-11, ethoxylated are not intermediate They have been widely used as than that of 4-nonylphenol, expected to be a PBT substance laundry detergents, in household branched and linear, ethoxylated – data within the REACH cleaners, institutional and registration dossier suggests that industrial cleaners, cosmetics, Cost: Unclear ethoxylated alcohols are readily agriculture, and in textile, paper, biodegradable. Alcohols, C9-11, oil and other process industries ethoxylated presently it does not have any environmental There rapid degradation might classifications mean they are unsuitable for some applications Human health hazard: Alcohols, C9-11, ethoxylated is not classified under CLP; however, it has been suggested by registrants as causing serious eye irritation (H319) Alcohols, C12-15, 2 Alcohol ethoxylates are a major Loadings: Unclear, perhaps Environmental hazard: Alcohols, Registered at 100 – 1,000 tonnes ethoxylated class of non-ionic surfactants. comparable or higher than that C12-15, ethoxylated is not per annum They have been widely used as of 4-nonylphenol, branched and classified under CLP; however, it laundry detergents, in linear, ethoxylated has been suggested by household cleaners, registrants as being very toxic to institutional and industrial Cost: Around €1440-1610 per aquatic life (H400) and is harmful

Substitution of Chemical Substances of Potential Concern | 173 Table 9-32: Assessment of potential alternatives for 4-nonylphenol, branched and linear, ethoxylated Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability cleaners, cosmetics, agriculture, tonne to aquatic life with long lasting and in textile, paper, oil and effects (H412). However, they other process industries are not PBT substances – data shows that ethoxylated alcohols There rapid degradation might are readily biodegradable, mean they are unsuitable for longer chains may be less readily some applications biodegradable than short chained alcohol ethoxylates

Human health hazard: Alcohols, C12-15, ethoxylated is not classified under CLP; however, it has been suggested by registrants as causing skin irritation (H315) Alcohol Ethoxylate 2 Alcohol ethoxylates are a major Loadings: Unclear, perhaps Environmental hazard: Alcohol Not registered under REACH Propoxylate class of non-ionic surfactants. comparable or higher than that Ethoxylate Propoxylate is They have been widely used as of 4-nonylphenol, branched and suggested as harmful to aquatic laundry detergents, in household linear, ethoxylated life with long lasting effects. cleaners, institutional and However, they are not expected industrial cleaners, cosmetics, Cost: Unclear as a PBT substance – alcohol agriculture, and in textile, paper, ethoxylate propoxylate are oil and other process industries anticipated as of a low concern for persistence The degradation rate might mean they are unsuitable for some applications Human health hazard: Alcohol Ethoxylate Propoxylate is suggested by some registrants as harmful if inhaled (H332) Benzenesulfonic 2 Benzenesulfonic acid, C10-13- Loadings: Unclear, perhaps Environmental hazard: Not registered under REACH. acid, C10-13-alkyl alkyl derivs., sodium salts are a comparable or higher than that Benzenesulfonic acid, C10-13- derivs., sodium salts type of surfactant more of 4-nonylphenol, branched and alkyl derivs., sodium salts is not commonly known as Linear linear, ethoxylated. classified under CLP; however, it

Substitution of Chemical Substances of Potential Concern | 174 Table 9-32: Assessment of potential alternatives for 4-nonylphenol, branched and linear, ethoxylated Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability alkylbenzene sulphonate (LAS) has been suggested by surfactants. These are anionic Cost: Unclear registrants as considered to be surfactants that are typically harmful to aquatic life with long used in cleaning products in lasting effects (H412). However, concentrations ranging from 1% the substance is not a PBT to 37%, other industrial substance – REACH registration applications include use in the dossier information suggests field of textile and fibers, that it is readily biodegradable chemicals, agriculture, cosmetics and it has a low bioaccumulation and glues potential

Human health hazard: Benzenesulfonic acid, C10-13- alkyl derivs., sodium salts is not classified under CLP; however, it has been suggested by registrants as being harmful if inhaled (H332) Sodium dodecyl 2 Sodium dodecyl sulphate is an Loadings: Unclear, perhaps Environmental hazard: Sodium Registered at 1,000 – 10,000 sulphate anionic surfactant, it is widely comparable or higher than that dodecyl sulphate is not classified tonnes per annum used in cleaning products, of 4-nonylphenol, branched and under CLP; however, it has been cosmetic, and personal care linear, ethoxylated. suggested by registrants as products. Higher considered to be harmful to concentrations may be found in Cost: Around €1570 per tonne aquatic life with long lasting industrially products including effects (H412). It is not a PBT engine degreasers, floor substance – REACH registration cleaners, and car wash soaps dossier information suggests that it is rapidly biodegradable and it has a low bioaccumulation potential

Human health hazard: Sodium dodecyl sulphate is not classified under CLP; however, it has been

Substitution of Chemical Substances of Potential Concern | 175 Table 9-32: Assessment of potential alternatives for 4-nonylphenol, branched and linear, ethoxylated Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability suggested by registrants as being harmful if swallowed (H302), causes serious eye damage (H318), is a flammable solid (H228), is harmful if inhaled (H332), causes skin irritation (H315) and may cause respiratory irritation (H335) Sodium lauryl ether 2 Sodium lauryl ether sulfate is an Loadings: Unclear, perhaps Environmental hazard: Sodium Not registered under REACH sulfate anionic surfactant, it is widely comparable or higher than that lauryl ether sulfate is not used in personal care products, it of 4-nonylphenol, branched and classified under CLP; however, it is also used as an industrial linear, ethoxylated has been suggested by foaming agent, in agriculture, in registrants as being harmful to the construction industry and Cost: Around €930-1060 per aquatic life with long lasting with oil fields products tonne effects (H412). The substance is not expected to be a PBT substance

Human health hazard: Sodium lauryl ether sulfate is not classified under CLP; however, it has been suggested by registrants as causing serious eye damage (H318), is harmful if swallowed (H302) and causes skin irritation (H315) Sorbitan stearate 2 Sorbitan stearate is a non-ionic Loadings: Unclear, perhaps Environmental hazard: Sorbitan Registered at 1,000+ tonnes per surfactant, it has emulsifying, comparable or higher than that stearate is not classified under annum dispersing and wetting of 4-nonylphenol, branched and CLP and it is not a PBT substance. properties. It has a wide variety linear, ethoxylated Data suggests that the substance of uses, it is used within fabric, is not P, B or T. Its lowest PNEC textile, and leather products, Cost: Around €1270-1355 per is 0.032 mg/L in marine water lubricants and greases, personal tonne care products, water treatment Human health hazard: Sorbitan

Substitution of Chemical Substances of Potential Concern | 176 Table 9-32: Assessment of potential alternatives for 4-nonylphenol, branched and linear, ethoxylated Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability products, in the manufacture of stearate is not classified under food and healthcare products, in CLP coatings, in oil field products, etc Sources: DfE Alternatives Assessment for Nonylphenol Ethoxylates, https://www.epa.gov/sites/production/files/2014-06/documents/npe_final.pdf (Accessed 27 July 2017) ECHA website for substance classifications, https://echa.europa.eu/

Substitution of Chemical Substances of Potential Concern | 177 A1.9 Substance 9: Toluene

A1.9.1 Identity of the substance

Table 9-33: Identity of Toluene Name of substance Toluene Synonyms EC Number 203-625-9 CAS Number 108-88-3 Molecular formula C7H8

REACH Registration tonnage band 1,000,000 – 10,000,000 tonnes per year Sources: ECHA website, https://echa.europa.eu/substance-information/-/substanceinfo/100.003.297

(accessed XX July 2017)

A1.9.2 Functionality and applications

Table 9-34: Functionality and applications for Toluene General description of functionality and Toluene is primarily used in coatings, paint and lacquers, mainly in wood furniture and fixtures, contianers and closure, automotive key physico-chemical parameters finishes and machinery. Its other main uses are adhesives, cleaning solvents, inks, fuels and fuel additives, agricultural chemicals and laboratory chemicals. Family the substance belongs to Aromatic hydrocarbon

Substitution of Chemical Substances of Potential Concern | 178 Table 9-34: Functionality and applications for Toluene Coatings Sector of Use SU 10: Formulation [mixing] of preparations and/or re-packaging (excluding alloys) SU 0: Other Product category PC 1: Adhesives, sealants PC 4: Anti-freeze and de-icing products PC 8: Biocidal products (e.g. disinfectants, pest control) PC 9a: Coatings and paints, thinners, paint removes PC 9b: Fillers, putties, plasters, modelling clay PC 9c: Finger paints PC 15: Non-metal-surface treatment products PC 18: Ink and toners PC 23: Leather tanning, dye, finishing, impregnation and care products PC 24: Lubricants, greases, release products PC 31: Polishes and wax blends PC 34: Textile dyes, finishing and impregnating products; including bleaches and other processing aids Industrial/Professional/ Consumer Industrial: use at industrial sites and in manufacturing Professional: widespread uses in formulation or re-packing Consumer: use by consumers in articles Description Toluene is primarily used in coating products for a wide variety of applications. Eastman Chemical Company state that 54% of end uses are for coatings, laquers and paints Fuels Sector of Use SU 10: Formulation [mixing] of preparations and/or re-packaging (excluding alloys) Product category PC 13: Fuels Industrial/Professional/ Consumer Industrial: use at industrial sites and in manufacturing Professional: widespread uses in formulation or re-packing Consumer: use by consumers in articles Description Toluene can be used as an octane booster in gasoline fuels for internal combustion engines. It is used in jet fuel surrogate blends due to its content of aromatic compounds Cleaning agents Sector of Use SU 10: Formulation [mixing] of preparations and/or re-packaging (excluding alloys) SU 0: Other Product category PC 8: Biocidal products (e.g. disinfectants, pest control)

Substitution of Chemical Substances of Potential Concern | 179 Table 9-34: Functionality and applications for Toluene Industrial/Professional/ Consumer Industrial: use at industrial sites and in manufacturing Professional: widespread uses in formulation or re-packing Consumer: use by consumers in articles Description According to Eastman Chemcial Company, less than 22% of end uses of toluene are for cleaning agents Intermediate Sector of Use SU 8: Manufacture of bulk, large scale chemicals (including petroleum products) SU 9: Manufacture of fine chemicals SU 0: Other Product category PC 19: Intermediate Industrial/Professional/ Consumer Industrial: use at industrial sites and in manufacturing Professional: widespread uses in formulation or re-packing Consumer: no contact Description Sources: ECHA website, https://echa.europa.eu/substance-information/-/substanceinfo/100.001.133 (accessed on xx 2017)

A1.9.3 Potential alternatives

Table 9-35: Identification of potential alternatives for Toluene Application 1 Various (see below for different blend applications) Name/description of alternative Eastman Chemical Company have suggested alternative blends to toluene (100% volume, these solvent blends are only suggested starting points for developing alternative systems): Blend 1: Cleaners, inks, nitrocellulose lacquers Blend 2: Automative, coil, architectural interior Blend 3: Wood furniture, auto refinish Blend 4: Thinners, sealants, lacquers, varnishes Identifiers (if chemical substance) Substance name EC Number CAS Number Blend 1 Eastman isobutanol (isobutyl alcohol) (volume = 20%) 201-148-0 78-83-1 Eastman isobutyl acetate (volume = 50%) 203-745-1 110-19-0 Aliphatic hydrocarbon (volume = 30%)

Substitution of Chemical Substances of Potential Concern | 180 Table 9-35: Identification of potential alternatives for Toluene Blend 2 Eastman MPK (methyl n-propyl ketone) (volume = 80%) 203-528-1 107-87-9 Eastman isobutyl acetate 203-745-1 110-19-0 Blend 3 Eastman IBIB (isobutyl isobutyrate) (volume = 9%) 202-612-5 97-85-8 Eastman isobutyl acetate (volume = 91%) 203-745-1 110-19-0 Blend 4 Isopar™ C 292-458-5 64742-66-8/ 90622-56-3 Eastman isobutyl acetate (volume = 70%) 203-745-1 110-19-0 Description of applicability of alternatives The blends developed by Eastman Chemical Company have a range of applications stated above Application 2 Applications where toluene is present in small quantities Name/description of alternative TOTAL have suggested alternatives to toluene. In formulations where toluene is present in relatively small amounts (10% volume), toluene can be replaced by methylcyclohexane and/or acetates almost as a direct drop in as long as evaporation rates of the final blend are similar Identifiers (if chemical substance) Substance name EC Number CAS Number Blend 5 Solane 60/95 (volume = 55%) 203-624-3 108-87-2 Methylcyclohexane (volume = 15%) 201-159-0 78-93-3 Methyl ethyl ketone (volume = 30%) Blend 6 Solane 60/95 (volume = 60%) 109-60-4 n-propyl acetate (volume = 10%) 201-159-0 78-93-3 Methyl ethyl ketone (volume = 30%) Description of applicability of alternatives The blends developed by TOTAL have a range of applications as stated above Application 3 Adhesives Name/description of alternative For adhesives, such as polychloroprene-based adhesives, toluene is often present in a fairly large quantity (60% volume). In this scenario, the substitution will have to take into account additional factors such as the rheological behaviour of the final blend during application. If toluene is substituted by acetone for example, several issues such as hardening during calendaring operations may be encountered as acetone has a very different volatility and solvency power than toluene. On the other hand, a solvent such as methylcyclohexane - which is closer in behaviour to toluene reduces the chances of encountering these problems Identifiers (if chemical substance) Substance name EC Number CAS Number

Substitution of Chemical Substances of Potential Concern | 181 Table 9-35: Identification of potential alternatives for Toluene Blend 7 Ethyl acetate (volume = 35%) 205-500-4 141-78-6 Methylcyclohexane (volume = 35%) 203-624-3 108-87-2 Methyl ethyl ketone (volume = 30%) 201-159-0 78-93-3 Blend 8 Ethyl acetate (volume = 25%) 205-500-4 141-78-6 Methylcyclohexane (volume = 50%) 203-624-3 108-87-2 Methyl ethyl ketone (volume = 25%) 201-159-0 78-93-3 Blend 9 Solane 60/95 (volume = 45%) Ethyl acetate (volume = 25%) 205-500-4 141-78-6 Methyl ethyl ketone (volume = 30%) 201-159-0 78-93-3 Description of applicability of alternatives The blends suggested by TOTAL have been suggested as alternatives for adhesive applications where toluene is present in large quantities Sources: Eastman solvents – performance sheet, http://www.eastman.com/Literature_Center/T/TT41.pdf

Alternativesto Toluene & Xylene: TOTAL’s answer for industry, http://total.link.be/be/B2B_FLUIDES_NL/Solutions_Peintures_EN.pdf

A1.9.4 Assessment of feasibility of potential alternatives

Substitution of Chemical Substances of Potential Concern | 182 Table 9-36: Assessment of potential alternatives for Toluene Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Blend 1 1 Dependent on exact application No information available Eastman isobutanol Commercially available (isobutyl alcohol) – CLI for Skin Irritation (H315), Eye Damage 1 (H318, STOT SE 3 (H335, H336).

Eastman isobutyl acetate – no harmonised classifications for human health or environmental endpoints. Self classifications for Acute Tox. 5 (H333), STOT SE 3 (H336), Eye Irrit. 2 (H319)

Blend 2 1 Dependent on exact application No information available Eastman MPK (methyl n-propyl Commercially available ketone) – no harmonised classifications for human health or environmental endpoints. Self classifications for Aquatic chronic 3(H412), Skin Irrit 2 (H315), Eye Irrit (H319), STOT SE 3 (H335).

Eastman isobutyl acetate – no harmonised classifications for human health or environmental endpoints. Self classifications for Acute Tox. 5 (H333), STOT SE 3 (H336), Eye Irrit. 2 (H319)

Substitution of Chemical Substances of Potential Concern | 183 Table 9-36: Assessment of potential alternatives for Toluene Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Blend 3 1 Dependent on exact application No information available Eastman IBIB (isobutyl Commercially available isobutyrate) - no harmonised classifications for human health or environmental endpoints. Self classifications for Aquatic chronic 3(H412), Skin Irrit 2 (H315), Eye Irrit (H319), STOT SE 3 (H335).

Eastman isobutyl acetate – no harmonised classifications for human health or environmental endpoints. Self classifications for Acute Tox. 5 (H333), STOT SE 3 (H336), Eye Irrit. 2 (H319) Blend 4 1 Dependent on exact application No information available Isopar™ C - no harmonised Commercially available classifications for human health or environmental endpoints. Self classifications for Skin Irrit 2 (H315), STOT SE 3 (H336), Aquatic chronic 2 (H412), Aquatic Acute 1 (H400)

Eastman isobutyl acetate – no harmonised classifications for human health or environmental endpoints. Self classifications for Acute Tox. 5 (H333), STOT SE 3 (H336), Eye Irrit. 2 (H319)

Substitution of Chemical Substances of Potential Concern | 184 A1.10 Substance 10: Formaldehyde

A1.10.1 Identity of the substance

Table 9-37: Identity of formaldehyde Name of substance formaldehyde Synonyms Methanal Formalin Methylene oxide Formol Methaldehyde EC Number 200-001-8 CAS Number 50-00-0 Molecular formula CH2O

REACH Registration tonnage band 1,000,000+ tonnes per annum Sources: https://echa.europa.eu/registration-dossier/-/registered-dossier/15858/1

A1.10.2 Functionality and applications

Table 9-38: Functionality and applications for formaldehyde General description of functionality and This substance has biocidal properties and is currently under review for the product types1: key physico-chemical parameters • 2 – Disinfectants and algaecides not intended for direct application to humans or animals; • 3 – veterinary hygiene; • 22 – Embalming and taxidermist fluids

Substitution of Chemical Substances of Potential Concern | 185 Table 9-38: Functionality and applications for formaldehyde

It has biocidal effects against fungi and bacteria at a concentration of ≥0.5% within short term contact time and ≥0.05% within long term contact time. Disinfecting efficacy against viruses has been observed at concentrations between ≥0.064 and ≥0.92 after 120 minute exposure. It is assumed that the concentration of formaldehyde in biocidal products would be 0.05% - 12%.2 Formaldehyde is used in liquid form or in combination with low pressure steam for biocidal purposes. The formaldehyde solutions placed on the market tend to contain 35-55% formaldehyde, with methanol (0.5-2%w/w), formic acid (~0.3% w/w), iron (<0.0001% w/w) impurities.3

The main use of formaldehyde is as an intermediate in the production of condensed resins for wood, textile and paper processing industries. It is found in paints and lacquers (conc. Up to 10%), adhesives (conc. 0.1-10%), cleaning agents (conc. 0.1-50%), biocides (conc. 0.1-100%) and disinfectants (conc. 0.1-100%). It has additional uses in fish farming, to treat sheep foot rot, as a fumigant for animal husbandry and as an insecticide/ preservative in museums and buildings of historic interest.3 Professional and consumer uses given by ECHA are: adhesives and sealants, coating products, laboratory chemicals, polymers, biocides (e.g. disinfectants, pest control products), polishes and waxes, cosmetics and personal care products, fuels, washing & cleaning products, and the manufacture of textile, leather or fur, wood and wood products and pulp, paper and paper products4. It is also used in embalming and taxidermist fluids.

