DRAFT ANALYSIS OF THE MOST APPROPRIATE RISK MANAGEMENT OPTION FOR NICKEL SULPHATE Substance name: Nickel sulphate EC number: 232-104-9 CAS number: 7786-81-4 Submitted by: FRANCE (Anses - French Mandated National Institute) Date: April 2014 This report is a non-confidential version that can be made publicly available. All data considered confidential by the registrants have been hidden. Table of contents 1 Background information ................................................................................... 4 1.1 Substance identity ..................................................................................... 4 1.2 Classification and labelling .......................................................................... 6 1.3 Information on the REACH registration status ............................................... 6 1.3.1 Registration status .............................................................................. 6 1.3.2 Registrants’ identity............................................................................. 7 1.4 Information on any previous risk assessment, risk reduction strategy and RMO analyses ........................................................................................................... 7 1.4.1 Previous risk assessment carried out under Council Regulation 793/93 ...... 7 1.4.2 Previous risk reduction strategy carried out under Council Regulation 793/93 10 1.4.3 Previous RMO analysis carried out on environment by Denmark ...............11 1.5 Current legal requirements for nickel and nickel compounds under REACH and other EU legislations ..........................................................................................12 1.5.1 EU general legislations on dangerous chemicals covering nickel compounds 12 1.5.2 EU workplace legislation regarding occupational health and safety............13 1.5.3 EU legislation regarding consumer protection .........................................13 1 1.5.4 EU legislation regarding protection of the environment and/or covering human health safety through environmental exposure ........................................14 1.5.5 Focus on current instruments setting occupational exposure limit values ...15 2 Uses, volumes, market picture and alternatives per main use ..............................18 2.1 Volumes manufactured and used in the EU ..................................................20 2.1.1 The data quality issue .........................................................................20 2.1.2 Estimated volumes .............................................................................20 2.2 Production of nickel sulphate .....................................................................22 2.3 Downstream uses of nickel sulphate ...........................................................22 2.3.1 Production of other nickel salts ............................................................23 2.3.2 Treatment of metal surfaces ................................................................24 2.3.3 Batteries manufacturing ......................................................................41 3 Risk assessment and objectives for further risk management ..............................53 3.1 Hazard identification .................................................................................53 3.2 Risk assessment based on the registration dossiers under REACH ..................53 3.3 Health hazard related to nickel sulphate ......................................................54 3.3.1 Toxicokinetics ....................................................................................54 3.3.2 Acute toxicity .....................................................................................56 3.3.3 Irritation ...........................................................................................56 3.3.4 Sensitisation ......................................................................................57 3.3.5 Repeated dose toxicity ........................................................................58 3.3.6 Mutagenicity ......................................................................................59 3.3.7 Carcinogenicity ..................................................................................60 3.3.8 Toxicity for reproduction .....................................................................64 3.4 Derivation of Reference Values ...................................................................66 3.4.1 Derivation of workers-DNEL .................................................................66 3.5 Exposure data and risk characterization ......................................................70 3.5.1 Data description .................................................................................70 3.5.2 Risk characterization per GES ..............................................................72 3.5.3 Overall conclusion on exposure assessment and risk characterization ..... 121 3.6 Need and objectives for further risk assessment and risk management ......... 123 3.6.1 Need for further risk assessment ........................................................ 123 3.6.2 Need for further risk management ...................................................... 123 2 4 Identification and assessment of current and further risk management options ... 124 4.1 Existing non-REACH legislations or recommendations ................................. 125 4.1.1 EU general legislations on hazardous chemicals ................................... 