LIST OF DESIGNATED HAZARDOUS SUBSTANCES [NOHSC:10005(1999)]

Transcription

1 National Occupational Health and Safety Commission LIST OF DESIGNATED HAZARDOUS SUBSTANCES [NOHSC:10005(1999)] April 1999 National Occupational Health and Safety Commission Sydney

2 Commonwealth of Australia 1999 ISBN First Edition 1994 Second Edition 1999 This work is copyright. Apart from any use as permitted under the Copyright Act 1968, no part may be produced by any process without written permission from the Commonwealth available from AusInfo. Requests and inquiries concerning reproduction and rights should be addressed to the Manager, Legislative Services, AusInfo, GPO Box 84, Canberra ACT ii

3 Foreword The National Occupational Health and Safety Commission (NOHSC) is a tripartite body established by the Commonwealth Government to lead and coordinate national efforts to prevent or reduce the incidence and severity of occupational injury and disease by providing healthy and safe working environments. In seeking to improve Australia s occupational health and safety (OHS) performance, NOHSC works to: support and add value to efforts in the jurisdictions to tailor approaches to prevention improvement; facilitate, through strategic alliances, the development and implementation of better approaches to achieving improved prevention outcomes; and integrate the needs of small business into its work. NOHSC s priorities, as endorsed by the Labour Ministers Council (LMC) at its meeting on 27 November 1998, are: providing comprehensive and accurate national data, particularly to support LMC s comparative performance monitoring; facilitating and coordinating research efforts; developing and updating a nationally consistent standards framework (subject to LMC agreement); coordinating and disseminating information including industry specific practical guidance material; and developing a National OHS Improvement Strategy. iii

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5 Foreword iii Preface vii 1. Introduction 1 2. Using the List 3 Using the List to classify pure substances 9 Using the List to classify mixtures 12 Referenced documents 20 Appendices Appendix I Risk Phrases (Health Effects only) 21 Appendix II Risk Phrases (Physico-chemical and Environmental) 25 Appendix III Safety Phrases 26 Appendix IV Mixture Classification 29 List of Designated Hazardous Substances 37 Notes for this edition 38 Abbreviations and Notations 39 CAS Number Index (self-contained section-125p) Blue section Alphabetical Index (self-contained section-134p) How to use the List of Designated Hazardous Substances A Short Guide Buff Section Fold-out at back of book v

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7 Preface Under the National Commission's National Model Regulations for the Control of Workplace Hazardous Substances [NOHSC:1005(1994)] 1 and the Commonwealth, State and Territory government regulations introduced in accordance with the national model regulations, manufacturers and importers of substances supplied for use at work are required to determine whether they are hazardous to health before supply. Labels and Material Safety Data Sheets (MSDS) are also required to be produced for all hazardous substances, with appropriate information about the hazards of these substances. In order to help manufacturers, importers and suppliers meet these responsibilities, the National Commission requested that a list be developed of the more commonly used workplace hazardous substances. This publication, the List of Designated Hazardous Substances [NOHSC:10005(1994 and 1999)], is designed as an advisory document providing the first reference point for suppliers determining if any substance they supply is hazardous and providing guidance on appropriate risk and safety information. This the second edition of the List of Designated Hazardous Substances [NOHSC:10005(1999)] is extensively updated with a completely new format for presentation of the classification data. This publication is one of six titles produced by the National Commission which were released together as part of its workplace hazardous substances regulatory package. The six titles that currently comprise the set (April 1999) are: National Model Regulations for the Control of Workplace Hazardous Substances [NOHSC:1005(1994)] (which is produced under the same cover as the national code of practice); National Code of Practice for the Control of Workplace Hazardous Substances [NOHSC:2007(1994)]; National Code of Practice for the Preparation of Material Safety Data Sheets [NOHSC:2011(1994)]; National Code of Practice for the Labelling of Workplace Substances [NOHSC:2012(1994)]; Approved Criteria for Classifying Hazardous Substances [NOHSC:1008(1999)]; and List of Designated Hazardous Substances [NOHSC:10005(1999)]. vii

8 These publications are supplemented by the following titles: Guidance Note for the Assessment of Health Risks Arising from the Use of Hazardous Substances in the Workplace [NOHSC:3017(1994)]; and Guidance Note for the Control of Workplace Hazardous Substances in the Retail Sector [NOHSC:3018(1994)]. As more information becomes available or practices and formats change, the National Commission maintains the regulatory package with reviews and updates of the individual titles from time to time. It is advisable to check the currency of a document prior to purchasing. Each of the above publications may be purchased separately through Commonwealth Government Info Shops. Telephone (Toll Free) or alternately may be viewed at the National Occupational Health and Safety Commission website at viii

9 1. Introduction 1.1 Under the National Model Regulations for the Control of Workplace Hazardous Substances [NOHSC:1005(1994)] 1 a 'hazardous substance' means a substance which: (a) (b) is listed on the National Commission's List of Designated Hazardous Substances [NOHSC:10005(1999)] (the List); or has been classified as a hazardous substance by the manufacturer or importer, in accordance with the National Commission's Approved Criteria for Classifying Hazardous Substances [NOHSC:1008(1999)] 2 (the Approved Criteria). 1.2 The List and the Approved Criteria 2 are intended for use by manufacturers and importers, not by employers and employees. Employers and employees using substances in the workplace will normally identify hazardous substances from the supplier's label and MSDS. 1.3 The List contains information about the more common workplace hazardous substances. The List therefore provides an initial reference source for hazardous substance identification and classification. 1.4 Where a substance is on the List, it is a hazardous substance under the National Model Regulations for the Control of Workplace Hazardous Substances [NOHSC:1005(1994)] 1. If a substance does not appear on the List, it will be necessary to consider information on its health effects against the Approved Criteria 2 in order to determine whether it is hazardous or not. 1.5 The Approved Criteria 2 supersedes the National Commission's Guidance Note for Determining and Classifying a Hazardous Substance [NOHSC:3011(1991)]. 1.6 The Approved Criteria 2 are cited in the National Model Regulations for the Control of Workplace Hazardous Substances [NOHSC:1005(1994)] 1 and are expected to be cited in Commonwealth, State and Territory legislation introduced in accordance with these national model regulations to provide the mandatory criteria for classifying hazardous substances. The Approved Criteria 2 also provide examples showing how to apply the criteria to classify a hazardous substance as a single (pure) chemical and as a mixture.

