Nickel Background EU Risk Assessment Report March 2008 Final Draft

Nickel and nickel compounds

Background Document
in support of individual

RISK ASSESSMENT REPORTS
of nickel compounds
prepared in relation to
Council Regulation (EEC) 793/93

Final version
March 2008

Chapters 0, 1, 2, 4, 5, 6 and 7 – human health only.

Danish Environmental Protection Agency

R_NickelBackground_0308_hh_chapter0124567.doc

Information on the Rapporteur.
The Danish Environmental Protection Agency is the Rapporteur for the risk assessment reports of metallic
nickel, nickel sulphate, nickel chloride, nickel nitrate and nickel carbonate. The Rapporteur is responsible for the
contents of this report.

Contact persons:
Poul Bo Larsen & Henrik Tyle
Chemicals Division
Danish Environmental Protection Agency
Strandgade 29
DK-1401 Copenhagen K
DENMARK

Tel: +45 72 54 40 00
E-mail: HTY@mst.dk / PBL@mst.dk / DEPA-ESR@mst.dk

Acknowledgements.
The scientific assessments included in this Background report have been prepared by the following organisations
by order of the Rapporteur:
• Danish National Working Environment Authority (Occupational Exposure, Chapter 4)
• Danish Technological Institute (Aquatic effects Assessment, Chapter 3)
• Department of Toxicology and Risk Assessment, Danish Food and Veterinary Research, (Consumer
and Indirect Exposure, Human health effects, Chapter 4)
• National Environmental Research Institute, Denmark (Terrestrial effects Assessment, Chapter 3).
• URS Corporation, London, UK (Chapter 3, UK environment exposure)

The Rapporteur would also like to acknowledge the contributions from the following individuals:
• Professor Aage Andersen and Dr. Tom K. Grimsrud of the Cancer Registry of Norway, Institute of
Population-based Cancer Research, for their assistance in the preparation of the section on nickel
carcinogenicity in Chapter 4,
• Ivor Kirman, London, UK for general information about nickel,
• Drs. Hudson Bates, Adriana Oller, Katherine Heim, Lisa Ortego, and Chris Schlekat, NiPERA, Durham,
North Carolina, USA, for providing information on the health and environmental effects of nickel,
• Jim Hart, Sherborne, Dorset, UK, for the preparation of Chapters 1, and 2, and sections of Chapters 4 and 7,
• Professor Torkil Menné MD, Gentofte Hospital, Copenhagen, Denmark for his assistance in the preparation
and critical review of the sections on the sensitising effects of nickel in Chapter 4,
• Dr. Sally Pugh Williams, Inco, Wales, UK for general information on nickel.

2


Foreword to Draft Risk Assessment Reports

Risk assessment of priority substances is carried out in accordance with Council Regulation (EEC) 793/93 (EEC,
1993b) on the evaluation and control of the risks of “existing” substances. Regulation 793/93 provides a
systematic framework for the evaluation of the risks to human health and the environment of these substances if
they are produced or imported into the Community in volumes above 10 tonnes per year.

There are four overall stages in the Regulation for reducing the risks: data collection, priority setting, risk
assessment and risk reduction. Data provided by Industry are used by Member States and the Commission
services to determine the priority of the substances which need to be assessed. For each substance on a priority
list, a Member State volunteers to act as “Rapporteur”, undertaking the in-depth Risk Assessment and if
necessary, recommending a strategy to limit the risks of exposure to the substance.

Denmark is Rapporteur for five nickel substances: nickel metal, nickel sulphate, nickel chloride, nickel nitrate
and nickel carbonate. This Background Report has been prepared by the Rapporteur for a number of reasons.
Firstly, this Background report includes general information about nickel that is common to all the individual
reports. This is particularly relevant for information about the release of nickel into the environment, and many
of the environmental properties of nickel. This background report also provides information about other nickel
compounds for which separate reports are not being prepared, but where information on their properties is useful
for drawing conclusions on the hazards and risks of the five specific substances under review. Finally, this report
provides a brief review of the other nickel compounds on the EU market to provide a starting point for further
assessment of their hazards and risks.

Draft Risk Assessment Reports on nickel metal and other nickel compounds are currently under discussion in the
Competent Group of Member State experts with the aim of reaching consensus. During the course of these
discussions, the scientific interpretation of the underlying scientific information may change, more information
may be included and even the conclusions reached in this draft may change. The Competent Group of Member
State experts seek as wide a distribution of these drafts as possible, in order to assure as complete and accurate
an information basis as possible. The information contained in these Draft Risk Assessment Reports do not,
therefore, necessarily provide a sufficient basis for decision making regarding the hazards, exposures or the risks
associated with the priority substances under consideration.

This Draft Background Risk Assessment Report is the responsibility of the Member State rapporteur. In order to
avoid possible misinterpretations or misuse of the findings in this draft, anyone wishing to cite or quote this
report is advised to contact the Member State rapporteur beforehand.

3


CONTENTS

0. OVERALL RESULTS OF THE RISK ASSESSMENT........................... 9

1. GENERAL SUBSTANCE INFORMATION ......................................... 10
1.1 NICKEL AND NICKEL COMPOUNDS 10
1.2 PHYSICO-CHEMICAL PROPERTIES OF SELECTED NICKEL COMPOUNDS. 10
Solubility of nickel compounds................................................................................................ 12
1.2.1
Summary....................................................................................................................................... 13
1.2.2
1.3 CLASSIFICATION. 14
1.3.1 Current classification ................................................................................................................ 14
1.3.1.1 UN Transport labelling. 14
1.3.1.2 Classification according to Directive 67/548/EEC. 15
1.3.2 Proposed classification ............................................................................................................. 22
1.3.2.1 UN Transport labelling. 22
1.3.2.2 Classification according to Directive 67/548/EEC. 22

2. GENERAL INFORMATION ON EXPOSURE TO NICKEL AND
NICKEL COMPOUNDS......................................................................... 24
2.1 SOURCES OF NICKEL. 24
2.1.1 Industrial production and use of nickel and nickel compounds...................................................... 24
2.1.1.1 Production. 24
2.1.1.1.1 Mining .............................................................................................................................. 24
2.1.1.1.2 Beneficiation and smelting ............................................................................................... 26
2.1.1.1.3 Refining............................................................................................................................ 26
2.1.1.1.4 Nickel chemicals production. ........................................................................................... 26
2.1.1.1.4.1 High production volume nickel containing chemicals. 26
2.1.1.1.4.2 Low production volume nickel containing chemicals. 28
2.1.1.1.4.3 Other low production volume nickel containing chemicals. 30
2.1.1.2 Nickel Use. 31
2.1.1.2.1 Uses of nickel and nickel compounds .............................................................................. 32
2.1.1.2.1.1 High production volume nickel-containing chemicals. 32
2.1.1.2.1.2 Low production volume nickel-containing chemicals. 33
2.1.1.2.1.3 Other low production volume nickel-containing chemicals. 34
2.1.1.2.2 Uses of nickel containing products................................................................................... 35
2.1.1.3 Disposal. 35
2.1.1.4 Nickel emissions from production and use of nickel and nickel-containing chemicals and
products. 35
2.1.2 Other anthropogenic sources of nickel........................................................................................... 36
2.1.2.1 Non-ferrous metals production. 36
2.1.2.2 Combustion processes. 36
2.1.2.3 Other Industrial Processes. 37
2.1.2.4 Emission to soil. 38
2.1.3 Natural sources of nickel................................................................................................................ 38
2.1.3.1 Nickel emissions from natural sources. 39
2.1.4 Summary of nickel exposure information. ...................................................................................... 40
2.1.4.1 Trends in nickel emissions. 40
2.1.5 Nickel Lifecycle. ............................................................................................................................. 40
2.2 LEGISLATIVE CONTROLS. 41
2.2.1 General Measures. ......................................................................................................................... 41
2.2.1.1 Directive 67/548/EEC on dangerous substances. 41
2.2.1.2 Directive 1999/45/EC on dangerous preparations. 41
2.2.1.3 Other EU legislation. 41
2.2.1.4 National Initiatives. 42
2.2.2 Protection of workers. .................................................................................................................... 42
2.2.3 Protection of consumers. ................................................................................................................ 44