Formaldehyde prices are set on a quarterly basis and prices track the methanol feedstock.

Physico-chemical properties5: Boiling point: -19.5°C (at 1013 hPa) Melting point: -92°C Density: 0.72kg/m3 Vapour pressure: 5490 Pa at 27°C Partition coefficient (log Pow): 0.35 Water solubility : well soluble (up to 55%) pH : mildly acidic (50% solution) Henry Law constant: 0.034Pa m3/mol at 25°C

CLH6: Acute Tox. 3 – H301, H311, H331 Skin Corr. 1B – H314 Skin Sens. 1 – H317 Mutagen 2 – H341 Carcinogen 1B – H350

Substitution of Chemical Substances of Potential Concern | 186 Table 9-38: Functionality and applications for formaldehyde Family the substance belongs to Aldehydes Manufacture of plastics for coatings Sector of Use SU 12: Manufacture of plastic products, including compounding and conversion Product category PC 9a: Coatings and paints, thinners, paint removers Industrial/Professional/ Consumer7 Industrial users: • PROC 2: Use in closed, continuous process with occasional controlled exposure • PROC 4: Use in batch and other process (synthesis) where opportunity for exposure arises • PROC 5: Mixing or blending in batch processes for formulation of preparations and articles (multistage and/or significant contact) • PROC 6: Calendering operations • PROC 8a: Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at non-dedicated facilities • PROC 8b: Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities • PROC 9: Transfer of substance or preparation into small containers (dedicated filling line, including weighing) Professional users: • PROC 5: Mixing or blending in batch processes for formulation of preparations and articles (multistage and/or significant contact) • PROC 8a: Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at non-dedicated facilities • PROC 8b: Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities • PROC 10: Roller application or brushing • PROC 11: Non industrial spraying • PROC 13: Treatment of articles by dipping and pouring • PROC 15: Use as laboratory reagent • PROC 16: Using material as fuel sources, limited exposure to unburned product to be expected • PROC 19: Hand-mixing with intimate contact and only PPE available • PROC 21: Low energy manipulation of substances bound in materials and/or articles • PROC 22: Potentially closed processing operations with minerals/metals at

Substitution of Chemical Substances of Potential Concern | 187 Table 9-38: Functionality and applications for formaldehyde elevated temperature. Industrial setting • PROC 23: Open processing and transfer operations with minerals/metals at elevated temperature • PROC 24: High (mechanical) energy work-up of substances bound in materials and/or articles

Exposure for industrial and professional users tends to be via the dermal or inhalation routes. Description Formaldehyde acts as a raw material in the manufacture of resins that can be used as coatings (and some paints). Urea formaldehyde (UF) resins, phenol formaldehyde (PF) resins and melamine formaldehyde (MF) resins may be used as coatings. Pentaerythritol is used in the production of alkyd resins which are used in paints, but formaldehyde is the raw material for Penta, not the resin or paints themselves. Hexamine is used to make epoxy resins and as such is a raw material for resins that are then used in coatings (similar situation as above)8. MF and PF can be used in surface coatings and decorative laminates in the automotive industry. Firelighters Sector of Use SU 0: Other : SU 22 Product category PC 13: Fuels (firelighters) Industrial/Professional/ Consumer Industrial users: • PROC 5: Mixing or blending in batch processes for formulation of preparations and articles (multistage and/or significant contact) • PROC 8b: Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities • PROC 14: Production of preparations or articles by tabletting, compression, extrusion, palletisation Professional and consumer users: • PROC 16: Using material as fuel sources, limited exposure to unburned product to be expected Description Urea-formaldehyde resins and other formaldehyde-based resins are blended with a combustible material (most likely liquid hydrocarbons such as kerosene or paraffin) and left to set in tablet or scored board form9. Biocides Sector of Use None given Product category PC 8: Biocidal products Industrial/ Professional/ Consumer Professional users: • PROC 10: Roller application or brushing

Substitution of Chemical Substances of Potential Concern | 188 Table 9-38: Functionality and applications for formaldehyde • PROC 11: Non industrial spraying • PROC 19: Hand-mixing with intimate contact and only PPE available. PT 3: Formaldehyde based biocidal products are intended for wet disinfection (spraying/sprinkling/scrubbing application), fogging in a closed environment, direct contact with animal feet through footbaths. There may be dermal and inhalation exposure during dilution (mixing and loading). Closed system fogging should not allow for exposure.

Consumers are not expected to be exposed through this PT, although residues may exist on animals who have been treated directly by formaldehyde and this is to be assessed during biocidal product authorisation.

Unable to ascertain other PT intended uses. Description The intended uses of formaldehyde in PT 3 are for wet disinfection and fumigation of animal houses, hatcheries, vehicles and direct contact with animal feet. The intended target organisms are obligate or facultive pathogenic bacteria, fungi and viruses. Amount of active substance applied per application: • Animal houses wet disinfection (sprayed) – 0.35-1.2% ≈ 3.5-12 g/l • Animal houses fumigation (fumigation/fogging) – 16% ≈ 160g/l • Hatcheries fumigation (fumigation/fogging) – 20% ≈ 200g/l, 7g/m3 • Vehicles (sprayed) – 4% ≈ 40g/l • Animal feet (footbath) – 2% ≈ 20g/l Sources: 1 https://echa.europa.eu/information-on-chemicals/biocidal-active- substances?p_p_id=echarevbiocides_WAR_echarevbiocidesportlet&p_p_lifecycle=1&p_p_state=normal&p_p_mode=view&p_p_col_id=column- 1&p_p_col_pos=1&p_p_col_count=2&_echarevbiocides_WAR_echarevbiocidesportlet_javax.portlet.action=searchBiocidesAction 2 http://dissemination.echa.europa.eu/Biocides/ActiveSubstances/1306-03/1306-03_Assessment_Report.pdf 3 UNEP (2002) OECD SIDS: Formaldehyde. Available at: http://www.inchem.org/documents/sids/sids/formaldehyde.pdf 4 https://echa.europa.eu/substance-information/-/substanceinfo/100.000.002 5 European Commission (2016) Regulation (EU) No 528/2012 concerning the making available on the market and use of biocidal products. Evaluation of active substances, assessment report: Formaldehyde. 6 https://echa.europa.eu/information-on-chemicals/cl-inventory-database/-/discli/details/55163 7 https://echa.europa.eu/registration-dossier/-/registered-dossier/15858/3/1/5 8 http://www.formacare.org/applications/

Substitution of Chemical Substances of Potential Concern | 189 Table 9-38: Functionality and applications for formaldehyde 9 Brydson, J. A. (1999) Plastic Materials. Butterworth-Heinemann. P679

A1.10.3 Potential alternatives

Table 9-39: Identification of potential alternatives for formaldehyde Application 1 Manufacture of plastics for coatings Name/description of • Bioresins (from proteins or from tannins), e.g. 5-hydroxymethylfurfural (5-HMF)10 alternative • Synthetic resins: o Methylenebis)4-phenyl isocyanate) (MDI or pMDI) o Polyurethane adhesives o Emulsion polymer isocyanate (EPI) o Polyvinyl acetate (PVA)/ ethyl vinyl acetate (EVA) o Acrylic adhesives o epoxy Identifiers (if chemical Substance name EC Number CAS Number substance)11 5-hydroxymethylfurfural (5-HMF) 200-654-9 67-47-0 4,4’-methylenediphenyl diisocyanate (MDI or pMDI) 202-966-0 101-68-8 Polyurethane adhesives Emulsion polymer isocyanate (EPI) Polyvinyl acetate (PVA)/ ethyl vinyl acetate (EVA) Acrylic adhesives 618-358-7/ 607-457-0 9003-20-7/ 24937-78-8 epoxy Description of applicability of Alternative substances alternatives11 • 5-hydroxymethylfurfural (5-HMF) is a bio-based chemical which can replace formaldehyde in the production of phenolic and urea resins. This currently being researched and may not be available as of yet. Other bioresins may also be applicable, derived from tannins, lignins, Cashew Nut Shell Liquid (CNSL), carbohydrates, triglycerides, proteins, bioalkyds, waxes. Many of these are waste or by-products of other manufacturing processes. Bioresins can be used for decorative plywood for interior use, laminated flooring, particleboard,

Substitution of Chemical Substances of Potential Concern | 190 Table 9-39: Identification of potential alternatives for formaldehyde oriented strandboard, medium density fibreboard and a partial replacement for phenolic adhesives in composites and plywood panel products. • MDI – can be used for exterior particleboard, exterior OSB, laminated strand lumber, MDF and other specially engineered composites/ flakeboards, particleboards and strand-wood products. • Polyurethane adhesives – can be used for construction adhesive for panelised floor and wall systems, laminating plywood to metal and plastic sheet materials, speciality laminates. These are formed through the reaction of various types of isocyanates with polyols. • EPI – can be used for laminated beams for interior and exterior use, lamination of plywood to steel metals and plastics, doors and architectural materials. These are formed by a two part system based on an acrylate, polyurethane or vinyl acetate and an isocyanate hardener. • PVA/ EVA – can be used for assembly of wood and paper products, wood bonding for construction of furniture. • Acrylic adhesives – can be used for surface treating and as an insulation binder. • Epoxy – can be used for laminating veneer and lumber in cold-moulded wood boat hulls, assembly of wood components in aircraft, lamination of architectural railings and posts, repair of laminated wood beams and architectural building components, laminating sports equipment. Formed by the polymerisation of acrylic or methylacrylic acids through a reaction with a catalyst. Application 2 Firelighters Name/description of Biomass, such as sawdust, and vegetable wax alternative Identifiers (if chemical Substance name EC Number CAS Number substance) - - - Description of applicability of Biomass and vegetable wax alternatives12 Firelighters made from biomass and vegetable wax neither contain nor release formaldehyde. They can be used in multi-fuel appliances and wood only appliances. The vegetable wax acts as the binding agent, whilst the biomass is the fuel. Application 3 Biocides Name/description of Chemical alternatives: alternative11 • Glutaraldehyde • Hydrogen peroxide • Peracetic acid Non-chemical alternatives • Microfiber mopping • Substitution through design – selection of flooring material that reduces the need for cleaning with disinfectants. Substance name EC Number CAS Number

Substitution of Chemical Substances of Potential Concern | 191 Table 9-39: Identification of potential alternatives for formaldehyde Identifiers (if chemical Glutaraldehyde 203-856-5 111-30-8 substance) Hydrogen peroxide 231-765-0 7722-84-1 Peracetic acid 201-186-8 79-21-0

Description of applicability of • Glutaraldehyde – Approved for use in PT2, 3. It can be used a hard surface disinfectant in hospitals and industrial areas, and for poultry alternatives and pig farm disinfection. Glutaraldehyde works against bacteria, mycobacteria, bacterial spores, fungi, viruses, algae and biofilms. 13 • Hydrogen peroxide – approved for use in PT 2, 3. It can be used for surface disinfection by VHP process and disinfection of animal housing. The target organisms are bacteria, fungi and viruses. 14 • Peracetic acid – approved for use in PT 2, 3. It can be used for disinfection of surfaces in industrial, public and healthcare areas and the disinfection of animal houses. It shows evidence of toxic effects on bacteria and fungi in PT2 and bacteriocidal and virucidal activity in PT 2 and 3.15 • Substitution through design – selection of flooring material that reduces the need for cleaning with disinfectants e.g. swapping from conventional VCT flooring that requires regular stripping and waxing to luxury vinyl tiles that does not require this treatment.16 • Microfiber mops – mop heads are changed after every room that is cleaned, preventing the spread of infection, whereas conventional mop heads are changed every 3-4 rooms.16

Sources: 10 https://www.biobasedworldnews.com/project-to-replace-carcinogenic-formaldehyde-with-bio-based-5-hmf-underway 11 http://www.subsport.eu/wp-content/uploads/data/formaldehyde.pdf 12 http://www.modernstoves.co.uk/fire-up-fire-lighters-co2-neutral.html 13 http://dissemination.echa.europa.eu/Biocides/factsheet?id=1310-02 14 http://dissemination.echa.europa.eu/Biocides/factsheet?id=1315-02 15 http://dissemination.echa.europa.eu/Biocides/factsheet?id=1340-02 16 https://noharm-asia.org/sites/default/files/documents-files/65/Green_Cleaning_in_Healthcare.pdf

A1.10.4 Assessment of feasibility of potential alternatives

Substitution of Chemical Substances of Potential Concern | 192 Table 9-40: Assessment of potential alternatives for formaldehyde Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Bioresins (from 1 Bioresins made from tannins: can Average price of 5-HMF €374.11 Environmental Hazards Not registered proteins or from be used for decorative plywood per kg. Does not appear to 5-HMF has no CLH. It has self-classifications tannins), e.g. 5- for interior use, laminated currently be priced for industrial for harmful to the aquatic environment 3 hydroxymethylfurfura flooring, particleboard, and quantities. (chronic (H412)). l (5-HMF)10 oriented strandboard, (OSB), particle board, medium density Human health Hazards fibreboard, Partial replacement 5-HMF has no CLH. It has self classifications for phenolic adhesives in for Skin Irritant 2 (H315), Eye Irritant 2 composites and plywood panel (H319), STOT SE 3 (H335 respiratory products. These bioresins have system) high viscosity, inconsistent reactivity, and the composition can vary depending on the growing conditions of the plant that the tannins are from.

Bioresins from proteins: can be used for decorative plywood for interior use, laminated flooring, particleboard, and oriented strandboard (OSB). These bioresins according to the producer and user of a soy-based resin (Purebon, 2013), it has the same properties like formaldehyde based resins.

Substitution of Chemical Substances of Potential Concern | 193 Table 9-40: Assessment of potential alternatives for formaldehyde Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Methylenebis(4- 1 Can be used for wood-based Average price €1708.73 per Environmental hazards Registered 100,000 – phenyl isocyanate) products such as exterior tonne MDI has no CLH for environmental hazards. 1,000,000 per (MDI or pMDI) particleboard, exterior OSB, annum laminated strand lumber (LSL), Human health Hazards MDF, or other specially MDI has CLH for Skin Irritant 2 (H315), Eye engineered composites/ Irritant 2 (H319), Skin Sensitiser 1 (H317), Flakeboards; particleboard, Acute Tox 4 (H332), STOT SE 3 (H335), strand-wood products. Respiratory Sensitiser 1 (H334), Carcinogen 2 (H351), STOT RE 2 (H373)

High dry and wet strength; very resistant to water and damp atmosphere; adheres to metals and plastics, good wetting and penetration behaviour,

Polyurethane 1 Can be used for general purpose Average price for MDI as Human Health Hazards Polymer so not adhesives home and shop; construction constituent €1708.73 per tonne. Concerns relate to the use of isocyanate in registered adhesive for panelised floor and the production of polyurethane. wall systems; laminating Average price for glycerol as Isocyanates can cause asthma, lung and plywood to metal and plastic constituent €1334.44 per tonne. skin irritation. May have sensitising sheet materials; specialty properties (H317, H334).17 laminates. Average price for propylene oxide as constituent €1124.32 High dry and wet strength; per tonne. resistant to water and damp atmosphere; limited resistance Requires the formation of a to prolonged and repeated polyol before the reaction of the wetting and drying; gap-filling. diisocyanate and the polyol can form the polyurethane.

Substitution of Chemical Substances of Potential Concern | 194 Table 9-40: Assessment of potential alternatives for formaldehyde Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Emulsion polymer 1 Can be used laminated beams for Can use MDI. Average price for Human Health Hazards Polymer so not isocyanate (EPI) interior and exterior use; MDI as constituent €1708.73 per May have sensitising properties (H317, registered lamination of plywood to steel tonne. H334) due to the presence of isocyanates. metals and plastics; doors and architectural materials

High dry and wet strength; moisture resistance, resistant to prolonged and repeated wetting and drying; adheres to metals and plastics.

Two part component adhesive system based on a water based polymer cured with an isocyanate. Polyvinyl acetate 1 Can be used general purpose in Approximate cost per tonne VA Environmental hazards PVA not registered (PVA)/ ethyl vinyl home and shop, assembly of monomer = €699.39 PVA has no CLH or self-classifications. EPA as polymer. EVA not acetate (EVA) wood and paper products, used Approximate cost per tonne EVA has no CLH for environmental hazards. currently registered for wood bonding, such as = €1710.55 furniture construction. Human health Hazards PVA has no CLH or self-classifications. EPA has no CLH but has self-classifications for High dry strength; low resistance Skin Sensitiser 1 (H317) and Carcinogen 2 to moisture and elevated (H351). temperatures; joints yield under continued stress

Substitution of Chemical Substances of Potential Concern | 195 Table 9-40: Assessment of potential alternatives for formaldehyde Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Acrylic adhesives 1 Can be used for surface treating, Approximate cost per tonne = Human Health Hazards paper treating, insulation binder. €527.50 May cause Skin irritation (H315), Skin sensitisation (H317) and respiratory Bonds well to plastics, and to irritation (STOT SE 3 (H335)) due to the metals, but not to wood. presence of methyl methacrylate.

Epoxy 1 Can be used for laminating Approximate cost per tonne = Human Health Hazards Polymer so not veneer and lumber in cold- €1500 Most likely hazards associated with epoxy registered moulded wood boat hulls; resins are Eye irritation 2 (H319), Skin assembly of wood components in Irritation 2 (H315), Skin Sensitisation 1 aircraft; lamination of (H317). Possible other hazards include architectural railings and posts; STOT SE 3 (H335), respiratory sensitiser 1 repair of laminated wood beams (H334). May present skin sensitising, and architectural building carcinogenic and reprotoxic properties due components; laminating sports to the presence of epichlorohydrin and equipment. bisphenol A. 18

High dry and wet strength to wood, metal, glass, and plastic; formulations for wood resist water and damp atmospheres; delaminate with repeated wetting and drying.

Substitution of Chemical Substances of Potential Concern | 196 Table 9-40: Assessment of potential alternatives for formaldehyde Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Biomass and 2 Can be used in multi-fuel or wood Costs approximately €0.07 per Environmental Hazards Not registered vegetable wax only applications such as open briquette (sold in bags of 72 = May increase air pollutants. fires, wood burning stoves and €5.40) barbecues. This is an entirely new Human Health Hazards product as opposed to a May contribute to respiratory illness due to replacement of formaldehyde combustion. within the process of manufacturing of firelighters. The use of vegetable wax and biomass prevents the need for formaldehyde coated petrochemical firelighters entirely. Glutaraldehyde 3 Approved for PT2 and 3, no Average cost per tonne = €1546 Environmental hazards Registered 1000+ application for PT 22. Unable to Glutaraldehyde has CLH for harmful to the tonnes per annum quantify how many biocidal aquatic environment (acute 1 (H400), products it is currently used in as chronic 2 (H411)). not present in R4BP3 database. Human health Hazards Number of Article 95 list Glutaraldehyde has CLH for Acute Toxicity suppliers (as of 2017) = PT 2 – 2; and 3 (H330 and H301); Skin Corrosion 1B PT 3 – 2. (H314); Skin Sensitisation 1A (H317); STOT SE 3 (H335); Respiratory Sensitisation 1 Target organisms: bacteria (e.g. (H334). E.coli, staphylococcus aureus), mycobacteria, bacterial spores, fungi, viruses, algae and biofilms. It works faster than formaldehyde and is most reactive at alkaline pH.

