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A Guide toThe Globally Harmonized System of Classification and Labeling of Chemicals (GHS) Acronyms/Abbreviations ANSI: American National Standards Institute APEC: Asia-Pacific Economic Cooperation ASTM: American Society of Testing and Materials CA: Competent Authority CAS: Chemical Abstract Service CBI: Confidential Business Information CFR: Code of Federal Regulations CG/HCCS: Coordinating Group for the Harmonization of Chemical Classification Systems CPSC: Consumer Product Safety Commission DOT: Department of Transportation EINECS: European Inventory of Existing Commercial Chemical Substances EPA: Environmental Protection Agency EU: European Union FIFRA: Federal Insecticide, Fungicide and Rodenticide Act GHS: Globally Harmonized System of Classification and Labelling of Chemicals HCS: Hazard Communication Standard IARC: International Agency for the Research on Cancer IFCS: International Forum on Chemical Safety ILO: International Labor OrganizationI OMC: Inter-organization Program on the Sound Management of Chemicals ISO: International Standards OrganizationI UPAC: International Union of Pure and Applied Chemistry LD50 : Lethal dose 50mg/kg: Milligram per kilogram MSDS: Material Safety Data Sheet NAFTA: North American Free Trade Agreement OSHA: Occupational Safety and Health Administration OECD: The Organization for Economic Cooperation and Development QSARs: Quantitative Structure-Activity Relationships SDS: Safety Data Sheet SME: Small and medium sized enterprises TFHCL: Task Force on the Harmonization of Classification and Labeling TSCA: Toxic Substances Control Act UN: United Nations UNCED: United Nations Conference on Environment and Development UNCETDG: United Nations Committee of Experts on the Transport of Dangerous Goods UNCETDG/GHS: United Nations Committee of Experts on the Transport of Dangerous Goods and on the Globally Harmonized System of Classification and Labelling of Chemicals UNITAR: United Nations Institute for Training and Research WG: work group WHMIS: Workplace Hazardous Materials Information System WSSD: World Summit on Sustainable Development TABLE OF CONTENTS 1. Background 1.1 What is the GHS? 1.2 Why was the GHS developed? 1.3 What was the International Mandate? 1.4 How was the GHS developed? 1.5 How will the GHS be maintained and updated? 1.6 When will the GHS be implemented? 1.7 What are the benefits? 2. How is the GHS to be applied? 2.1 Are all chemicals covered by the GHS? 2.2 Will all hazardous chemicals require a GHS label and Safety Data Sheet? 2.3 How will the GHS impact existing regulations? 2.4 What is meant by GHS Building Blocks? 2.5 How should the GHS Building Blocks by applied? 2.5.1 Transport 2.5.2 Workplace 2.5.3 Consumer 2.5.4 Pesticides 2.6 How will the GHS impact countries without existing regulations? 3. What is Classification? 3.1 What are the GHS Physical Hazards? 3.1.1 Explosives 3.1.2 Flammable Gases 3.1.3 Flammable Aerosols 3.1.4 Oxidizing Gases 3.1.5 Gases Under Pressure 3.1.6 Flammable Liquids 3.1.7 Flammable Solids 3.1.8 Self-Reactive Substances 3.1.9 Pyrophoric Liquids 3.1.10 Pyrophoric Solids 3.1.11 Self-Heating Substances 3.1.12 Substances Which in Contact with Water Emit Flammable Gases 3.1.13 Oxidizing Liquids 3.1.14 Oxidizing Solids 3.1.15 Organic Peroxides 3.1.16 Substances Corrosive to Metal 3.2 What are the GHS Health and Environmental Hazards? 3.2.1 Acute Toxicity 3.2.2 Skin Corrosion 3.2.3 Skin Irritation 3.2.4 Eye Effects 3.2.5 Sensitization 3.2.6 Germ Cell Mutagenicity 3.2.7 Carcinogenicity 3.2.8 Reproductive Toxicity 3.2.9 Target Organ Systemic Toxicity: Single Exposure & Repeated Exposure 3.2.10 Aspiration Toxicity 3.3 Environmental Hazards 3.3.1 Hazardous to the Aquatic Environment 3.3.1.1 Acute Aquatic Toxicity 3.3.1.2 Chronic Aquatic Toxicity 3.4 What is the GHS approach to classifying mixtures? 3.5 What are bridging principles? 3.6 What testing is required? 4. Hazard Communication 4.1 What factors influenced development of the GHS communication tools? 4.2 Labels 4.2.1 What does a label look like? 4.2.2 USA Examples 4.2.3 International Examples 4.3 What are the GHS label elements? 4.3.1 Symbols (hazard pictograms) 4.3.2 Signal Words 4.3.3 Hazard Statements 4.3.4 Precautionary Statements and Pictograms 4.3.5 Product Identifier (Ingredient Disclosure) 4.3.6 Supplier Identification 4.3.7 Supplemental Information 4.4 How are multiple hazards handled on labels? 4.5 Is there a specific GHS label format / layout? 4.6 What about risk? 4.7 Are workplace containers covered in the GHS? 4.8 What is the GHS Safety Data Sheet (SDS)? 4.9 What is the difference between the GHS SDS and existing MSDSs/SDSs? 4.10 When should SDSs and labels be updated? 4.11 How does the GHS address Confidential Business Information (CBI)? 4.12 Does the GHS address training? 5. References 6. Glossary 7. Appendices A Comparison of MSDSs/SDSs Elements B GHS MSDS examples 1.0 Background The purpose of this document is to describe the United Nations Globally Harmonized System of Classification and Labeling of Chemicals (GHS), why it was developed, and how it relates to the sound management of chemicals. 1.1 What is the GHS? The GHS is an acronym for The Globally Harmonized System of Classification and Labeling of Chemicals. The GHS is a system for standardizing and harmonizing the classification and labeling of chemicals. It is a logical and comprehensive approach to:
The GHS itself is not a regulation or a standard. The GHS Document (referred to as "The Purple Book") establishes agreed hazard classification and communication provisions with explanatory information on how to apply the system. The elements in the GHS supply a mechanism to meet the basic requirement of any hazard communication system, which is to decide if the chemical product produced and/or supplied is hazardous and to prepare a label and/or Safety Data Sheet as appropriate. Regulatory authorities in countries adopting the GHS will thus take the agreed criteria and provisions, and implement them through their own regulatory process and procedures rather than simply incorporating the text of the GHS into their national requirements.The GHS Document thus provides countries with the regulatory building blocks to develop or modify existing national programs that address classification of hazards and transmittal of information about those hazards and associated protective measures. This helps to ensure the safe use of chemicals as they move through the product life cycle from "cradle to grave." 1.2 Why was the GHS developed? The production and use of chemicals is fundamental to all economies. The global chemical business is more than a $1.7 trillion per year enterprise. In the U.S., chemicals are more than a $450 billion business and exports are greater than $80 billion per year. Chemicals directly or indirectly affect our lives and are essential to our food, our health, and our lifestyle. The widespread use of chemicals has resulted in the development of sector-specific regulations (transport, production, workplace, agriculture, trade, and consumer products). Having readily available information on the hazardous properties of chemicals, and recommended control measures, allows the production, transport, use and disposal of chemicals to be managed safely. Thus, human health and the environment are protected. The sound management of chemicals should include systems through which chemical hazards are identified and communicated to all who are potentially exposed. These groups include workers, consumers, emergency responders and the public. It is important to know what chemicals are present and/or used, their hazards to human health and the environment, and the means to control them. A number of classification and labeling systems, each addressing specific use patterns and groups of chemicals, exist at the national, regional and international levels. The existing hazard classification and labeling systems address potential exposure to chemicals in all the types of use settings listed above. While the existing laws and regulations are similar, they are different enough to require multiple labels for the same product both within the U.S. and in international trade and to require multiple safety data sheets for the same product in international trade. Several U.S. regulatory agencies and various countries have different requirements for hazard definitions as well as for information to be included on labels or material safety data sheets. The numerical values on the hazard index scale in the table are not to scale. For example, a product may be considered flammable or toxic by one agency or country, but not by another. We can see by comparing a few hazards how complex it is to comply with all domestic and global regulations. Acute oral toxicity (LD50) is a good example (Figure 1.2). Although most existing systems cover acute toxicity, we can see in the figure that what is considered hazardous varies considerably. These differences allow the same product to be hazardous in one country/system and not in another. At the very least, the same product has different labels and SDSs. Figure 1.3 The numerical values on the hazard index scale in the table are not to scale. Flammable liquid is another hazard that is covered by most existing systems. As shown in Figure 1.3, the coverage varies between existing systems within the U.S. and globally. This means that the same product can be non-hazardous or hazardous with different labels/SDSs. In Section 4, Figures 4.1 through 4.7 show the diverse domestic and international labels for a fictitious product (ToxiFlam) which has both oral toxicity and flammability hazards. These differences in hazards and SDS/labels impact both protection and trade. In the area of protection, users may see different label warnings or safety data sheet information for the same chemical. In the area of trade, the need to comply with multiple regulations regarding hazard classification and labeling is costly and time-consuming. Some multinational companies have estimated that there are over 100 diverse hazard communication regulations for their products globally. For small and medium size enterprises (SMEs) regulatory compliance is complex and costly, and it can act as a barrier to international trade in chemicals. 