10 1.7 Both the List and Approved Criteria 2 focus solely on hazards to health. Substances that are hazardous by virtue of their physicochemical properties only and those with nuisance dust and asphyxiant properties have been excluded from the List. Physicochemical hazards are addressed under the relevant dangerous goods legislation of the Commonwealth, State and Territory governments. Dangerous goods are defined in the Australian Code for the Transport of Dangerous Goods by Road and Rail (ADG Code) The List currently contains about 2,300 substances (individual chemicals and generic compounds), and was compiled from Annex 1 of the EEC Council Directive 67/548/EEC 4 (as updated by EC Council Directive 96/54/EC 8 ). EEC Council Directive 67/548/EEC deals with the approximation of the laws, regulations and administrative provisions relating to the classification, pa ckaging and labelling of dangerous substances. The List has been supplemented, where not already included, from the National Commission's Adopted National Exposure Standards for Atmospheric Contaminants in the Occupational Environment [NOHSC:1003(1995)] The National Commission will maintain the List and issue updates from time to time to ensure that it remains a useful aid to manufacturers and importers. In general, the List reflects the status of Annex 1 of EEC Council Directive 67/548/EEC 4 (as updated by EC Council Directive 96/54/EC 8 ). This situation also reflects the status of the Approved Criteria 2, which includes the classification criteria of EEC Council Directive 67/548/EEC 4. 2

11 2. Using the List 2.1 The List is to be used as an aid in determining and classifying hazardous substances including single ingredients and mixtures. 2.2 Classification is the process whereby the hazards of a substance are identified and categorised by reference to the Approved Criteria 2. This process enables risk phrases to be selected and concentration cut-off levels determined. The majority of substances on the List have already had their hazards identified and concentration cut-off levels determined. Therefore the List provides a useful reference source for this informatio n. 2.3 While an entry in the List means that the substance is hazardous, the absence of an entry is not an indication that the substance is not hazardous. Consequently, it is essential that all unlisted substances are assessed against the Approved Criteria 2 to determine if they are hazardous. 2.4 If a substance is on the List, suitable risk phrases for labelling and MSDS may be identified for that substance at any concentration by using the information provided in the List. 2.5 The information fields contained in the List are of different types: Substance identification data (three fields): substance name; CAS Number; and United Nations number. Hazard classification data (three fields): classification; labelling; and concentration cut-off levels. 3

12 Source Most entries are derived from European Union sources and are hence designated as EU. Other sources include A for Australian Exposure Standard. For full details see the Abbreviations and Notations section preceding the alphabetical List. 2.6 The first six information fields are described in the following sections, with guidance on how to use the List for determining and classifying hazardous substances. Substance identification data 2.7 To enable the identification of a substance on the List, the List has been sorted: (a) (b) numerically, by CAS Number (the 'CAS Number index'). alphabetically, by the name of the substance (the 'alphabetical index'). 2.8 Both the CAS Number index and the alphabetical index contain all six fields of information. However, not all entries in the list will contain data in each of seven fields. Substance name 2.9 Every entry contains information in this field The substance name may be the recognised chemical name, the common name or, in some cases, a generic name Names in this field are those appearing in the sources used to compile the List together with synonyms obtained from Australian reference publications. For this reason, substance names in the List may not necessarily accord with the recognised chemical names The listing of synonyms for a substance will not necessarily be exhaustive. 4

13 2.13 Synonyms contained in the List may be used in the preparation of substance labels and MSDS. Guidance for assigning preferred substance names in the preparation of labels is provided in the National Commission's National Code of Practice for the Labelling of Workplace Substances [NOHSC:2012(1994)] 6. Guidance on MSDS is provided in the National Commission's National Code of Practice for the Preparation of Material Safety Data Sheets [NOHSC:2011(1994)] 7. Chemical Abstract Service Registry Number 2.14 A Chemical Abstract Service Registry Number (CAS Number) is assigned to a single chemical by the Chemical Abstract Service, a referencing organisation based in the United States. Some mixtures, but not many, are assigned a CAS Number When the CAS Number for a substance is known, then it is easier to search the CAS Number index as any synonyms for a substance will be grouped together. When only the chemical name is known, then the alphabetical index should be searched The List is a useful source of CAS Numbers for the preparation of MSDS for hazardous substances. United Nations Number 2.17 The United Nations number (UN number) is a four digit identification number developed by the United Nations Committee of Experts on the Transport of Dangerous Goods. UN numbers may be assigned to a single substance or to a group of substances with similar characteristics or hazardous properties. For example: Organophosphorus pesticides, liquid, toxic - UN number The List is a useful source of UN numbers for the preparation of labels and MSDS for hazardous substances Not all substances on the List have been allocated a UN number. A numerical listing of UN numbers can be found in section 9.5 of the ADG Code 3. 5