Substitution of Chemical Substances of Potential Concern | 197 Table 9-40: Assessment of potential alternatives for formaldehyde Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Hydrogen peroxide 3 Approved for use in PT2 and 3, no Commercially available in Environmental Hazards Registered 100,000 – application for PT 22. Unable to concentrations of 3-90%. Hydrogen peroxide has no CLH. 10,000,000 tonnes quantify how many biocidal per annum products it is currently used in as Average cost per tonne = Human Health Hazards not present in R4BP3 database. €436.91 Hydrogen peroxide has CLH for Acute Toxicity 4 (H302, H332) and Skin Corrosion Number of Article 95 list 1A (H314). suppliers (as of 2017) = PT 2 – 25; PT 3 – 25.

Has broad spectrum efficacy against viruses, bacteria (greater in gram-positive than gram- negative), bacterial spores and yeasts.

Substitution of Chemical Substances of Potential Concern | 198 Table 9-40: Assessment of potential alternatives for formaldehyde Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Peracetic acid 3 Approved for use in PT 2 and 3, Average cost per tonne = Environmental hazards: Peracetic acid has Registered at 1000 – no application for PT 22. Unable €547.71 a harmonised classification for harmful to 10,000 tonnes. to quantify how many biocidal the aquatic environment (acute 1, H400). It products it is currently used in as is not a PBT substance based on its intrinsic not present in R4BP3 database. properties.

Number of Article 95 list Human Health hazards: Peracetic acid has suppliers (as of 2017) = PT 2 – 24; harmonised classifications for Acute PT 3 – 24. Toxicity 4 (H302, H312, H332) and Skin Corrosion 1A More potent than hydrogen peroxide at low concentrations (<0.3%). Disinfection time from 10 minutes and stable between 1 and 30 days. A concentration of 0.2% is active against microorganisms. Target organisms are spores, bacteria, viruses and fungi.

Less harmful decomposition products: acetic acid and water. Substitution through 3 Use of sheet vinyl which does not Average cost is €3.62 per square Human Health Hazards design need stripping or waxing and has foot. May be coated with urethane resin. less seams than traditional Urethane is classified as a carcinogen 1B flooring. The sheets can be heat (H350). welded or chemically bonded, with heat welding most appropriate for preventing contamination and the plastic is melted together to form a seal. This flooring system can also be continued up the wall (flash caving).

Substitution of Chemical Substances of Potential Concern | 199 Table 9-40: Assessment of potential alternatives for formaldehyde Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Microfiber mops 3 Densely constructed polyester or Approximate cost per mop head Environmental Hazards polyamide fibres that can hold six = €0.96 Some are not biodegradable which may times its weight in water. The lead to persistence. positively charged microfibers Readily available in different attract dust and fibres that could forms. Human Health Hazards penetrate the microscopic May cause respiratory irritation due to surface pores of flooring exposure to PET fibres. 21 materials. 19

Can reduce bacteria by up to 99% compared with 30% for normal cotton cloths. As it can hold more solution, it reduces the amount of water and biocide needed. 20 17 http://www.acmanet.org/resources-tools/17-member-resources/269-polyurethane-workplace-hazards 18 https://oshwiki.eu/wiki/Occupational_exposure_to_epoxy_resins#Major_health_risks 19 https://www3.epa.gov/region9/waste/p2/projects/hospital/mops.pdf 20 http://deohs.washington.edu/sites/default/files/brochures/microfiber-factsheet.pdf 21 https://toxnet.nlm.nih.gov/cgi-bin/sis/search/a?dbs+hsdb:@term+@DOCNO+7712

A1.11 Substance 11: Di-isononyl phthalate (DINP)

A1.11.1 Identity of the substance

Table 9-41: Identity of DINP Name of substance Di-“isononyl” phthalate Synonyms DINP 1,2-Benzenedicarboxylic acid, diisononyl ester Isononyl alcohol, phthalate

Substitution of Chemical Substances of Potential Concern | 200 Table 9-41: Identity of DINP EC Number 249-079-5 CAS Number 28553-12-0 68515-48-0 Molecular formula C26H42O4

REACH Registration tonnage band 100,000 – 1,000,000 tonnes per annum Sources: ECHA website, https://echa.europa.eu/substance-information/-/substanceinfo/100.044.602 (accessed on 1 August 2017)

A1.11.2 Functionality and applications

Table 9-42: Functionality and applications for DINP General description of functionality DINP is used to soften or plasticise polyvinyl chloride (PVC). DINP is a general purpose plasticiser used in a multitude of vinyl products and key physico-chemical parameters that demand flexibility, durability and specific functionality. While DINP’s primary function is as a softener, it is also used in sealants, paints and lubricants. DINP is the largest-volume and preferred general-purpose high-molecular-weight plasticiser for PVC and a key substitute for Di-(2-ethylhexyl) phthalate (DEHP or DOP) in most flexible PVC applications Family the substance belongs to High-molecular-weight phthalate plasticisers

Substitution of Chemical Substances of Potential Concern | 201 Table 9-42: Functionality and applications for DINP Polymers Sector of Use SU0: Other SU1: Agriculture, forestry, fishery SU5: Manufacture of textiles, leather, fur SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU12: Manufacture of plastics products, including compounding and conversion SU16: Manufacture of computer, electronic and optical products, electrical equipment SU17: General manufacturing, e.g. machinery, equipment, vehicles, other transport equipment SU19: Building and construction work SU20: Health services Product category PC0: Other PC32: Polymer preparations and compounds Industrial/Professional/ Consumer Industrial/Professional/Consumer Description DINP is used as a plasticiser in a wide variety of PVC articles and plastisol. These include: - Calendering: Film, sheet and coated products, Flooring, roofing, wall covering - Extrusion: Hoses and profiles, Wires and cables, Clear, medical, film - Injection moulding: Footwear and miscellaneous - Plastisol spread coating: Flooring, General (coated fabric, wall covering, etc.) - Other plastisol applications: Car undercoating and sealants - Slush/rotational moulding Coatings, inks and artists’ colours Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU9: Manufacture of fine chemicals Product category PC9a: Coatings and paints, thinners, paint removes PC9b: Fillers, putties, plasters, modelling clay PC18: Ink and toners Industrial/Professional/ Consumer Industrial/Professional/Consumer Description DINP can be used in applications such as anti-corrosion paints, anti-fouling paints, lacquers, inks (including screen printing inks) and the plastification of nitro-cellulosics for wood coatings Adhesives and sealants Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU12: Manufacture of plastics products, including compounding and conversion SU19: Building and construction work Product category PC1: Adhesives, sealants PC32: Polymer preparations and compounds Industrial/Professional/ Consumer Industrial/Professional/Consumer

Substitution of Chemical Substances of Potential Concern | 202 Table 9-42: Functionality and applications for DINP Description DINP is used in in acrylic-based adhesives, acrylic window sealants (caulks), automotive sealants, tub and tile sealants (caulks), polyurethane sealants, MS-polymer based and silane- terminated systems where it acts as a plasticiser and offers benefits such as: - Reduced volatility - Increased permanence - Viscosity reduction (easier compounding) - Cost reduction (plasticisers cost less than base polymer and allow for higher filler loading) - Reduced glass transition temperature (lower tensile strength, hardness and increased elongation) Lubricants Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU15: Manufacture of fabricated metal products, except machinery and equipment Product category PC24: Lubricants, greases, release products PC25: Metal working fluids Industrial/Professional/ Consumer Industrial/Professional Description DINP can be used as a base oil for some applications Phlegmatiser Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU9: Manufacture of fine chemicals Product category PC11: Explosives PC32: Polymer preparations and compounds PC35: Washing and cleaning products Industrial/Professional/ Consumer Industrial Description DINP can be used as a phlegmatiser for organic peroxides to suppress the explosive character of organic peroxide products

Substitution of Chemical Substances of Potential Concern | 203 Table 9-42: Functionality and applications for DINP Sources: ECHA website, https://echa.europa.eu/documents/10162/31b4067e-de40-4044-93e8-9c9ff1960715 (accessed on 1 August 2017) Prospector website, https://www.ulprospector.com/en/na/Lubricants/Detail/21027/546809/Diisononyl-Phthalate-DINP (accessed on 1 August 2017) Evonik website, http://corporate.evonik.com/_layouts/Websites/Internet/DownloadCenterFileHandler.ashx?fileid=1127 (accessed on 1 August 2017) SpecialChem website, http://adhesives.specialchem.com/product/a-exxonmobil-chemical-jayflex-dinp (accessed on 1 August 2017) Krahn website, https://www.krahn.eu/en/ch/products/adhesives-sealants/product/jayflextm-dinp-3/ (accessed on 1 August 2017) PMA website, http://www.pmahome.org/files/4714/1884/4820/2014_PMA_PTS_Funderburg.pdf (accessed on 1 August 2017) Krahn website, https://www.krahn.eu/en/ch/products/coatings-construction-chemicals/plasticizers/phthalates/product/jaylextm-dinp/#productSearchFilters (accessed on 1 August 2017) Prospector website, https://www.ulprospector.com/en/eu/Coatings/Detail/3932/542263/Diisononyl-Phthalate-DINP (accessed on 1 August 2017)

A1.11.3 Potential alternatives

Table 9-43: Identification of potential alternatives for DINP Application 1 Polymers Name/description of alternative Families of potential alternatives include: - High molecular weight phthalates (but these substances may face regulatory pressures similar to DINP) - Aliphatic dibasic acid esters - Adipates - Sebacates & Azelates - Benzoate esters - Citrates - Epoxy esters - Phosphate esters - Terephthalates - Triglyceride plasticisers - Trimellitates - Glycerol Acetylated esters Low molecular weight phthalates (DEHP, DBP, BBP and DIBP) are subject to restrictions are not considered here. Below, example members of the above families are identified Identifiers (if chemical substance) Substance name EC Number CAS Number Tributyl o-acetyl citrate (ATBC) 201-067-0 77-90-7 Sulfonic acids, C10-21- alkane, Ph esters (ASE) 293-728-5 91082-17-6

Substitution of Chemical Substances of Potential Concern | 204 Table 9-43: Identification of potential alternatives for DINP Bis(2-propylheptyl) phthalate (DPHP) 258-469-4 53306-54-0 Bis(2-ethylhexyl) adipate (DEHA) 203-090-1 103-23-1 Di-octyl adipate (DOA) Bis(2-ethylhexyl) terephthalate (DEHT) 229-176-9 6422-86-2 Dioctyl terephthalate (DOTP) Di-isodecyl phthalate (DIDP) 247-977-1 26761-40-0 1,2-Cyclohexanedicarboxylic acid, 1,2-diisononyl 605-439-7 166412-78-8 Ester (DINCH) Bis(2-ethylhexyl) sebacate (DEHS) 204-558-8 122-62-3 Soybean oil, epoxidised (ESBO) 232-391-0 8013-07-8 Glycerides, castor-oil mono-, hydrogenated, acetates (COMGHA) 616-005-1 736150-63-3 330198-91-9 33599-07-4 Tris(2- ethylhexyl) benzene- 1,2,4- tricarboxylate (TOTM/ TEHTM) 222-020-0 3319-31-1 Diiso-nonyl adipate (DINA) 251-646-7 33703-08-1 Glycerol triacetate (GTA) 203-051-9 102-76-1 Diethylene glycol dibenzoate (DEGD) 204-407-6 120-55-8 Oxydipropyl dibenzoate (DGD) 248-258-5 27138-31-4 1,2-Benzene dicarboxylic acid, benzyl C7-9- branched and linear alkyl esters (INBP) 271-082-5 68515-40-2 Description of applicability of The applicability of the above families of plasticisers can be summarised as follows: alternatives - High molecular weight phthalates: include DIDP, DPHP, DIUP, and DTDP and represent about 85% of all the phthalates currently being produced in Europe; - Aliphatic dibasic acid esters: based on aliphatic dibasic acids with carbon numbers ranging from C5 (glutaric) to C10 (sebacic); - Adipates: Alcohols of similar chain length to those used in phthalate manufacturing (typically in the C8 to C10) range can be esterified with adipic acid, rather than PA, to produce a range of adipate plasticisers, e.g. di-2-ethylhexyl adipate (DEHA). In PVC applications, adipates offer enhanced low temperature properties compared to phthalates. In plastisol applications, adipates impart low plastisol viscosities due to their lower neat viscosities: - Sebacates & Azelates: Di-2-ethylhexyl sebacate (DOS) and di-2-ethylhexyl azelate (DOZ) are the most common members of this group, but di-isodecyl sebacate (DIDS) is also used. These plasticisers impart low temperature performances superior to adipates but also command a significant premium, and their use is generally limited to extremely demanding low temperature flexibility specifications (e.g. underground cable sheathing in arctic environments) - Benzoate esters: Di-benzoate plasticisers are obtained by direct esterification of benzoic acid with glycols. Used primarily in non PVC applications such as PVAc based adhesives, latex caulks and polysulphide

Substitution of Chemical Substances of Potential Concern | 205 Table 9-43: Identification of potential alternatives for DINP - Citrates: Citric acid is the starting material for a number of citrate ester plasticisers, such as tributyl citrate, acetyl tributyl citrate, triethyl citrate, acetyl triethyl citrate and tri-2-ethylhexyl citrate. Applications include toys, Pacifiers, Medical devices, Packaging films. 58% are used in food and beverage applications, 24% in household detergents and cleaners, 9% in pharmaceuticals and 9% in industrial applications - Epoxy esters: Esters containing an epoxy group such as epoxidised soybean oil (ESBO) and epoxidised linseed oil (ELO). They are formed by the oxidation of an olefinic double bond to an oxirane structure. Used to improve heat stability in the production of PVC articles by techniques such as extrusion, calendering, injection moulding, rotational moulding and spread coating. They are also used in rubbers, epoxy resins, paints and coatings. These can act as lubricants but also act as secondary stabilisers for PVC due to their epoxy content which can remove HCl from the degrading polymer - Phosphate esters : Triaryl phosphates and alkyl diaryl phosphates are the two important categories of flame retardant phosphate plasticisers. Phosphate esters can help produce low smoke, low flammable flexible PVC. The principal advantage of phosphate esters is their improved fire retardancy compared to phthalates. The fire performance of PVC, relative to other polymeric materials, is extremely good due to its high halogen content, but the addition of certain plasticisers may impair this property - Terephthalates: Terephthalates are the other commercial isomeric form of phthalates. Terephthalates are esters of terephthalic acid and include the 1,4 benzenedicarboxilic acid ester often referred to as DEHT (di-(2ethylhexyl) terephthalate) or DOTP (di-octyl terephthalate). Applications focused on low temperature properties, better resistance to soapy water extraction and lower volatility. In plastisols, DEHT provides lower initial viscosity and better viscosity stability but requires higher fusion and processing temperature - Triglyceride plasticisers: Different types of glycerol esters have been proposed as alternatives to low phthalates, their limited availability and higher costs currently limit their use - Trimellitates: Trimellitates are produced by the esterification of C7-C10 alcohols with trimellitic anhydride (TMA), which is similar in structure to PA with the exception of a third functionality on the aromatic ring. Consequently, esters are produced in the ratio of three moles of alcohol to one mole of anhydride. Common esters in this family are Tris-2-ethyhexyl trimellitate (Tri- octyl trimellitate - TOTM), L79TM, an ester of mixed semi-linear C7 and C9 alcohols, and L810TM, an ester of mixed C8 and C10 linear alcohols. Due to their low volatility, these plasticisers are used in the automotive industry (dashboard PVC skin produced by slush moulding) and in the insulation or sheathing of electrical cables - Glycerol Acetylated esters: This plasticiser is made from fully hardened castor oil and acetic acid. Castor oil is extracted from the seeds of the castor oil plant, which is an annual plant grown in India, Brazil and China. The castor oil contains between 85% to 95% ricinoleic acid. The performance of castor oil is improved by modifying its structure (hardening) and replacing the longer chain acids with acetic acid. The resulting fully acetylated glycerol monoester has a lower molecular weight, improving the compatibility and processability of the plasticiser. Expected main PVC applications for such esters are toys, bottle cap liners, screw cap liners for e.g. jam, teething rings, cling film, tubes and conveyor belts in the food industry and medical equipment Application 2 Coatings, inks and artists’ colours Name/description of alternative Some of the above alternatives may also be suitable for use in coating and ink applications. Examples are shown below

Substitution of Chemical Substances of Potential Concern | 206 Table 9-43: Identification of potential alternatives for DINP Identifiers (if chemical substance) Substance name EC Number CAS Number Bis(2-propylheptyl) phthalate (DPHP) 258-469-4 53306-54-0 Di-isodecyl phthalate (DIDP) 247-977-1 26761-40-0 Bis(2-ethylhexyl) adipate (DEHA) 203-090-1 103-23-1 Di-octyl adipate (DOA) Soybean oil, epoxidised (ESBO) 232-391-0 8013-07-8 Sulfonic acids, C10-21- alkane, Ph esters (ASE) 293-728-5 91082-17-6 Tributyl o-acetyl citrate (ATBC) 201-067-0 77-90-7 Glycerides, castor-oil mono-, hydrogenated, acetates (COMGHA) 616-005-1 736150-63-3 330198-91-9 33599-07-4 Glycerol triacetate (GTA) 203-051-9 102-76-1 Diethylene glycol dibenzoate (DEGD) 204-407-6 120-55-8 Oxydipropyl dibenzoate (DGD) 248-258-5 27138-31-4 Description of applicability of See discussion on plasticiser families above alternatives Application 3 Adhesives and sealants Name/description of alternative Some of the above alternatives may also be suitable for use in adhesive and sealant applications. Examples are shown below Identifiers (if chemical substance) Substance name EC Number CAS Number Bis(2-propylheptyl) phthalate (DPHP) 258-469-4 53306-54-0 Di-isodecyl phthalate (DIDP) 247-977-1 26761-40-0 1,2-Cyclohexanedicarboxylic acid, 1,2-diisononyl 605-439-7 166412-78-8 Ester (DINCH) Sulfonic acids, C10-21- alkane, Ph esters (ASE) 293-728-5 91082-17-6 Tributyl o-acetyl citrate (ATBC) 201-067-0 77-90-7 Glycerides, castor-oil mono-, hydrogenated, acetates (COMGHA) 616-005-1 736150-63-3 330198-91-9 33599-07-4 Diiso-nonyl adipate (DINA) 251-646-7 33703-08-1 Glycerol triacetate (GTA) 203-051-9 102-76-1 Diethylene glycol dibenzoate (DEGD) 204-407-6 120-55-8 Oxydipropyl dibenzoate (DGD) 248-258-5 27138-31-4 Sulfonic acids, C10-21- alkane, Ph esters (ASE) 293-728-5 91082-17-6 Description of applicability of See discussion on plasticiser families above