1.3 What was the International Mandate? The single most important force that drove the creation of the GHS was the international mandate (Figure 1.4) adopted in the 1992 United Nations Conference on Environment and Development (UNCED), often called the "Earth Summit". The harmonization of classification and labeling of chemicals was one of six program areas that were endorsed by the United Nations General Assembly to strengthen international efforts concerning the environmentally sound management of chemicals. It was recognized that an internationally harmonized approach to classification and labeling would provide the foundation for all countries to develop comprehensive national programs to ensure the safe use of chemicals. 1.4 How was the GHS developed? In conjunction with its Convention and Recommendation on Safety in the Use of Chemicals at Work, the International Labor Organization (ILO) studied the tasks required to achieve harmonization. The ILO concluded that there were four major existing systems that needed to be harmonized to achieve a global approach. No international organization covers all aspects of chemical classification and labeling. A broad scope and extensive expertise and resources were required to develop a system. In order to proceed, several decisions were needed: (a) what systems would be considered "major" and thus the basis for harmonization, and (b) how could the work be divided to get the best expertise for different aspects. Four existing systems (Figure #1.5) were deemed to be major and the primary basis for the GHS. While not considered major, requirements of other systems were examined as appropriate, and taken into account as proposals were developed. A Coordinating Group for the Harmonization of Chemical Classification Systems (CG/HCCS) was created under the Inter-organization Program for the Sound Management of Chemicals (IOMC) and they were charged with coordinating and managing development of the system. The GC/HCCS worked on a consensus basis and included representatives from major stakeholders, including national governments, industry and workers. They created a set of guiding principles (Figure 1.6). The scope and guiding principles created a common framework for the organizations that were charged with developing the different elements of the system. In order to get the best expertise and resources, the work was divided among three technical focal points. Figure 1.7 shows how the work was assigned to the three technical focal points and the overall responsibilities of the Coordinating Group itself. The UN Committee of Experts on Transport of Dangerous Goods was selected as the lead for work on physical hazards, in cooperation with the ILO. Based on their work in the testing guidelines and other chemical issues, the Organization for Economic Cooperation and Development (OECD) was selected for health/environmental hazards and mixtures. ILO has a long history in MSDS/labels, and was selected to be the lead in hazard communication. The OECD and ILO groups also included representatives from governments, industry and workers. Figure 1.7 1.5 How will the GHS be maintained and updated? In October 1999, the United Nations Economic and Social Council decided (resolution 1999/65) to enlarge the mandate of the Committee of Experts on the Transport of Dangerous Goods by reconfiguring it into a Committee of Experts on the Transport of Dangerous Goods and on the Globally Harmonized System of Classification and Labeling of Chemicals (UNCETDG/GHS). At the same time, a new Sub-Committee of Experts on the Globally Harmonized System of Classification and Labeling of Chemicals (GHS Sub-Committee) was also created. When the IOMC completed developing the GHS, the system was presented to the UN GHS Sub-Committee, which formally adopted the system at its first session in December 2002. It was subsequently endorsed by the UNCETDG/GHS. The UN Economic and Social Council endorsed the GHS in July 2003. The Sub-Committee of Experts on the Globally Harmonized System of Classification will:
1.6 When will the GHS be implemented? There is no international implementation schedule for the GHS. It is likely that different national systems/sectors will require different timeframes for GHS implementation. Existing systems will need to consider phase-in strategies for transition from their current requirements to the new GHS requirements. Several international bodies have proposed implementation goals. The World Summit on Sustainable Development (WSSD) and the Intergovernmental Forum for Chemical Safety (IFCS) have encouraged countries to implement the new GHS as soon as possible with a view to having the system fully operational by 2008. The Ministers of the Asia-Pacific Economic Cooperation (APEC) have also said that as many APEC economies as possible should implement, on a voluntary basis, the GHS by 2006. Under the North American Free Trade Agreement (NAFTA), the Tri-national Occupational Safety and Health Group and the NAFTA Pesticides Technical Working Group are discussing the GHS. Some of the major existing systems have begun discussions about GHS implementation and situational analyses comparing existing requirements to GHS requirements. Some countries are considering harmonization to the greatest extent possible between their national sectors. 1.7 What are the benefits? The basic goal of hazard communication is to ensure that employers, employees and the public are provided with adequate, practical, reliable and comprehensible information on the hazards of chemicals, so that they can take effective preventive and protective measure for their health and safety. Thus, implementation of effective hazard communication provides benefits for governments, companies, workers, and members of the public. The GHS has maximum value if it is accepted in all major regulatory systems for chemical hazard communication. The diversity of hazard definitions is shown in Figures 1.2 and 1.3. The array of domestic and global labels for one product is shown in Figures 4.1 to 4.7. In the USA implementation of the GHS would harmonize hazard definitions and label information among U.S. regulatory agencies (CPSC, DOT, EPA, OSHA, etc.). If the GHS is implemented globally, consistent information will be communicated on labels and SDSs. It is anticipated that application of the GHS will:
2.0 How is the GHS to be applied? The GHS Classification and Communication elements are the foundation of programs to ensure the safe use of chemicals, as shown in Figure 2.1. The first two steps in any program to ensure the safe use of chemicals are to identify intrinsic hazard(s) (i.e., classification) and then to communicate that information. The design of the GHS communication elements reflect the different needs of various target audiences, such as workers and consumers. To proceed further up the pyramid, some existing national programs also include risk management systems as part of an overall program on the sound management of chemicals. The general goal of these systems is to minimize exposure, resulting in reduced risk. The systems vary in focus and include activities such as establishing exposure limits, recommending exposure monitoring methods and creating engineering controls. However, the target audiences of such systems are generally limited to workplace settings. With or without formal risk management systems, the GHS is designed to promote the safe use of chemicals. 2.1 Are all chemicals covered by the GHS? The GHS covers all hazardous chemicals. There are no complete exemptions from the scope of the GHS for a particular type of chemical or product. The term "chemical" is used broadly to include substances, products, mixtures, preparations, or any other terms that may be used by existing systems. The goal of the GHS is to identify the intrinsic hazards of chemical substances and mixtures and to convey hazard information about these hazards. The GHS is not intended to harmonize risk assessment procedures or risk management decisions, as described above. "Articles" as defined in the OSHA Hazard Communication Standard (HCS) (29 CFR 1910.1200), or by similar definitions, are outside the scope of the GHS. Chemical inventory (e.g., TSCA, EINECS, etc.) and chemical control requirements in various countries are not harmonized by the GHS.Classification in the GHS is criteria-based, not limiting coverage to a list that can become outdated. It is not anticipated that the GHS will develop or maintain an international classification authority or international classification list. Several countries currently maintain regulatory lists. GHS classification criteria can be used to reclassify chemicals on lists, if desired. Existing lists, such as those provide by organizations that evaluate cancer hazards, could be used in conjunction with the GHS to promote harmonization. 2.2 Will all hazardous chemicals require a GHS label and Safety Data Sheet? Figure 2.2 The need for GHS labels and/or Safety Data Sheets is expected to vary by product category or stage in the chemical's lifecycle from research/production to end use. The sequence of lifecycle events is shown in Figure 2.2. For example, pharmaceuticals, food additives, cosmetics and pesticide residues in food will not be covered by the GHS at the point of consumption, but will be covered where workers may be exposed (workplaces), and in transport. Also, the medical use of human or veterinary pharmaceuticals is generally addressed in package inserts and is not part of existing hazard communication systems. Similarly, foods are generally not labeled under existing hazard communication systems. The exact requirements for labels and Safety Data Sheets will continue to be defined in national regulations. However, national requirements are expected to be consistent with the detailed discussion of scope provided in Chapter 1.1 of the GHS document. 