125 4.1.2 EU workplace legislation and recommendations regarding occupational health 125 4.2 Risk management measures under REACH ................................................ 132 4.2.1 REACH Annex XVII - Restriction ......................................................... 132 4.2.2 REACH Annex XIV - Authorisation...................................................... 156 5 Conclusions on the most appropriate (combination of) risk management option(s) 169 3 ANALYSIS OF THE MOST APPROPRIATE RISK MANAGEMENT OPTION FOR NICKEL SULPHATE Substance name: Nickel sulphate EC number: 232-104-9 CAS number: 7786-81-4 Submitted by: FRANCE (Anses - French Mandated National Institute) Date: April 2014 Nickel sulphate (NiSO ) belongs to the family of nickel compounds including nickel metal, 4 nickel salts, organometallic nickel substances, etc. More than a hundred are classified under the CLP Regulation. At least 26 nickel compounds are registered under REACH1, 16 as full dossiers (REACH Article 10), 8 as intermediate dossiers (REACH article 18) and 2 with both full and intermediate dossiers (see Appendix 1). Additional registrations can also be expected. From those 26 nickel compounds, 6 have been selected by the French Competent Authority, on the basis of Anses’s proposal, for further assessment (nickel sulphate, hydroxycarbonate, dichloride, dinitrate, bis(hydrogen)phosphate and monoxide). Substances registered only as intermediate have been excluded at this stage. In a first approach, risk management option analysis (RMOA) are carried out on NiSO 4 and nickel monoxide as both salts cover substantially the majority the uses reported for nickel compounds. The Nickel Institute groups nickel containing chemicals into five main classes: metallic nickel, nickel carbonyl, oxidic nickel (e.g. nickel oxides, hydroxide, silicates, carbonates, complex nickel oxides), sulfidic nickel (e.g. nickel sulfide, nickel subsulfide) and water- soluble nickel containing chemicals (e.g. nickel sulfate hexahydrate, nickel chloride hexahydrate). The group of “oxidic nickel” includes substances with a range of different water solubility, from chemicals of very low solubility (e.g. nickel oxide) to chemicals with a water solubility a hundred times greater (e.g. nickel hydroxide). Insoluble nickel containing chemicals include nickel oxide, nickel sulfide and nickel subsulfide. 1 BACKGROUND INFORMATION 1.1 Substance identity Nickel sulphate is one of the most soluble nickel compounds with the chloride, the nitrate and the sulphamate salts. 1 The ECHA database provides additional nickel containing compounds (reaction mass, NONs substances, pigments, leachates, etc.) that are not considered here. 4 Nickel sulphate (or Nickel (II) sulphate) is produced by dissolving nickel metal (or nickel oxide) in sulphuric acid. It is most widely used in its salt form but can also be available in solution. It is a highly soluble salt that is most commonly produced in hydrated (hexahydrate or heptahydrate) form with a blue-green colour. In its anhydrous form the salt is yellow in colour. Table 1: Substance identity2 Public Name Nickel sulphate EC number 232-104-9 EC name Nickel sulphate 7786-81-4 (anhydrous) CAS number (in the EC inventory) 10101-97-0 (hexahydrate) 10101-98-1 (heptahydrate) Nickel sulphate CAS name Nickel sulfate (solution) IUPAC name Nickel(+2)sulfate Index number in Annex VI of the CLP Regulation 028-009-00-5 Molecular formula Ni SO4 Molecular weight range 154.756 nickel monosulphate; nickelous sulphate; nickel sulphate (1:1); nickel (II) sulphate; nickel Synonyms (2+) sulphate; sulphuric acid, nickel (2+) salt (1:1) Structural formula: 2 The criteria for reporting for the EINECS Inventory states in Point 14:“Hydrates of a substance or hydrated ions, formed by association of a substance with water should not be reported. The anhydrous form can be reported and will, by implication, represent all hydrated forms.” The EINECS inventory therefore lists the CAS number for the anhydrous form (7786-81-4) together with the EINECS number (232-104-9) associated with this CAS number. As the rule quoted above indicates, this EINECS number represents by implication all hydrated forms. 5 1.2 Classification and labelling NiSO is currently classified under Annex VI of the CLP Regulation (EC No.1272/2008) as 4 follow. Table 2. Harmonized classification of NiSO in Annex VI of the CLP Regulation (EC 4 No.1272/2008) Index International EC No CAS No Classification Spec. Notes No Chemical Conc. Identification Limits, M-factors Hazard Class and Hazard Category Code(s) statement code(s) 028- Nickel sulphate Acute tox. 4 H302 Skin none 232-104-9 7786- 009- Sens. 1; 00-5 81-4 Skin Irrit. 2 H315 H317: C ≥ 0,01% Skin Sens. 1 H317 STOT RE Acute Tox. 4 H332 1; H373: C ≥ 1% Resp Sens. 1 H334 STOT RE Muta. 2 H341 2; H373: 0,1% ≤ Carc. 1A H350i C < 1% Repr. 1B H360D Skin Irrit. 2; H315: STOT RE 1 H372 C ≥ 20% Aquatic acute 1 H400 M=1 Aquatic chronic 1 H410 NiSO is not classified for any physical-chemical properties. 4 1.3 Information on the REACH registration status 1.3.1 Registration status NiSO is registered in accordance with Article 10 (i.e. full registration dossier) and also 4 with Article 18 (i.e. registration of transported isolated intermediates - TII). Twelve full dossiers and four TII dossiers are registered under REACH (last check dated December 2013). The risk management option analysis (RMOA) has been carried out on the last available update from the lead registrant, dated 31 July 2013. Nickel sulphate is registered with a public tonnage band of 10,000 to 100,000 tonnes per year. Volumes manufactured and used are provided in section 2. 