14 2.20 Some substances on the List have more than one UN number listed. Different numbers are often used by the United Nations Committee of Experts on the Transport of Dangerous Goods to differentiate between: physical properties, for example, a solid or liquid substance; and levels of impurities or activity, for example, the available chlorine or degree of hydration. Classification 2.21 The majority of substances on the List have been classified, that is, given risk and safety phrases for each of the hazards and concentration cut-off levels. The classification information does include the details of the required health risk assessment as well as the physicochemical and environmental criteria which are supplied for information purposes only. For further clarification, see the Abbreviation and Notation section preceding the alphabetical List The source of this data is currently the European Communities legislation on dangerous substances. The classification data in this edition reflects that given by the European Communities up to and including EC Council Directive 96/54/EC 8 published in September Where a substance is on the List without hazard classification data, this does not mean that the substance has no hazardous properties: it simply means that the substance has not been classified by the European Communities or equivalent processes in Australia. The manufacturer or importer of a substance will have responsibilities to determine its hazards under Commonwealth, State and Territory government legislation introduced in accordance with the National Model Regulations for the Control of Workplace Hazardous Substances [NOHSC:1005(1994)] Hazard classification data is essential for classifying mixtures of hazardous ingredients as different concentration cut-off levels apply to different health hazards. 6

15 Labelling 2.25 The labelling column includes a shortened repeat of the classification data. This information does include the details of the required health risk assessment as well as the physicochemical and environmental criteria which are supplied for information purposes only Notes included in this column define the exact chemical conditions which apply to the classification and labelling of specific chemicals and must be referred to for accurate classification and labelling (see below for an introduction on the use of risk and safety phrases). The Use of Risk and Safety Phrases 2.27 Risk phrases convey a general description of the physicochemical, environmental and health hazards of a substance. Safety phrases provide information on safe storage, handling, disposal, personal protection and first aid For practical purposes, the National Commission directed that the risk and safety phrases provided by the European Communities legislation on dangerous substances should be used in the List where they have been classified under that system Risk and safety phrases appear in the List as a series of numbers coded according to the European Communities system 4. A key to the numbers appearing in the List is provided at Appendices I to II of this technical report. For the purposes of the List, risk and safety phrases are expressed either as numbers separated by a space to denote separate statements or an oblique stroke (/) to denote a combined statement of the phrases involved Figures appearing in brackets after risk phrases R40, R45, R46, R47 and R49 refer to the classification category, for example, R45(2) is a category 2 carcinogen. Because R40 can be used to denote either a category 3 carcinogen or mutagen, the convention in the List is to denote a mutagen classification as R40 This classification categorisation also applies to Toxic for Reproduction classifications (R60-R63) The List contains suggested risk phrases for both health, physicochemical and environmental hazards and therefore provides a useful source of risk and safety phrases when preparing labels and MSDS for hazardous substances. The health 7

16 hazard risk phrases are the only ones required for health hazard assessment. The environmental and physico-chemical phrases are provided for information purposes only. For more details on the application of risk and safety phrases, refer to the National Commission's National Code of Practice for the Labelling of Workplace Substances [NOHSC:2012(1994)] 6. Concentration cut-off levels 2.32 A concentration cut-off level for a substance in the List represents a level (expressed as a percentage on a weight/weight basis) at and above which that substance must be considered hazardous A mixture is classified as a hazardous substance if it contains at least one ingredient at a concentration equal to or above the lowest concentration cut-off level given for that ingredient Concentration cut-off levels refer to health hazards only, and are not associated with the physicochemical hazards of a substance The List contains five designations of concentration cut-off levels which allow mixtures to be classified according to one or more of the following hazard categories: Harmful (X n ); Toxic (T); Very Toxic (T + ); Irritant (X i ); and Corrosive (C) Concentration cut-off levels are designed to provide a practical level of protection and should not be interpreted as a definitive level below which an effect cannot occur. In this regard, certain mixtures may be classified as hazardous substances despite containing hazardous ingredients at concentrations below their minimum concentration cut-off levels. This is because the health effects of certain types of hazardous substances are regarded as additive, for example, irritants and acutely toxic substances. Two corrosives in a mixture present below their individual cut-off points may be classified together as Corrosive when their effects are added. Appendix IV provides further information on this point. 8

17 2.37 Concentration cut-off levels have been assigned in accordance with the Approved Criteria 2 unless individually listed in Annex 1 of the European Communities legislation on dangerous substances 4. Using the List to classify pure substances 2.38 A pure substance is a unique or distinct chemical entity. Impurities may be present generally up to a concentration of 0.1% before the substance should be considered a mixture and classified accordingly (see 'Using the List to classify mixtures') All impurities should be checked against the List as a few substances, notably carcinogens, have concentration cut-off levels below 0.1% All substances on the List have been determined as hazardous according to the National Model Regulations for the Control of Workplace Hazardous Substances [NOHSC:1005(1994)] For pure substances, the risk phrases given in the List will allow a full classification of the hazardous substance with the appropriate hazard categories To extract this information from the List, the risk phrases along with the respective hazard category or categories, are included in the classification, labelling, and cut-offs columns Table 1 has been prepared to assist with this process. The risk phrases assigned in the List can simply be checked against Table 1 to determine the appropriate hazard category The full classification for a pure substance can then be prepared by simply listing the hazard category or categories obtained, together with the relevant risk phrases It is the convention in classifying pure substances to list the relevant hazard categories in the following order: Very Toxic > Toxic > Harmful > Corrosive > Irritant > Carcinogen > Mutagen > Toxic to Reproduction For example, Ethylene oxide would be classified as follows: Toxic R23 Irritant R36/37/38 Carcinogen (category 2) R45 Mutagen (category 2) R46 9