2.3 How will the GHS impact existing regulations? The GHS is a voluntary international system that imposes no binding treaty obligations on countries. To the extent that countries adopt the GHS into their systems, the regulatory changes would be binding for covered industries. For countries with existing systems, it is expected that the GHS components will be applied within the framework/infrastructure of existing hazard communication regulatory schemes. For example, exceptions and exemptions found in existing regulations would not be expected to change (e.g., transportation of limited quantities). However, the specific hazard criteria, classification processes, label elements and SDS requirements within an existing regulation will need to be modified to be consistent with the harmonized elements of the GHS. It is anticipated that ALL existing hazard communication systems will need to be changed in order to apply the GHS. For example, in the U.S. EPA and OSHA would be expected to require hazard pictograms/symbols on labels. Canada and the EU would be expected to adopt the GHS pictograms/symbols instead of those currently in use. The transport sector is expected to adopt the changed criteria (LD50/LC50) for the GHS Acute Toxicity Categories 1 - 3. OSHA HCS, WHMIS and the EU would all need to change their acute toxicity criteria. Test data already generated for the classification of chemicals under existing systems should be accepted when classifying these chemicals under the GHS, thereby avoiding duplicative testing and the unnecessary use of test animals. 2.4 What is meant by GHS Building Blocks? The GHS classification and communication requirements can be thought of as a collection of building blocks. In regulatory schemes, coverage and communication of hazards vary by the needs of target audiences/sectors. Accordingly, the GHS was designed to contain the hazard endpoints and communication tools necessary for application to known regulatory schemes. The GHS is structured so that the appropriate elements for classification and communication, which address the target audiences, can be selected. The full range of harmonized elements is available to everyone, and should be used if a country or organization chooses to cover a certain effect when it adopts the GHS. The full range of these elements does not have to be adopted. Countries can determine which of the building blocks will be applied in different parts of their systems (consumer, workplace, transport, pesticides, etc.). For example, some options for implementing the GHS include:
2.5 How should the GHS Building Blocks by applied? Appropriate implementation of the GHS means that the hazards covered by a Competent Authority (CA) are covered consistently with the GHS criteria and requirements. The EPA, Health Canada and OSHA are examples of Competent Authorities. Competent Authorities will decide how to apply the various elements of the GHS based on the CA needs and the needs of target audiences. When a regulatory scheme covers something that is in the GHS, and implements the GHS, that coverage should be consistent. Once an endpoint and subclasses are selected, as needed, the GHS classification criteria, assigned label elements and SDS provisions should be followed as specified in the GHS. If a regulatory system covers carcinogenicity, for example, it should follow the harmonized classification scheme, the harmonized label elements and, where appropriate, the SDS. Figure 2.3 shows some of the hazard endpoint/subcategory and hazard communication building block choices for the transport, workplace, consumer and pesticide sectors. Figure 2.3 To gain a better understanding of the building block approach, it is helpful to look at the specific sectors/target audiences. The needs and regulations of the various sectors vary depending on the type of chemical and use pattern. Different target audiences or sectors receive and use hazard information in different ways. The primary sectors/target audiences are transport, workplace, consumers and agriculture (pesticides). These sectors are described in more detail below. 2.5.1 Transport For transport, it is expected that application of the GHS will be similar to application of current transport requirements.
2.5.2 Workplace In the workplace, it is expected that most of the GHS elements will be adopted, including;·
All workplace systems may not have the jurisdiction to adopt environmental hazards. 2.5.3 Consumer For the consumer sector, it is expected that labels will be the primary focus of GHS application.·