4


2.2.3.1 Directive 98/83/EC on the quality of water intended for human consumption 45
2.2.3.2 Food contact materials, Food supplements, additives and contaminants. 45
2.2.3.3 Council Directive 90/385/EEC on active implantable Medical Devices, Council Directive
93/42/EEC on Medical Devices and Council Directive 98/79/EEC on in vitro-diagnostic
Medical Devices 45
2.2.3.4 Council Directive 88/378/EEC on the Safety of Toys 46
2.2.3.5 Council Directive 89/106/EEC on Construction Products 46
2.2.3.6 Directive 2001/95/EC on general product safety 46
2.2.4 Emissions to water.......................................................................................................................... 46
2.2.4.1 Directive 96/61/EC concerning integrated pollution prevention and control (IPPC) 46
2.2.4.2 Directive 76/464/EEC on pollution of the aquatic environment by certain dangerous
substances. 47
2.2.4.3 Directive 2000/60/EC establishing a framework for Community action in the field of water
policy. 47
2.2.4.4 Directive 80/68/EEC on the protection of groundwater against pollution caused by certain
dangerous substances 47
2.2.4.5 Directive 2000/76/EC on the incineration of waste. 48
2.2.4.6 National Legislation. 48
2.2.5 Emissions to air .............................................................................................................................. 49
2.2.5.1 Directive 96/61/EC concerning integrated pollution prevention and control (IPPC) 49
2.2.5.2 Directive 96/62/EC on ambient air quality assessment and management. 49
2.2.5.3 Directive 2000/76/EC on the incineration of waste. 50
2.2.5.4 Directive 2001/80/EC on Large Combustion Plant Directive. 50
2.2.5.5 UN ECE Protocol on heavy metals. 50
2.2.5.7 Other measures. 50
2.2.6 Soil.................................................................................................................................................. 51
2.2.6.1 Directive 86/278/EEC on Sludge in Agriculture. 51
2.2.7 Waste management......................................................................................................................... 52
2.2.7.1 Directive 96/61/EC concerning integrated pollution prevention and control 52
2.2.7.2 Council Directive 91/689/EEC of 12 December 1991 on hazardous waste 52

3. ENVIRONMENT .................................................................................... 53

4. HUMAN HEALTH ................................................................................. 54
4.1 HUMAN HEALTH (TOXICITY) 54
4.1.1 Exposure assessment. ..................................................................................................................... 54
4.1.1.1 General 54
4.1.1.2 Occupational exposure. 54
4.1.1.3 Consumer exposure. 54
4.1.1.3.1 Exposure to nickel in food................................................................................................ 54
4.1.1.3.2 Exposure to nickel in water .............................................................................................. 57
4.1.1.3.3 Combined exposure to nickel from food and drinking water. .......................................... 58
4.1.1.3.4 Exposure to nickel from smoking..................................................................................... 59
4.1.1.4 Indirect exposure via the environment 59
4.1.2 Human health effects assessment.................................................................................................... 59
4.1.2.1 Toxico-kinetics, metabolism and distribution 60
4.1.2.1.1 Absorption ........................................................................................................................ 60
4.1.2.1.1.1 Inhalation 60
4.1.2.1.1.1.1 Discussion and conclusion, absorption following inhalation ................................................ 62
4.1.2.1.1.2 Oral 64
4.1.2.1.1.2.1 Discussion and conclusion, absorption following oral administration .................................. 66
4.1.2.1.1.3 Dermal 67
4.1.2.1.1.3.1 Discussion and conclusion, absorption following dermal contact......................................... 68
4.1.2.1.1.4 Other routes 68
4.1.2.1.2 Distribution and elimination............................................................................................. 69
4.1.2.1.2.1 Transport 69
4.1.2.1.2.2 Distribution 69
4.1.2.1.2.3 Transplacental transfer 70

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4.1.2.1.2.4 Cellular uptake 71
4.1.2.1.2.5 Elimination 72
4.1.2.1.2.6 Transfer to the milk 73
4.1.2.1.3 Conclusions ...................................................................................................................... 74
4.1.2.2 Acute toxicity 75
4.1.2.2.1 Animal studies.................................................................................................................. 75
4.1.2.2.1.2 Oral 76
4.1.2.2.1.3 Dermal 76
4.1.2.2.1.4 Other routes 76
4.1.2.2.2 Human studies .................................................................................................................. 76
4.1.2.2.3 Discussion and conclusion ............................................................................................... 77
4.1.2.2.3.2 Oral 77
4.1.2.2.3.3 Dermal 77
4.1.2.3 Irritation /corrosivity 78
4.1.2.3.1 Animal studies.................................................................................................................. 78
4.1.2.3.1.1 Skin and eye irritation 78
4.1.2.3.1.2 Respiratory irritation 79
4.1.2.3.2 Human data....................................................................................................................... 79
4.1.2.3.2.1 Skin irritation 79
4.1.2.3.2.2 Respiratory irritation 80
4.1.2.3.2.3 Conclusion 80
4.1.2.4 Sensitisation 81
4.1.2.4.1 Skin sensitisation.............................................................................................................. 81
4.1.2.4.1.1 Animal studies 81
4.1.2.4.1.2 Human data 82
4.1.2.4.1.2.1 Nickel allergy........................................................................................................................ 82
4.1.2.4.1.2.2 Mechanism for the development of nickel allergy. ............................................................... 83
4.1.2.4.1.2.3 Immunological tolerance....................................................................................................... 83
4.1.2.4.1.2.4 Occurrence of nickel allergy ................................................................................................. 83
4.1.2.4.1.2.5 Hand eczema......................................................................................................................... 86
4.1.2.4.1.2.6 Experimental sensitisation .................................................................................................... 86
4.1.2.4.1.2.7 The ability of nickel salts, nickel and nickel alloys to elicit nickel allergy ........................... 86
4.1.2.4.1.2.7.1 Skin contact ................................................................................................................... 86
4.1.2.4.1.2.7.2 Oral challenge................................................................................................................ 89
4.1.2.4.1.2.7.3 Hyposensitisation .......................................................................................................... 90
4.1.2.4.1.2.8 Occupational nickel allergy .................................................................................................. 90
4.1.2.4.1.3 Conclusion on skin sensitisation 91
4.1.2.4.1.3.1 Thresholds for elicitation ...................................................................................................... 92
4.1.2.4.1.3.1.1 Skin................................................................................................................................ 92
4.1.2.4.1.3.1.2 Oral................................................................................................................................ 92
4.1.2.4.2 Respiratory sensitisation................................................................................................... 92
4.1.2.4.2.1 Conclusion on respiratory sensitisation 92
4.1.2.4.3 Conclusion........................................................................................................................ 93
4.1.2.5 Repeated dose toxicity 93
4.1.2.5.1 Animal studies.................................................................................................................. 93
4.1.2.5.1.1.1 NTP studies of nickel sulphate hexahydrate, nickel subsulphide and nickel oxide............... 95
4.1.2.5.1.1.1.1 16-day rat studies........................................................................................................... 95
4.1.2.5.1.1.1.2 16-day mouse studies..................................................................................................... 96
4.1.2.5.1.1.1.3 13-week rat studies ........................................................................................................ 97
4.1.2.5.1.1.1.4 13-week mouse studies.................................................................................................. 98
4.1.2.5.1.1.1.5 2-year rat studies............................................................................................................ 99
4.1.2.5.1.1.1.6 2-year mouse studies ..................................................................................................... 99
4.1.2.5.1.1.2 Other inhalation studies ...................................................................................................... 100
4.1.2.5.1.1.3 Supporting mechanistic data for lung effects ...................................................................... 101
4.1.2.5.1.2 Oral 102
4.1.2.5.1.3 Dermal 102
4.1.2.5.2 Conclusion...................................................................................................................... 102
4.1.2.5.2.1 Inhalation 102
4.1.2.5.2.2 Oral 103
4.1.2.5.2.3 Dermal 103
4.1.2.6 Mutagenicity 103