18 2.47 Note that the most hazardous hazard category for the pure substance can be found in the top line of both the labelling and cut-offs column. This category will supersede the lesser categories but may diminish with dilution in mixture formulations. The hierarchy of classification is further explained in the Approved Criteria A full classification of a substance is fundamental to the correct assignment of concentration cut-off levels and is therefore important to manufactures and importers when formulating mixtures (see 'Using the List to classify mixtures') The National Code of Practice for the Labelling of Workplace Substances [NOHSC:2012(1994)] 6 provides further guidance for assigning risk and safety phrases in the preparation of labels. 10

19 Table 1 Classification index for pure hazardous substances Risk phrase(s) Health hazard category R20 and/or R21 and/or R22 Harmful R23 and/or R24 and/or R25 Toxic R26 and/or R27 and/or R28 Very Toxic R34 Corrosive R35 Corrosive R36 and/or R37 and/or R38 and/or R41 Irritant R39 plus R23 and/or R24 and/o r R25 Toxic R39 plus R26 and/or R27 and/or R28 Very Toxic R40 plus R20 and/or R21 and/or R22 Harmful R40(3) Carc. Cat. 3, Harmful R40(M3) Muta. Cat. 3, Harmful R42 Harmful R42/43 Harmful R43 Irritant R45(1) or R49(1) Carc. Cat. 1, Toxic R45(2) or R49(2) Carc. Cat. 2, Toxic R46(1) Muta. Cat. 1, Toxic R46 (2) Muta. Cat. 2, Toxic R48 plus R20 and/or R21 and/or R22 Harmful R48 plus R23 and/or R24 Toxic and/or R25 R60(1) Repr-Fert. Cat. 1 Toxic R60(2) Repr-Fert. Cat. 2 Toxic R61(1) Repr-Devel.Cat. 1, Toxic R61(2) Repr-Devel. Cat. 2, Toxic R62(3) Repr-Fert Cat 3, Harmful R63(3) Repr-Devel Cat 3, Harmful R64 Harmful R65 Harmful Cat. Carc. Muta. Repr. Fert Devel Category Carcinogen Mutagen Toxic to Reproduction Fertility Developmental 11

20 Using the List to classify mixtures 2.50 A mixture is a physical combination of chemical substances resulting from either the deliberate mixing of substances or from a chemical reaction A mixture may be determined to be a hazardous substance by either: (a) (b) considering the health effects of the whole substance if the mixture has been tested as such; or by assessing the health effects of each ingredient if the mixture has not been tested To determine whether a mixture is a hazardous substance by using the List, a two step process is followed: Step A Identify each ingredient using one or more of the 'substance identification' information fields, that is, substance name, CAS Number or UN number. Step B Determine whether the concentration of each ingredient is above the minimum concentration cut-off level in the the bottom entry in the cut-offs column. If any ingredient is present above its minimum concentration cut-off level, then the mixture is determined to be Hazardous Should any ingredient in the mixture not appear on the List or be listed without at least one concentration cut-off level, the Approved Criteria 2 will need to be used in addition to the List to classify the mixture. Note: If a mixture contains more than one ingredient that is on the List and all ingredient concentrations are below their respective minimum concentration cut-off levels (last entry cut-offs column), the mixture may still be considered hazardous if one or more of these ingredients exhibit Corrosive, Irritant or acute lethal effects. The formulae for classifying mixtures where individual ingredient concentrations do not exceed concentration cut-off levels are provided in Appendix IV If an ingredient is hazardous, the List can be used further to classify the ingredient, that is, to assign hazard category and risk phrases, at the concentration at which it is present in the mixture. 12

21 2.55 The process of classifying mixtures involves the identification of hazard category and risk phrases for each hazardous ingredient (at specific concentrations) which are then combined to provide the overall hazard category and risk phrases for the mixture Classification of mixtures is important in preparing labels and MSDS, particularly with respect to selecting appropriate risk phrases. For example, below a specified concentration, most Corrosive ingredients are only classified as Irritants The following steps show how the List can be used to classify mixtures. In the case of a mixture containing a number of ingredients, it will be helpful to complete a classification table, such as Table 2, to record the information extracted from the List. Table 2 Classification table for hazardous ingredient(s) Classification Concentration limits HC Risk phrases Conc. > < Conc. < < Conc. < < Conc. < < Conc. < HC Hazard category Conc. Concentration Step 1 Identify each ingredient using one or more of the 'substance identification' information fields, that is, substance name, CAS Number or UN number. Step 2 Determine whether the concentration of each ingredient is above the minimum concentration cut-off level in last entry in the cutoffs column in the List. If any ingredient is present above its minimum concentration cut-off level, then the mixture is determined to be Hazardous. Step 3 To classify a hazardous mixture, take each ingredient in turn and using the cut-offs column transcribe the details from the line entry for the relevant concentration into the classification table (Table 3). 13

