GHS New legislation on classification and labelling
Preface 2
Table of contents Preface... 2 Table of contents... 3 Introduction/Background... 6 Building blocks... 6 Difference between UN and EU... 7 Part of UN but not part of EU... 7 Part of EU but not part of UN... 8 Downstream legislation... 8 Classification criteria... 9 Physical hazards... 9 Explosives... 11 Flammable gases... 11 Flammable aerosols... 11 Oxidizing gases... 11 Gases under pressure... 11 Flammable liquids... 11 Flammable solids... 12 Self-reactive substances and mixtures... 12 Pyrophoric liquids... 12 Pyrophoric solids... 12 Self-heating substances and mixtures... 12 Substances and mixtures which in contact with water emit flammable gases... 12 Oxidizing liquids... 12 Oxidizing solids... 12 Organic peroxides... 13 Corrosive to metals... 13 Health hazards... 14 Acute toxicity... 15 Skin corrosion/irritation... 15 Serious eye damage/eye irritation... 15 Respiratory or skin sensitisation... 15 Germ cell mutagenicity... 15 Carcinogenicity... 15 Reproductive toxicity... 15 Specific target organ toxicity (STOT) single exposure... 15 Specific target organ toxicity (STOT) repeated exposure... 15 Aspiration hazard... 16 Environmental hazards.... 17 Hazardous for the ozone layer.... 17 Differences between DSD and CLP... 18 Physical hazards... 18 Flammable liquids... 18 Health hazards... 20 Acute toxicity inhalation... 20 3
Acute toxicity dermal... 20 Acute toxicity oral... 20 Skin corrosion/irritation... 20 Eye damage/eye irritation... 21 Sensitisation... 21 Mutagenicity... 21 Carcinogenicity... 21 Reproductive toxicity... 22 STOT, single exposure... 22 STOT, repeated exposure... 22 Environmental hazards... 23 Classification of substances... 24 Classification of mixtures... 24 Bridging Principles... 24 Dilution... 25 Batching... 25 Concentration of highly hazardous mixtures... 25 Similar mixtures... 26 Changes in compositions... 27 Aerosols... 27 Calculation principles... 28 Cut-off values... 28 Acute toxicity... 28 Classification based on concentration thresholds... 31 Labelling... 38 Labelling of unclassified mixtures... 38 Content of the label... 39 Hazard Pictograms... 39 Principles of precedence for hazard pictograms... 41 Signal words... 41 Hazard statements... 42 Additional EU-statements... 42 Precautionary statements... 43 Product identifiers... 45 Supplemental information... 45 Special rules for packaging not exceeding 125 ml... 45 Language... 47 Format of a label... 47 Outer and inner packaging... 47 Transport regulation and CLP... 48 Example of a label... 48 Update of label information... 49 Who is affected by CLP and how?... 50 Importers and manufacturers of substances... 50 Classification and labelling inventory... 50 Formulators... 50 4
Distributors... 50 End-users of chemicals... 50 Preparation for CLP in the organisation... 51 CLP / GHS in the future... 51 Transitional period... 52 Transitional period for substances... 52 Transitional period for mixtures... 52 Conversion tables... 53 Links... 54 GHS/CLP Vocabulary... 55 Exercises... 57 Exercise 1. Classification of substances translation table... 57 Exercise 2. Classification of mixtures calculation... 57 Exercise 3. Labelling label for previous classified mixture... 57 Product identifier(s)... 57 Signal Words... 58 Hazard pictograms... 58 Hazard Statements... 58 Supplemental information... 58 Exercise 4. Principles of Precedence Choosing hazard pictograms... 58 Solutions... 59 Exercise 1... 59 Exercise 2... 59 Exercise 3... 62 Exercise 4... 64 Final labels... 65 5
Introduction/Background GHS was adopted by UN in 2002. The intention was to introduce a global system for classification and labelling of chemical substances and mixtures. Without a global system a chemical substance may have quite different classifications from country to country and from region to region. Some substances may be considered toxic in one country and harmless in another country. Harmonised criteria for evaluating the hazardous properties of chemicals will, by time, ensure uniform classifications all over the world. This will make it easier for companies to import and export chemicals and hopefully it will lead to a better protection of man and environment. GHS should by time be implemented worldwide. However, the timeline for implementation varies. Some countries have already implemented GHS while others are still in the process of analyzing how to do it. In EU GHS entered into force in January 2009. GHS is implemented as Regulation of the European Parliament and of the council on classification, labelling and packaging of substances and mixtures, in short: CLP system or just: CLP. CLP is in many ways similar to the current EU system for classification and labelling, and EU has implemented most of the building blocks from GHS. The global GHS text also states criteria for preparation of safety data sheets. The GHS safety data sheets are almost similar to the EU safety data sheets, however in EU safety data sheets will not be regulated under CLP as they are already regulated under REACH. In this course the current EU-system for classification and labelling of substances (directive 67/548/EEC) will be referred to as Dangerous Substance Directive, DSD, while the current EU-criteria for classification and labelling of mixtures (directive 1999/45/EC ) will be referred to as Dangerous Preparations Directive, DPD. Building blocks GHS introduces the term Building block approach. GHS is build up by a large number of blocks, and each country or region (e.g. EU) is free to pick the building blocks they want, so even if the intention is a globally harmonized system there may still be differences in the implementation from country to country or region to region. However, if a country or region chooses to implement a building block they have to implement the building block as a whole without any changes. If two countries have chosen to implement the same building block (for example the classification for acute toxicity category 4) both countries will use the same criteria when classifying chemicals as toxic. See criteria for Acute toxicity, page 28 6