Substitution of Chemical Substances of Potential Concern | 207 Table 9-43: Identification of potential alternatives for DINP alternatives Application 4 Lubricants Name/description of alternative Some of the above alternatives may also be suitable for use in lubricant applications. Examples are shown below Identifiers (if chemical substance) Substance name EC Number CAS Number Bis(2-propylheptyl) phthalate (DPHP) 258-469-4 53306-54-0 Di-isodecyl phthalate (DIDP) 247-977-1 26761-40-0 Soybean oil, epoxidised (ESBO) 232-391-0 8013-07-8 Description of applicability of See discussion on plasticiser families above alternatives Application 5 Phlegmatiser Name/description of alternative Phlegmatisers are preferably selected from alkanols, cycloalkanols, alkylene glycols, alkylene glycol monoalkyl ethers, cyclic ether substituted alcohols, cyclic amides, esters, ketones (preferably other than the ketone that is used to make the ketone peroxide being phlegmatised), aromatic solvents, halogenated hydrocarbon solvents, and mixtures thereof. Some specific examples mentioned in the literature as shown below. Identifiers (if chemical substance) Substance name EC Number CAS Number 1,2-Cyclohexanedicarboxylic acid, 1,2-diisononyl 605-439-7 166412-78-8 Ester (DINCH) Dimethyl phthalate (DMP) 205-011-6 131-11-3 2,2,4-trimethyl-1,3-pentanediol-diisobutyrate 229-934-9 6846-50-0 C12-C14 Isoalkanes 271-369-5 68551-19-9 Hydrocarbons, C11-C16, isoalkanes, < 2% aromatics 920-901-0 64742-47-8 927-676-8 Description of applicability of The aforementioned substances are referred to in technical data sheets for organic peroxide products that are sold in a stabilised form alternatives Sources: (accessed on 2 August 2017) ECHA website, https://echa.europa.eu/documents/10162/b088340c-07bf-41b5-aed7-993166d79a85 (accessed on 2 August 2017) Evonik website, http://www13.evonik.com/asp/documents/safetysummary/3166_Safety_Summary_Report.pdf (accessed on 2 August 2017) Proviron website, http://www.proviron.com/product/provichemr-1611 (accessed on 2 August 2017) Chevron Philips website, http://www.cpchem.com/msds/100000068456_SDS_EU_EN.PDF (accessed on 2 August 2017) Exxon Mobil website, https://www.exxonmobilchemical.com/Chem-English/Files/Resources/isopar-m-fluid-product-safety-summary.pdf (accessed on 2 August 2017) Johannes Karl Fink (2013): Reactive Polymers Fundamentals and Applications: A Concise Guide to Industrial Polymers, https://books.google.co.uk/books?id=T2C3diHrnFgC (accessed on 2 August 2017) US Patent 20020137972 A1, http://www.google.ch/patents/US20020137972 (accessed on 2 August 2017)

Substitution of Chemical Substances of Potential Concern | 208 A1.11.4 Assessment of feasibility of potential alternatives

Substitution of Chemical Substances of Potential Concern | 209 Table 9-44: Assessment of potential alternatives for DINP Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability Tributyl o-acetyl citrate 1, 2, 3 Primarily suitable for food Loading: potentially lower than Both DINP and ATBC do not Registered at 10,000 – 100,000 (ATBC) packaging - cling wrap, toys, DINP have a harmonised tonnes per annum medical applications. Some classification. Self- applications in sealants, Cost: considerably higher than classification does not raise coatings and inks DINP concerns NB: there is a proposal for a harmonised classification of Repr. 1B for DINP Sulfonic acids, C10-21- 1, 2, 3 Primarily suitable for toys, Loading: somewhat higher Both DINP and ASE do not have Registered at 10,000 – 100,000 alkane, Ph esters (ASE) waterbeds, coated fabrics. than DINP a harmonised classification. tonnes per annum Some applications in sealants, Self-classification for ASE does coatings and inks Cost: higher than DINP not exist either Bis(2-propylheptyl) 1, 2, 3, 4, 5 Generally used across all Loading: potentially lower than Both DINP and DPHP do not Registered at 100,000 – phthalate (DPHP) applications of DINP, including DINP have a harmonised 1,000,000 tonnes per annum flooring, wall coverings, classification. Self- cladding & roofing, cables & Cost: similar to DINP classification for DPHP does wires, film & sheet, not exist either. However, the automotive, tubes & hoses, substance is subject to coated fabrics evaluation under the CoRAP with the following justification: - Potential endocrine disruptor - Exposure of sensitive populations - High (aggregated) tonnage - Wide dispersive use Bis(2-ethylhexyl) adipate 1, 2 Primarily used in flooring, wall Loading: substitution factor of Both DINP and DEHA do not Registered at 10,000 – 100,000 (DEHA) coverings, cladding & roofing, 0.88 have a harmonised tonnes per annum Di-octyl adipate (DOA) film & sheet, automotive, classification. However, DEHA tubes & hoses, coated fabrics, Cost: higher than DINP is subject to evaluation under inks & waxes, food packaging - the CoRAP with the following cling wrap, toys justification:

Substitution of Chemical Substances of Potential Concern | 210 Table 9-44: Assessment of potential alternatives for DINP Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability - Suspected CMR - Consumer use - High (aggregated) tonnage - Wide dispersive use Bis(2-ethylhexyl) 1 Primarily used in Flooring, Food Loading: substitution factor of Both DINP and DEHT do not Registered at 10,000 – 100,000 terephthalate (DEHT) packaging - Cling Wrap, Toys, 0.97 have a harmonised tonnes per annum Dioctyl terephthalate Medical Applications classification. (DOTP) Cost: similar to DINP An RMOA by France concluded that there is no need to initiate further regulatory risk management action at this time Di-isodecyl phthalate 1, 2, 3, 4, 5 Generally used across all Loading: substitution factor of Both DINP and DIDP do not Registered at 100,000 – (DIDP) applications of DINP, including 1.04 have a harmonised 1,000,000 tonnes per annum flooring, cladding & roofing, classification. However the cables & wires, film & sheet, Cost: similar to DINP substance is typically grouped automotive, tubes & hoses, with DINP and is subject to the coated fabrics, inks & waxes, same REACH restrictions as sealants, and coatings DINP; overall, similar level of hazard but lower liver effects than DINP 1,2- 1, 2, 3, 5 Generally used across the Loading: similar to DINP It is considered more benign Known to be available on the Cyclohexanedicarboxylic applications of DINP. Primarily than DINP market; EU capacity is in the acid, 1,2-diisononyl used in flooring, wall coverings, Cost: higher than DINP region of 100,000-1,00,000 Ester (DINCH) film and sheet, automotive, tonnes adhesives & sealants, tubes & hoses, coated fabrics, food packaging - cling wrap, toys, medical applications Bis(2-ethylhexyl) sebacate 1 Suitable only for specialist Loading and costs are unknown Both DINP and DEHA do not Registered at 1,000 – 10,000 (DEHS) applications but given the specialisation of have a harmonised tonnes per annum the substance, costs are likely classification. DEHS are

Substitution of Chemical Substances of Potential Concern | 211 Table 9-44: Assessment of potential alternatives for DINP Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability to be higher than DINP unlikely to raise concerns but it is accompanied by uncertainty Soybean oil, epoxidised 1, 2, 4 Used to improve heat stability No information is available Both DINP and ESBO do not Registered at 10,000 – 100,000 (ESBO) in the production of PVC have a harmonised tonnes per annum articles by techniques such as classification. ESBO is extrusion, calendering, considered more benign than injection moulding, rotational DINP moulding and spread coating. It is also used in rubbers, epoxy resins, paints and coatings. It can act as lubricants but also act as secondary stabilisers for PVC due to their epoxy content which can remove HCl from the degrading polymer. It tends to be perceived as a secondary plasticiser used alongside phthalate plasticisers Glycerides, castor-oil 1, 2, 3 Expected main PVC Loading: substitution factor of Both DINP and COMGHA do Not registered by available on mono-, hydrogenated, applications for such esters are 0.94 not have a harmonised the market acetates (COMGHA) toys, bottle cap liners, screw classification. Self- cap liners for e.g. jam, teething Cost: significantly higher than classification for COMGHA rings, cling film, tubes and DINP does not exist either. conveyor belts in the food industry and medical equipment as well as adhesives and printing inks Tris(2- ethylhexyl) 1 Primarily used in Cables and Loading: substitution factor of Both DINP and TOTM do not Registered at 10,000 – 100,000 benzene- 1,2,4- wires, Film and sheet, Medical 1.1 have a harmonised tonnes per annum tricarboxylate (TOTM/ Applications classification, however self- TEHTM) Cost: higher than DINP classification of TOTM would indicate a potential Repr Cat 2 hazard.

Substitution of Chemical Substances of Potential Concern | 212 Table 9-44: Assessment of potential alternatives for DINP Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability TOTM was subject to substance evaluation by the Austrian authorities for its PBT properties and additional information has been requested of its registrants Diiso-nonyl adipate (DINA) 1, 3 Primarily used in Adhesives & Loading: substitution factor of Both DINP and DINA do not Registered at 10+ tonnes per Sealants, Food packaging - 0.92 have a harmonised annum Cling Wrap, Toys & childcare classification. Self- articles Cost: higher than DINP classification for DINA does not exist either Glycerol Triacetate (GTA) 1, 2, 3 Primarily used in adhesives, Loading: unknown Both DINP and GTA do not have Registered at 10,000 – 100,000 inks, coatings but also in a harmonised classification tonnes per annum calendering, extrusion and Cost: higher than DINP injection moulding Diethylene glycol 1, 2, 3 Primarily used in flooring, Loading: unknown Both DINP and DEGD do not Registered at 1,000 – 10,000 dibenzoate (DEGD) spread coating applications, have a harmonised tonnes per annum adhesives, coatings and inks Cost: similar to DINP classification. DEGD is under substance evaluation with the following justification: - Consumer use - Exposure of environment - Exposure of workers - High (aggregated) tonnage - Suspected Reprotoxic - Wide dispersive use Oxydipropyl dibenzoate 1, 2, 3 Primarily used in flooring, Loading: substitution factor of Both DINP and DGD do not Registered at 1,000 – 10,000 (DGD) spread coating applications, 0.92 have a harmonised tonnes per annum adhesives, coatings and inks classification; however for DGD Cost: similar to DINP a classification of Aquatic Chronic 3 has been notified in

Substitution of Chemical Substances of Potential Concern | 213 Table 9-44: Assessment of potential alternatives for DINP Alternative Application Technical feasibility Economic feasibility Hazard comparison Market availability its registration dossier 1,2-Benzene dicarboxylic 1 Might be used in polymer and Unknown (likely to be more Both DINP and INBP do not Registered at 10,000 – 100,000 acid, benzyl C7-9- non-polymer applications costly than DINP) have a harmonised tonnes per annum branched and linear alkyl (limited information available) classification; however for DGD esters (INBP) a classification of Aquatic Chronic 1 has been notified (but not in its registration dossier) Dimethyl phthalate (DMP) 5 Used as a phlegmatiser. Its - Both DINP and DMP do not Registered at 1,000 – 10,000 specific applicability and have a harmonised tonnes per annum technical parameters of use are classification. A classification is not known not notified in its registration dossier 2,2,4-trimethyl-1,3- 5 Used as a phlegmatiser. Its - The substance has a notified Registered at 1,000 – 10,000 pentanediol-diisobutyrate specific applicability and classification of Aquatic tonnes per annum technical parameters of use are Chronic 3 not known C12-C14 Isoalkanes 5 Used as a phlegmatiser. Its - The substance has a notified Registered at 0-10 tonnes per specific applicability and classification of Asp. Tox. 1 annum technical parameters of use are not known Hydrocarbons, C11-C16, 5 Used as a phlegmatiser. Its - The substance has a notified Registered at 100,000 – isoalkanes, < 2% aromatics specific applicability and classification of Asp. Tox. 1 1,000,000 tonnes per annum technical parameters of use are not known Sources: ECHA website, https://echa.europa.eu/documents/10162/18f2a7e5-3f23-49b0-966b-fa13f2ce047f (accessed on 2 August 2017) ECHA website, https://echa.europa.eu/documents/10162/e017665d-b45f-4e54-a070-2a44baed4e9a (accessed on 3 August 2017)

Substitution of Chemical Substances of Potential Concern | 214 A1.12 Substance 12: Ethane-1,2-bis(pentabromophenyl) (EBP)

A1.12.1 Identity of the substance

Table 9-45: Identity of EBP Name of substance 1,1'-(ethane-1,2-diyl)bis[pentabromobenzene] Synonyms Ethane-1,2-bis(pentabromophenyl) (EBP) Decabromodiphenyl ethane EC Number 284-366-9 CAS Number 84852-53-9 Molecular formula C14H4Br10

REACH Registration tonnage band 10000 - 100000 tonnes per annum Sources: ECHA website, https://echa.europa.eu/substance-information/-/substanceinfo/100.076.669 (accessed on 23 June 2017)

Substitution of Chemical Substances of Potential Concern | 215 A1.12.2 Functionality and applications

Table 9-46: Functionality and applications for EBP General description of functionality The substance is a brominated flame retardant used in a variety of applications. It has long been considered and marketed as a direct and key physico-chemical parameters “drop-in” replacement for decabromodiphenyl ether (DecaBDE) which was recently restricted under REACH. One mechanism accounting for the effectiveness of brominated flame retardants is their ability to release active bromine atoms (free radicals) into the gas phase as the material is decomposed in the fire. These bromine atoms effectively quench the chemical reactions occurring in the flame, reducing the heat generated and slowing or even preventing the burning process. EBP can be used in conjunction with antimony trioxide (a synergist) in a wide variety of plastics, including thermoplastics (HIPS, ABS, polyolefins, TPU, polyesters (PBTE), PA), thermosets and in coatings Family the substance belongs to Brominated flame retardants Flame retardant in polymers Sector of Use SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU11: Manufacture of rubber products SU12: Manufacture of plastics products, including compounding and conversion SU13: Manufacture of other non-metallic mineral products, e.g. plasters, cement SU14: Manufacture of basic metals, including alloys SU15: Manufacture of fabricated metal products, except machinery and equipment SU16: Manufacture of computer, electronic and optical products, electrical equipment SU17: General manufacturing, e.g. machinery, equipment, vehicles, other transport equipment SU19: Building and construction work Product category PC1: Adhesives, sealants PC9a: Coatings and paints, thinners, paint removes PC9b: Fillers, putties, plasters, modelling clay PC18: Ink and toners PC20: Products such as ph-regulators, flocculants, precipitants, neutralisation agents PC24: Lubricants, greases, release products PC32: Polymer preparations and compounds PC35: Washing and cleaning products (including solvent based products) Industrial/Professional/ Consumer Industrial: formulation and uses Professional: Application for FR formulations (coatings and inks) Consumer: Use of FR articles and application of FR formulations (coatings and inks) – not sold directly to general public

Substitution of Chemical Substances of Potential Concern | 216 Table 9-46: Functionality and applications for EBP Description EBP is advertised as a general-purpose (additive) flame retardant for a variety of polymer applications. It is used together with antimony trioxide as a synergist in the ratio 2:1 to 3:1. Polymer applications include: - Adhesives - Building insulation and roofing materials - Cables - Coatings - Electronic components - Transportation Typical loadings are in the 10-15% by weight range Flame retardant in textiles Sector of Use SU5: Manufacture of textiles, leather, fur SU6b: Manufacture of pulp, paper and paper products SU18: Manufacture of furniture Product category PC8: Biocidal products (e.g. disinfectants, pest control) PC9a: Coatings and paints, thinners, paint removes PC18: Ink and toners PC20: Products such as pH-regulators, flocculants, precipitants, neutralisation agents PC23: Leather tanning, dye, finishing, impregnation and care products PC26: Paper and board dye, finishing and impregnation products: including bleaches and other processing aids PC28: Perfumes, fragrances PC31: Polishes and wax blends PC32: Polymer preparations and compounds PC34: Textile dyes, finishing and impregnating products; including bleaches and other processing aids PC35: Washing and cleaning products (including solvent based products) Industrial/Professional/ Consumer Industrial: formulation and uses Professional: Application for FR formulations (coatings and inks) Consumer: Use of FR articles – not sold directly to general public

Substitution of Chemical Substances of Potential Concern | 217 Table 9-46: Functionality and applications for EBP Description EBP is an additive flame retardant for textiles used for furniture and furnishings. The quantities are relatively low compared to polymer applications. EBP is used as a component of latex-based backcoatings for drapery and upholstery fabric. Typical loadings for various fabrics are in the range 30-80 g dry coating per square metre of fabric; the brominated flame retardant makes up around 30-40% of the dry coating weight Sources: RPA (2014), Support to an Annex XV Dossier on Bis-(pentabromophenyl) ether (DecaBDE), https://echa.europa.eu/documents/10162/13641/annex_xvi_consultant_report_decabde_en.pdf (accessed on 23 June 2017) EBFRIP (2008), How Brominated Flame Retardants work, http://www.ebfrip.org/main-nav/our-substances/how-brominated-flame-retardants-work (accessed on 23 June 2017) Environment Agency (2007), Environmental risk evaluation report: 1,1'-(Ethane-1,2-diyl)bis[penta-bromobenzene], https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/290840/scho0507bmor-e-e.pdf (accessed on 23 June 2017)

A1.12.3 Potential alternatives

Table 9-47: Identification of potential alternatives for EBP Application 1 Flame retardant in polymers Name/description of alternative Alternative substances: - Brominated FRs (BFRs): e.g. brominated epoxies, brominated polystyrene, ethylene bis(tetrabromophthalimide), poly(pentabromobenzyl acrylate), tetrabromobisphenol-A (TBBPA), TBBPA carbonate oligomer, tris(bromoneopentyl) phosphate, TBBPA (2,3-dibromopropyl ether) - Chlorinated FRs: e.g. chloroparaffins, hexachloroendomethylene tetrahydrophthalic acid, tris(chloropropyl) phosphate - Organophosphorous FRs: these may include phosphines, phosphine oxides, phosphonium compounds, elemental red phosphorous and phosphates, e.g. bisphenol-A bis(diphenyl phosphate), cresyl diphenyl phosphate, dimethylpropane phosphonate, polyphosphonates, metal phosphinate, phosphorous polyol, resorcinol bis(diphenyl phosphate), tricresyl