22 Step 4 Read off the hazard category and risk phrases from the tables for each ingredient at the specific concentrations that each ingredient is present in the mixture. Step 5 Determine the overall hazard category for the mixture by combining all the hazard categories (for each ingredient) determined in Step 3. If more than one category from Harmful (X n ), Toxic (T) and Very Toxic (T + ) apply, use only one category according to the priority order T + > T > X n. A mixture will only be classified as an Irritant (X i ) overall if it only contains hazardous ingredients classified by X i. Step 6 Combine all risk phrases for each ingredient (Step 3) to give the risk phrases appropriate for the mixture. Certain risk phrases should not be used together (such as R20 and/or R21 and/or R22 with R23 and/or R24 and/or R25, or R36 and/or R37 and/or R38 with R34 or R35). In these cases the most severe risk phrase is used. For example, R26, Very Toxic by inhalation, supersedes R23, Toxic by inhalation, supersedes R20 Harmful by inhalation. Note: The List also includes safety phrases for most substances. The identification of safety phrases is not an integral part of classification, but is important for the production of labels and MSDS. The selection of appropriate safety phrases for these purposes is discussed in the National Code of Practice for the Labelling of Workplace Substances [NOHSC:2012(1994] 6 and the National Code of Practice for the Preparation of Material Safety Data Sheets [NOHSC:2011(1994)] 7 respectively In the following examples, reference is made to the above procedure (Steps 1 to 6) to illustrate how the List can be used to classify mixtures containing hazardous ingredients. 14

23 Example 1 A mixture containing 2% Propylene imine Step 1 The only hazardous ingredient present in the mixture is Propylene imine. It is identified in the alphabetical listing of substance names. The health hazard cut-off data for Propylene imine (from the alphabetical index part of the List) is as follows: Table 3 Name Cas No Un No Cut-offs Propylene imine Conc>10%: T+; R45; R26/27/28; R41 >7%Conc<10%: T+; R45; R26/27/28; R36 >5%Conc<7%: T; R45; R23/24/25; R36 >1%Conc<5%: T; R45; R23/24/25 >0.1%Conc<1%: T; R45; R20/21/22 Step 2 The 2% concentration is above the lowest concentration cut-off level for Propylene imine (that is, 0.1%), so the mixture is determined to be Hazardous. Step 3 The relevant line from the cut-off column: >1%Conc<5%: T; R45; R23/24/25, is inserted into the table. Step 4 Since there is only one ingredient, no further entries are needed Step 5 The hazard category is Toxic, R45; R23/24/25 Step 6 Since there is only one hazardous substance in the ingredients no further classification is necessary. Note: R11 (which is found in the Classification column of the List for propylene imine) is a physicochemical risk phrase (see Table 4). Such risk phrases are given in the List for completeness as they have been assigned in the European listing of classifications. Readers should refer to State and Territory dangerous goods legislation for criteria for identification of physicochemical hazards. 15

24 Example 2 A mixture containing 0.5% Carbon tetrachloride, 15% Vinylidene chloride and 15% Propargyl alcohol; Step 1 All three ingredients Carbon tetrachlorid e, Vinylidene chloride and Propargyl alcohol have entries in the List. They are identified from the alphabetical index part of the List as follows: Table 4 Name Cas No UN No Cut-offs TETRACHLOROMETHANE [CARBON TETRACHLORIDE] 1,1-DICHLOROETHYLENE [VINYLIDENE CHLORIDE] PROP-2-YN-1-OL [PROPARGYL ALCOHOL] Conc>1%: T; R40; R23/24/25; R48/23 >0.2%Conc<1%: Xn; R20/21/22; R48/ Conc>12.5%: Xn; R40; R20 >1%Conc<12.5%: Xn; R Conc>25%: T; R23/24/25; R34 >10%Conc<25%: C; R34; R20/21/22 >5%Conc<10%: Xn; R20/21/22; R36/38 >3%Conc<5%: Xn; R20/21/22 Step 2 All three ingredients are present in the mixture at concentrations exceeding the lowest concentration cut-off level. The mixture is therefore determined to be Hazardous. Step 3 The relevant lines from the cut-off columns are inserted in the table: That is: Carbon tetrachloride >0.2%Conc<1%: Xn; R20/21/22; R48/20, Vinylidene chloride Conc>12.5%: Xn; R40; R20 Propargyl alcohol >10%Conc<25%: C; R34; R20/21/22 are inserted into the table. Step 4 Appropriate risk phrases and classifications are then identified: From the extracts from the List in Table 4 it can be seen that For Carbon tetrachloride From 1% to 100% classified as Toxic: Conc>1%: T; R40; R23/24/25; R48/23. From 0.2% up to 1% classified as Harmful: 0.2%Conc<1%: Xn; R20/21/22; R48/20 For Vinylidene chloride From 12.5% to 100% classified as Harmful: Conc>12.5%: Xn; R40; R20 From 1% up to 12.5% classified as Harmful: >1%Conc<12.5% Xn; R40 For Propargyl alcohol From 25% to 100% classified as Toxic : Conc>25%: T; R23/24/25; R34 From 1% up to 12.5% classified as Harmful: >10%Conc<25%:C, R34; R20/21/22 16

25 Note: R10 is a physicochemical risk phrase (see Table 6). Such risk phrases are given in the List for completeness as they have been assigned in the European listing of classifications. Readers should refer to State and Territory dangerous goods legislation for criteria for identification of physicochemical hazards. Step 5 Apply the appropriate equations for risk classifications for mixtures which are additive. For these calculations of mixtures refer to the Approved Criteria 2 Chapter 6 for the appropriate equations to use. For Toxic (T) mixtures with risk phrases (R23/24/25). In our example both carbon tetrachloride and propargyl alcohol are classifiable in the toxic category Mixtures containing more than one Toxic (T) ingredient are classified as Toxic (R23/24/25) if: where, P T L T Σ( P T ) 1 L T is the percentage by weight or by volume of each Toxic (R23, R24, R25) ingredient in the mixture. is the Toxic (T) concentration cut-off level specified for each Toxic (R23, R24, R25) ingredient expressed as a percentage by weight or by volume. = = = 1.17 Since the sum is greater than 1 the mixture is classified as Toxic and risk phrases R23/24/25 apply. Note: Since this classification is a more severe classification than Harmful R20/21/22 no classification of harmful cut-offs needs to be performed as it would simply reiterate this result at a less hazardous level. 17