Difference between UN and EU When implementing the UN GHS, EU has left out some hazard classes and categories and introduced some not represented in the UN GHS. An overview of the main differences between CLP and the GHS proposal from UN is found in Table 1. UN Flammable liquid, category 4 Acute toxicity, category 5 Skin irritation, category 3 Aspiration Hazard, category 2 Hazardous to the aquatic environment, Acute category 2 and 3 Not part of the UN GHS Safety data sheets Table 1. UN-GHS versus EU-CLP Not part of CLP Not part of CLP Not part of CLP Not part of CLP Nor part of CLP EU Hazardous for the ozone layer Not part of CLP. Safety data sheets are regulated under REACH. However, the format and contents of a GHS safety data sheet and an EU safety data sheet are almost similar. Furthermore CLP covers some hazards that lead to additional labelling which is not part of GHS. These additional hazards are described further under Additional EU statements. Part of UN but not part of EU In EU a flammable liquid is a liquid with a flashpoint of not more than 60 C. In UN a flammable liquid is a liquid having a flashpoint of not more than 93 C. In EU the flammable liquids are divided into category 1, 2 and 3 while in UN there is also a category 4 covering liquids with a flashpoint between 60 C and 93 C. In EU an acute toxic substance is a substance having an LD 50 -value of not more than 2000 mg/kg. The hazard class Acute Toxic is divided into four categories with category 4 presenting the lowest level of hazard. UN introduces an Acute Toxic category 5 for chemicals having an LD 50 -value between 2000 and 5000 mg/kg. This category 5 is not a part of CLP. In EU there are two categories for skin corrosion/irritation, namely category 1 and 2. In UN there is a category 3 for mild skin irritation which is not a part of CLP. In EU there is one category for the hazard class Aspiration Hazard while in UN there is both category 1 and 2. Regarding Environmental hazards, EU has chosen to implement one category for acute toxicity, but the UN system introduces three categories. 7
Part of EU but not part of UN In EU there is an additional hazard class, which is not part of the UN system, namely the classification as Hazardous for the ozone layer Downstream legislation CLP will affect most chemical legislation including REACH. REACH and other legislations often refer to specific classifications and specific R-phrases. With CLP these R-phrases will no longer exist and therefore, in time, downstream legislation has to be updated. 8
Classification criteria Classification of chemical substances and mixtures means that the physical hazards, the health hazards and the environmental hazards of the substance/mixture are determined. A classification consists of a hazard class and a hazard category. Table 2, Table 3 and Table 4 lists the CLP hazard classes and hazard categories implemented in EU. This course will briefly go through the definitions and some of the criteria for each hazard class. Furthermore you will find a short description of the differences between the CLP criteria and the criteria from the DSD. Physical hazards To decide whether a substance or mixture is classified with one or more physical hazards specific tests must always be performed. Most of the physical tests required according to the CLP regulation are identical to the tests described in the UN Recommendations on the transport of Dangerous Goods, Manual of Tests and Criteria. An overview of the physical hazard classes and hazard categories is found in Table 2. In addition to the table you will find a brief description of each hazard class. 9
Hazard Class Hazard category Explosives Unstable explosives Division 1.1 Division 1.2 Division 1.3 Division 1.4 Division 1.5 Division 1.6 Flammable gasses 1 2 Flammable aerosols 1 2 Oxidizing gases 1 Gases under pressure Compresses gas Liquefied gas Refrigerated liquefied gas Dissolved gas Flammable liquids 1 2 3 Flammable solids 1 2 Self-reactive substances and mixtures Type A Type B Type C&D Type E&F Type G Pyrophoric liquids 1 Phyrophoric solids 1 Self-heating substances and mixtures 1 2 Substances and mixtures which in 1 contact with water emit flammable gases 2 3 Oxidizing liquids 1 2 3 Oxidizing solids 1 2 3 Organic peroxides Type A Type B 10
Type C&D Type E&F Type G Corrosive to metals 1 Table 2. Physical hazards Explosives The class of explosives comprises solid and liquid substances and mixtures as well as articles. To classify a substance, a mixture or an article as explosive, tests needs to be performed. This hazard class is found under DSD. However, DSD does not contain as many hazard categories for explosives as CLP. Flammable gases A flammable gas is a gas or a gas mixture having a flammable range with air at 20 C and a pressure of 101.3 kpa. The gas or the gas mixture must be tested to decide whether it meets the criteria. In DSD gasses are classified as flammable, but DSD only operate with one term Flammable, which is used for both liquids and gasses. Flammable aerosols An aerosol dispenser containing compressed gas under pressure shall be classified as flammable if it contains components classified as flammable liquids, flammable gases or flammable solids. This hazard class is not a part of DSD. Oxidizing gases An oxidizing gas is a gas or a gas mixture which may provide oxygen and thereby contribute to the combustion of other material more than air does. In DSD oxidising gasses are classified but they are classified together with other oxidising substances. Gases under pressure The gases under pressure comprise compressed gases, liquefied gases, dissolved gases and refrigerated liquefied gases. This hazard class is not a part of DSD. Flammable liquids A flammable liquid is a liquid having a flash point of 60 C or less. Flammable liquids are classified under DSD, but the criteria are different. 11