Substitution of Chemical Substances of Potential Concern | 218 Table 9-47: Identification of potential alternatives for EBP phosphate, triphenyl phosphate. It is noted that in some cases phosphorous/halogen compounds are used to increase the effectiveness of the FR or act (in parallel) as plasticisers - Nitrogen-containing FRs: e.g. ammonium polyphosphate, melamine cyanurate, melamine, melamine poly aluminium and zinc phosphates - Inorganic FRs: e.g. aluminium hydroxide, magnesium hydroxide, red phosphorous (also in combination with a halogen-free FR (HFFR)) - Other substances: sulphonate salts, boron compounds, silicates, etc. - Intumescent systems - Nanocomposites - Expandable graphite Alternative materials: - Polymer blends: readily flammable polymers (e.g. HIPS or ABS) may be blended with less readily flammable polymers such as PC, PPO (also referred to as PPE) or polyphenylene sulphide (PPS). This enables lower FR loadings to be used with limited impact on other technical properties. Another option is layering where an article is produced using layers of highly FR filled polymer and low or non-flame retardant polymer - Use of inherently flame-retardant matrices: halogenated polymers such as PVC have FR properties because they release halogen radicals, which have the same effect during combustion as halogen radicals released from halogenated FRs. This effect can be enhanced by the addition of synergists such as ATO to halogenated polymer blends. Polymers that char, such as polyimides, polyaramides, liquid crystal polyesters, polyphenylene sulphide, polyarylenes and many thermosets also tend to have a greater resistance to fire. Where the base polymer has FR properties, depending on the end use, a sufficient level of fire performance may be achieved without the need for chemical FRs or much lower loadings may be required. Phenolics, have been developed without smoke suppressants additives, which practically do not release any smoke. Other polymer materials that are inherently flame-retardant include: halogen-free polyketone and high performance thermoplastics such as polysulphone, polyaryletherketone (PAEK) or polyethersulphone (PES) - Polylactic acid blended with ammonium polyphosphate Alternative articles: - Replacement of the original polymer material with another in combination with shielding of power supplies (this has been the case with a move from HIPS to ABS and additional shielding in printers and related equipment) - Removal of the power supply from the product thus reducing the fire retardancy requirements of the electronic enclosure. Examples of alternative substances selected below are based on an analysis of alternatives for DecaBDE which effectively has the same range of applications as EBP Identifiers (if chemical substance) Substance name EC Number CAS Number Triphenyl phosphate (TPP) 204-112-2 115-86-6 Magnesium hydroxide 215-170-3 1309-42-8

Substitution of Chemical Substances of Potential Concern | 219 Table 9-47: Identification of potential alternatives for EBP Aluminium trihydroxide 244-492-7; 21645-51-2; 8064-00-4 617-137-2 Tetrabromobisphenol-A bis (2,3-dibromopropyl ether) 244-617-5 21850-44-2 Ethylene bis(tetrabromophthalimide) 251-118-6 32588-76-4 Resorcinol bis(diphenylphosphate) (RDP) 260-830-6; 57583-54-7; 125997- 603-113-9 21-9 Bisphenol-A bis(diphenyl phosphate) (BDP/BAPP) 611-829-8; 5945-33-5; 181028-79- 605-913-3 5 Substituted amine phosphate mixture (P/N intumescent systems) 613-872-8 66034-17-1 Red phosphorous 231-768-7 7723-14-0 Description of applicability of The selected substances represent a variety of different FR families. Literature suggests that in some cases, apart from the substitution alternatives of the FR, the polymer might ideally also be substituted to ensure that the required levels of fire retardancy is achieved. The resin conversions that might typically be required would be: ABS Æ PC/ABS HIPS Æ PPO/HIPS and would apply to Triphenyl phosphate, Tetrabromobisphenol-A bis (2,3-dibromopropyl ether), Resorcinol bis(diphenyl phosphate) and Bisphenol-A bis(diphenyl phosphate) (based on an analysis of alternatives for DecaBDE). In addition, the loadings of alternative FRs might vary. They might range between 5-8% for red phosphorus, all the way up to 50-60% for aluminium trihydroxide. Application 2 Flame retardant in textiles

Substitution of Chemical Substances of Potential Concern | 220 Table 9-47: Identification of potential alternatives for EBP Name/description of alternative Alternative flame retardants: - Chemical finishes: Phosphates, Polyphosphates, Phosphorous amides, Phosphonium derivatives, Borax and boric acid, Halogenated FRs - Chemical coatings: Triaryl phosphate, Cresyl diphenyl phosphate or phosphinate, Hexabromocyclododecane (HBCD), Ethylene bis(tetrabromophthalimide), Alumina trihydrate, Exfoliating graphite containing coatings - Other: Swelling (intumescent) systems, Plasma-induced-graft-polymerisation, Nanocomposites Improvement of FR properties of synthetic fibres by copolymerisation and fibre blending: - Viscose or rayon: Bis(2-thio-5,5-dimethyl-1,3,2-dioxaphosphorinyl)oxide - Viscose FR, Polysilicic acid (Visil®) and aluminium (Visil AP®) - Polyester: Comonomeric phosphinic acid in PET – Trevira, Bisphenol-S-oligomer derivatives -Toyobo GH, Cyclic phosphonates - Antiblaze CU and 1010, Phosphinate salts - Polypropylene: Phosphorous-containing, Halogen-containing, Silicon-containing, Metal hydrate and oxide (effective but required in high levels, typically >20% w/w), Tris(tribomoneopentyl) phosphate (FR 372, ICL) Use of inherently heat resistant and FR fibres Fire barriers and composite textile assemblies Replacement of textiles by alternative materials (e.g. natural leather, artificial leather FR with borates). Examples selected below are based on an analysis of alternatives for DecaBDE Identifiers (if chemical substance) Substance name EC Number CAS Number Magnesium hydroxide 215-170-3 1309-42-8 Tris(1,3-dichloro-2-propyl) phosphate 237-159-2 13674-87-8 Aluminium trihydroxide 244-492-7; 21645-51-2; 8064-00-4 617-137-2 Tetrabromobisphenol-A bis (2,3-dibromopropyl ether) 244-617-5 21850-44-2 2,2'-Oxybis[5,5-dimethyl-1,3,2-dioxaphosphorinane] 2,2'-disulphide 223-829-1 4090-51-1 Ethylene bis(tetrabromophthalimide) 251-118-6 32588-76-4 Resorcinol bis(diphenylphosphate) (RDP) 260-830-6; 57583-54-7; 125997- 603-113-9 21-9 Bisphenol-A bis(diphenyl phosphate) (BDP/BAPP) 611-829-8; 5945-33-5; 181028-79- 605-913-3 5 Substituted amine phosphate mixture (P/N intumescent systems) 613-872-8 66034-17-1 Red phosphorous 231-768-7 7723-14-0 Description of applicability of Loadings of alternative FRs may vary; 2,2'-Oxybis[5,5-dimethyl-1,3,2-dioxaphosphorinane] 2,2'-disulphide may be used at a loading lower alternatives than EBP (although at a much higher cost), while magnesium hydroxide would typically require a loading five times higher than EBP’s

Substitution of Chemical Substances of Potential Concern | 221 Table 9-47: Identification of potential alternatives for EBP Sources: RPA (2014), Support to an Annex XV Dossier on Bis-(pentabromophenyl) ether (DecaBDE), https://echa.europa.eu/documents/10162/13641/annex_xvi_consultant_report_decabde_en.pdf (accessed on 23 June 2017)

A1.12.4 Assessment of feasibility of potential alternatives

Substitution of Chemical Substances of Potential Concern | 222 Table 9-48: Assessment of potential alternatives for EBP Alternative Applicatio Technical Economic Hazard Market n feasibility feasibility comparison availabilit y Triphenyl phosphate 1 Used in a wide Loading: Environmental Registere (TPP) variety of between 8% hazards: not a d at 1000 polymer-based (PC/ABS) and PBT substance – 10,000 applications, 30% based on its tonnes including (HIPS/PPO) intrinsic per coatings. Price: properties. It annum Typical Available shows aquatic applications information toxicity TPP with include: would self-notified HIPS/PPO, suggest that classification for PC/ABS, it could have aquatic toxicity phenolic resins a higher (H400/H410) and and epoxy price than associated low resins. EBP but the PNEC values for It would require price water and manufacturers difference sediment to switch to could different resins, balance out Human health e.g. from HIPS to if the cost of hazards: TPP HIPS/PPO plastic antimony poses moderate trioxide is hazards to human taken into health, including account. The concerns over loading of neurotoxicity and the endocrine substance disruption. The could be substances is on significantly the CoRAP List higher than DecaBDE. Nevertheless , literature describes TPP as affordable Magnesium hydroxide 1, 2 It can be used in Loading: it Environmental Registere almost the full requires high hazards: as an d at range of filler levels of inorganic 100,000 – applications that about 45 to substance, it 1,000,000 are relevant to 50% to reach cannot be tonnes EBP but it UL 94 V-0. classified a PBT per cannot be Because of Human health annum assumed that it its limited hazards: it raises would perform temperature little concern as efficiently as stability, it is overall EBP/Antimony mainly used Trioxide in low glass formulations fibre PA-6. Price: it has a price per kg significantly lower than EBP. It does

Table 9-48: Assessment of potential alternatives for EBP Alternative Applicatio Technical Economic Hazard Market n feasibility feasibility comparison availabilit y not require the use of Antimony Trioxide. Calculations of the substitution cost for the use of magnesium hydroxide in polymers and textiles suggests that the use of the substance would lead to cost savings Tris(1,3-dichloro-2- 1, 2 It can be used in Loading: it Environmental Registere propyl) phosphate foam requires hazards: it d at 1000 (TDCPP) applications marginally displays – 10,000 which are higher persistence and tonnes generally of loadings aquatic chronic per limited compared to toxicity and its annum significance to EBP. registration EBP as well as in Price: it is dossier bears a textile likely to have classification of backcoating. Its a price per kg Aquatic Chronic 2 applicability lower than (H411). It has does not span all EBP. It does PNEC values fabrics of not require which are relevance to EBP the use of considerably low. Antimony TDCPP is not a Trioxide. PBT substance Calculations of the Human health substitution hazards: It is cost for the classified as Carc use of TDCPP Cat 2 in its REACH in textiles registration and is suggests that accompanied by the use of (low) acute the toxicity (Acute substance Tox. 4 (H302), could lead to self-classification cost savings in the C&L inventory). Recent research raises concerns with regard to the neurotoxicity

Table 9-48: Assessment of potential alternatives for EBP Alternative Applicatio Technical Economic Hazard Market n feasibility feasibility comparison availabilit y properties of the substance. Under the ESR, potential female fertility effects were identified Aluminium trihydroxide 1, 2 It can be used in Loading: it Environmental Registere a wide range of may require hazards: it does d at applications that loadings 5 not give rise to 1,000,000 are relevant to times higher any concern and, – EBP but it does than EBP in as an inorganic 10,000,00 not necessarily polymer substance, it is 0 tonnes perform as applications not a PBT per efficiently or and 3 times Human health annum effectively as higher in hazards: it raises EBP/Antimony textile little concern trioxide applications. overall, although formulations Price: it is recent research likely to have has highlighted a price per kg behavioural and significantly neuropathologica lower than l outcomes with EBP. It does aluminium not require trihydroxide the use of Antimony trioxide. Calculations of the substitution cost for the use of aluminium trihydroxide in polymers and textiles suggests that the use of the substance could lead to cost savings Tetrabromobisphenol-A 1 (2) It can find Loading: it Environmental Registere bis (2,3-dibromopropyl applications may require hazards: it may d at 1000 ether) mainly in similar raise concerns – 10,000 polymers loadings to about its tonnes (mainly PP, HIPS, EBP and persistence and per PE, elastomers), requires the bioaccumulation annum and less so in use of but it is not a textiles Antimony recognised PBT. trioxide. Its breakdown Price: it products have could be also been under

Table 9-48: Assessment of potential alternatives for EBP Alternative Applicatio Technical Economic Hazard Market n feasibility feasibility comparison availabilit y lower than the spotlight but EBP but is current uncertain. knowledge is Substitution limited. In cost theory, the estimates in substance may polymers have some vary and it potential to form may result in TBBPA in the cost savings environment in PP but also through a increased (bio)degradation costs in process but the PPO/HIPS significance of this is unknown

Human health hazards: concerns have been raised about its potential carcinogenic properties but no conclusive results appear to be available in the literature Ethylene 1, 2 It is one of the Loading: Environmental Registere bis(tetrabromophthalimid substances with similar to hazards: it is very d at 100 - e) the widest range EBP persistent and its 1000 of applications Price: bioaccumulation tonnes as a EBP similar to raises concerns per replacement EBP (also but the substance annum and can be used requires the does not appear both in polymers use of to meet the and textiles Antimony criteria for a PBT. trioxide) On the other hand, the issue of debromination in the environment has been raised in the literature

Human health hazards: no particular concern is raised on the basis of REACH registration information, but the US EPA has

Table 9-48: Assessment of potential alternatives for EBP Alternative Applicatio Technical Economic Hazard Market n feasibility feasibility comparison availabilit y raised concerns over carcinogenicity and developmental toxicity due to the lack of data 2,2'-Oxybis[5,5-dimethyl- 2 It may only find Loading: it It is very Registere 1,3,2- uses as a FR in requires persistent (based d at 100 - dioxaphosphorinane] 2,2'- viscose textiles. lower on Annex XIII and 1000 disulphide It is probably loadings screening tonnes used mainly in than EBP (ca. criteria), per clothing, so its 10%) however, it does annum share in EBP- Price: it has not meet all PBT related products a higher criteria and its is expected to be price than human health very low. EBP and hazard profile It has claimed to requires the does not appear have technical use of more to raise concerns characteristics expensive equivalent of raw material better than EBP- fibres, but backcoated does not textiles, while require the offering better use of aesthetics and Antimony lifetime trioxide. The cost of production and the market price of the textile articles becomes considerably higher Resorcinol 1 (2) It is suitable for Loading: it Environmental Registere bis(diphenylphosphate) replacing EBP in may require hazards: it does d at 1000 (RDP) plastic blends lower not meet all PBT – 10,000 (primarily for loadings criteria but it tonnes E&E applications than EBP. shows signs of per where the use of Price: it may persistence in the annum DecaBDE has have a lower environment; its been eliminated price per kg biodegradation under the RoHS and it does products are yet Directive). It is not require unclear. In an aryl the use of addition, there is phosphate Antimony uncertainty which is used as trioxide, but about its a substitute for requires a bioaccumulation. halogenated FRs change to The US EPA as well as for the resin expressed TPP because it (e.g. from concerns over its

Table 9-48: Assessment of potential alternatives for EBP Alternative Applicatio Technical Economic Hazard Market n feasibility feasibility comparison availabilit y has a lower HIPS to a aquatic toxicity volatility, a blend). higher thermal Substitution Human health stability, and a cost hazards: the higher P-content estimates in substance has no in comparison to polymers hazard TPP. It is used as vary and in classification but a substitute for PC/ABS a recent analyses TCPP as it is less cost saving by the US EPA volatile, and has been have raised some therefore less estimated. “moderate” likely to be For concern over released into PPO/HIPS, carcinogenicity, the increased developmental, environment. costs are neurological and It cannot be likely to arise repeated dose used in HIPS as a effects drop-in replacement for EBP. In order to use RDP, the manufacturer must use a different plastic to achieve the same fire rating (HIPS/PPO or PC/ABS) Bisphenol-A bis(diphenyl 1 (2) Mostly used in Loading: it Environmental Not phosphate) (BDP/BAPP) polymers such appears to hazards: while it registered as PC/ABS and be used at does not meet all under PPO/HIPS, much loadings PBT criteria, REACH less so in textiles similar to significant (a niche EBP. concerns have application Price: its per been expressed area) kg price is on its assumed to degradation and be the products of comparable such degradation to EBP, but it by does not dephosphorylatio require the n (namely, use of bisphenol-A and Antimony phenol). trioxide. Although no However, its conclusive use may research has require a been identified, change to some analyses by different EU State and resin and other notable organisations investment consider it an

Table 9-48: Assessment of potential alternatives for EBP Alternative Applicatio Technical Economic Hazard Market n feasibility feasibility comparison availabilit y costs. unsuitable Substitution replacement for cost DecaBDE. In estimates in addition, a polymers classification for vary and in chronic aquatic PC/ABS a toxicity is cost saving suggested both in or a modest the registration cost can be dossier and the estimated. C&L Inventory For Human health PPO/HIPS, a hazards: no cost increase significant may be concern has been expected identified; the US EPA highlighted the lack of information on carcinogenicity

Substituted amine 1 (2) It may find Loading: in Environmental Not phosphate mixture applications in PE/PP the hazards: the very registered (P/N intumescent polymers used loading of limited under systems) in electronics, this information REACH wire and cable, alternative available does public buildings, may be 20- not highlight any construction 30% higher areas of concern materials, than EBP. with the automotive, Price issues: exception of aviation, storage it has a price persistence and distribution per kg higher based on products. than that of experimental Example resins EBP but it data for the include does not organic elastomers, require the components EVA, PP, PE and presence of TPU. Textiles is Antimony Human health not a prominent trioxide. The hazards: some application area overall price concern on the increase for acute toxicity of the final the substituted article is amine phosphate estimated as mixture has been considerable raised by the US compared to EPA. “Moderate” EBP-based concern was also articles. raised for Certain carcinogenicity operating (based on the costs are substituted also likely to amine phosphate change component),

Table 9-48: Assessment of potential alternatives for EBP Alternative Applicatio Technical Economic Hazard Market n feasibility feasibility comparison availabilit y genotoxicity (based on both components), reproductive effects (based on piperazine), developmental effects (based on piperazine), repeated dose effects (based on the substituted amine phosphate component), respiratory sensitisation (based on the substituted amine phosphate component), and eye irritation (based on both components) Red phosphorous 1, 2 Suitable for Loading: it is Environmental Registere polymer an effective hazards: red d at 1000 applications FR additive phosphorous – 10,000 (PA, PE/PP, at a may be tonnes Epoxy, etc.) in concentratio considered per dark colours and n ranging persistent in the annum semi-durable from 2-10% environment but finishes on by weight, as an inorganic cotton-rich i.e. lower compound textiles, than EBP. cannot be subject generally Price: to the PBT unsuitable for notably criteria. It is man-made lower per kg accompanied by fibres price than an Aquatic A drawback of EBP. It does Chronic 3 the use of red not require classification (but phosphorus is the use of test data could the formation of Antimony suggest a more toxic phosphine trioxide severe gas during classification combustion and might be long-term warranted) storage. Precautions Human health against hazards: with the degradation exception of have to be irritant taken. properties and Improved some uncertainty techniques in over genotoxicity

Table 9-48: Assessment of potential alternatives for EBP Alternative Applicatio Technical Economic Hazard Market n feasibility feasibility comparison availabilit y the production and hepatoxicity, process and no significant increased concerns for expertise in human health compounding appear to exist. red Its physico- phosphorous is chemical hazards advised. In and the risk of order to disproportionatio improve the safe n products are handling of red reduced through phosphorous encapsulation powder at the and stabilisation workplace, it is usual to stabilise it, microencapsulat e the surface with thermoset resins, and add dust suppressant agents Sources: RPA (2014), Support to an Annex XV Dossier on Bis-(pentabromophenyl) ether (DecaBDE), https://echa.europa.eu/documents/10162/13641/annex_xvi_consultant_report_decabde_en.pdf (accessed on 23 June 2017)

A1.13 Substance 13: Trichloroethylene

A1.13.1 Identity of the substance

Table 9-49: Identity of trichloroethylene Name of substance Trichloroethylene Synonyms Ethylene trichloride TCE Trichloroethene Trilene EC Number 201-167-4 CAS Number 79-01-6 Molecular formula C2HCl3

REACH Registration 10,000 – 100,000 tonnes per annum tonnage band

Table 9-49: Identity of trichloroethylene Sources: ECHA website, https://echa.europa.eu/documents/10162/9af34d5f-cd2f-4e63-859c- 529bb39da7ae (accessed on 20 July 2017)

A1.13.2 Functionality and applications

Table 9-50: Functionality and applications for trichloroethylene General description of Trichloroethylene is a clear colourless volatile liquid with a chloroform-like functionality and key odour. It is denser than water and it is slightly soluble in water. It is also non- physico-chemical combustible. Trichloroethylene is used as a solvent, fumigant, in the parameters manufacture of other chemicals, and it is an inhalation anaesthetic.