6


4.1.2.6.1 Summary of mutagenicity test results for the five selected nickel compounds. ............. 103
4.1.2.6.1.1 Summary of mutagenicity test results in vitro. 103
4.1.2.6.1.1.1 DNA damage and repair. .................................................................................................... 103
4.1.2.6.1.1.2 Gene mutation..................................................................................................................... 104
4.1.2.6.1.1.3 Chromosomal effects. ......................................................................................................... 105
4.1.2.6.1.1.4 Cell transformation. ............................................................................................................ 106
4.1.2.6.1.2 Summary of mutagenicity test results in vivo. 106
4.1.2.6.1.2.1 DNA damage and repair. .................................................................................................... 106
4.1.2.6.1.2.2 Gene mutations. .................................................................................................................. 107
4.1.2.6.1.2.3 Chromosomal effects. ......................................................................................................... 107
4.1.2.6.2 Genotoxicity of other nickel compounds........................................................................ 108
4.1.2.6.2.1 Other soluble nickel compounds. 108
4.1.2.6.2.2 Insoluble compounds. 108
4.1.2.6.3 Conclusions on the mutagenicity of the five selected nickel compounds....................... 110
4.1.2.7 Carcinogenicity 112
4.1.2.7.1 Animal data .................................................................................................................... 112
4.1.2.7.1.1 Inhalation 112
4.1.2.7.1.1.1 Nickel sulphate ................................................................................................................... 112
4.1.2.7.1.1.2 Nickel metal........................................................................................................................ 112
4.1.2.7.1.1.3 Nickel chloride, nickel nitrate, and nickel carbonate .......................................................... 114
4.1.2.7.1.1.4 Nickel oxide........................................................................................................................ 114
4.1.2.7.1.1.5 Nickel subsulphide.............................................................................................................. 114
4.1.2.7.1.2 Oral 114
4.1.2.7.1.2.1 Nickel sulphate ................................................................................................................... 114
4.1.2.7.1.2.2 Nickel chloride, nickel nitrate, nickel carbonate, and nickel metal ..................................... 115
4.1.2.7.1.2.3 Nickel acetate...................................................................................................................... 115
4.1.2.7.1.3 Dermal 115
4.1.2.7.1.3.1 Nickel sulphate, nickel chloride, nickel nitrate, nickel carbonate, and nickel metal ........... 115
4.1.2.7.1.3.2 Other nickel compounds ..................................................................................................... 115
4.1.2.7.1.4 Other routes of administration 115
4.1.2.7.1.4.1 Nickel sulphate ................................................................................................................... 115
4.1.2.7.1.4.2 Nickel chloride.................................................................................................................... 116
4.1.2.7.1.4.3 Nickel nitrate....................................................................................................................... 117
4.1.2.7.1.4.4 Nickel carbonate ................................................................................................................. 117
4.1.2.7.1.4.5 Nickel metal........................................................................................................................ 117
4.1.2.7.1.5 Initiator-Promoter studies 118
4.1.2.7.1.5.1 Nickel sulphate ................................................................................................................... 118
4.1.2.7.1.5.2 Nickel chloride.................................................................................................................... 119
4.1.2.7.1.5.3 Nickel metal........................................................................................................................ 120
4.1.2.7.1.5.4 Nickel nitrate, nickel carbonate........................................................................................... 120
4.1.2.7.1.6 Discussion and conclusions, carcinogenicity in experimental animals 121
4.1.2.7.1.6.1 Inhalation ............................................................................................................................ 121
4.1.2.7.1.6.2 Oral ..................................................................................................................................... 123
4.1.2.7.1.6.3 Dermal ................................................................................................................................ 123
4.1.2.7.1.6.4 Other routes of administration ............................................................................................ 123
4.1.2.7.1.6.5 Initiator-Promoter studies ................................................................................................... 124
4.1.2.7.1.6.6 Conclusions in reviews on nickel compounds..................................................................... 125
4.1.2.7.1.6.6.1 CSTEE (2001) ............................................................................................................. 125
4.1.2.7.1.6.6.2 TERA (1999) ............................................................................................................... 125
4.1.2.7.1.6.6.3 IARC (1999)................................................................................................................ 125
4.1.2.7.1.6.6.4 NiPERA (1996) ........................................................................................................... 125
4.1.2.7.1.6.6.5 IPCS (1991) ................................................................................................................. 125
4.1.2.7.1.6.6.6 IARC (1990)................................................................................................................ 125
4.1.2.7.1.7 Conclusion, carcinogenicity in experimental animals 126
4.1.2.7.2 Human data..................................................................................................................... 126
4.1.2.7.2.1 Epidemiology 126
4.1.2.7.2.2 Exposures 127
4.1.2.7.3 Discussion ...................................................................................................................... 128
4.1.2.7.4 Overall Conclusion for carcinogenicity.......................................................................... 130
4.1.2.8 Toxicity for reproduction 131
4.1.2.8.1 Effects on fertility........................................................................................................... 131
4.1.2.8.1.2 Human data 132

7


4.1.2.8.2 Developmental toxicity .................................................................................................. 132
4.1.2.8.2.1.1 Oral exposure...................................................................................................................... 132
4.1.2.8.2.1.2 Inhalation ............................................................................................................................ 132
4.1.2.8.2.1.3 Other routes ........................................................................................................................ 133
4.1.2.8.2.2 Human data 133
4.1.2.8.3 Conclusions .................................................................................................................... 133
4.1.3 Risk characterisation.................................................................................................................... 134
4.2 HUMAN HEALTH (PHYSICO-CHEMICAL PROPERTIES) 134
4.2.1 Exposure assessment .................................................................................................................... 134
4.2.2 Effects assessment: ....................................................................................................................... 134
4.2.2.1 Explosivity 134
4.2.2.2 Flammability 134
4.2.2.3 Oxidising potential 134
4.2.3 Risk characterisation.................................................................................................................... 134

5. CONCLUSIONS/RESULTS ................................................................. 135

6. REFERENCES ...................................................................................... 136

7. APPENDICES ....................................................................................... 154
7.1 WATER SOLUBILITY OF SELECTED NICKEL COMPOUNDS. 154
7.2 NICKEL AND NICKEL COMPOUNDS IN EINECS 155
7.2.1 Nickel, nickel compounds, and complex substances containing nickel included in EINECS. ...... 155
7.2.2 Nickel compounds included in Elincs ........................................................................................... 164
7.2.3 Additional Nickel compounds included in TSCA (through 08/2000) but not included in EINECS.
...................................................................................................................................................... 165
7.2.4 Additional Nickel compounds listed in ECICS (European Customs Inventory of chemical
substances), but not included in EINECS or the TSCA Inventory. ............................................... 166
7.2.5 Additional Nickel compounds in Annex I to Directive 67/548/EEC but not in EINECS or TSCA.166
7.2.6 Additional nickel compound found in the course of compiling the inventory of nickel compounds
...................................................................................................................................................... 166
7.2.7 Additional nickel hydroxycarbonate compounds not included in the lists above ......................... 167
7.2.8 Nickel containing minerals (from IARC, 1990 and NiPERA, 1996)............................................. 167
7.3 NICKEL CONTENT IN FOOD. 168

8


0. OVERALL RESULTS OF THE RISK ASSESSMENT
The risk assessment of the production and use of metallic nickel, nickel sulphate, nickel chloride, nickel
carbonate and nickel nitrate is described in the individual risk assessment reports on these substances.

A full risk assessment of the production and use of the other nickel compounds described in this report has not
been attempted by the Rapporteur, as these other nickel compounds are not included in a priority list under the
Existing Substances Regulation. However, the Rapporteur considers that the approach used in the risk
assessments of the five nickel compounds listed above may prove helpful to others when preparing a risk
assessment for specific nickel compounds.

Risk characterisations of scenarios not directly related to the production and use of nickel and nickel compounds
(e.g. combustion processes) where exposure to nickel occurs is outside the scope of these risk assessments.

9


1. GENERAL SUBSTANCE INFORMATION

1.1 NICKEL AND NICKEL COMPOUNDS
Nickel can be found in a variety of oxidation states ranging from 0 to IV. However, Ni (II) is the only oxidation
state occurring in ordinary chemistry. Ni (III) and Ni (IV) occur in certain complexes and in specific oxide
systems, the higher oxidation states, however, being considerably less stable than Ni (II). Ni (0) and Ni (I)
compounds are scarce (Cotton & Wilkinson, 1968, quoted from Carlsen, 2001a).