Flammable solids A flammable solid is a powdered, granular or pasty substance or mixture which can be easily ignited by brief contact with an ignition source. This hazard class is not a part of DSD. Self-reactive substances and mixtures A self-reactive substance or mixture is a thermally unstable liquid or solid. The liquid or solid is liable to undergo a strongly, exothermic decomposition even without the presence of air. This hazard class is not a part of DSD. Pyrophoric liquids A pyrophoric liquid is a liquid which, even in small amounts, within 5 minutes of coming into contact with air is liable to ignite. This hazard class is not a part of DSD. Pyrophoric solids A pyrophoric solid is a solid which, even in small amounts, within 5 minutes of coming into contact with air is liable to ignite. This hazard class is not a part of DSD. Self-heating substances and mixtures A self-heating substance or mixture differs from a pyrophoric liquid or solid in that it will ignite only in large amounts (kilograms) and after a long period of time (hours or days). This hazard class is not a part of DSD. Substances and mixtures which in contact with water emit flammable gases Hereby means solid or liquid substances or mixtures which in contact with water become spontaneously flammable or give off flammable gases in dangerous quantities. The hazard class is also found in DSD. Oxidizing liquids An oxidizing liquid is a liquid substance or a liquid mixture which may provide oxygen and thereby contribute to the combustion of other material. The oxidizing liquid is not necessarily combustible itself. Part of DSD. Oxidizing solids An oxidizing solid is a solid substance or a solid mixture which may provide oxygen and thereby contribute to the combustion of other material. The oxidizing solid is not necessarily combustible itself. Part of DSD. 12
Organic peroxides Organic peroxides are liquid or solid organic substances containing the O-O structure. Whether an organic peroxide is classified or not, depends on the amount of available oxygen. Organic peroxides are classified under DSD, but they do not have a separate hazard category. In DSD organic peroxides are classified together with other oxidising substances. Corrosive to metals A substance or mixture is corrosive to metals if it materially damage or destroy metals. Whether it is classified or not depend on the corrosion rate on either steel or aluminium. Not a part of DSD. 13
Health hazards The criteria for classifying a substance or a mixture for one or more health hazards are very close to the criteria known from the EU system described in DSD. An overview of the health hazard classes and hazard categories is found in Table 3. In addition to the table you will find a brief description of each hazard class. Hazard Class Hazard category Acute toxicity 1 2 3 4 Skin corrosion/irritation 1A 1B 1C 2 Serious eye damage/eye irritation 1 2 Respiratory or skin sensitisation Skin sensitiser Respiratory sensitiser Germ cell mutagenicity 1A 1B 2 Carcinogenicity 1A 1B 2 Reproductive toxicity 1A 1B 2 Additional category for effects on or via lactation Specific target organ toxicity 1 single exposure 2 3 Specific target organ toxicity 1 repeated exposure 2 Aspiration hazard 1 Table 3. Health hazards 14
Acute toxicity Acute toxicity differs between oral, dermal and inhalation exposure. Acute toxicity takes into consideration effects occurring after a single dose of a substance or mixture. The criteria in CLP are different from the criteria described in DSD. Skin corrosion/irritation A corrosive substance or mixture is capable of producing irreversible damage to the skin, while irritating substances and mixtures produce reversible damage to the skin. The criteria in CLP differ from the criteria in DSD. Serious eye damage/eye irritation Chemicals irritating to eyes or chemicals causing serious eye damage are able to damage the tissue in the eye or to cause a physical decay of vision. Serious eye damage is not fully reversible while the eye irritation is fully reversible. Respiratory or skin sensitisation A respiratory sensitiser will cause hypersensitivity of the airways if inhaled. A skin sensitiser will cause an allergic response following skin contact. Germ cell mutagenicity To meet the criteria for germ cell mutagenicity, a chemical is able to permanently change the structure or amount of the genetic material in a cell (DNA). The chemical meeting these criteria will be called a mutagen. Carcinogenicity A chemical classified as carcinogen may either cause cancer or increase the incidence of cancer. The classification does not differ between different types of cancer. Reproductive toxicity Reproductive toxicity is the ability to affect the sexual function and the fertility of adult male and female. Furthermore a chemical toxic to reproduction may be able to affect the development of the offspring. Specific target organ toxicity (STOT) single exposure Specific target organ toxicity single exposure is defined as non lethal target organ toxicity. The effects are significant and specific and they occur after only one exposure to the chemical. Both reversible and irreversible effects are included in this definition. Specific target organ toxicity (STOT) repeated exposure The definition of specific target organ toxicity repeated exposure is similar to the Specific target organ toxicity single exposure except that for the repeated exposure the effects will only appear after two or more exposures. 15
Aspiration hazard Chemicals that pose an aspiration hazard are liquids or solids able to enter the lungs e.g. following vomiting. The chemicals may cause chemical pneumonia or other severe injuries. 16
Environmental hazards. When classifying for environmental hazards only the effects to the aquatic environment are considered. To classify a chemical you will need to know the acute and chronic toxicity to aquatic organisms as well as the potential to bioaccumulate and the ability of biodegradation. An overview of the environmental hazard classes and hazard categories is found in Table 4. Hazard Class Hazardous to the aquatic environment - Acute Hazardous to the aquatic environment - Chronic Hazardous for the ozone layer Table 4. Environmental hazards Hazard category 1 1 2 3 4 Hazardous for the ozone layer. EU has chosen to use an additional hazard class and enable the classification of a chemical as hazardous for the ozone layer. 17