26 Other risk phrases and hazard classifications: From carbon tetrachloride R48/23 applies since R23 applies (above), From vinylidene chloride R40 applies From propargyl alcohol R34 applies, (Please note R34 asssumes R41 is included and should be added whenever R34/35 applies) Note none of these hazard classifications is additive or exclusive so therefore all apply. Steps 6 The hazard category(ies) and risk phrases for any mixture containing these ingredients are obtained by combining the relevant information for each substance from the above, that is: Conclusion: For a mixture containing 0.5% carbon tetrachloride, 15% vinylidene chloride and 15% propargyl alcohol the final hazard/risk phrase classification is T (toxic), C (corrosive): R23/24/25, R34/41, R48/23, R It should be noted that where a mixture contains two or more ingredients that are on the List but which are present in the mixture below their respective minimum concentration cut-off levels, the criteria and formulae in Appendix IV should be applied, provided no ingredients are present in the mixture above their maximum concentration cut-off levels If the above ingredients were present in another mixture all below their respective minimum concentration cut-off levels, the mixture could still be designated as Hazardous overall (see below 2.60). Carbon tetrachloride and Propargyl alcohol are classified as Toxic ingredients (R23/24/25). Vinylidene chloride is classified as a Harmful ingredient (R20) Mixtures containing more than one Very Toxic (T + ), Toxic (T) or Harmful (Xn) ingredient are classified as Harmful (R20, R21, R22) if: Σ( P + T L Xn + P T L Xn + P Xn L Xn ) 1 where, P T+ is the percentage by weight or by volume of each Very Toxic (R26, R27, R28) ingredient in the mixture. 18

27 P T P Xn L Xn is the percentage by weight or by volume of each Toxic (R23, R24, R25) ingredient in the mixture. is the percentage by weight or by volume of each Harmful (R20, R21, R22) ingredient in the mixture. is the Harmful (Xn) concentration cut-off level specified for each Very Toxic (R26, R27, R28), Toxic (R23, R24, R25) or Harmful (R20, R21, R22) ingredient expressed as a percentage by weight or by volume Applying this formula to the following two examples: (a) A mixture containing 0.1% Carbon tetrachloride, 0.5% Vinylidene chloride and 2% Propargyl alcohol: = = 1.67 As the sum of the quotients is greater than 1, that is, 1.67, the above mixture is determined to be hazardous and should be classified as Harmful with risk phrase R20/21/22. (b) A mixture containing 0.1% Carbon tetrachloride, 0.2% Vinylidene chloride and 0.5% Propargyl alcohol: = = 0.87 As the sum of the quotients is less than 1, that is, 0.87, the above mixture is determined not to be hazardous. 19

28 Referenced documents 1. National Occupational Health and Safety Commission, 'National Model Regulations for the Control of Workplace Hazardous Substances' [NOHSC:1005(1994)], in Control of Workplace Hazardous Substances: National Model Regulations and National Code of Practice, AusInfo, Canberra, National Occupational Health and Safety Commission, Approved Criteria for Classifying Hazardous Substances [NOHSC:1008(1999)], AusInfo, Canberra, Federal Office of Road Safety, Australian Code for the Transport of Dangerous Goods by Road and Rail, 6th Edition, AusInfo, Canberra, EEC Council Directive 67/548/EEC on the approximation of the laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances, Official Journal of the European Communities, No. L196 (16 August 1967). 5. National Occupational Health and Safety Commission, 'Adopted National Exposure Standards for Atmospheric Contaminants in the Occupational Environment' [NOHSC:1003(1995)], in Exposure Standards for Atmospheric Contaminants in the Occupational Environment, AusInfo, Canberra, National Occupational Health and Safety Commission, National Code of Practice for the Labelling of Workplace Substances [NOHSC:2012(1994)], AusInfo, Canberra, National Occupational Health and Safety Commission, National Code of Practice for the Preparation of Material Safety Data Sheets [NOHSC:2011(1994)], AusInfo, Canberra, EC Council Directive 96/54/EC adapting to technical progress for the twenty-second time Council Directive 67/548/EEC on the approximation of the laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances, Official Journal of the European Communities No. L248 (30 September 1996) 20

29 Appendix I Key to relevant Risk Phrases (health effects only) Includes combination Risk Phrases R20 R21 R22 R23 R24 R25 R26 R27 R28 R29 R31 R32 R33 R34 R35 R36 R37 R38 R39 R40 R41 R42 R43 R45 R46 R48 R49 R60 Harmful by inhalation. Harmful in contact with skin. Harmful if swallowed. Toxic by inhalation. Toxic in contact with skin. Toxic if swallowed. Very toxic by inhalation. Very toxic in contact with skin. Very toxic if swallowed. Contact with water liberates toxic gas. Contact with acids liberates toxic gas. Contact with acids liberates very toxic gas. Danger of cumulative effects. Causes burns. Causes severe burns. Irritating to eyes. Irritating to respiratory system. Irritating to skin. Danger of very serious irreversible effects. Possible risks of irreversible effects. Risk of serious damage to eyes. May cause sensitisation by inhalation. May cause sensitisation by skin contact. May cause cancer. May cause heritable genetic damage. Danger of serious damage to health by prolonged exposure. May cause cancer by inhalation. May impair fertility 21