6 1.3.2 Registrants’ identity Registrants and suppliers publically identified on ECHA dissemination website are the following3: A.M.P.E.R.E. INDUSTRIE 5-7 Rue de Bretagne Z.I. des Béthunes, 95310, SAINT-OUEN- L'AUMONE VAL D'OISE, France Aurubis AG Hovestrasse 50, 20539, Hamburg Hamburg, Germany Bochemie a.s. Lidicka 326, 735 95, Bohumin, Czech Republic Boliden Harjavalta Oy Teollisuuskatu 1, 29200, Harjavalta, Finland Boliden Mineral AB Rönnskärsverken, 93281, Skelleftehamn, Sweden Hainan, S.L. Pol. Ind. “La Timba”, Ctra. N-260, Km. 41,2, 17742, Avinyonet de Puigventós Figueres, Catalunya, SpainHalma Export & Import GmbH Reichsratsstrasse 11/3A, 1010, Vienna, Austria KGHM Polska Miedz S.A. M. Sklodowskiej-Curie 48, 59301, Lubin, Poland Königswarter & Ebell, Chemische Fabrik GmbH Im Ennepetal 19-21, 58135, Hagen, Germany Montanwerke Brixlegg AG Werkstraße 1-3, 6230, Brixlegg Tirol, Austria Nickelhütte Aue GmbH Rudolf-Breitscheid-Straße, D-08280, Aue, Germany Norilsk Nickel Harjavalta Oy Teollisuuskatu 1, FI-29200, Harjavalta, Finland SAFT AB Jungnergatan - Box 709, 572 28, OSKARSHAMN, Sweden TODINI AND CO. SPA Corso Milano 46 B, 20900, MONZA ITALIA, Italy Umicore NV/SA Rue du Marais 31, 1000, Brussels, Belgium Vale Europe Limited Acton Refinery Bashley Road, NW10 6SN, London GB, United Kingdom 1.4 Information on any previous risk assessment, risk reduction strategy and RMO analyses 1.4.1 Previous risk assessment carried out under Council Regulation 793/93 A risk assessment has been carried out in accordance with Council Regulation (EEC) 793/93 on the evaluation and control of the risks of existing substances for five nickel compounds. Indeed nickel metal, nickel sulphate, nickel dichloride, nickel dinitrate and nickel carbonate have been included in the third and the fourth priority lists of substances for assessment under this Regulation due to concerns for human health and the large annual quantities used. The final approved version of the risk assessment report (RAR) is dated May 2009; the chapter 4 (Addendum 2-year inhalation study in rats) has been added in November 2009. The work assessed the effects and risks 3 Updated July 2014 7 - on the environment and human exposed indirectly via environment for nickel (metal) and the four nickel salts, - on the human health for NiSO (workers and consumers). 4 The risk assessment covered the following occupational uses of the five compounds (those flagged with * were relevant for NiSO ) 4 - production of nickel metal* and nickel salts*, - alloy production including nickel plating* activities and chemical pre-treatments of plated metals, - battery production, - catalyst production*, - production of nickel-containing chemicals*, - use in coins, - contact with tools and other nickel-releasing surfaces, - end-uses of nickel-containing products (batteries, catalysts, welding rods). The main risks identified by the risk assessment are the occupational inhalation exposure and the skin sensitisation of consumers. Main results are reported in appendix 3 of this document. 1.4.1.1 Risk assessment outcome for workers Risks were identified for all the following manufacture and use scenarios considered in the risk assessment (those flagged with * were relevant for NiSO ): 4 1. Production of nickel metal: refining* 2. Production of nickel salts* 3. Production of alloys - melting and foundry techniques, - powder metallurgy, - nickel plating* - chemical pre-treatment of metals* 4. Battery production 5. Catalyst production* 6. Production of nickel-containing chemicals* Based on the information and the classification available at that time (identified uses and exposure levels, hazard characterization and subsequent classification, agreed DNELs, etc.), risks were identified for workers based on inhalation exposure (to nickel salts) and on the following health effects (see table3): - acute inhalational toxicity (short-term peak exposures to nickel salts), - respiratory sensitisation (occupational asthma following inhalation exposure to nickel salts), - chronic inhalational toxicity (full-shift exposure), - inhalational carcinogenicity (for all scenarios except those where the exposure is purely to metallic nickel), - reproductive toxicity (fertility and developmental toxicity following inhalation). Note that there were no concern for workers after oral exposure, as it was assumed that this is prevented by personal hygiene measures. 8 Table 3: Summary of the RAR conclusion on the occupational risk assessment for NiSO 4 Conclusion Endpoints of concern Reasoning (i) on hold. There is need Effects on fertility and There is need for further studies to evaluate for further information development the possible effects of nickel sulphate on and/or testing germ cells, but further testing is not considered practicable (iii) There is a need for Acute toxicity, respiratory The risk assessment has shown that a limiting the risks: risk sensitisation, repeated dose concern with inhalational exposure is reduction measures which toxicity, carcinogenicity, expressed for all inhalational exposure are already being applied effects on fertility and scenarios in relation to worst case exposure shall be taken into account development levels. For typical exposure levels concern is expressed to the majority of the endpoints/exposure scenarios (ii) There is at present no Effects on fertility and The risk assessment has shown that following need for further development, dermal typical inhalational exposure for some information and/or testing exposures for acute and scenarios (effects on fertility and or for risk reduction repeated