Differences between DSD and CLP Even though the principles for classification are the same in DSD and CLP some criteria are different. The tables below give an overview of the main differences between the classification criteria according to DSD and CLP for health hazards and environmental hazards. Physical hazards There are major changes between DSD and CLP when it comes to physical hazards. Some criteria for existing hazard classes have changed, but the main difference is the addition of a number of hazard classes, which are not part of DSD. The differences between DSD and CLP for flammable liquid are shown in Table 5, while Table 6 and Table 7 give an overview of the additional hazard classes under CLP. Describing all criteria for classification will be much too comprehensive for this course. Please see the CLP-legislation for details. Flammable liquids DSD CLP Extremely flammable Flash point < 0 C and boiling point 35 C Category 1 Flash point < 23 C and boiling point 35 C Highly flammable Flash point < 21 but not extremely flammable Category 2 Flash point < 23 C and boiling point > 35 C Flammable 21 C flash point 55 C Category 3 23 flash point 60 C Table 5. Comparison between DSD and CLP for flammable liquids Hazard classes R-phrases Explosives E;R2 E;R3 Oxidizing substances O;R7 O;R8 O;R9 Flammable substances F+;R12 F;R11 F;R15 F;R17 R10 Table 6. Physical hazard classes under DSD 18
Hazard classes Hazard categories Explosives Unstable Div 1.1 Div 1.2 Div 1.3 Div 1.4 Div 1.5 Div 1.6 Flammable gases 1 2 Flammable aerosols 1 2 Oxidizing gases 1 Gases under pressure Compressed gas 1 Liquified gas 1 Refrigerated liquefied gas 1 Dissolved gas 1 Flammable liquids 1 2 3 Flammable solids 1 2 Self-reactive substances and mixtures Type A Type B Type C Type D Type E Type F Type G Pyrophoric liquids 1 Pyrophoric solids 1 Self-heating substances and mixtures 1 2 Substances and mixtures which in contact with water emit flammable gases 1 2 3 Oxidizing liquids 1 2 3 Oxidizing solids 1 2 3 Organic peroxides Type A Type B Type C Type D Type E Type F Type G Corrosive to metals 1 Table 7. Hazard classes under CLP 19
Health hazards Acute toxicity inhalation DSD R26 R23 R20 LC 50 (mg/l/4 hours) 0,5 0,5-2 2-10 10-20 CLP Category 1 Category 2 Category 3 Category 4 Acute toxicity dermal DSD R27 R24 R21 LD 50 (mg/kg) 50 50-200 200-400 400-1000 1000-2000 CLP Category 1 Category 2 Category 3 Category 4 Acute toxicity oral DSD R28 R25 R22 LD 50 (mg/kg) 5 5-25 25-50 50-200 200-300 300-2000 CLP Category 1 Category 2 Category 3 Category 4 Skin corrosion/irritation DSD R35 R34 R38 Exposure 3 min 3 min 1 hour 1 hour 4 hours See DSD for criteria See CLP for criteria CLP Category 1A Category 1B Category 1C Category 2 20
Eye damage/eye irritation DSD R41 R36 See DSD for criteria See CLP for criteria CLP Category 1 Category 2 Sensitisation DSD R42 R43 CLP Respiratory sensitiser, Category 1 Skin sensitiser, Category 1 Mutagenicity DSD Mut, cat 1;R46 Mut, cat 2;R46 Mut, cat 3;R68 See DSD for criteria See CLP for criteria CLP Category 1A Category 1B Category 2 Carcinogenicity DSD Carc, cat 1;R45 and R49 Carc, cat 2;R45 and R49 See DSD for criteria See CLP for criteria Carc, cat 3;R40 CLP Category 1A Category 1B Category 2 21
Reproductive toxicity DSD Rep, cat 1;R60 and R61 Rep, cat 2;R60 and R61 See DSD for criteria See CLP for criteria Rep, cat 3;R62 and R63 CLP Category 1A Category 1B Category 2 STOT, single exposure DSD Tx;R39 T;R39 R68 R37, R67 See DSD for criteria See CLP for criteria CLP Category 1 Category 2 Category 3 STOT, repeated exposure DSD T;R48 Xn;R48 See DSD for criteria See CLP for criteria CLP Category 1 Category 2 22
Environmental hazards DSD R50 R52 L(E)C 50 1 mg/l See DSD for criteria CLP Acute, Category 1 DSD R50/53 R51/53 R52/53 R53 L(E)C 50 1 mg/l <1 L(E)C 50 10 <10 L(E)C 50 100 Log P ow 3 log K ow 4 CLP Chronic, category 1 3 4 Chronic, category 2 3 4 Chronic, category 3 See DSD and CLP for criteria Chronic, category 4 23
Classification of substances Classification of a substance is based on test data (in vitro tests and animal data), QSARresults and human experience. For each hazard class and hazards category criteria are set up which enable the manufacturer of a substance to classify the substance based on available data. Classification of mixtures To classify a mixture the same tests as for substances can be performed and the mixture can be classified based on data for the mixture. However, test data are normally not available for mixtures. As it is desirable to avoid animal testing and since testing may be very expensive, it is possible to classify a mixture if sufficient data for the ingredient substances are available. Classification of a mixture based on substance data can only be done for health and environmental hazards. The physical hazards of a mixture cannot be calculated based on classification on ingoing substances. Therefore tests always have to be performed for the mixture itself to determine the physical hazards. Bridging Principles If test data are not available for a mixture but there are available test data for a similar mixture, it is possible to classify the untested mixture using bridging principles. There are different types of bridging principles. 24
Dilution If a mixture is diluted with a substance with an equivalent or lower hazard category classification than the least hazardous original substance and the diluent is not expected to affect the hazard classification of any other substances in the mixture, one of the following shall be applied: Mixture A Tested Diluent Equivalent or lower hazard than original substance Mixture B Same classification as mixture A Mixture A Tested Diluent Water or other nonhazardous substance Mixture B Calculation based on dilution Batching When producing a batch of a hazardous substance or mixture under controlled conditions the hazards of each new batch can be assumed to be equivalent to the previous batch. If there is reason to believe the composition may vary significantly, a new evaluation is required. Concentration of highly hazardous mixtures When a mixture is already classified in the highest hazard category increasing the concentration of ingredients in that category shall lead to classification in the same hazard category without additional testing. 25