Trichloroethylene is classified as a substance that may cause cancer (H350) (Carc. Cat. 1B), causes serious eye irritation (H319), is suspected of causing genetic defects (H341) (Muta. Cat. 2), is harmful to aquatic life with long lasting effects (H412), causes skin irritation (H315) and may cause drowsiness or dizziness (H336). Registrants also indicate that trichloroethylene may cause an allergic skin reaction (H317).

Trichloroethylene is a SVHC substance due to its carcinogenic classification and it is subject to authorisation. Family the substance Halogenated hydrocarbons belongs to Application 1 Sector of Use SU 8: Manufacture of bulk, large scale chemicals Intermediate (including petroleum products) SU 9: Manufacture of fine chemicals Product category PC 19: Intermediate Industrial/Professional/ Industrial: Manufacture of bulk and fine chemicals Consumer Professional: N/A Consumer: N/A Description The major use of trichloroethylene appears to be in closed systems as an intermediate chemical for manufacturing refrigerant chemicals - hydrofluorocarbon (HFC) refrigerants, An estimated 84 percent of TCE is used as an intermediate in manufacturing the hydrofluorocarbon 1,1,1,2- Tetrafluoroethane (HFC-134a), and as an alternative refrigerant to CFC-12 Application 2 Solvent Sector of Use SU 8: Manufacture of bulk, large scale chemicals (adhesive and cleaning) (including petroleum products) SU 9: Manufacture of fine chemicals Product category PC 1: Adhesives, sealants PC 35: Washing and cleaning products Industrial/Professional/ Industrial: Industrial adhesive and cleaning Consumer Professional: Used within adhesives and cleaning products Consumer: N/A Description Trichloroethylene is also used as a solvent for waterless dying. Trichloroethylene is also found and used in products such as dyes, printing inks, paints, adhesives, paint removers, typewriter correction fluids, as well as spot removers. Within these

Table 9-50: Functionality and applications for trichloroethylene products trichloroethylene is used as a solvent carrier

Trichloroethylene is used in adhesives for which a solvent of low flammability is required that also possesses the desired drying time. There is no specialised application for trichloroethylene based adhesives. Also, alternative low flammability solvents are likely to be available Application 3 Extraction Sector of Use SU 8: Manufacture of bulk, large scale chemicals solvent (cleaning (including petroleum products) chemical including metal SU 9: Manufacture of fine chemicals degreasing and Product category PC 35: Washing and cleaning products caprolactam extraction Industrial/Professional/ Industrial: Industrial dry cleaning and surface amongst others) Consumer cleaning Professional: Professional dry cleaning Consumer: N/A Description Trichloroethylene is used as part of vapor degreasing of metal parts is highly important. Used by automotive and metal industries, trichloroethylene proves to be powerful in the removal of grease, oil, fat, wax and tar. Trichloroethylene is also used for caprolactam extraction, removal and recovery of resin from dyed cloth, to recover and purify resin from process water, a processing aid in the biotransformation of starch to obtain betacyclodextrin, a solvent in the synthesis of vulcanization accelerating agents for fluoroelastomers and other uses Sources: Accessed 1st August: https://www.epa.gov/sites/production/files/2017- 02/documents/trichloroethylene.pdf

A1.13.3 Potential alternatives

Table 9-51: Identification of potential alternatives for trichloroethylene Application 1 Intermediate Name/description of Alternative substances/processes: alternative - Isomerisation/hydro-fluorination of 1,1,2-trichloro-1,2,2- trifluoroethane (CFC-113) to 1,1,-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a) followed by hydro-dechlorination of the latter - Hydro-fluorination of tetrachloroethylene to 1-chloro-1,2,2,2- tetrafluoroethane (HCFC-124) and subsequent hydro-dechlorination to HFC-134a Identifiers (if chemical Substance name EC Number CAS Number substance) 1,1,2-trichloro-1,2,2- 200-936-1 and 200-937- 76-13-1 and 76-14-2 trifluoroethane and 1,1,- 7 dichloro-1,2,2,2- tetrafluoroethane Tetrachloroethylene and 204-825-9 and 220-629- 127-18-4 and 2837-89-0 1-chloro-1,2,2,2- 6 tetrafluoroethane Description of The main method for producing HFC-134a is hydro-fluorination of applicability of trichloroethylene, via 1-chloro-2,2,2-trifluoroethane (HCFC-133a). However, alternatives CFC’s and HFC’s can be used to manufacture of HFC-134a, these methods

Table 9-51: Identification of potential alternatives for trichloroethylene involve isomerisation and hydro-fluorination to form other CFCs/HFCs and then hydro-dechlorination to form 1,1,1,2-Tetrafluoroethane Application 2 Solvent (adhesive and cleaning) Name/description of Alternative substances: alternative - Methylene chloride - Acetone - Acetone/heptane blends - Ethyl acetate - Toluene - N-propyl bromide - Petroleum substances (e.g. mineral spirits, petroleum solvents, petroleum distillates and VM&P naphtha’s) - Aqueous-based carriers using latex or latex-synthetic blends - Tetrachloroethylene (perchlorethylene) - Mechanical rubbing and high-pressure water spray - Ultrasonic removal Identifiers (if chemical Substance name EC Number CAS Number substance) Methylene chloride 200-838-9 75-09-2 Acetone 200-662-2 67-64-1 Acetone / heptane 200-662-2 / 205-563-8 67-64-1 / 142-82-5 blends Ethyl acetate 205-500-4 141-78-6 Toluene 203-625-9 108-88-3 N-propyl bromide 203-445-0 106-94-5 Petroleum substances Various Various (e.g. mineral spirits, petroleum solvents, petroleum distillates and VM&P naphtha’s) Tetrachloroethylene 204-825-9 127-18-4 (perchlorethylene) Mechanical rubbing and N/A N/A high-pressure water spray Ultrasonic removal N/A N/A Description of There are a range of adhesives which are designed to perform specific actions, applicability of these adhesives will require specific concentrations of solvents and the required alternatives concentration of the alternative may be similar to that of trichloroethylene Application 3 Extraction solvent used in metal cleaning applications and separators used in lead-acid batteries Name/description of Alternative substances: alternative - N-propyl bromide - Methylene chloride - 1,2-Trans-Dichloroethylene - n-Hexane - D-Limonene - Acetone - Methyl ethyl ketone (MEK) - Iso-propyl alcohol (IPA) - Toluene - Benzene - Heptane and heptanol mixture Identifiers (if chemical Substance name EC Number CAS Number substance) N-propyl bromide 203-445-0 106-94-5 Methylene chloride 200-838-9 75-09-2

Table 9-51: Identification of potential alternatives for trichloroethylene 1,2-Trans- 205-860-2 156-60-5 Dichloroethylene n-Hexane 203-777-6 110-54-3 D-Limonene 227-813-5 5989-27-5, 68606-81-5 Acetone 200-662-2 67-64-1 Methyl ethyl ketone 201-159-0 78-93-3 (MEK) Iso-propyl alcohol (IPA) 200-661-7 67-63-0 Toluene 203-625-9 108-88-3 Benzene 200-753-7 71-43-2, 1076-43-3 Heptane and heptanol 205-563-8 & 203-897-9 142-82-5 & 111-70-6 mixture Cyclohexane 203-806-2 110-82-7 Ethanol 200-578-6 64-17-5 / 97281-11-3 Methanol 200-659-6 67-56-1 Pentane 203-692-4 109-66-0 Diethyl ether 200-467-2 60-29-7 Ethylbenzene 202-849-4 100-41-4 Chloroform 200-663-8 67-66-3 Carbon tetrachloride 200-262-8 56-23-5 1,2-dichlorobenzene 202-425-9 95-50-1 1,1,2-trichloroethane 201-166-9 79-00-5 1,4-dioxane 204-661-8 123-91-1 1,2-dichloroethane 203-458-1 107-06-2 Description of A range of solvents exisit that would be able to degrease metal components and applicability of be used for other applications including lead-acid batteries and as an extraction alternatives solvent in caprolactam production. However, the physical properties of some of these alternative substances may mean that they are not appropriate of all applications. For example, some may increase the hazard posed to human health (and the environment) in certain situations. This is indicated by the CLP classifications (or those suggested by registrants) of some of the substances that are equal to or are greater than those of trichloroethylene Sources: ECETOC, http://www.ecetoc.org/wp-content/uploads/2014/08/JACC-050.pdf (Accessed 7 August 2017) ECHA website, https://echa.europa.eu/documents/10162/18584504/afa_tce-0020-01-aa_en.pdf (Accessed 7 August 2017) ECHA Website https://echa.europa.eu/documents/10162/9a728963-e57f-48de-b977-7d05462c43e9 (Accessed 1 August 2017)

A1.13.4 Assessment of feasibility of potential alternatives

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability 1,1,2-trichloro- 1 This is a proven Loading: In the Environmental 1,1,2-trichloro- 1,2,2- method of initial stage neat hazard: 1,1,2- 1,2,2- trifluoroethane production that 1,1,2-trichloro- trichloro-1,2,2- trifluoroethane and 1,1,- can be used to 1,2,2- trifluoroethane and 1,1,- dichloro-1,2,2,2- produced HFC- trifluoroethane is not classified dichloro-1,2,2,2- tetrafluoroethan 134a undergoes under CLP; tetrafluoroethan e isomerisation/hy however, it has e are not dro-fluorination been suggested by the by registrants as application of being toxic to hydrogen aquatic life with registered under fluoride long lasting REACH effects (H411) Price: Unclear, it and being Hydrogen costs around hazardous to the fluoride is €455 for 2.5 litres ozone layer registered at of analytical (EUH059) 100,000 – grade 1,1,2- 1,000,000 trichloro-1,2,2- 1,1,-dichloro- tonnes per trifluoroethane, 1,2,2,2- annum hydrogen tetrafluoroethan fluoride costs e is not classified around €595-760 under CLP; however, it has been suggested by registrants as being hazardous to the ozone layer (EUH059)

Both 1,1,2- trichloro-1,2,2- trifluoroethane and 1,1,- dichloro-1,2,2,2- tetrafluoroethan e persistent substances

Hydrogen fluoride is not classified for the environment and it is not a PBT substance

Human health hazard: 1,1,2- trichloro-1,2,2- trifluoroethane is not classified under CLP; however, it has been suggested by registrants as causing serious eye irritation (H319) and harms public health (and the environment) by destroying ozone in the upper atmosphere (H420)

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability 1,1,-dichloro- 1,2,2,2- tetrafluoroethan e is not classified under CLP; however, it has been suggested by registrants as being harmful to public health (and the environment) by destroying ozone in the upper atmosphere (H420) and being a gas contained under pressure that may explode if heated (H280)

Hydrogen fluoride is classified as fatal if swallowed (H300), is fatal in contact with skin (H310), is fatal if inhaled (H330) and causes severe skin burns and eye damage (H314) Tetrachloroethyl 1 This is a proven Loading: In the Environmental Tetrachloroethyl ene and 1- method of initial stage, neat hazard: ene is registered chloro-1,2,2,2- production that tetrachloroethyle Tetrachloroethyl at 100,000 – tetrafluoroethan can be used to ne undergoes ene is classified 1,000,000 e produce HFC- hydro- as a substance tonnes per 134a fluorination by that is toxic to annum the application of aquatic life with hydrogen long lasting 1-chloro-1,2,2,2- fluoride effects (H411); tetrafluoroethan however, it not e is not Price: it costs classified as a registered under around €760 per PBT substance – REACH tonne of it meets the tetrachloroethyle criteria of being Hydrogen ne, hydrogen persistent but fluoride is fluoride costs not the criteria registered at around €595-760 of being 100,000 – 1,000,000 bioaccumulative tonnes per or toxic annum

1-chloro-1,2,2,2- tetrafluoroethan e is not classified under CLP; however, it has been suggested by registrants as being hazardous to the ozone layer (EUH059)

Hydrogen fluoride is not classified for the environment and it is not a PBT substance

Human health hazard: Tetrachloroethyl ene is classified as suspected of causing cancer (Carc. Cat. 2) (H351)

1-chloro-1,2,2,2- tetrafluoroethan e is not classified under CLP; however, it has been suggested by registrants as being harmful to public health (and the environment) by destroying ozone in the upper atmosphere (H420) and being a gas contained under pressure that may explode if heated (H280)

Hydrogen fluoride is classified as fatal if swallowed (H300), is fatal in contact with skin

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability (H310), is fatal if inhaled (H330) and causes severe skin burns and eye damage (H314)

Tetrachloroethyl ene is a CoRAP substance but the evalution concluded that no further regulatory action was required Methylene 2, 3 Methylene Loading: Environmental Registered at chloride chloride shares Depending the hazard: 100,000 – similar precise Methylene 1,000,000 properties with applications of chloride does tonnes per trichloroethylen the adhesive the not have any annum e, it is a volatile content of environmental liquid, miscible trichloroethylene classification and in organic will vary it is not a PBT solvents and can (generally 10- substance be used as a 40%), it is solvent. It is also anticipated that Human health already used similar levels of hazard: within aerosol alternative Methylene sprays as a substances chloride is propellant would be classified as required causing cancer Trials suggest (Carc. Cat. 2.) that it may be Price: The price is (H351). suitable for around €340 per Although not vapour tonne which is classified, degreasing and slightly cheaper registrants have separators used than also suggested in lead-acid trichloroethylene that the batteries substance causes serious eye irritation (H319), causes skin irritation (H315) and may cause drowsiness or dizziness (H336)

Methylene chloride is subject to REACH restrictions (paint strippers), it is PACT listed

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability under evaluation for potential endocrine disruption and it is a CoRAP substance due to its concern as carcinogenic, suspected mutagenic, suspected reprotoxic, potential endocrine disruptor, suspected sensitiser and high (aggregated) tonnage Acetone 2, 3 Acetone shares Loading: Environmental Registered at similar Depending the hazard: Acetone 1,000,000 – properties with precise does not have 10,000,000 trichloroethylen applications of any tonnes per e, it is a volatile the adhesive the environmental annum liquid, miscible content of classification and in water and trichloroethylene it is not a PBT organic solvents will vary substance and can be used (generally 10- as a solvent. It is 40%), it is Human health also already anticipated that hazard: Acetone used within similar levels of is classified as adhesives, alternative being a highly sealants, substances flammable liquid coatings and would be and vapour paints, is it also required (H225), causes used with serious eye aerosol Price: The price is irritation (H319) adhesives around €850 per and may cause tonne which is drowsiness or Trials suggest around double dizziness (H336) that it may not the price of be suitable for trichloroethylene separators used in lead-acid batteries. It does not seem to perform the function of removing process oil effectively and this would suggest that it

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability would be unsuitable for this application Acetone/heptan 2 For acetone see Loading: Environmental Acetone is e blends above. Heptane Depending the hazard: Acetone registered at is a volatile precise does not have 1,000,000 – liquid, it is applications of any 10,000,000 insoluble in the adhesive the environmental tonnes per water and can be content of classification and annum used as a trichloroethylene it is not a PBT solvent. It is also will vary substance Heptane is already used (generally 10- registered at within 40%), it is Heptane is 1,000 tonnes per adhesives, anticipated that classified as very annum sealants, similar levels of toxic to aquatic coatings and alternative life (H400) and is paints substances very toxic to would be aquatic life with required long lasting effects (H410), Price: The price however, it is not for heptane is a PBT substance >€850 per tonne which is around Human health double the price hazard: Acetone of is classified as trichloroethylene being a highly , acetone is also flammable liquid around €850 per and vapour tonne (H225), causes serious eye irritation (H319) and may cause drowsiness or dizziness (H336)

Heptane is classified as being a highly flammable liquid and vapour (H225), may be fatal if swallowed and enters airways (H304), causes skin irritation (H315) and may cause drowsiness or dizziness (H336) Ethyl Acetate 2 Ethyl Acetate is a Loading: The Environmental Registered at flammable loading of the hazard: Ethyl 100,000 – solvent, it’s solvent may be Acetate is not a 1,000,000

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability technical restricted, PBT substance tonnes per feasibility has continuous or and it does not annum not be proven batch processing have any may not be environmental suitable due to classifications the explosive and fire risks Human health hazard: Ethyl Price: Ethyl Acetate is Acetate is widely classified as available and being highly reasonably cheap flammable liquid at around €595 – and vapour 765 per tonne. (H225), causes However, serious eye investment costs irritation (H319) will be high, and may cause especially drowsiness or compared to dizziness (H336) non-flammable solvents

N-propyl 2, 3 N-propyl Loading: Environmental Registered at bromide bromide is a Depending the hazard: 1,000 – 10,000 volatile liquid precise N-propyl tonnes per and it is slightly applications of bromide does annum soluble in water. the adhesive the not have any It has been used content of environmental as both a liquid trichloroethylene classification and and gases will vary it is not a PBT solvent, (generally 10- substance. including as a 40%), it is However, it solvent for anticipated that appears to fulfil adhesives and similar levels of the criteria of glues alternative being toxic, it substances does not appear Trials suggest would be to be readily that it may be required, the biodegradable suitable for loading required (data suggests vapour for degreasing is inherently degreasing and unclear – it might biodegradable) separators used be equal to or but it does not in lead-acid higher than appear to be batteries trichloroethylene bioaccumulative

Price: The price Human health for N-propyl hazard: N-propyl bromide is bromide is around >€1695 classified as a per tonne which substance that is around double may damage the price of fertility and may trichloroethylene damage the unborn child (H360FD), is a highly flammable liquid and vapour (H225), causes serious eye irritation (H319), may cause damage to organs through prolonged or repeated exposure (H373), causes skin irritation (H315), may cause respiratory irritation (H335) and may cause drowsiness or dizziness (H336)

N-propyl bromide has also been identified

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability as a Substance of Very High Concern (SVHC) and it has been added to the Authorisation list. This makes it an unsuitable alternative substance

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability Petroleum 2 Petroleum Loading: Environmental Various substances (e.g. substances are Depending the hazard: petroleum mineral spirits, volatile liquid precise Petroleum substances are petroleum and it is slightly applications of substances are REACH solvents, soluble in water. the adhesive the likely to be registered petroleum It has been used content of considered as distillates and as both a liquid trichloroethylene toxic to aquatic VM&P and gases will vary life with long naphtha’s) solvent, (generally 10- lasting effects including as a 40%), it is (H411), in some solvent for anticipated that cases they might adhesives and similar levels of be considered as glues alternative toxic and substances bioaccumulative would be but (generally) required their rapid biodegradation Price: Various will mean that they are not considered as PBT substances

Human health hazard: Petroleum substances will be substances that are excepted as potentially cancer causing (Carc. Cat. 2.) (H351). They are also likely to be extremely flammable liquid and vapour (H224) and may causes skin irritation (H315) and may cause drowsiness or dizziness (H336)

Some petroleum fractions may be PACT listed due to their CMR properties

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability Tetrachloroethyl 2 Tetrachloroethyl Loading: it is Environmental Tetrachloroethyl ene ene is a non- anticipated that hazard: ene is registered flammable similar levels of Tetrachloroethyl at 100,000 – solvent with alternative ene is classified 1,000,000 physical substances as a substance tonnes per properties close would be that is toxic to annum to those of required aquatic life with trichloroethylen long lasting e Price: it costs effects (H411); around €760 per however, it not tonne of classified as a tetrachloroethyle PBT substance – ne, however, it meets the invest would be criteria of being required, there persistent but may be higher not the criteria operational costs of being and bioaccumulative tetrachloroethyle or toxic ne is also subject to regulatory Human health review hazard: Tetrachloroethyl ene is classified as suspected of causing cancer (Carc. Cat. 2) (H351)

Tetrachloroethyl ene is a CoRAP substance but the evalution concluded that no further regulatory action was required Mechanical 2 Although this Loading: N/A Environmental N/A rubbing and method will hazard: N/A high-pressure offer some Price: N/A water spray cleaning Human health potential, it may hazard: N/A not be technically feasible to remove some dirt and grease.