Ni (II) forms a wide variety of compounds ranging from simple inorganic complexes (salts) to complexes with
various organic ligands. Ni can be found in various oxides. It appears that in the aqueous chemistry Ni (II) is the
only oxidation state that has to be considered. In the absence of strong complexing agents Ni (II) appears in
aqueous solution as the green hexaquonickel (II) ion Ni (H2O)62+ (Cotton & Wilkinson, 1968, quoted from
Carlsen, 2001a).

There are over three hundred entries in EINECS for nickel and nickel compounds and other, often complex,
substances containing nickel. These are shown in Appendix 7.2.1. It should be noted that the EINECS reporting
rules (CEC, 1982) implicitly include hydrates of the anhydrous salts listed in EINECS. Hence the numbers of
substances (and the numbers of CAS numbers) implicitly included in EINECS is much greater than this figure.
Three nickel compounds are included in Einecs (Appendix 7.2.2).

An additional 40 nickel containing compounds not listed in EINECS but included in the US EPA TSCA
inventory are shown in Appendix 7.2.3.

A number of nickel compounds are included in the European Customs Inventory of Chemical Substances
(ECICS, 1997). ECICS includes a numerical list showing correlations between the CAS number and the EU
CUS number (a five-digit number). Appendix 7.2.1 also includes the CUS numbers where relevant. It can be
seen that whilst most HPVC nickel compounds have individual CUS numbers, there are several LPVC chemicals
that do not. Similarly, there are many nickel compounds that have individual CUS numbers, although according
to the information in IUCLID, they do not appear to be marketed in significant quantities. Additional compounds
listed in ECICS (the European Customs inventory of chemical substances) not included in either EINECS or
TSCA are shown in Appendix 7.2.4.

Substances in the ECICS are included in the European Community’s Combined Nomenclature (eight digit CN
code). The CN is based on the “Harmonized Commodity Description and Coding System” emanating from
WCO, in use throughout the world. Nickel metal, nickel sulphate and nickel chloride have CN numbers that
identify these substances individually. Nickel oxides and hydroxides are identified under a separate CN No.
(2825 40 00). However, other nickel compounds are included in CN numbers that also include varying numbers
of other non-nickel-containing compounds.

Appendix 7.2.5 shows additional substances included as part of group entries in Annex I to Directive
67/548/EEC but not included in the previous lists. Finally, other nickel containing compounds (including
minerals and other nickel compounds listed in IARC) not included in any of the lists above are shown in
Appendices 7.2.6, 7.2.7 and 7.2.8.

1.2 PHYSICO-CHEMICAL PROPERTIES OF SELECTED NICKEL
COMPOUNDS.
Table 1.2.A shows the physical-chemical properties of some nickel compounds shown in order of decreasing
water solubility. Data for the four high volume nickel compounds for which individual reports have been
prepared are included for comparison. This data has been compiled from a number of reviews of nickel and
nickel compounds. A more detailed discussion of the water solubility of nickel and nickel compounds is given in
the following section.
Table 1.2.A: Summary of physical properties of selected nickel compounds (compiled from UK
HSE, 1987, IARC, 1990, NiPERA, 1996, TERA, 1999)

Nickel Atomic Physical Melting Boiling Density Oxidation Water
compound: weight State Point (°C) Point (g/cm3) state Solubility
(°C) 3)

10


nickel chloride 237.70 solid - - 1.92 +2 2540 g/l at
(hexahydrate) 20°C.
nickel nitrate 290.79 solid 56.7 136.7 1) 2.05 +2 2385 g/l at
(hexahydrate) 0°C.
nickel sulphate 280.85 solid 99 - 1.95 +2 756 g/l at
(heptahydrate) 20°C.
nickel chloride 129.60 solid 973 2) 1001 3.55 +2 642 g/l at
(anhydrous) 20°C.
nickel sulphate 262.84 solid 53.3 - 2.07 +2 625 g/l at
(hexahydrate) 20°C.
1)
nickel 286.88 - +2 300 g/l at
ammonium 20°C.
sulphate
(anhydrous)
nickel sulphate 154.75 solid 848 1) - 3.68 +2 293 g/l at
(anhydrous) 20°C.
1)
nickel acetate 176.78 solid 16.6 1.80 +2 166 g/l at
(anhydrous) 20°C.
1)
nickel acetate 248.84 solid 16 +2 160 g/l at
(tetrahydrate) 20°C.
nickel 394.94 - - 1.92 +2 104 g/l at
ammonium 20°C.
sulphate
(hexahydrate)
nickel fluoride 96.69 solid +2 40 g/l at
25°C
1)
nickel 340.42 solid 2.14 Soluble
fluoroborate
(hexahydrate)
nickel formate 184.76 solid 2.15 +2 soluble
1)
nickel 322.95 solid 200 +2 Soluble
sulphamate
(tetrahydrate)
nickel 170.73 liquid - 25 43 1.32 0 0.18 g/l at
carbonyl 9.8°C
nickel 92.7 solid 230 1) - 4.15 +2 0.13 g/l
hydroxide
1)
nickel 118.70 solid - 5.822 +2 0.0093 g/l
carbonate at 25°C.
nickel sulphide 90.75 solid 797 - 5.5 +2 0.003618
(amorphous) g/l
nickel 74.69 solid 1990 - 4.83 / +2 0.0011 g/l
monoxide 6.67 at 20°C.
1)
basic nickel 376.17 solid 2.6 +2 Insoluble
carbonate
1)
nickel 587.67 solid - 2.6 +2 Insoluble
hydroxy-
carbonate
nickel 174.71 solid - - 5.82 +2 Insoluble in
chromate water
Nickelocene 188.88 solid 171-173 - +2 Insoluble
1)
nickel titantate 154.57 solid 1000 - +2 Insoluble

11


nickel 180.44 solid 1158 1400 1) NS 4) Insoluble
antimonide
nickel arsenide 133.61 solid 968 - 7.17 NS 4) Insoluble
(NiAs)
nickel selenide 137.65 solid red heat - NS 4) Insoluble
nickel 333.99 solid - - Insoluble
subselenide
nickel 240.19 solid 790 - 5.82 NS 4) Insoluble in
subsulphide cold water
nickel telluride 186.29 solid 600 – 900 1) - NS 4) Insoluble
1) 2) 3)
Decomposes. Sublimes Further details are given in the following section.
4)
NS: Not Specified; mixed formal oxidation states of nickel and/or complex coordination in the solid form.

1.2.1 Solubility of nickel compounds.
In the Table above, the water solubility of many of these compounds are described as either “soluble” or
“insoluble”. Many substances commonly considered as “insoluble” are however sufficiently soluble under
certain conditions to give rise to effects of concern. This simple distinction is not always helpful.

The available literature of the solubility of inorganic (Carlsen, 2001a) and organic (Carlsen, 2001b) Ni (II)
species has been reviewed. This review was carried out in order to provide a systematic basis on which to group
in particular inorganic nickel compounds on the basis of their solubility in water.

For inorganic nickel compounds, a grouping of inorganically based nickel species has been suggested. Nickel
metal and nickel metal compounds (see Appendix 7.1.1) can all be considered as insoluble. Nickel oxides and
mixed metal oxides are also very similar in terms of their solubility (Carlsen, 2001a).

In Table 1.2.B a grouping of the nickel ligands with Group 13, 14, 15, 16 and 17 ligands is suggested. The term
‘insoluble’ means that the solubility of the species is less that 10-4 mol/l, ‘slightly soluble’ covers the solubility
range 10-4 - 10-2 mol/l, ‘soluble’ the range 10-2 - 5·10-1 mol/l and ‘very soluble’ refers to solubility above 5·10-1
mol/l (Carlsen, 2001a).

The grouping made in Table 1.2.B is based exclusively on water as the medium. Thus, the apparent increased
solubility of otherwise slightly - or even insoluble - nickel species observed in biological fluids (Maximilien,
1989) is not covered in the grouping made below (Carlsen, 2001a).

A few species, i.e., NiXN and NiTeO4 are not included in Table 1.2.B. No indications concerning the solubility
of these species have been retrieved (Carlsen, 2001a).
Table 1.2.B: Grouping of nickel species based on inorganic ligands in water (Carlsen, 2001a).