Interpolation For three mixtures which contain the same hazardous substances, where mixtures A and B are in the same hazard category and mixture C contains the same active hazardous substances with concentrations intermediate to the concentrations of those hazardous substances in mixtures A and B, then mixture C is assumed to be in the same hazard category as A and B. 80% 20% 30% 70% Mixture A STOT Kat. 1 50% 50% Mixture B STOT Kat. 1 30% to 80% 20% to 70% Mixture C Interpolate STOT Kat. 1 Similar mixtures Two mixtures both contain two substances, where the concentration of substance B is essentially the same in both mixtures Mixture 1: A + B (tested) Mixture 2: B + C (not tested) If the hazard category of substance A and C is the same and the concentration of A equals that of C then mixture 2 can be assigned the same hazard category as mixture 1. 26
Changes in compositions Applying bridging principles the following variations in composition is allowed: Initial concentration range Permitted variation in initial concentration 2.5 % ± 30 % 2.5 % < C 10 % ± 20 % 10 % < C 25 % ± 10 % 25 % < C 100 % ± 5 % Be aware of substance specific concentration limits and the M-factor for substances classified for environmental hazards. Aerosols An aerosol form of a mixture shall be classified in the same hazard category as the nonaerosolized mixture unless it is assumed that the propellant will affect the hazards upon spraying. 27
Calculation principles If the hazardous properties of a mixture is unknown but the hazard properties of some or every ingoing substances are known it is possible to classify the mixture using calculation. Cut-off values Depending on the classification of a substance there are so-called cut-off values to take into consideration when calculating the classification of a mixture. If a substance is present in a mixture in a concentration below the cut-off value the hazardous properties of the substance should not be taken into consideration when calculating. CLP lays down a table containing generic cut-off values for substances. For substances present on the list of harmonised substances there may be individual concentration limits lower than the generic cut-off values. In this case, the lowest value must be used. The same goes for substances present on the Agency s Classification and labelling inventory. For substances hazardous to the aquatic environment where an M-factor has been set the generic cut-off value must be adjusted accordingly. The generic cut-off values for solid and liquid substances are found in Table 8. Hazard Class Cut-off value (weight percentage) Acute toxicity, category 1-3 0.1 % Acute toxicity, category 4 1 % Skin corrosion / irritation 1 % Serious damage to eyes / eye irritation 1 % Hazardous to aquatic environment Acute 0.1 % category 1 Hazardous to aquatic environment 0.1 % Chronic category 1 Hazardous to aquatic environment 1 % Chronic category 2-4 Table 8. Cut-off values Acute toxicity The acute toxicity estimate, ATE, equals the LD 50 /LC 50 -values for a substance or mixture. To decide whether a mixture should be classified as acute toxic, the ATE for the mixture must be calculated. Every ingoing substance classified as acute toxic and present in concentrations above the cut-off limit must be taken into consideration when calculating the ATE for a mixture. When using the formula substances classified for both dermal, oral and inhalation toxicity must be included. The formula for calculating the ATE for a mixture where information for all ingoing substances is available is: 28
100 ATE mix = n Ci ATEi Where: C i = concentration of ingredient i (% w/w or v/v) i = the individual ingredient from 1 to n n = the number of ingredients ATE i = acute toxicity estimate for ingredient i. The formula may also be used even if data are not available for all substances as long as the concentration of unknown substances does not exceed 10 %. In some cases actual LD 50 /LC 50 -values for a substance are not available, but as long as the classification of the substance is known it is possible to find a converted ATE using Table 9. Exposure routes Oral (mg/kg bodyweight) Dermal (mg/kg bodyweight) Gases (ppmv) Vapours (mg/l) Dust/mist (mg/l) Table 9. Converted ATE for substances Classification Category or experimentally obtained acute toxicity range estimate 0 < Category 1 5 5 < Category 2 50 50 < Category 3 300 300 < Category 4 2000 0 < Category 1 50 50 < Category 2 200 200 < Category 3 1000 1000 < Category 4 2000 0 < Category 1 100 100 < Category 2 500 500 < Category 3 2500 2500 < Category 4 20000 0 < Category 1 0.5 0.5 < Category 2 2.0 2.0 < Category 3 10.0 10.0 < Category 4 20.0 0< Category 1 0.05 0.05 < Category 2 0.5 0.5 < Category 3 1.0 1.0 < Category 4 5.0 Converted Acute Toxicity point estimate 1 0.5 5 100 500 5 50 300 1100 10 100 700 4500 0.05 0.5 3 11 0.005 0.05 0.5 1.5 1 These values are designed to be used in the calculation of the ATE for classification of a mixture based on its components and do not represent test results. 29
Using either actual ATE-values for each substance or converted ATE-values, the ATE for the mixture is determined. Once the ATE for the mixture is known, the classification is found using Table 10. Exposure Route Category 1 Category 2 Category 3 Category 4 Oral (mg/kg bodyweight) ATE 5 5 < ATE 50 50 < ATE 300 300 < ATE 2000 Dermal (mg/kg bodyweight) ATE 50 50 < ATE 200 200 < ATE 1000 1000 < ATE 2000 Gases (ppmv) ATE 100 100 < ATE 500 500 < ATE 2500 2500 < ATE 20000 Vapours (mg/l) ATE 0.5 0.5 < ATE 2.0 2.0 < ATE 10.0 10.0 < ATE 20.0 Dusts and Mists (mg/l) Table 10. Hazard categories and ATE ATE 0.05 0.05 < ATE 0.5 0.5 < ATE 1.0 1.0 < ATE 5.0 Example: If a mixture A contains 10 % of substance 1 classified as acute toxic category 3, oral and 5 % of substance 2 classified as acute toxic, category 2, oral, and the rest of the substances are known to be not hazardous, then the calculations will be as follow: The converted ATE-values for each substance are found using Table 9. ATE oral for substance 1: = 100 ATE oral for substance 2 = 5 The converted ATE-values are inserted in the formula. 100 10 5 = + ATEmix, oral = 91 ATEmix, oral 100 5 Using Table 10 we find that an ATE for oral exposure of 91 gives a classification as acute toxic, category 3 Therefore the classification of mixture A will be acute toxicity, category 3, oral It is not yet clear how a mixture containing substances classified for acute toxicity but with different routes of exposure should be handled. Guidance from ECHA is foreseen in summer 2009. More than 10 % unknown. If data are missing for more than 10 % of the ingoing substances, it is still possible to classify the mixture using calculation. In this case the formula is: 30