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability Ultrasonic 2 Although this Loading: N/A Environmental N/A removal method will hazard: N/A offer some Price: N/A cleaning Human health potential, it may hazard: N/A not be technically feasible to remove some dirt and grease. 1,2-Trans- 3 1,2-Trans- Loading: Environmental Registered at Dichloroethylen Dichloroethylen Between 60-90% hazard: 1,2- 100 – 1,000 e e is a clear of a product Trans- tonnes per colorless liquid would contain Dichloroethylen annum with ether-like 1,2-Trans- e is classified as odor, it has a low Dichloroethylene harmful to flash point (2.2- aquatic life with 3.9°C), it is Price: Unclear, long lasting denser than analytical grade effects (H412). water and sold by Sigma The substance is insoluble in Aldrich costs not a PBT water. Vapours €310 for 100 substance are heavier than grams, other air estimates Human health suggest a cost of hazard: 1,2- Based on trials it around €3.8 per Trans- may be possible kilogram. The Dichloroethylen to use 1,2-trans- costs are likely to e is classified as a dichloroethylene be considerable highly as an alternative. more than flammable liquid However, it is trichloroethylene and vapour slower than (H225), and is extracting There may be harmful if residual oil than other economic inhaled (H332) trichloroethylen problems, e and recovery switching to 1,2- could be Trans- problematic Dichloroethylene might require changes to operations and the hazard profile (highly flammable) may require additional considerations and costs

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability n-Hexane 3 Based on trials it Loading: The Environmental Registered at may be possible amount required hazard: n- 1,000 – 10,000 to use n-Hexane might be Hexane is tonnes per as an alternative, comparable to classified as toxic annum n-Hexane is level of to aquatic life faster at trichloroethylene with long lasting extracting , as n-Hexane is effects (H411). residual oil than faster at The substance is trichloroethylen extracting not considered e. However, residual oil than as a PBT there may be trichloroethylene substance some difficulties perhaps lower due to loadings may be Human health substances high required hazard: n- volatility Hexane is Price: The price classified as fatal for n-Hexane is if swallowed and around €1270 enters airways per tonne which (H304), is a is around 50% highly more than the flammable liquid price of and vapour trichloroethylene (H225), is suspected of There may be damaging other economic fertility (H361F), problems, may cause switching to n- damage to Hexane might organs through require changes prolonged or to the processing repeated plant and the exposure hazard profile (H373), causes (highly skin irritation flammable) may (H315) and may require cause additional drowsiness or considerations dizziness (H336) and costs n-Hexane is a CoRAP substance based on concerning about its CMR properties, other hazard based concerns, high (aggregated) tonnage and its wide dispersive use

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability D-Limonene 3 Based on trials, it Loading: The Environmental Registered at may be possible amount required hazard: D- 1,000 – 10,000 to use D-might be Limonene is tonnes per Limonene as an comparable to classified as very annum alternative. level of toxic to aquatic However, it is trichloroethylene life (H400) and is slower at , however as D- very toxic to extracting Limonene is aquatic life with residual oil than slower at long lasting trichloroethylen extracting effects (H410). e and there may residual oil than D-Limonene is be problems trichloroethylene not a PBT with solvent perhaps longer substance recovery and durations (or recycling higher loadings) Human health are required hazard: D- Limonene is Price: The price classified as a for D-Limonene is flammable liquid around €2965- and vapour 3390 per tonne (H226), causes which is around skin irritation four times as (H315) and may expensive than cause an allergic the price of skin reaction trichloroethylene (H317)

There might also be larger energy costs associated with the use of D- Limonene and large parts of the production process and equipment might need replacing Methyl ethyl 3 Methyl ethyl Loading: The Environmental Registered at ketone (MEK) ketone is an amount required hazard: Methyl 100,000 – alternative might be ethyl ketone 1,000,000 solvent that may comparable to bromide does tonnes per be an alternative level of not have any annum due to its higher trichloroethylene environmental degree of classifications solvency to Price: A 55 (US) and it is not a process oil than gallon drum of PBT substance some other methyl ethyl stubstances. ketone costs Human health However, due to around €420 (1 hazard: Methyl its flammability US gallon is the ethyl ketone is a there may be equivalent to highly additional around 3.79 flammable liquid problems and litres) and vapour costs of using (H225), it causes

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability methyl ethyl serious eye ketone irritation (H319) and may cause drowsiness or dizziness (H336)

Methyl ethyl ketone is a CoRAP substance based on the grounds of concern that it is a suspected reprotoxic substance, it has wide dispersive use, consumer use, exposure of environment, exposure of workers, high RCR, high (aggregated) tonnage and it is a potential endocrine disruptor Iso-propyl 3 Isopropyl alcohol Loading: The Environmental Registered at alcohol (IPA) is an alternative amount required hazard: Iso- 100,000 – solvent, it is might be propyl alcohol 1,000,000 capable of comparable to does not have tonnes per dissolving many level of any annum oils trichloroethylene environmental classifications Price: Isopropyl and is not a PBT alcohol costs substance around €995 euro a tonne, this Human health is slightly higher hazard: than the cost of Isopropyl alcohol trichloroethylene is classified as being a highly flammable liquid and vapour (H225), it causes serious eye irritation (H319) and may cause drowsiness or dizziness (H336)

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability Toluene 3 Toluene has the Loading: As Environmental Registered at ability to toluene is less hazard: Toluene 1,000,000 – partition organic effective at does not have 10,000,000 compounds extracting some any tonnes per which has led to substances that environmental annum it widely being trichloroethylene classifications used as a solvent (e.g. and is not a PBT in industrial caprolactam) the substance extraction loading will need processes. to be larger Human health However, hazard: Toluene toluene is only Price: The price is classified as able to extract of toluene being a about a third of fluctuates based substance that the levels of on petrol may be fatal if caprolactam that demand and swallowed and trichloroethylen other global enters airways e is able to economic (H304), is a extract. Toluene factors, however, highly will also need a the price is flammable liquid longer time for around €425 – and vapour separation than 510 per tonne, (H225), is trichloroethylen lower that the suspected of e cost of damaging the trichloroethylene unborn child (H361d), may Lower extractive cause damage to recovery will organs through require higher prolonged or loadings and repeated higher capital exposure expenditure and (H373), causes operational costs skin irritation (H315) and may cause drowsiness or dizziness (H336)

Toluene has been subject to a CoRAP decision, PACT listing and it is subject to restrictions in adhesives and spray paints intended for supply to the general public

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability Benzene 3 Benzene has the Loading: The Environmental Registered at ability to amount required hazard: Benzene 1,000,000 – partition organic might be does not have 10,000,000 compounds comparable to any tonnes per which has led to level of environmental annum and it widely being trichloroethylene classifications registered as an used as a solvent under CLP; intermediate in industrial Price: The price however, it has extraction of benzene is been suggested processes. around €510 – by registrants as Benzene has a 675 per tonne being harmful to similar capacity aquatic life with to long lasting trichloroethylen effects (H412) e for the extraction of Human health caprolactam hazard: Benzene from is classified as caprolactam oil being a substance that may be fatal if swallowed and enters airways (H304), may cause genetic defects (H340) (Muta. Cat. 1B), may cause cancer (H350) (Car. Cat. 1A), causes damage to organs through prolonged or repeated exposure (H372), is a highly flammable liquid and vapour (H225), causes serious eye irritation (H319) and causes skin irritation (H315)

Benzene is subject to REACH restrictions and PIC. Heptane and 3 Research (as Loading: The Environmental Heptane is heptanol indicated in the amount required hazard: Heptane registered at mixture SEA for might be is classified as Trichloroethylen comparable to being very toxic

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability e) has been level of to aquatic life >1,000 tonnes conducted by trichloroethylene (H400) and is per annum Müller (2013) very toxic to and van Delden Price: Unclear. aquatic life with Heptanol is (2006) in However, there long lasting registered at heptane and will be additional effects (H410), 1,000 – 10,000 heptanol costs associated however it is not tonnes per mixtures for with the handling a PBT substance annum caprolactam (unloading, extraction. They storing and Heptanol does identified that a mixing) of the not have any 40% w/w two solvents. environmental mixture of 1- There will also be classifications heptanol in n- some capital under CLP and it heptane costs is not a PBT provides the substance optimal properties. The Human health mixture was hazard: Heptane shown to is classified as perform well in being a comparison with substance that TCE. However, may be fatal if the process has swallowed and only been shown enters airways to work at (H304), is a laboratory level highly and so far, it is flammable liquid untested at and vapour larger industrial (H225), causes scales skin irritation (H315) and may cause drowsiness or dizziness (H336)

Heptanol is not classified under CLP; however, it has been suggested by registrants as causing serious eye irritation (H319) Cyclohexane 3 Some of the Loading: The Environmental Registered at properties of amount required hazard: 1,000,000 – cyclohexane might be Cyclohexane is 10,000,000 would make it a comparable to not a PBT tonnes per suitable level of substance but it annum alternative, trichloroethylene is classified as solubility of being very toxic polystyrene at Price: The price to aquatic life <40°C and it has of cyclohexane is (H400) and very

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability an appropriate >€750 – 950 per toxic to aquatic boiling point. tonne life with long However, the lasting effects substance might (H410) not be suitable due to it being Human health flammable hazard: Cyclohexane is classified as being highly flammable liquid and vapour (H225), causes skin irritation (H315), may be fatal if swallowed and enters airways (H304) and may cause drowsiness or dizziness Ethanol 3 Some of the Loading: The Environmental Registered at properties of amount required hazard: Ethanol 1,000,000 – ethanol would might be is not a PBT 10,000,000 make it a comparable to substance and it tonnes per suitable level of does not have annum alternative, it is trichloroethylene any chemical environmental resistant to Price: The price classifications polyethylene of ethanol is terephthalate, >€850 per tonne Human health and it has an hazard: Ethanol appropriate is classified as boiling point. being a However, the flammable liquid substance might (H225), the not be suitable classification due to it not provided by having solubility companies to of polystyrene at ECHA in REACH <40°C and its registrations flammability identifies that this substance is toxic if swallowed (H301), is toxic in contact with skin (H311), is toxic if inhaled (H331), causes damage to organs (H372), causes serious eye

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability damage (H318) and causes skin irritation (H315) Methanol 3 Some of the Loading: The Environmental Registered at properties of amount required hazard: 10,000,000 – methanol would might be Methanol is not 100,000,000 make it a comparable to a PBT substance tonnes per suitable level of and it does not annum alternative, for trichloroethylene have any example it has environmental an appropriate Price: The price classifications boiling point. of methanol is However, the around €410 per Human health substance might tonne hazard: not be suitable Methanol is due to it not classified as having solubility being a of polystyrene at flammable liquid <40°C and its (H225), it is toxic flammability if swallowed (H301), is toxic in contact with skin (H311), is toxic if inhaled (H331) and it also causes damage to organs (H370) Pentane 3 Although some Loading: The Environmental Registered at of the properties amount required hazard: Pentane 100,000 – of pentane may might be is not a PBT 1,000,000 make it suitable, comparable to substance but it tonnes per it is unlikely to be level of is classified as annum suitable due to it trichloroethylene being toxic to not having aquatic life with solubility of Price: The price long lasting polystyrene at of pentane is effects (H411) <40°C, its boiling around €1000 – point and its 1500 per tonne Human health flammability hazard: Pentane is classified as being a flammable liquid (H225), it may be fatal if swallowed and enters airways (H304) and it may cause drowsiness or dizziness (H336) Diethyl ether 3 Some of the Loading: The Environmental Registered at properties of amount required hazard: Diethyl 1,000 – 10,000 diethyl ether might be ether is not a tonnes per would make it a comparable to PBT substance annum

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability suitable level of and it does not alternative, for trichloroethylene have any example it is environmental resistant to Price: The price classifications polyethylene per tonne is terephthalate, unclear Human health however, the hazard: Diethyl substance might ether is classified not be suitable as being a due to it not flammable liquid having solubility (H224), harmful of polystyrene at if swallowed <40°C, its boiling (H302) and may point and its cause flammability drowsiness or dizziness (H336)

Diethyl ether is also a CoRAP substance on the initial grounds for concern of being a suspected carcinogenic, suspected mutagenic, suspected reprotoxic, other hazard based concern, consumer use, exposure of environment, high (aggregated) tonnage and its wide dispersive use Ethylbenzene 3 Some of the Loading: The Environmental Registered at properties of amount required hazard: 1,000,000 – ethylbenzene might be Ethylbenzene is 10,000,000 would make it a comparable to not a PBT tonnes per suitable level of substance and it annum alternative, for trichloroethylene does not have example its any solubility of Price: The price environmental polystyrene at of ethylbenzene classifications <40°C. However, is around €1750 – the substance 2350 per tonne Human health might not be hazard: suitable due to it Ethylbenzene is not being classified as resistant to being a

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability polyethylene flammable liquid terephthalate, (H225), harmful its boiling point if inhaled (H332), and it being may be fatal if flammable swallowed and enters airways (H304) and may cause damage to organs through prolonged or repeated exposure (H373) Chloroform 3 Some of the Loading: The Environmental Registered at properties of amount required hazard: 100,000 – chloroform might be Chloroform is 1,000,000 would make it a comparable to not a PBT tonnes per suitable level of substance and it annum alternative, for trichloroethylene does not have example its any solubility of Price: The price environmental polystyrene at of chloroform is classifications <40°C, its boiling around €330 – point and it is 585 per tonne Human health not flammable. hazard: However, the Chloroform is substance is not classified as resistant to being harmful if polyethylene swallowed terephthalate (H302), causes skin irritation (H315), causes serious eye irritation (H319), is toxic if inhaled (H331) is suspected of causing cancer (H351 – Carc. Cat. 2), is suspected of damaging the unborn (H361d – Repr. Cat. 2) and causes dame to organs through prolonged or repeated exposure (H372) Carbon 3 A number of the Loading: The Environmental Registered at tetrachloride properties of amount required hazard: Carbon 1,000 – 10,000 carbon might be tetrachloride is tonnes per tetrachloride comparable to not a PBT annum would make it a substance but it suitable is classified as

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability alternative, for level of being harmful to example its trichloroethylene aquatic life with solubility of long lasting polystyrene at Price: The price effects (H412) <40°C, it is per tonne is and harms public resistant to unclear health and the polyethylene environment by terephthalate, it destroying has a suitable ozone in the boiling point and upper it is not atmosphere flammable. (Ozone 1) However, the substance has a Human health more hazardous hazard: Carbon profile than tetrachloride is other substances classified as being toxic is swallowed (H301), is toxic in contact with skin (H311), is toxic if inhaled (H331), is suspected of causing cancer (H351 – Carc. Cat. 2), causes damage to organs through prolonged or repeated exposure (H372) and harms public health and the environment by destroying ozone in the upper atmosphere (Ozone 1)

Carbon tetrachloride is a CoRAP substance on the initial grounds for concern due to its CMR properties, exposure of workers and its high (aggregated) tonnage

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability 1,2- 3 A number of the Loading: The Environmental Registered at dichlorobenzene properties of amount required hazard: 1,2- 10,000 – 1,2- might be dichlorobenzene 100,000 tonnes dichlorobenzene comparable to is not a PBT per annum (and similar level of substance but it substances, e.g. trichloroethylene is classified as 1,3- very toxic to dichlorobenzene Price: The price aquatic life and 1,4- of 1,2- (H400) and very dichlorobenzene dichlorobenzene toxic to aquatic ) might make it is around €915 – life with long suitable, but the 1200 per tonne lasting effects boiling points (H410) are considered to be too high Human health and this would hazard: 1,2- involve dichlorobenzene investment or is classified as prolong being harmful if separation times swallowed which may lead (H302), causes to the skin irritation decomposition (H315), causes of the desired serious eye substance irritation (H319) and may cause respiratory irritation (H335)

1,2- dichlorobenzene is also a CoRAP substance on the initial grounds for concern of having high (aggregated) tonnage, being a suspected CMR substance and its wide dispersive use 1,1,2- 3 A number of the Loading: The Environmental Registered as an trichloroethane properties of amount required hazard: 1,1,2- intermediate 1,1,2- might be trichloroethane only trichloroethane comparable to is not a PBT (and similar level of substance and it substances, e.g. trichloroethylene does not have dichloromethan any e and Price: The price environmental trichloromethan per tonne is classifications e) might make it unclear suitable. Human health However, it is hazard: 1,1,2-

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability suggested that trichloroethane the water is classified as solubility might being harmful if be too high and swallowed it has CMR (H302), harmful properties. in contact with skin (H312), harmful if inhaled (H332) and is suspected of causing cancer (H351 – Carc. Cat. 2) 1,4-dioxane 3 The properties Loading: The Environmental Registered at of 1,4-dioxane amount required hazard: 1,4- 1,000+ tonnes (and similar might be dioxane is not a per annum oxygen based comparable to PBT substance flammable level of and it does not substances) trichloroethylene have any might make it environmental suitable, for Price: The price classifications example, having per tonne is a low boiling around €1250 – Human health point, however 1900 per tonne hazard: 1,4- the flammability dioxane is might make classified as these types of being a highly substance flammable liquid unsuitable and vapour (H225), causing serious eye irritation (H319), may cause respiratory irritation (H335) and is suspected of causing cancer (H351 – Carc. Cat. 2) 1,2- 3 The properties Loading: The Environmental Registered at dichloroethane of 1,2- amount required hazard: 1,2- 1,000,000 – dichloroethane might be dichloroethane 10,000,000 might make it comparable to is not a PBT tonnes per suitable, for level of substance and it annum example it has a trichloroethylene does not have suitable boiling any point but it has Price: The price environmental CMR properties per tonne is classifications and is flammable unclear Human health hazard: 1,2- dichloroethane is classified as being a highly