Group 13 Group 14 Group 15 Group 16 Group 17 Misc.
Insoluble NiXBa NiXSia NiXPYa NiXSY Ni2Fe(CN)6
a
NiXAs NiXSe
NiXSbYa NiXTe
Ni2P2O7
Ni3(AsO3)2a
Ni3(AsO4)2
Ni(AsO3)2a
Slightly Ni(CO)4 Ni3(PO4)2 NiSO3a Ni(IO3)2 Ni2Fe(CN)5NOb
soluble
Ni(CN)2 Ni[NiP2O7] NiSeO3
NiCO3
Ni(HCO3)2

12


Soluble NiK2(SO4)2 NiF2
Very NiB6O10 Ni(SCN)2 Ni(NO3)2 NiSO4 NiCl2
soluble
Ni(BF4)2 NiSiF6 Ni(H2PO2)2 Ni(SO3NH2)2a Ni(ClO3)2
NiSeO4 Ni(ClO4)2
NiBr2
Ni(BrO3)2
NiI2
a
No quantitative data have been retrieved
b
Placed due to the possible higher solubility as discussed by Linke (1965).

It is noted that the solubility in general follows the ‘rules of thumb’ for inorganic salts. Thus, halides are easily
soluble, apart from the fluoride, nitrates are easily soluble, carbonates and phosphates are typically only slightly
soluble, hydroxides of non-alkali metals are often very slightly soluble, etc. (Carlsen, 2001a).

In the study by Carlsen (2001a) the focus is on the concentration of the free nickel (II) ion, Ni(H2O)62+ as
responsible for biological effects of nickel compounds. However, the free ligands and/or the intact nickel
complexes may also give rise to biological effects. It should be emphasized that the grouping in Table 1.2.B is
made without taking into account the possible lowering of the concentration of the free nickel ions due to
complex formation. For hazard and risk assessment purposes this corresponds to a conservative approach to the
possible maximum concentration of Ni(H2O)62+ (Carlsen, 2001a).

No comparable grouping of organic ligands has yet been carried out (Carlsen, 2001b). In contrast to the
inorganic nickel compounds it is not obvious how to group the organically based species based on solubility
alone. Aqueous solubility is, not unexpectedly, seen to decrease with increasing molecular weight and increasing
carbon content of the ligand. On the other hand, the introduction of hydrophilic and/or polar functional groups,
such as OH, C=O, COO-, NH, SH and SO3- cause increased solubility. Further it should be emphasized that the
solubility of the complexes cannot immediately be related to the solubility of the single ligands (Carlsen 2001b).
Hence, it seems more appropriate to group organically based nickel complexes based on the stability of the
complexes. As a first attempt, grouping the individual complexes based on the nature of the ligand appears as an
obvious choice, even though significant variations in stability may prevail within the single groups.
Monocarboxylic acids serve as an example to illustrate the applicability of this concept. It appears that the
stability constant for the first complex typically is found in the range around 1 and the second in the range of 1-2.
Significant outliers are the sulphur-containing acids thiolactic acid and (phenylthio)acetic acid. Apart from the
sulphur-containing acids, it would seem appropriate to treat nickel monocarboxylate complexes as a single
group, based on the salts of formic and acetic acid. Both these salts are highly soluble: thus, the approach would
be conservative. In order to evaluate the possible concentration of free nickel ions, as well as other nickel
containing species in solution, it is important to take the actual acidity of the solution into consideration (Carlsen,
2001b).

1.2.2 Summary
The availability of physical chemical data for the nickel compounds in Appendix 7.1 is very variable. However,
there is data available for the water solubility of many inorganic nickel (II) compounds, although there are many
complex nickel-containing substances with no solubility data. Grouping many of the conventional inorganic
nickel (II) compounds on the basis of their water solubility is fairly straightforward. Grouping the much larger
numbers of organic complexes is a more complicated process.

Many legislative controls group all nickel compounds together (see Chapter 2.2). In other cases, nickel
compounds are divided into groups on the basis of their water solubility (e.g. TERA, 1999). This grouping of
compounds reflects the assumption that the biological effects of nickel reflect the activity of the nickel ion,
Ni(H2O)62+. NiPERA (1996) groups nickel compounds into five main classes: metallic nickel, nickel carbonyl,
oxidic nickel (e.g. nickel oxides, hydroxide, silicates, carbonates, complex nickel oxides), sulphidic nickel (e.g.
nickel sulphide, nickel subsulphide), and water-soluble nickel compounds (e.g. nickel sulphate hexahydrate,
nickel chloride hexahydrate). The group of “oxidic nickel” includes substances with a range of different water
solubility, from compounds of very low solubility (e.g. nickel oxide) to compounds with a water solubility a
hundred times greater (e.g. nickel hydroxide). There is little difference in the water solubility of sulphidic nickel
and that of nickel oxides. Whilst these groupings reflect the substances encountered in nickel metal production,
they do not reflect well the wider range of HPVC and LPC substances seen in practice (see Chapter 2).

13


However, it is important to be able to recognise similarities and differences in biological behaviour across groups
of chemically related compounds. Derogation statements by Industry for not carrying out testing for particular
endpoints is based on the recognition of similarities in effects between nickel-containing compounds where data
is available, and other related compounds where experimental data is not available. Assumptions are made in the
risk assessment reports of the individual compounds reviewed by the Rapporteur about the possibility to
extrapolate data between these compounds. The data reviewed for the five individual substances can also be used
as a basis for similar extrapolations to other related nickel compounds.

1.3 CLASSIFICATION.

1.3.1 Current classification

1.3.1.1 UN Transport labelling.
Four nickel compounds are included as specific entries in the UN Recommendations on the Transport of
Dangerous Goods (UN, 2001) and ADR (UN ECE 2001b).

UN Number Class Subsidiary Packaging
risk Group
Nickel carbonyl (nickel tetracarbonyl) 1259 6.1 3 I
Nickel cyanide (Nickel (II) cyanide) 1653 6.1 II
Nickel nitrate (Nickel (II) nitrate, nickelous nitrate) 2725 5.1 III
Nickel nitrite (Nickel (II) nitrite, nickelous nitrite) 2726 5.1 III

None of these four entries are included in Annex B.2 – Appendix 4 of the ADN (UN ECE, 2001a).

According to information supplied by Industry to the Rapporteur, nickel containing compounds and products are
classified under the following n.o.s. entries:

UN Name UN Number Class Subsidiary Packaging
risk Group
nickel carbonate Environmentally UN 3077 9 M7 III
hazardous substance,
solid, n.o.s
nickel chloride (solid) Toxic solid, inorganic. UN 3288 6.1 T5 III
n.o.s.
nickel chloride (liquid) Toxic liquid, inorganic. UN 3287 6.1 T4 III
n.o.s.
Lithium nickel Lithium batteries. UN 3091 9, M4 II
batteries
nickel catalyst, dry, metal catalyst, dry, UN 2881 4.2 I / II
nickel catalyst, spent flammable solid, organic UN 1325 4.1 III
n.o.s.
nickel metal powder metal powder, UN 3089 4.1 II
with very fine particle flammable, n.o.s.
size (e.g. INCO 210)
nickel powder less Environmentally UN 3077 9 M7 III.
than 100 microns hazardous substance,
solid n.o.s
nickel sulphate Environmentally UN 3077 9 M7 III
hazardous substance
solid n.o.s.

The Rapporteur has no information on the Transport classification used for other nickel compounds

14


1.3.1.2 Classification according to Directive 67/548/EEC.
Thirteen nickel compounds are included in Annex I to Directive 67/548/EEC (EEC, 1992a) as separate entries.
Three of these are notified substances. The classification of all these entries (including substances reviewed in
the individual risk assessment reports are shown below. In some cases, a number of different compounds have
the same classification.