100 ( C unknown) = ATE mix n Ci ATEi Where C unknown is the concentration of each substance where hazard data are not available. Classification based on concentration thresholds Additive concentration limits Additive concentration limits are used for some hazard classes. Each substance in these hazard classes contributes to the overall classification of the mixture. The following hazard classes use additive concentration limits. Skin corrosion/irritation Serious eye damage/eye irritation Hazardous to the aquatic environment Skin corrosion/irritation When using the additivity approach to calculate the classification of a mixture each ingredient classified as skin corrosive or skin irritant should be taken into account. A weighing factor of 10 is used for a corrosive substance present at a concentration below the generic cut-off value, if manufacturers or importers find it relevant to take this substance into consideration when classifying. Table 11 shows the generic concentration limits using the additivity approach. Below is given examples of calculations based on the additivity approach. Sum of ingredients classified as: Concentration limits for classification as: Skin corrosive, category 1 Skin irritant, category 2 Skin corrosive, categories 1A, 1B, 1C 5 % 2 1 % but < 5 % Skin irritant, category 2 10 % (10 x skin corrosive, category 1A, 1B, 1C) + skin irritant, category 2 10 % Table 11. Generic concentration limits of ingredients classified for skin corrosive/irritant hazards 2 If the sum of the Skin Corrosive Category 1A ingredients is 5 %, the mixture shall be classified as Skin Corrosive Category 1A. If the sum of the Skin Corrosive Category 1A ingredients is < 5 % but the sum of Category 1A+1B ingredients is 5 %, the mixture shall be classified as Skin Corrosive Category 1B. Similarly, if the sum of Skin Corrosive Category 1A+1B ingredients is < 5 % but the sum of Category 1A+1B+1C ingredients is 5 % the mixture shall be classified as Skin Corrosive Category 1C. 31
Examples of classification using the additivity approach. It is assumed that substance classified in category 1A should be taken into consideration when present in amounts below 1 %: + + Mixture classified as skin corrosive, category 1B 4% Category 1A 1% Category 1B 1% Category 1C + + Mixture classified as skin corrosive, category 1C 3% Category 1A 1% Category 1B 1% Category 1C + Mixture classified as skin irritant, category 2 0.5% Category 1A 6% Category 2 32
Care must be taken when classifying mixtures containing ingredients such as strong acids and bases, inorganic salts, aldehydes, phenols, surfactants etc. as the additivity approach may not be applicable for many of these ingredients. For mixtures containing strong acids or strong bases the ph shall be used as classification criteria since ph is a better indicator than concentration limits. Mixtures that cannot be classified using the additivity approach shall be classified using the approach shown in Table 12. Ingredient Concentration Classification Acid with ph 2 1 % Skin corrosive, category 1 Base with ph 11.5 1 % Skin corrosive, category 1 Other skin corrosive, categories 1A, 1B, 1C 1 % Skin corrosive, category 1 Other skin irritant, category 2 3 % Skin irritant, category 2 Table 12. Generic concentration limits of ingredients for which the additivity approach does not apply Serious eye damage/eye irritation When using the additivity approach to calculate the classification of a mixture each ingredient classified as corrosive or irritant should be taken into account. A weighing factor of 10 is used for a corrosive substance present at a concentration below the generic cut-off value, if manufacturers or importers find it relevant to take this substance into consideration when classifying. Table 13 shows the generic concentration limits using the additivity approach. Below is given examples of calculations based on the additivity approach. Sum of ingredients classified as: Concentration limits for classification as: Eye damage, category 1 Eye irritation, category 2 Eye damage, category 1 or Skin corrosive, categories 1A, 1B, 1C 3 % 1 % but < 3 % Eye irritation, category 2 10 % (10 * eye damage, category 1) + eye irritation, category 2 10 % Skin corrosive, categories 1A, 1B, 1C + eye damage, category 1 3 % 1 % but < 3 % 10 * (skin corrosive, category 1A, 1B, 1C + eye damage, category 1) + eye irritation, category 2 10 % Table 13. Generic concentration limits of ingredients classified for corrosive/irritant hazards Care must be taken when classifying mixtures containing ingredients such as strong acids and bases, inorganic salts, aldehydes, phenols, surfactants etc. as the additivity approach may not be applicable for many of these ingredients. For mixtures containing strong acids or strong bases the ph shall be used as classification criteria since ph is a better indicator than concentration limits. Mixtures that cannot be classified using the additivity approach shall be classified using the approach shown in Table 14. 33
Ingredient Concentration Classification Acid with ph 2 1 % Eye damage, category 1 Base with ph 11.5 1 % Eye damage, category 1 Other corrosive, category 1 1 % Eye damage, category 1 Other irritant, category 2 3 % Eye irritation, category 2 Table 14. Generic concentration limits of ingredients for which the additivity approach does not apply Non-additive concentration limits For some hazard classes the concentration limits are non-additive. If any ingredient in the mixture exceeds the limit the mixture shall be classified in the respective hazard class. The following hazard classes use non-additive concentration limits: Sensitisers (respiratory and skin) CMR-substances STOT Aspiration hazard Hazardous to the ozone layer Sensitisation The mixture shall be classified as a respiratory or skin sensitiser when at lease one ingredient has been classified as a respiratory or skin sensitiser and is present at or above the concentration limits shown in Table 15. Concentration limits for classification as: Ingredient classified Skin sensitiser Respiratory sensitiser as: Solid / liquid gas Skin sensitiser 0.1 % 3 - - 1 % - - Respiratory - 0.1 % 3 0.1 % 3 sensitiser - 1 % 0.2 % Table 15. Generic concentration limits of ingredients classified for sensitising hazards 3 This concentration limit is used for application of specific label requirements. Safety Data Sheet is required for mixtures containing ingredients above this limit. 34