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability flammable liquid and vapour (H225), is harmful if swallowed (H302), causes skin irritation (H315), causing serious eye irritation (H319), may cause respiratory irritation (H335) and may cause cancer (H350 – Carc. Cat. 1B)

1,2- dichloroethane is a SVHC due to its cancer causing potential 60% 1-octanol in 3 The properties Loading: The Environmental Cyclohexane is cyclohexane of a 60% 1- amount required hazard: registered at octanol in might be Cyclohexane is 1,000,000 – cyclohexane comparable to not a PBT 10,000,000 mixture might level of substance but it tonnes per make it suitable trichloroethylene is classified as annum for applications being very toxic but it appears to Price: The price to aquatic life 1-octanol is be commercially of cyclohexane is (H400) and very registered at unproven €750 – 950 per toxic to aquatic 10,000 – tonne life with long 100,000 tonnes lasting effects per annum The price of 1- (H410) octanol is around €2500 – 3300 per 1-Octanol is not tonne a PBT substance and it currently does not have any environmental classification, however notifiers indicate that the substance is harmful to aquatic life with long lasting effects (H412)

Human health hazard:

Table 9-52: Assessment of potential alternatives for trichloroethylene Alternative Applicati Technical Economic Hazard Market on feasibility feasibility comparison availability Cyclohexane is classified as being highly flammable liquid and vapour (H225), causes skin irritation (H315), may be fatal if swallowed and enters airways (H304) and may cause drowsiness or dizziness

1-Octanol currently does not have any hazardous classifications, however notifiers indicate that the substance causes serious eye irritation (H319), is harmful if swallowed (H302) and is harmful in contact with skin (H312) Sources: ECHA website; Socio-economic analysis of Trichloroethylene, https://echa.europa.eu/documents/10162/8cea6e84-03b6-41ca-adf3-7d9217c020ea (Accessed 3 August 2017) ECETOC, http://www.ecetoc.org/wp-content/uploads/2014/08/JACC-050.pdf (Accessed 7 August 2017) ECHA website, https://echa.europa.eu/documents/10162/18584504/afa_tce-0020-01-aa_en.pdf (Accessed 7 August 2017) ECHA website https://echa.europa.eu/documents/10162/9a728963-e57f-48de-b977-7d05462c43e9 (Accessed 1 August 2017) ECHA website for substance classifications, https://echa.europa.eu/ ECHA website https://echa.europa.eu/addressing-chemicals-of-concern/authorisation/applications-for- authorisation-previous-consultations (Accessed 13 September 2017)

A1.14 Substance 14: Tetrachloroethylene

A1.14.1 Identity of the substance

Table 9-53: Identity of tetrachloroethylene Name of substance Tetrachloroethylene Synonyms tetrachloroethene, perchloroethylene, 1,1,2,2-tetrachloroethylene, and ethylene tetrachloride EC Number 204-825-9 CAS Number 127-18-4 Molecular formula C2Cl4

REACH Registration 100,000 – 1,000,000 tonnes per annum tonnage band Sources: ECHA website, https://echa.europa.eu/substance-information/-/substanceinfo/100.004.388 (accessed on 21 July 2017)

A1.14.2 Functionality and applications

Table 9-54: Functionality and applications for tetrachloroethylene General description of Tetrachloroethylene is a liquid it is volatile, stable, non-flammable and it is functionality and key insoluble in water. It physical and chemical properties mean that it is used as a physico-chemical solvent for organic materials. parameters Tetrachloroethylene is classified as being toxic to aquatic life with long lasting effects (H411) and is suspected of causing cancer (H351) (Carc. Cat. 2).

Registrants also indicate that it causes serious eye irritation (H319), causes skin irritation (H315), may cause an allergic skin reaction (H317) and may cause drowsiness or dizziness (H336).

Tetrachloroethylene was a CoRAP substance due to its CMR properties, it high (aggregated) tonnage, it being a suspected PBT/vPvB substances and its wide dispersive use. However, the it was concluded that there was no need for regulatory follow-up action. Family the substance Chlorocarbons belongs to Application 1 Solvent Sector of Use SU 8: Manufacture of bulk, large scale chemicals (used for cleaning (including petroleum products) applications) SU 9: Manufacture of fine chemicals Product category PC 35: Washing and cleaning products Industrial/Professional/ Industrial: Industrial surface cleaner and dry Consumer cleaning Professional: Used in dry cleaning Description Tetrachloroethylene is widely used in dry cleaning, it is also used in degreasing of metal parts.

Table 9-54: Functionality and applications for tetrachloroethylene Sources: ECHA website, https://echa.europa.eu/registration-dossier/-/registered-dossier/14303 (accessed on 21 July 2017)

A1.14.3 Potential alternatives

Table 9-55: Identification of potential alternatives for tetrachloroethylene Application 1 Solvent used in cleaning applications (surface cleaning and dry cleaning) Name/description of Alternative substances: alternative - N-propyl bromide - Methylene chloride - 1,2-Trans-Dichloroethylene - n-Hexane - D-Limonene - Acetone - Methyl ethyl ketone (MEK) - Iso-propyl alcohol (IPA) - Dipropylene glycol n-butyl ether (DPnB) - Dipropylene glycol tert-butyl ether (DPtB) Identifiers (if chemical Substance name EC Number CAS Number substance) N-propyl bromide 203-445-0 106-94-5 Methylene chloride 200-838-9 75-09-2 1,2-Trans- 205-860-2 156-60-5 Dichloroethylene n-Hexane 203-777-6 110-54-3 D-Limonene 227-813-5 5989-27-5, 68606-81-5 Acetone 200-662-2 67-64-1 Methyl ethyl ketone 201-159-0 78-93-3 (MEK) Iso-propyl alcohol (IPA) 200-661-7 67-63-0 Dipropylene glycol n- 249-951-5 29911-28-2 butyl ether (DPnB) Dipropylene glycol tert- 683-624-1 132739-31-2 butyl ether (DPtB) Sources: Evaluation of Glycol Ether as an Alternative to Perchloroethylene in Dry Cleaning, Hesari N., et al, http://www.mdpi.com/2305-6304/2/2/115 (Accessed 3 August 2017) ECHA website, https://echa.europa.eu/documents/10162/18584504/afa_tce-0020-01-aa_en.pdf (Accessed 7 August 2017) ECHA Website https://echa.europa.eu/documents/10162/9a728963-e57f-48de-b977-7d05462c43e9 (Accessed 1 August 2017)

A1.14.4 Assessment of feasibility of potential alternatives

Table 9-56: Assessment of potential alternatives for tetrachloroethylene Alternative Applicatio Technical feasibility Economic feasibility Hazard Market n comparison availability N-propyl 1 N-propyl bromide is Loading: Environmental Registered bromide a volatile liquid and Depending the hazard: at 1,000 – it is slightly soluble precise applications N-propyl 10,000 in water. It has of the adhesive the bromide does tonnes per been used as both a content of not have any annum liquid and gaseous tetrachloroethylen environmental solvent, including e will vary classification (generally 10-40%), and it is not a

Table 9-56: Assessment of potential alternatives for tetrachloroethylene Alternative Applicatio Technical feasibility Economic feasibility Hazard Market n comparison availability as a solvent for it is anticipated that PBT substance. adhesives and glues similar levels of However, it alternative appears to fulfil Trials suggest that it substances would the criteria of may be suitable for be required being toxic, it vapour degreasing does not appear and separators Price: The price for to be readily used in lead-acid N-propyl bromide is biodegradable batteries around >€1695 per (data suggests tonne which is inherently around double the biodegradable) price of but it does not tetrachloroethylen appear to be e bioaccumulative

Human health hazard: N- propyl bromide is classified as a substance that may damage fertility and may damage the unborn child (H360FD), is a highly flammable liquid and vapour (H225), causes serious eye irritation (H319), may cause damage to organs through prolonged or repeated exposure (H373), causes skin irritation (H315), may cause respiratory irritation (H335) and may cause drowsiness or dizziness (H336)

N-propyl bromide has also been identified as a Substance of Very High

Table 9-56: Assessment of potential alternatives for tetrachloroethylene Alternative Applicatio Technical feasibility Economic feasibility Hazard Market n comparison availability Concern (SVHC) and it has been added to the Authorisation list. This makes it an unsuitable alternative substance Methylene 1 Methylene chloride Loading: Environmental Registered chloride shares similar Depending the hazard: at 100,000 properties with precise applications Methylene – 1,000,000 tetrachloroethylen of the adhesive the chloride does tonnes per e, it is a volatile content of not have any annum liquid, miscible in tetrachloroethylen environmental organic solvents e will vary classification and can be used as (generally 10-40%), and it is not a a solvent. It is also it is anticipated that PBT substance already used within similar levels of aerosol sprays as a alternative Human health propellant substances would hazard: be required Methylene Trials suggest that it chloride is may be suitable for Price: The price is classified as vapour degreasing around €340 per causing cancer and separators tonne which is (Carc. Cat. 2.) used in lead-acid slightly cheaper (H351). batteries than Although not tetrachloroethylen classified, e registrants have also suggested that the substance causes serious eye irritation (H319), causes skin irritation (H315) and may cause drowsiness or dizziness (H336)

Methylene chloride is subject to REACH restrictions (paint strippers), it is PACT listed under evalutioan for potential endocrine disruption and it

Table 9-56: Assessment of potential alternatives for tetrachloroethylene Alternative Applicatio Technical feasibility Economic feasibility Hazard Market n comparison availability is a CoRAP substance due to its concern as carcinogenic, suspected mutagenic, suspected reprotoxic, potential endocrine disruptor, suspected sensitiser and high (aggregated) tonnage 1,2-Trans- 1 1,2-Trans- Loading: Between Environmental Registered Dichloroethylen Dichloroethylene is 60-90% of a hazard: 1,2- at 100 – e a clear colorless product would Trans- 1,000 liquid with ether- contain 1,2-Trans- Dichloroethylen tonnes per like odor, it has a Dichloroethylene e is classified as annum low flash point (2.2- harmful to 3.9 °C), it is denser Price: Unclear, aquatic life with than water and analytical grade long lasting insoluble in water. sold by Sigma effects (H412). Vapours are Aldrich costs €310 The substance is heavier than air for 100 grams, not a PBT other estimates substance Based on trials, it suggest a cost of may be possible to around €3.8 per Human health use 1,2-trans- kilogram. The costs hazard: 1,2- dichloroethylene as are likely to be Trans- an alternative. considerable more Dichloroethylen However, it is than e is classified as slower at extracting tetrachloroethylen a highly residual oil than e flammable tetrachloroethylen liquid and e and recovery There may be other vapour (H225), could be economic and is harmful if problematic problems, inhaled (H332) switching to 1,2- Trans- Dichloroethylene might require a complete change to operations and its hazard profile may require additional considerations and costs n-Hexane 1 Based on trials, it Loading: The Environmental Registered may be possible to amount required hazard: n- at 1,000 – use n-Hexane as an might be Hexane is 10,000 alternative, n- comparable to level classified as

Table 9-56: Assessment of potential alternatives for tetrachloroethylene Alternative Applicatio Technical feasibility Economic feasibility Hazard Market n comparison availability Hexane is faster at of toxic to aquatic tonnes per extracting residual tetrachloroethylen life with long annum oil than e, as n-Hexane is lasting effects tetrachloroethylen faster at extracting (H411). The e. However, there residual oil than substance is not may be some tetrachloroethylen considered as a difficulties due to e perhaps lower PBT substance substances high loadings might be volatility required Human health hazard: n- Price: The price for Hexane is n-Hexane is around classified as €1270 per tonne fatal if which is around swallowed and 50% more than the enters airways price of (H304), is a tetrachloroethylen highly e flammable liquid and There may be other vapour (H225), economic is suspected of problems, damaging switching to n- fertility (H361F), Hexane might may cause require a complete damage to change to the organs through processing plant prolonged or and the hazard repeated profile may require exposure additional (H373), causes considerations and skin irritation costs (H315) and may cause drowsiness or dizziness (H336)

n-Hexane is a CoRAP substance based on concerning about its CMR properties, other hazard based concerns, high (aggregated) tonnage and its wide dispersive use D-Limonene 1 Based on trials it Loading: The Environmental Registered may be possible to amount required hazard: D- at 1,000 – use D-Limonene as might be Limonene is 10,000 an alternative. comparable to level classified as tonnes per However, it is of being very toxic annum.

Table 9-56: Assessment of potential alternatives for tetrachloroethylene Alternative Applicatio Technical feasibility Economic feasibility Hazard Market n comparison availability slower at extracting trichloroethylene, to aquatic life residual oil than however as D- (H400) and is tetrachloroethylen Limonene is slower very toxic to e and there may be at extracting aquatic life with problems with residual oil than long lasting solvent recovery trichloroethylene effects (H410). and recycling perhaps longer D-Limonene is durations (or higher not a PBT loadings) are substance required Human health Price: The price for hazard: D- D-Limonene is Limonene is around €2965-3390 classified as a per tonne which is flammable around four times liquid and as expensive than vapour (H226), the price of causes skin tetrachloroethylen irritation (H315) e and may cause an allergic skin There might also be reaction (H317) larger energy costs associated with its potential us and large parts of the production process and equipment might need replacing Acetone 1 Acetone shares Loading: Environmental Registered similar properties Depending the hazard: Acetone at with precise applications does not have 1,000,000 – tetrachloroethylen of the adhesive the any 10,000,000 e, it is a volatile content of environmental tonnes per liquid, miscible in tetrachloroethylen classification annum water and organic e will vary and it is not a solvents and can be (generally 10-40%), PBT substance used as a solvent. It it is anticipated that is also already used similar levels of Human health within adhesives, alternative hazard: Acetone sealants, coatings substances would is classified as and paints, is it also be required. being a highly used with aerosol flammable adhesives Price: The price is liquid and around €850 per vapour (H225), tonne which is causes serious around double the eye irritation price of (H319) and may trichloroethylene cause drowsiness or dizziness (H336) Methyl ethyl 1 Methyl ethyl Loading: The Environmental Registered ketone (MEK) ketone is an amount required hazard: Methyl at 100,000

Table 9-56: Assessment of potential alternatives for tetrachloroethylene Alternative Applicatio Technical feasibility Economic feasibility Hazard Market n comparison availability alternative solvent might be ethyl ketone – 1,000,000 that may be an comparable to level bromide does tonnes per alternative due to of not have any annum its higher degree of tetrachloroethylen environmental solvency to process e classifications oil than some other and it is not a stubstances. Price: A 55 (US) PBT substance However, due its gallon drum of flammability there methyl ethyl Human health may be additionals ketone costs hazard: Methyl problems and costs around €420 (1 US ethyl ketone is of using methyl gallon is the classified as ethyl ketone equivalent to being a highly around 3.79 litres) flammable liquid and vapour (H225), it causes serious eye irritation (H319) and may cause drowsiness or dizziness (H336)

Methyl ethyl ketone is a CoRAP substance based on the grounds of concern that it is a suspected reprotoxic substance, it has wide dispersive use, consumer use, exposure of environment, exposure of workers, high RCR, high (aggregated) tonnage and it is a potential endocrine disruptor Iso-propyl 1 Isopropyl alcohol is Loading: The Environmental Registered alcohol (IPA) an alternative amount required hazard: Iso- at 100,000 solvent, it is might be propyl alcohol – 1,000,000 capable of comparable to level does not have tonnes per dissolving many oils of any annum tetrachloroethylen environmental e classifications and is not a PBT Price: Isopropyl substance alcohol costs

Table 9-56: Assessment of potential alternatives for tetrachloroethylene Alternative Applicatio Technical feasibility Economic feasibility Hazard Market n comparison availability around €995 euro a Human health tonne, this is hazard: slightly higher than Isopropyl the cost of alcohol is a trichloroethylene highly flammable liquid and vapour (H225), it causes serious eye irritation (H319) and may cause drowsiness or dizziness (H336) Dipropylene 1 Studies conducted Loading: Hesari et Environmental Dipropylen glycol n-butyl indicated that al (2014) suggest hazard: e glycol n- ether (DPnB) dipropylene glycol that short washer Dipropylene butyl ether n-butyl ether and cycles might be glycol n-butyl is not dipropylene glycol required with this ether does not registered tert-butyl ether alternative, a short presently have under both performed wash cycle would any REACH satisfactory as dry- correspond with environmental cleaning chemicals less chemical usage classifications in a range of tests and is not compared to Price: Unclear, expected to be tetrachloroethylen perhaps €1695- a PBT substance e 2540 per tonne. This would be more Human health than twice the cost hazard: of Dipropylene tetrachloroethylen glycol n-butyl e. ether is not classified under Analysis by Hesari CLP; however, it et al (2014) has been suggests that the suggested by operating costs of registrants as the dipropylene causing serious glycol n-butyl ether eye irritation and dipropylene (H319) glycol tert-butyl ether would be around 37% higher than that of tetrachloroethylen e. The risk proposed to employees might be lower Dipropylene 1 Studies conducted Loading: Hesari et Environmental Registered glycol tert-butyl indicated that al (2014) suggest hazard: at 10,000 – ether (DPtB) dipropylene glycol that short washer Dipropylene 100,000 n-butyl ether and cycles might be glycol tert-butyl tonnes per dipropylene glycol required with this ether does not annum

Table 9-56: Assessment of potential alternatives for tetrachloroethylene Alternative Applicatio Technical feasibility Economic feasibility Hazard Market n comparison availability tert-butyl ether alternative, a short presently have both performed wash cycle would any statisfactory as dry- correspond with environmental cleaning chemicals less chemical usage classification in a range of tests and is not a PBT compared to Price: Unclear substance tetrachloroethylen e Analysis by Hesari Human health et al (2014) hazard: suggests that the Dipropylene operating costs of glycol tert-butyl the dipropylene ether is not glycol n-butyl ether classified under and dipropylene CLP; however, it glycol tert-butyl has been ether would be suggested by around 37% higher registrants as than that of causing serious tetrachloroethylen eye irritation e. The risk (H319), causes proposed to skin irritation employees might (H315) and may be lower cause respiratory irritation (H335) Sources: ECHA website; Socio-economic analysis of Trichloroethylene, https://echa.europa.eu/documents/10162/8cea6e84-03b6-41ca-adf3-7d9217c020ea (Accessed 3 August 2017) ECHA website, https://echa.europa.eu/documents/10162/18584504/afa_tce-0020-01-aa_en.pdf (Accessed 7 August 2017) ECHA website https://echa.europa.eu/documents/10162/9a728963-e57f-48de-b977-7d05462c43e9 (Accessed 1 August 2017) Evaluation of Glycol Ether as an Alternative to Perchloroethylene in Dry Cleaning, Hesari N., et al, http://www.mdpi.com/2305-6304/2/2/115 (Accessed 3 August 2017) ECHA website for substance classifications, https://echa.europa.eu/