Individual entries are classified as follows:

Nickel carbonyl: 028-001-00-1 (EC No.: 236-669-2, CAS No.: 13463-39-3) (25th ATP, EC 1998b)
Classification
F; R11 Carc. Cat. 3; R40 Repr. Cat. 2; R61 T+; R26 N; R50-53
Labelling
Symbols F; T+; N
R Phrases 61-11-26-40-50/53 (Nota E)
S-Phrases 53-45-60-61

Nickel: 028-002-00-7 (EC No.: 231-111-4, CAS No.: 7440-02-0) (19th ATP, EEC, 1993d 1)
Classification
Carc. Cat. 3; R40 R43
Labelling
Symbols Xn
R Phrases 40-43
S-Phrases (2-)22-36

Nickel monoxide: 028-003-00-2 (EC No.: 215-215-7, CAS No.: 1313-99-1) (28th ATP, EC 2001e)
Nickel dioxide: 028-004-00-6 (EC No.: 234-823-3, CAS No.: 12035-36-8) (28th ATP, EC 2001e)
Nickel trioxide: 028-005-00-3 (EC No.: 215-217-8, CAS No.: 1314-06-3) (28th ATP, EC 2001e) 2
Classification
Carc. Cat. 1; R49 R43 R53
Labelling
Symbols T
R Phrases 49-43-53
S-Phrases 53-45-61

1
This entry has been revised in the 30th ATP which was adopted by a Technical Progress Committee in
February 2007, but not yet adopted by the Commission or published in the Official Journal. The revised entry is
classified as: Carc. Cat. 3; R40; T; R48/23 and R43. An additional entry for particle size < 1 mm including
calssification as R52-53 has been agreed by the TC C&L and included in a draft 31 ATP sent for comment in
July 2007.
2
Changes to these entries have been agreed by the TC C&L and included in a draft 31 ATP sent for comment in
July 2007. The revised entries are classified as: Carc. Cat. 1; R49; T; R48/23, R43 and R53.

15


Nickel sulphide: 028-006-00-9 (EC No.: 240-841-2, CAS No.: 16812-54-7) (28th ATP, EC 2001e) 3
Classification
Carc. Cat. 1; R49 R43 N; R50-53
Labelling
Symbols T; N
R Phrases 49-43-50/53
S-Phrases 53-45-60-61

Nickel subsulphide 1: 028-007-00-4 (EC No.: 234-829-6, CAS No.: 12035-72-2) (28th ATP, EC 2001e) 3
Classification
Carc. Cat. 1; R49 R43 N; R51-53
Labelling
Symbols T; N
R Phrases 49-43-51/53
S-Phrases 53-45-61
1)
Heazlewoodite given as a synonym by NiPERA (1996).

Nickel dihydroxide: 028-008-00-X (EC No.: 235-008-5, CAS No.: 12054-48-7) (28th ATP, EC 2001e) 4
Classification
Carc. Cat. 3; R40 Xn; R20/22 R43 N; R50-53
Labelling
Symbols Xn; N
R Phrases 20/22-40-43-50/53
S-Phrases (2-)22-36-60-61

Nickel sulphate: 028-009-00-5 (EC No.: 232-104-9, CAS No.: 7786-81-4) (25th ATP, EC 1998b) 5
Classification
Carc. Cat. 3; R40 Xn; R22 R42/43 N; R50-53
Labelling
Symbols Xn; N
R Phrases 22-40-42/43-50/53
S-Phrases (2-)22-36/37-60-61

3
Changes to this entry has been agreed by the TC C&L and included in a draft 31 ATP sent for comment in July
2007. The revised entry is classified as: Carc. Cat. 1; R49; Muta. Cat. 3; R68; T; R48/23, R43 and N; R50-53.
4
Changes to this entry has been agreed by the TC C&L and included in a draft 31 ATP sent for comment in July
2007. The revised entry is classified as: Carc. Cat. 1; R49; Repr. Cat. 2; R61; Muta. Cat. 3; R68; Xn; R20/22; T;
R48/23, Xi; R38; R42/43 and N; R50-53.
5
This entry has been revised in the 30th ATP. The revised entry is classified as: Carc. Cat. 1; R49; Repr. Cat. 2;
R61; Muta. Cat. 3; R68; Xn; R20/22; T; R48/23; (SCL of 1%); Xi; R38; (SCL of 20%); R42; R43 (SCL of
0.01%) and N; R50-53.

16


Nickel carbonate 1: 028-010-00-0 (EC No.: 222-068-2, CAS No.: 3333-67-3) (25th ATP, EC 1998b) 6
Classification
Carc. Cat. 3; R40 Xn; R22 R43 N; R50-53
Labelling
Symbols Xn; N
R Phrases 22-40-43-50/53
S-Phrases (2-)22-36/37-60-61
1): NiPERA (1996) also lists two other substances, not mentioned in Annex I as included in the same Annex I
entry (028-010-00-0). These are the 1:2 nickel hydroxycarbonate, with the EINECS name: [carbonato(2-)]
tetrahydroxytrinickel), CAS and EC Nos. 12607-70-4 and 235-715-9, and 2NiCO3.3Ni(OH)2.4H2O shown with
CAS No. 12122-15-5 and EC No. 235-715-9 (for comments on these CAS & EC Nos. see risk assessment report
on nickel carbonate).

Tetrasodium (c-(3-(1-(3-(e-6-dichloro-5-cyanopyrimidin-f-yl(methyl)amino)propyl)-1,6-dihydro-2-hydroxy-4-
methyl-6-oxo-3-pyridylazo)-4-sulfonatophenylsulfamoyl)phtalocyanine-a,b,d-trisulfonato(6-))nickelato II, where
a is 1 or 2 or 3 or 4,b is 8 or 9 or 10 or 11, c is 15 or 16 or 17 or 18, d is 22 or 23 or 24 or 25 and where e and f
together are 2 and 4 or 4 and 2 respectively: 607-288-00-2 (EC No.: 410-160-7, CAS No.: 148732-74-5) (26th
ATP, EC 2000a; repeated in 28th. ATP, EC 2001e)
Classification
Xi; R36 R43 R52-53
Labelling
Symbols Xi
R Phrases 36-43-52/53
S-Phrases (2-)22-26-36/37-61

Trisodium (1-(3-carboxylato-2-oxido-5-sulfonatophenylazo)-5-hydroxy-7-sulfonatophthalen-2-amido)nickel(II):
611-103-00-0 (EC No.: 407-110-1, CAS No.: -) (29th ATP, EC 2004a)
Classification
Xi; R41 R43 N; R51-53
Labelling
Symbols Xi; N
R Phrases 41-43-51/53
S-Phrases (2-)24-26-37/39-61

Hexasodium (di(N-(3-(4-[5-(5-amino-3-methyl-1-phenylpyrazol-4-yl-azo)-2,4-disulfo-anilino]-6-chloro-1,3,5-
triazin-2-ylamino)phenyl)-sulfamoyl](disulfo)-phthalocyaninato)nickel: 611-122-00-2 (EC No.: 417-250-5, CAS
No.: 151436-99-6) (29th ATP, EC 2004a)
Classification
Xi; R41
Labelling
Symbols Xi
R Phrases 41
S-Phrases (2-)26-39

6
This entry has been revised in the 30th ATP. The revised entry is classified as: Carc. Cat. 1; R49; Repr. Cat. 2;
R61; Muta. Cat. 3; R68; Xn; R20/22; T; R48/23; Xi; R38; R42; R43 and N; R50-53.

17


In addition, 25 other nickel compounds are included in Annex I to Directive 67/548/EEC as part of group
entries 7. The classification of these entries reflects the hazards of the main functional group forming the basis of
the group entry, and is not based on hazards related to nickel.

Nickel compounds in EINECS are included in group entries in Annex I to Directive 67/548/EEC for salts of
hydrogen cyanide (006-007-00-5), fluorosilicates (009-013-00-6), chromium (VI) compounds (024-017-00-8),
arsenic compounds (033-002-00-5), salts of arsenic acid (033-005-00-1), selenium compounds (034-002-00-8),
antimony compounds (051-003-00-9), barium compounds (056-002-00-7), lead compounds (082-001-00-6),
uranium compounds (092-002-00-3) salts of oxalic acid (607-007-00-3) and metal salts of thiocyanic acid (615-
032-00-6).