dose toxicity, development, and for all scenarios for dermal measures beyond those irritation, sensitisation, exposures for acute and repeated dose which are being applied carcinogenicity and toxicity, irritation, sensitisation, reproductive toxicity carcinogenicity and reproductive toxicity) there is no need for limiting the risks taking into account the risk reduction measures that are already being applied 1.4.1.2 Risk assessment outcome for dermal exposure and skin sensitization There appeared to be little concern for induction of skin allergy from contact with nickel- containing chemicals in the workforce, or for any other health effects related to dermal exposure. With respect to metallic nickel, whilst release of nickel from the metal or nickel-containing alloys during occupational exposure is possible, skin contact to these materials is unlikely to be prolonged, and therefore the possibility of induction of sensitization is much reduced compared to soluble nickel compounds. Thus a conclusion (ii) has been considered justified for all workplace scenarios for induction of nickel allergy. The exposure levels were also considered sufficiently low to justify a conclusion (ii) for the elicitation of symptoms of nickel allergy in previously sensitised individuals for workplace exposure. 1.4.1.3 Risk assessment outcome for welding activities The risk assessment reflects agreement with the conclusions drawn by IARC (1990) and Cross et al. (1999) that there is a concern for the welding process, although the concern is not specifically associated with the presence of nickel alone in either the materials used for welding or the materials being welded. Several substances potentially hazardous to health are present both as part of the welding materials (rod, core etc.) and as components of the surfaces to be welded. The hazards associated with the process are primarily associated with the fumes generated, exposure to nickel by inhalation cannot be excluded when nickel metal of nickel salts are involved in the welding process. Nevertheless, the composition of these fumes depends on the components of the welding process, as well as on the welding method used. Therefore no targeted risk characterisation has been carried out for the use of nickel in welding. 9 1.4.1.4 Risk assessment outcome for consumers Concerns for consumers are very different than from workers. Consumers are mainly exposed by skin contact (to nickel metal) and oral exposure (to nickel salts). Whilst dermal exposure is to nickel metal, oral exposure is to soluble nickel. There is indeed no significant inhalational exposure to nickel or nickel compounds for consumers. Both the induction of nickel allergy in non-sensitive people and the elicitation of allergic reactions in people already sensitive to nickel have been considered for the risk assessment. The main concern is related to direct and prolonged skin exposure to nickel(metal)- containing objects such as coins, earrings, clasps of necklaces, zippers, finger rings, medallions, metal identification tags, buttons, wire support of bra cups, buttons on jeans, watchbands, bracelets, spectacle frames etc. as well as to piercing posts used for ear- piercing and piercing of other parts of the body. Consumers can also be exposed to nickel orally from nickel released to food, nickel released from water heating devices (kettles), nickel released to drinking water, nickel in mineral supplements. With the exception of the use of NiSO and NiCl as a source of 4 2 nickel in food supplements, there would appear to be little or no consumer exposure to nickel sulphate, chloride, nitrate or carbonate. The risk assessment concluded that there is no concern for consumers for systemic effects by dermal exposure. The population at risk of developing symptoms after oral challenge are patients with severe nickel sensitization only. It was indeed agreed that the main group of people where there is particular concern are those who are already nickel-sensitive, and this is a group especially at risk from both dermal and oral exposure to nickel. However EU legislation has come into force (cf. Section 1.5.3) and has been considered adequate to prevent new cases of nickel allergy as well as to reduce the incidence of elicitation in consumers who are already sensitised to nickel from both objects in direct and prolonged contact with the skin as well as piercing posts. Note that the risk assessment for humans exposed to the environment has not been completed but it has been suggested that the sources of nickel, should this give rise to concern, would be controlled by any risk reduction measures required for concerns for the environment. Therefore no additional risk for humans from the environment was expected. 1.4.2 Previous risk reduction strategy carried out under Council Regulation 793/93 In order to identify appropriate measures to address the risks to human health raised in the risk assessment reports, a risk reduction strategy with respect to human health has been prepared by Denmark in 2007 in accordance with Council Regulation (EEC) 793/93 on the evaluation and control of the risks of existing substances. The report stated that nickel and nickel compounds were already widely regulated under EU legislation. The following risk reduction measures were proposed in relation to obligations under Community law: - to set occupational exposure limits for nickel metal and nickel compounds in the form of inhalable dust/aerosols under Directive 98/24/EC (chemicals at work) or Directive 2004/37/EC (carcinogens at work) as appropriate, 10