30 Risk Phrases (continued) R61 May cause harm to the unborn child. R62 R63 R64 R65 Possible risk of impaired fertility. Possible risk of harm to the unborn child. May cause harm to breastfed babies. Harmful: May cause lung damage if swallowed. R20/21 Harmful by inhalation and in contact with skin. R20/22 Harmful by inhalation and if swallowed. R20/21/22 Harmful by inhalation, in contact with skin and if swallowed. R21/22 Harmful in contact with skin and if swallowed. R23/24 Toxic by inhalation and in contact with skin. R23/25 Toxic by inhalation and if swallowed. R23/24/25 Toxic by inhalation, in contact with skin and if swallowed. R24/25 Toxic in contact with skin and if swallowed. R26/27 Very toxic by inhalation and in contact with skin. R26/28 Very toxic by inhalation and if swallowed. R26/27/28 Very toxic by inhalation, in contact with skin and if swallowed. R27/28 Very toxic in contact with skin and if swallowed. R36/37 Irritating to eyes and respiratory system. R36/38 Irritating to eyes and skin. R36/37/38 Irritating to eyes, respiratory system and skin. R37/38 Irritating to respiratory system and skin. R39/23 Toxic: danger of very serious irreversible effects through inhalation. R39/24 Toxic: danger of very serious irreversible effects in contact with skin. R39/25 Toxic: danger of very serious irreversible effects if swallowed. R39/23/24 R39/23/25 R39/24/25 R39/23/24/25 Toxic: danger of very serious irreversible effects through inhalation and in contact with skin. Toxic: danger of very serious irreversible effects through inhalation and if swallowed. Toxic: danger of very serious irreversible effects in contact with skin and if swallowed. Toxic: danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed. 22

31 Risk Phrases (continued) R39/26 Very toxic: danger of very serious irreversible effects through inhalation. R39/27 Very toxic: danger of very serious irreversible effects in contact with skin. R39/28 Very toxic: danger of very serious irreversible effects if swallowed. R39/26/27 Very toxic: danger of very serious irreversible effects through inhalation and in contact with skin. R39/26/28 Very toxic: danger of very serious irreversible effects through inhalation and if swallowed. R39/27/28 Very toxic: danger of very serious irreversible effects in contact with skin and if swallowed. R39/26/27/28 Very toxic: danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed. R40/20 Harmful: possible risk of irreversible effects through inhalation. R40/21 Harmful: possible risk of irreversible effects in contact with skin. R40/22 Harmful: possible risk of irreversible effects if swallowed. R40/20/21 Harmful: possible risk of irreversible effects through inhalation and in contact with skin. R40/20/22 Harmful: possible risk of irreversible effects through inhalation and if swallowed. R40/21/22 Harmful: possible risk of irreversible effects in contact with skin and if swallowed. R40/20/21/22 Harmful: possible risk of irreversible effects through inhalation, in contact with skin and if swallowed. R42/43 May cause sensitisation by inhalation and skin contact. R48/20 Harmful: danger of serious damage to health by prolonged exposure through inhalation. R48/21 Harmful: danger of serious damage to health by prolonged exposure in contact with skin. R48/22 Harmful: danger of serious damage to health by prolonged exposure if swallowed. R48/20/21 Harmful: danger of serious damage to health by prolonged exposure through inhalation and in contact with skin. R48/20/22 Harmful: danger of serious damage to health by prolonged exposure through inhalation and if swallowed. R48/21/22 Harmful: danger of serious damage to health by prolonged exposure in contact with skin and if swallowed. R48/20/21/22 Harmful: danger of serious damage to health by prolonged exposure through inhalation, in contact with skin and if swallowed. 23

32 Risk Phrases (continued) R48/23 Toxic: danger of serious damage to health by prolonged exposure through inhalation. R48/24 Toxic: danger of serious damage to health by prolonged exposure in contact with skin. R48/25 Toxic: danger of serious damage to health by prolonged exposure if swallowed. R48/23/24 Toxic: danger of serious damage to health by prolonged exposure through inhalation and in contact with skin. R48/23/25 Toxic: danger of serious damage to health by prolonged exposure through inhalation and if swallowed. R48/24/25 Toxic: danger of serious damage to health by prolonged exposure in contact with skin and if swallowed. R48/23/24/25 Toxic: danger of serious damage to health by prolonged exposure through inhalation, in contact with skin and if swallowed. 24

33 Appendix II Key to Non Health Effect Risk Phrases Physico-chemical (R1-19) and Environmental (R51-59) R1 Explosive when dry - R2 Risk of explosion by shock, friction, fire or other sources of ignition - R3 Extreme risk of explosion by shock, friction, fire or other sources of ignition - R4 Forms very sensitive explosive metallic compounds - R5 Heating may cause an explosion - R6 Explosive with or without contact with air - R7 May cause fire - R8 Contact with combustible material may cause fire - R9 Explosive when mixed with combustible material - R10 Flammable - R11 Highly Flammable - R12 Extremely Flammable - R14 Reacts violently with water - R15 Contact with water liberates extremely flammable gases - R16 Explosive when mixed with oxidising substances - R17 Spontaneously flammable in air - R18 In use may form flammable/explosive vapour-air mixture - R19 May form explosive peroxides R50: Very toxic to aquatic organisms R51: Toxic to aquatic organisms R52: Harmful to aquatic organisms R53: May cause long term adverse effects in the aquatic environment R54: Toxic to flora R55: Toxic to fauna R56: Toxic to soil organisms R57: Toxic to bees R58: May cause long term adverse effects in the environment R59: Dangerous for the ozone layer 25