EINECS name Annex I entry EC No. CAS No. Classification
nickel (II) 006-007-00-5 209-160-8 557-19-7 T+; R26/27/28 R32 N; R50-53
cyanide (1)
nickel(2+), 006-007-00-5 273-379-5 68958-89-4 T+; R26/27/28 R32 N; R50-53
bis(1,2-
ethanediamine-
N,N')-,
bis[bis(cyano-
C)aurate(1-)]
Copper(2+), 006-007-00-5 264-136-4 63427-32-7 T+; R26/27/28 R32 N; R50-53
bis(1,2-
ethanediamine-
N,N')-, (SP-4-1)-
tetrakis(cyano-
C)nickelate(2-)
(1:1)
Nickelate(2-), 006-007-00-5 237-877-6 14038-85-8 T+; R26/27/28 R32 N; R50-53
tetrakis(cyano-
C)-, disodium,
(SP-4-1)-
silicate(2-), 009-013-00-6 247-430-7 26043-11-8 Xn; R22
hexafluoro-,
nickel(2+) (1:1)(1)
nickel chromate 024-017-00-8 238-766-5 14721-18-7 Carc. Cat. 2; R49 R43 N: R50-53
(1)

nickel dichromate 024-017-00-8 239-646-5 15586-38-6 Carc. Cat. 2; R49 R43 N: R50-53
(1)

nickel diarsenide 033-002-00-5 235-103-1 12068-61-0 T; R23/25 N; R50-53
(1)

nickel arsenide 033-002-00-5 248-169-1 27016-75-7 T; R23/25 N; R50-53
(1)

nickel (II) 033-005-00-1 236-771-7 13477-70-8 Carc. Cat. 1; R45 T; R23/25 N; R50-53
arsenate (1)
Nickel selenide 034-002-00-8 215-216-2 1314-05-2 T; R23/25 R33 N; R50-53
(NiSe) (1)
selenious acid, 034-002-00-8 233-263-7 10101-96-9 T; R23/25 R33 N; R50-53
nickel(2+) salt
(1:1) (1)
selenic acid, 034-002-00-8 239-125-2 15060-62-5 T; R23/25 R33 N; R50-53
nickel(2+) salt
(1:1) (1)
antimony, compd. 051-003-00-9 234-827-5 12035-52-8 Xn; R20/22 N; R51-53
with nickel (1:1)

7
Two nickel acrylates and two nickel methacrylates were excluded from the Annex I group entries for these
compounds in the 28th. ATP (EC 2001e) when the nomenclature was changed to specify monoalkyl or monoaryl
or monoalkylaryl esters only.

18


antimony, compd. 051-003-00-9 235-676-8 12503-49-0 Xn; R20/22 N; R51-53
with nickel (1:3)
C.I. Pigment 051-003-00-9 232-353-3 8007-18-9 Xn; R20/22 N; R51-53
Yellow 53,
(Antimony nickel
titanium oxide
yellow,) (2)
antimony oxide 051-003-00-9 277-627-3 73892-02-1 Xn; R20/22 N; R51-53
(Sb203), solid
soln. with nickel
oxide (NiO) and
titanium oxide
Priderite, nickel 056-002-00-7 271-853-6 68610-24-2 Xn; R20/22
(1)

Speiss, lead, 082-001-00-6 308-765-5 98246-91-4 Repr. Cat. 1; R61; Xn; N; R50-53
nickel-contg. Repr. Cat. 3; R62 R20/22;
R33
Residues, copper- 082-001-00-6 310-050-8 102110-49-6 Repr. Cat. 1; R61; Xn; N; R50-53
iron-lead-nickel Repr. Cat. 3; R62 R20/22;
matte, sulfuric R33
acid-insol.
uranate(2-), 092-002-00-3 275-994-4 71767-12-9 T+; R26/28 R33 N; R51-53
tetrakis(acetato-
O)dioxo-
,nickel(2+)(1:1),
(OC-6-11)-
uranic acid 092-002-00-3 239-876-6 15780-33-3 T+; R26/28 R33 N; R51-53
(H2U3O10),
nickel(2+) salt
(1:1) (1)
ethandioic acid, 607-007-00-3 243-867-2 20543-06-0 Xn; R21/22
nickel salt (1)
ethandioic acid, 607-007-00-3 208-933-7 547-67-1 Xn; R21/22
nickel(2+) salt
(1:1) (1)
thiocyanic acid, 615-032-00-6 237-205-1 13689-92-4 Xn; R20/21/22 R32 N; R50-53
nickel(2+) salt (1)
1
) Chemical included in draft 31st ATP
2
) Low production volume chemical. See chapter 2.1.1.1.4. Classification discussed in preparation of draft 31st
ATP (Hart, 2007).

For nickel compounds not included in Annex I, Industry is required to evaluate the available data to assess the
hazard, and to apply a provisional classification.

Information is available from Industry for the provisional classifications of the HPVC nickel compounds
reviewed by the Rapporteur: 8
Com- Classification Reference
pound
Nickel T; R25 Xn; R40/20 Xi; R36/37 R42/43 N; R50 Eramet, 2002
chloride
Nickel O; R8 Xn; R22 R43 HEDSET

8
These two compounds have now been included in the 30th ATP. Nickel dichloride is classified as: Carc. Cat. 1;
R49; Repr. Cat. 2; R61; Muta. Cat. 3; R68; T; R23/25; T; R48/23; (SCL of 1%); Xi; R38; (SCL of 20%); R42;
R43 (SCL of 0.01%) and N; R50-53. Nickel dinitrate is classified as: O; R8; Carc. Cat. 1; R49; Repr. Cat. 2;
R61; Muta. Cat. 3; R68; Xn; R20/22; T; R48/23; (SCL of 1%). Xi; R38 (SCL of 20%); Xi; R41; R42; R43 (SCL
of 0.01%) and N; R50-53

19


nitrate (2002a)
Carc. Cat. 1; R45 T; R23/24/25 C; R34 IUCLID, 2001
O; R8 Carc. Cat. 3; R40 Xn; R22 C; R34 R42/43 HEDSET
(2002b)
O; R8 Carc. Cat. 1; R45 Xn; R22 R43 HEDSET
(1)
(2003a)
O; R8 Carc. Cat. 3; R40 Xn; R22 C; R34 R43 N; R50/53 IUCLID
(2003b)
O; R8 Carc. Cat. 3; R40 Xn; R22 R42/43 N; R50/53 IUCLID
(2)
(2003b)
O; R8 Xn; R22 Xi; R38/41 HEDSET
(2003b)
1) The classification category is not shown. Category 1 is assumed on the basis of the IARC conclusion and the
lack of any animal data.
2) R42 is applied when the nickel solution is used as an aerosol (IUCLID, 2003b).

Only one of the HPVC nickel compounds not specifically reviewed by the Rapporteur (see Table 2.1.1.C) is
included in Annex I. This is nickel oxide (Annex I entry 028-003-00-2).

None of the remaining 14 substances includes a provisional classification in the IUCLID database at the ECB
(IUCLID 2002). Several of the files include the remark that “UVCB-Stoffe sind zum größten teil nicht
eingestuft” (UVCB substances are not normally classified). There is no derogation from the requirement for
provisional classification for complex UVCB substances in the Directive, and guidance on the classification of
these substances is given in section 1.7.2.1. of Annex VI (EC, 2001e).

However, some information is available. Section C.5 of the IUCLID file for “ferronickel manufacturing slags”
(EC No. 273-729-7) considers the substance fulfils the criteria for classification as Carc. Cat 3; R40 and R43.
Section 1.15. 5 of the IUCLID file for “nickel matte” (EC No. 273-746-9) recognises that the main component is
nickel subsulphide which is classified as Carc. Cat. 1 in Annex I (Annex I entry 028-007-00-4). It states that the
dust is irritating for the respiratory tract and that it may also be a respiratory sensitiser.
A comment in the IUCLID file for “Frits, chemicals” (EC No. 266-047-6) notes that classification depends on
the composition of an individual product.
One manufacturer’s IUCLID file for “Leach residues, zinc ore-calcine, cadmium-copper ppt.” (EC No. 293-311-
8) includes a provisional classification as Xn; R20 (harmful by inhalation) (IUCLID, 1996). This provisional
classification is not included in the main IUCLID file. (IUCLID 2002).
One manufacturer’s IUCLID file for “Leach residues, zinc ore-calcine, iron contg.,” (EC No. 293-312-3)
includes a classification with R45, R46 and R61 (May cause cancer, may cause heritable genetic damage, may
cause harm to the unborn child). It also includes a classification as T; R23/25 (Toxic by inhalation and if
swallowed), Xn; R20/21/22) (Harmful by inhalation, in contact with skin and if swallowed); and R33 (danger of
cumulative effects). This evaluation is based on the classification of the main components, lead, cadmium and
arsenic. (IUCLID, 1995). This provisional classification is not included in the main IUCLID file. This does
however include a comment under section 1.15 from another manufacturer noting a composite classification
based on the properties of lead and arsenic (IUCLID 2002).
These “classifications” are shown in the table below.