CMR-effects The mixture shall be classified as a carcinogen when at least one ingredient has been classified as a category 1A, 1B or 2 carcinogen and is present at or above the concentration limits shown in Table 16. Concentration limits for classification as: Ingredient classified as: Category 1A carcinogen Category 1B carcinogen Category 2 carcinogen Category 1A carcinogen 0.1 % Category 1B carcinogen 0.1 % Category 2 carcinogen 1 % 4 Table 16. Generic concentration limits of ingredients classified for carcinogenic hazards The mixture shall be classified as a mutagen when at least one ingredient has been classified as a category 1A, 1B or 2 mutagen and is present at or above the concentration limits shown in Table 17 Concentration limits for classification as: Ingredient classified as: Category 1A mutagen Category 1B mutagen Category 2 mutagen Category 1A mutagen 0.1 % Category 1B mutagen 0.1 % Category 2 mutagen 1 % Table 17. Generic concentration limits of ingredients classified for germ cell mutagenic hazards The mixture shall be classified as a reproductive toxicant when at least one ingredient has been classified as a category 1A, 1B or 2 reproductive toxicant and is present at or above the concentration limits shown in Table 18. The mixture shall be classified for effects on or via lactation when at lease one ingredient has been classified for effects on or via lactation and is present at or above the concentration limits shown in Table 18. Ingredient classified as: Category 1A reproductive toxicant Concentration limits for classification as: Category 1B Category 2 reproductive reproductive toxicant toxicant Effects on or via lactation Category 1A reproductive toxicant 0.3 % 5 Category 1B reproductive toxicant 0.3 % 5 Category 2 reproductive toxicant 3 % 5 Effects on or via lactation 0.3 % 5 Table 18. Generic concentration limits of ingredients classified for reproductive toxic hazards 4 If a category 2 carcinogen is present in the mixture at a concentration 0,1% a safety data sheet shall be available on request. 5 If the concentration is 0,1% a safety data sheet shall be available on request. 35
STOT single exposure The mixture shall be classified as a specific target organ toxicant (specific organ specified), following single exposure when at least one ingredient has been classified as a category 1 or 2 specific target organ toxicant and is present at or above the concentration limits shown in Table 19. Ingredient classified as: Category 1, Specific Target Organ Toxicant Category 2, Specific Target Organ Toxicant Category 3, Specific Target Organ Toxicant Concentration limits for classification as: Category 1 Category 2 10 % 1 % conc. < 10 % 10 % 6 Concentration limit depends on the hazard(s) of the category 3 substance(s). However, a generic concentration limit of 20 % is normally appropriate. Table 19. Generic concentration limits of ingredients classified for specific target organ toxic hazards STOT repeated exposure The mixture shall be classified as a specific target organ toxicant (specific organ specified), following single exposure, repeat exposure, or both when at least one ingredient has been classified as a category 1 or 2 specific target organ toxicant and is present at or above the concentration limits shown in Table 20 Ingredient classified as: Category 1, Specific Target Organ Toxicant Category 2, Specific Target Organ Toxicant Concentration limits for classification as: Category 1 Category 2 10 % 1 % conc. < 10 % 10 % 7 Table 20. Generic concentration limits of ingredients classified for specific target organ toxic hazards Aspiration hazard Ingredient classified as: Classification of mixture Category 1, aspiration hazard Category 1, aspiration hazard 10 % 8,9 Table 21. Classification for Aspiration hazard 6 If the concentration is 1% a safety data sheet shall be available on request 7 If the concentration is 1% a safety data sheet shall be available on request 8 Kinematic viscosity of mixture is 20.5 mm 2 /s at 40 0 C 9 Mixtures with two or more distinct layers one of which classified Caterory 1, aspiration hazard and with a kinematic viscosity of mixture is 20.5 mm 2 /s at 40 0 C 36
Environmental effects All ingredients classified as Acute category 1 must be considered. The effects are additive. If the sum of the ingredients is 25 % the mixture shall be classified as Acute Category 1. The classification is summarised in Table 22 Sum of ingredients classified as: Classification of mixture Acute Category 1 * M 10 25 % Acute Category 1 Table 22. Classification for Acute hazards based on summation The classification of mixtures for Chronic (long term) hazards based on summation of classified ingredients is shown in Table 23. These effects are additive. Sum of ingredients classified as: Classification of mixture Chronic Category 1 x M 9 25 % Chronic Category 1 (M x 10 x Chronic Category 1) + Chronic Category 2 Chronic Category 2 25 % (M x 100 x Chronic Category 1) + (10 x Chronic Chronic Category 3 Category 2) + Chronic Category 3 25 % Chronic Category 1 + Chronic Category 2 + Chronic Chronic Category 4 Category 3 + Chronic Category 4 25 % Table 23. Classification for Chronic hazards based on summation Highly toxic components Acute category 1 and Chronic category 1 with toxicities below 1 mg/l contributes to the toxicity of the mixture even at low concentration and should therefore be multiplied by a factor instead of just adding up the percentages. Table 24 shows the corresponding L(E)C 50 value and multiplying factor M. L(E)C 50 value Multiplying factor (M) 0.1 < L(E)C 50 1 1 0.01 < L(E)C 50 0.1 10 0.001 < L(E)C 50 0.01 100 0.0001 < L(E)C 50 0.001 1000 0.00001 < L(E)C 50 0.0001 10000 continue in factor 10 intervals Table 24. Multiplying factor (M) Hazardous for the ozone layer Mixtures shall be classified as hazardous for the ozone layer on the basis of the individual concentration of the substance(s). This hazard is not an additive effect. Ingredient classified as: Classification of mixture Hazardous for the ozone layer 0.1 % Table 25. Classification as hazardous for the ozone layer 10 See Table 24 for explanation of the M-factor 37