34 Appendix III Key to safety phrases S1 S2 S3 S4 S5 S6 S7 S8 S9 S12 S13 S14 S15 S16 S17 S18 S20 S21 S22 S23 S24 S25 S26 S27 S28 S29 S30 S33 S35 S36 Keep locked up. Keep out of the reach of children. Keep in a cool place. Keep away from living quarters. Keep contents under... (there follows the name of a liquid). Keep under... (there follows the name of an inert gas). Keep container tightly closed. Keep container dry. Keep container in a well-ventilated place. Do not keep the container sealed. Keep away from food, drink and animal foodstuffs. Keep away from... (a list of incompatible materials will follow). Keep away from heat. Keep away from sources of ignition. Keep away from combustible material. Handle and open container with care. When using, do not eat or drink. When using do not smoke. Do not breathe dust. Do not breathe vapour. Avoid contact with skin. Avoid contact with eyes. In case of contact with eyes, rinse immediately with plenty of water and seek medical advice. Take off immediately all contaminated clothing. After contact with skin, wash immediately with plenty of soap-suds. Do not empty into drains. Never add water to this product. Take precautionary measures against static discharges. This material and its container must be disposed of in a safe way. Wear suitable protective clothing. 26

35 Safety Phrases (continued) S37 Wear suitable gloves. S38 S39 S40 S41 S42 S43 S45 S46 S47 S48 S49 In case of insufficient ventilation, Wear suitable respiratory equipment. Wear eye / face protection. To clean the floor and all objects contaminated by this material, use... (there follows suitable cleaning material). In case of fire and / or explosion do not breathe fumes. During fumigation / spraying wear suitable respiratory equipment. In case of fire use... (there follows the type of fire-fighting equipment to be used.) In case of accident or if you feel unwell, seek medical advice immediately (show the label whenever possible.) If swallowed, seek medical advice immediately and show this container or label. Keep at temperature not exceeding... To be kept wet with (there follows a material name). Keep only in the original container. S50 Do not mix with... S51 S52 S53 S56 S57 Use only in well ventilated areas. Not recommended for interior use on large surface areas. Avoid exposure - obtain special instructions before use. Dispose of this material and its container at hazardous or special waste collection point. Use appropriate container to avoid environmental contamination. S59 Refer to manufacturer / supplier for information on recovery / recycling. S60 This material and its container must be disposed of as hazardous waste. S61 Avoid release to the environment. Refer to special instructions / safety data sheets. S62 If swallowed, do not induce vomiting; seek medical advice immediately and show this container or label S1/2 Keep locked up and out of the reach of children - S3/7 Keep container tightly closed in a cool place - S3/9/14 Keep in a cool well ventilated place away from... (incomapatible materials to be indicated by manufacturer) - 27

36 Safety Phrases (continued) S3/9/14/49 Keep only in the original container in a cool well ventilated place away from... (incompatible materials to be indicated by the manufacturer) - S3/9/49 Keep only in the original container in a cool well ventilated place - S3/14 Keep in a cool place away from... (incompatible materials to be indicated by the manufacturer) - S7/47 Keep Container tightly closed and at a temperature not exceeding... C (to be specified by manufacturer) - S7/8 Keep container tightly closed and dry - S7/9 Keep container tightly closed and in a well ventilated place - S20/21 When using do not eat, drink or smoke - S24/25 Avoid contact with skin and eyes - S29/56 Do not empty into drains, dispose of this material and its container to hazardous or special waste collection point - S36/37 Wear suitable protective clothing and gloves - S36/37/39 Wear suitable protective clothing, gloves and eye/face protection - S36/39 Wear suitable protective clothing and eye/face protection - S37/39 Wear suitable gloves and eye/face protection - S47/49 Keep only in the original container at temperature not exceeding... C (to be specified by manufacturer) Note: There are no safety phrases S10, S11, S19, S31 or S32 in accordance with the National Commisson's National Code of Practice for the Labelling of Workplace Substances [NOHSC:2012(1994)] 6. 28

37 Appendix IV Classification of mixtures where ingredients do not exceed the concentration cut-off levels A1.1 For mixtures containing more than one hazardous substance in individual concentrations below the relevant concentration cutoff levels, formulae are provided to determine if the mixture is a hazardous substance, and to classify the substance so that the proper risk phrases can be assigned. A1.2 The formulae are applicable only for substances with either acute lethal, corrosive or irritant effects. The concentration cut-off levels from Chapter 5 (Approved Criteria) are used in the formulae. A1.3 These formulae provide a safeguard, as substances with similar health effects can produce an additive effect greater than would be suggested by their individual concentrations. A1.4 For calculating the additive effects of hazardous ingredients in mixtures (at concentrations below their concentration cut-off levels) in order to determine the hazard classification of the mixture, the following procedure is used: Identify the ingredient classification in the first column of the appropriate table in Chapter 5 (Approved Criteria). Compare the concentration of the ingredient in the mixture with the concentration cut-off levels in the table for the ingredient classification. Check to see if two or more ingredients are classified with acute lethal, corrosive or irritant effects. For each type of health effect (that is, acute lethal, corrosive or irritant effects) use the formulae listed below to classify the mixture, beginning with the most severe classification for each health effect. For example, determine whether the mixture is Very Toxic (T + ) before determining whether it is Toxic. For each denominator in the equation, select the concentration cut-off level for the ingredient which is 29