Compound Classification Reference
Slags, ferronickel- Carc. Cat. 3; R40 R43 C.5 in IUCLID
manufg. (2002)
(1)
nickel matte Carc. Cat. 1; R45 Xi; R37 R42 from section 1.15.5
in IUCLID (2002)
Leach residues, Xn; R20 IUCLID (1996)
zinc ore-calcine,
cadmium-copper
ppt
Leach residues, Carc. Cat. 1; R45 T; R23/25 Xn; R21 R33 IUCLID (1995)
zinc ore-calcine, Muta. Cat. 2; R46
iron contg. Repr. Cat. 1; R61

20


Carc. Cat. 1; R45 Xn; R33 from section 1.15 in
Repr. Cat. 1; R61 R20/22 IUCLID (2002)
1
) Chemical included in draft 31st ATP

There is no assessment of “Slimes and Sludges, copper electrolyte refining, decopperised, Ni sulfate”, EC No.
295-859-3, in the IUCLID file (IUCLID, 2002), even though the EINECS description of the substance indicates
nickel sulphate which is included in Annex I (028-009-00-5) as a main component.
Some HPVCs, such as Ceramic materials and wares, chemicals (EC No. 266-340-9) are regarded as non-
hazardous. For others, e.g. Slags, copper smelting EC No. 266-968-3 the substance is not classified due a lack of
information on the effects of the substance.

The nickel-containing LPVCs are listed in Table 2.1.1.D.
Nickel hydroxide (028-008-00-X) and nickel sulphide (028-006-00-9) are both included in Annex I. C.I. Pigment
Yellow (EC No. 232-353-3) is an antimony compound and, as such is included in the group entry (051-003-00-
9). Nickel, [carbonato(2-)]tetrahydoxytri- (EC No. 235-715-9) is regarded by NiPERA as included in the nickel
carbonate entry (028-010-00-0) although it is not actually listed as part of the entry.

The IUCLID data sets are not available for LPVCs in ESIS (IUCLID, 2002). The 37 IUCLID data sets submitted
by the producers of the 22 LPVCs not included in Annex I with specific entries have been supplied by the ECB
to the Danish Rapporteur. The Table below summarises the classifications shown in these files.

Compound Classification Reference.
Nickel, [carbonato(2- Carc. Cat. 3; R40 Xn; R22 R43 IUCLID, 2003a (1)
)]tetrahydroxytri-
Nickel fluoride (NiF2) Carc. Cat. 3; R40 Xn; R22 Xi; R36 R42/43 IUCLID, 2003a (2,3)
Carc. Cat. 3; R40 R43
Nickel bromide (NiBr2) no data available IUCLID, 2003a
for classification
Sulfamic acid, nickel(2+) Carc. Cat. 3; R40 Xn; R22 Xi; R36/38 R42/43 IUCLID, 2003a (2)
salt (2:1)
Carc. Cat. 3; R40 Xn; R22 R42/43
Acetic acid, nickel(2+) salt Carc. Cat. 3; R40 R43 IUCLID, 2003a
Acetic acid, nickel salt Carc. Cat. 3; R40 Xn; R22 R42/43 IUCLID, 2003a
Octanoic acid, nickel(2+) Carc. Cat. 3; R40 Xn; C; R35 R42/43 IUCLID, 2003a
salt R20/21/22
Nickel, Xi; R39 Xi; R36 IUCLID, 2003a (2, 4,
5)
bis(dibutylcarbamodithioato
-S,S’)-, (SP-4-1)- no dangerous
properties
Nickel, bis(3-amino-4,5,6,7- no dangerous IUCLID, 2003a (5)
tetrachloro-1H-isoindol-1- properties
one oximato-N(2)-,O(1))-
Nickel, bis[2,3- no dangerous IUCLID, 2003a (5)
bis(hydroxyimino)-N- properties
phenylbutanamidato-N(2)-
,N(3)-]-
Nickel, bis[2,3- no dangerous IUCLID, 2003a (5)
bis(hydroxyimino)-N-(2- properties
methoxyphenyl)butanamidat
o]-
Nickel, [29H,31H- no data available IUCLID, 2003a
phthalocyaninato(2-)-N(29)- for classification
,N(30)-,N(31)-,N(32)-]-,
(SP-4-1)-
Nickel, (1- R52/53 IUCLID, 2003a (2)

21


butanamine)[[2,2’-thiobis[4- Xn; R20 R52/53
(1,1,3,3-
tetramethylbutyl)phenolato]
](2-)-O,O’,S]-
Nickel, 5,5’-azobis- no dangerous IUCLID, 2003a (5)
2,4,6(1H,3H,5H)- properties
pyrimidinetrione complexes
Nickel, acetate carbonate Carc. Cat. 3; R40 Xn; R22 R42/43 IUCLID, 2003a
C8-C10-branched fatty
acids C9-C11-neofatty acids
complexes
Antimony-nickel-titanium- no dangerous IUCLID, 2003a (2, 5,
6, 7)
oxide-yellow-, C.I. Pigment properties
Yellow 53
Cobalt-nickel-gray- no dangerous IUCLID, 2003a (2, 3,
5,7)
periclase-, C.I. Pigment properties
Black 25.
Nickel-ferrite-brown-spinel- no dangerous IUCLID, 2003a (5, 7)
, C.I. Pigment Brown 34 properties
Nickel-iron-chromite-black- no dangerous IUCLID, 2003a (2, 5,
7)
spinel-, C.I. Pigment Black properties
30
Lead alloy, base, dross not applicable as IUCLID, 2003a
this is an UVCB
Ashes (residues), heavy fuel no data available IUCLID, 2003a
oil fly for classification
Slimes and Sludges, copper Carc. Cat. 3; R40 T; R23/25 R42/43 R33 IUCLID, 2003a (3, 8)
electrolyte refining, (R61 included on
decopperised the label)
1) As for nickel carbonate in Annex I but without the classification for the environment. Now included together
with other nickel hydroxycarbonates in 30th ATP
2) Different provisional classifications from different IUCLID data sets.
3) Included in draft 31st ATP.
4) R39 is associated with the symbol “T+” or “T” and not “Xn”. In addition Annex VI to Directive 67/548/EEC
(EC, 2001e) requires the route of administration to be included in the classification.
5) The file contains no experimental data to support the claim that there are no dangerous effects.
6) There are five producers of this substance. As an antimony compound, the group entry in Annex I requires the
substance to be classified as Xn; R20/22, N; R51-53.
7) The substance is a complex nickel oxide. Nickel oxide is classified as a Category 1 carcinogen in Annex I.
8) Based on a composite classification of components: arsenic, lead compounds, nickel sulphate.

1.3.2 Proposed classification

1.3.2.1 UN Transport labelling.
The International Council of Chemical Associations (ICCA) (UN CETDG, 2002) has made a proposal for a
schematic classification of organometallic substances (which would include many of the nickel compounds
shown in the Appendix) to the Committee of Experts on the Transport of Dangerous Goods (UN CETDG) and
on the Globally Harmonised System of classification and labelling of chemicals

1.3.2.2 Classification according to Directive 67/548/EEC.
Nickel chloride is problematic for Norway under the EEA Treaty. Norway has made a proposal to the European
Commission (European Commission, 1995a) to classify nickel chloride as:

Carc. Cat. 1; R45, Muta. Cat. 3; R40 T; R25 R42/43 N; R50-53 (1)
1) The environmental classification proposal was added later.

22

Nickel Background EU Risk Assessment Report March 2008 Final Draft

Nickel Background EU Risk Assessment Report March 2008 Final Draft

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Nickel Background EU Risk Assessment Report March 2008 Final Draft