Labelling The supplier of a substance or mixture shall ensure that any substance or mixture classified as hazardous according to the criteria described in CLP carries a label. Unclassified mixtures must, in some cases, be labelled as well. Labelling of unclassified mixtures Mixtures not classified as hazardous must be labelled if they fulfil the criteria described in Table 26. They should be labelled with one or more of the supplemental statements described in the chapter: Supplemental information. Please note that the criteria in some cases also apply for classified mixtures. Unclassified mixture containing: Lead 0.15 % Cyanoacrylate Cement containing > 0.0002 % Chromium (VI) Isocyanates Epoxy constituents, MW 700 > 1 % active chlorine and sold to the general public Cadmium and intended to be used for soldering or brazing Halogenated hydrocarbon and > 5 % flammable or highly flammable substances 0.1 % of a substance classified as skin or respiratory sensitiser, category 1 0.1 % of a substance classified as carcinogenic, category 2 0.1 % of a substance classified as toxic to reproduction, category 1A, 1B or 2 or with effects via lactation 1 % (0.2 % for gaseous mixtures) of a substance classified with other health or environmental hazards than mentioned above 1 % (0.2 % for gaseous mixtures) of a substance with an EU exposure limit value Table 26. Unclassified mixtures with demand for a label 38
Content of the label A label must contain the following information: 1. Name, address and telephone number of the supplier of the substance or mixture 2. For chemicals sold to the general public: The nominal quantity 3. Product identifiers (see page 45) 4. Hazard pictogram(s), if required 5. Signal word, if required 6. Hazard statement(s), if required 7. Precautionary statement(s), if required 8. Supplemental information, if required (see page 45) For placement of the above information on the label please see Example of a label, page 48. Hazard Pictograms With CLP new hazard pictograms are introduced. The EU symbols which are black on an orange background will no longer be used. The new hazard pictograms for physical/chemical hazards are found in Table 27. Pictogram Name Number Exploding bomb GHS01 Flame GHS02 Flame over circle GHS03 Gas cylinder GHS04 Corrosion GHS05 Table 27. Pictograms for physical/chemical hazards 39
The hazard pictograms for health hazards and environmental hazards are found in Table 28. Pictogram Name Number Skull and GHS06 crossbones Corrosion GHS05 Exclamation mark GHS07 Health hazard GHS08 Environment GHS09 Table 28. Pictograms for health hazards 40
Principles of precedence for hazard pictograms Labels for substances and mixtures labelled according to DSD and DPD will contain three hazard symbols as a maximum. This is due to the fact that only one hazard symbol for health hazards, one for physical/chemical hazards and one for environmental hazards must be stated on the label. With CLP there is no upper limit for the number of hazard pictograms. Therefore more than three pictograms on the label are possible. However, CLP introduces principles of precedence for hazard pictograms which will, in some cases, reduce the number of pictograms on the label. An overview of the principles of precedence is found in Table 29. If this pictogram is used Do NOT use Comments Flame and Flame over Circle must be on the label if both hazard pictograms are mandatory irritation for skin or eye for respiratory sensitisation Table 29. Principles of precedence for hazard pictograms for skin sensitisation or for skin and eye irritation Signal words CLP introduces two signal words: Danger and Warning. For each hazard class and category a signal word is assigned. Danger indicates the more severe hazard category while Warning indicates the less severe hazard categories. The signal words are used on the hazard labels for substances and mixtures. Only one signal word is used on a label. If Danger is used on the label, Warning shall not appear on the label. See also Example of a label page 48. 41
Hazard statements The CLP hazard statements correspond to the R-phrases (Risk phrases) known from the DSD/DPD system. There are no principles of precedence for the CLP hazard statements. All hazard statements resulting from the classification of a substance or a mixture must appear on the label. This includes hazards statements where the corresponding hazard pictogram has been left out due to precedence principles. However, a hazard statement may be omitted if there is evident duplication. Examples of hazard statements are shown in Table 30 and also in Example of a label. H225 H301 Highly flammable liquid and vapour Toxic if swallowed Table 30 Example of hazard statements Additional EU-statements To maintain the present level of protection for human and environment, EU has chosen to add some additional hazard statements and labelling elements. These hazard statements and labelling elements are not a part of the global GHS-system. The criteria for use are given in the Annex II of the CLP-regulation. CLP contains 14 additional hazard statements. The additional hazard statements are found in Table 31. EUH001 EUH006 EUH014 EUH018 EUH019 EUH030 EUH044 EUH029 EUH031 EUH032 EUH066 EUH070 EUH071 EUH059 Table 31. Additional EU hazard statements Explosive when dry Explosive with or without contact with air Reacts violently with water In use may form flammable/explosive vapour-air mixture May form explosive peroxides Can become highly flammable in use Risk of explosion if heated under confinement Contact with water liberates toxic gas Contact with acids liberates toxic gas Contact with acids liberates very toxic gas Repeated exposure may cause skin dryness or cracking Toxic by eye contact Corrosive to the respiratory tract Hazardous to the ozone layer Furthermore the CLP contains additional statements for labelling of certain substances and mixtures. The supplemental label elements are found in Table 32. 42