2.5.4 Pesticides For pesticides, it is expected that the GHS will be adopted.
2.6 How will the GHS impact countries without existing regulations? Developing and maintaining a classification and labeling system is not a simple task. The GHS can be used as a tool for developing national regulations. It is expected that countries that do not have systems will adopt GHS as their basic scheme. The GHS provides the building blocks from which countries can construct chemical safety programs. Although the GHS will facilitate the process, many challenges exist in creating new regulations. For example:
3.0 What is Classification? Classification is the starting point for hazard communication. It involves the identification of the hazard(s) of a chemical or mixture by assigning a category of hazard/danger using defined criteria. The GHS is designed to be consistent and transparent. It draws a clear distinction between classes and categories in order to allow for "self classification". For many hazards a decision tree approach (e.g., eye irritation) is provided in the GHS Document. For several hazards the GHS criteria are semi-quantitative or qualitative. Expert judgment may be required to interpret these data. Figure 3.1 shows the harmonized definition for hazard classification, which can be applied to all hazard categories in the system. The data used for classification may be obtained from tests, literature, and practical experience. The GHS health and environmental hazard criteria/definitions are test method neutral. Accordingly, tests that determine hazardous properties conducted according to internationally recognized scientific principles can be used for purposes of hazard classification. The GHS endpoints that cover physical, health and environmental hazards are listed in Figures 3.2 and 3.3, respectively. As mentioned earlier, the GHS hazard definitions are criteria-based. The following information provides an overview of the GHS definitions and classification criteria. It is recommended that the person responsible for GHS implementation consult the GHS Document or "Purple Book" for more complete information. 3.1 What are the GHS Physical Hazards? The GHS physical hazards criteria, developed by the ILO and UNCETDG, were largely based on the existing criteria used by the UN Model Regulation on the Transport of Dangerous Goods. Therefore, many of the criteria are already being used on a worldwide basis. However, some additions and changes were necessary since the scope of the GHS includes all target audiences. The physical hazards classification process provides specific references to approved test methods and criteria for classification. The GHS physical hazard criteria apply to mixtures. It is assumed that mixtures will be tested for physical hazards. In general, the GHS criteria for physical hazards are quantitative or semi-quantitative with multiple hazard levels within an endpoint. This is different from several of the existing systems that currently have qualitative criteria for various physical hazards (e.g., organic peroxide criteria under WHMIS and OSHA HCS). This could make classification under the GHS more consistent. In developing GHS criteria for physical hazards it was necessary to define physical states. In the GHS,
3.1.1 Explosives An explosive substance (or mixture) is a solid or liquid which is in itself capable by chemical reaction of producing gas at such a temperature and pressure and at such a speed as to cause damage to the surroundings. Pyrotechnic substances are included even when they do not evolve gases. A pyrotechnic substance (or mixture) is designed to produce an effect by heat, light, sound, gas or smoke or a combination of these as the result of non-detonative, self-sustaining, exothermic chemical reactions. Classification as an explosive and allocation to a division is a three-step process:
Table 3.1 Explosives
Explosive properties are associated with certain chemical groups that can react to give very rapid increases in temperature or pressure. The GHS provides a screening procedure that is aimed at identifying the presence of such reactive groups and the potential for rapid energy release. If the screening procedure identifies the substance or mixture to be a potential explosive, the acceptance procedure has to be performed. Substances, mixtures and articles are assigned to one of six divisions, 1.1 to 1.6, depending on the type of hazard they present. See, UN Manual of Tests and Criteria Part I Test Series 2 to 7. Currently, only the transport sector uses six categories for explosives. 3.1.2 Flammable Gases Flammable gas means a gas having a flammable range in air at 20°C and a standard pressure of 101.3 kPa. Substances and mixtures of this hazard class are assigned to one of two hazard categories on the basis of the outcome of the test or calculation method (ISO 10156:1996). 3.1.3 Flammable Aerosols Aerosols are any gas compressed, liquefied or dissolved under pressure within a non-refillable container made of metal, glass or plastic, with or without a liquid, paste or powder. The container is fitted with a release device allowing the contents to be ejected as solid or liquid particles in suspension in a gas, as a foam, paste or powder or in a liquid or gaseous state. Aerosols should be considered for classification as either a Category 1 or Category 2 Flammable Aerosol if they contain any component classified as flammable according to the GHS criteria for flammable liquids, flammable gases, or flammable solids. Classification is based on:
3.1.4 Oxidizing Gases Oxidizing gas means any gas which may, generally by providing oxygen, cause or contribute to the combustion of other material more than air does. Substances and mixtures of this hazard class are assigned to a single hazard category on the basis that, generally by providing oxygen, they cause or contribute to the combustion of other material more than air does. The test method is ISO 10156:1996. Currently, several workplace hazard communication systems cover oxidizers (solids, liquids, gases) as a class of chemicals. 3.1.5 Gases under Pressure Gases under pressure are gases that are contained in a receptacle at a pressure not less than 280 Pa at 20°C or as a refrigerated liquid. This endpoint covers four types of gases or gaseous mixtures to address the effects of sudden release of pressure or freezing which may lead to serious damage to people, property, or the environment independent of other hazards the gases may pose. For this group of gases, the following information is required:
Table 3.2 Gases under Pressure
Criteria that use the physical state or compressed gases will be a different classification basis for some workplace systems. Data can be found in the literature, and calculated or determined by testing. Most pure gases are already classified in the UN Model Regulations. Gases are classified, according to their physical state when packaged, into one of four groups as shown in Table 3.2. 3.1.6 Flammable Liquids Table 3.3 Flammable Liquids
Flammable liquid means a liquid having a flash point of not more than 93°C. Substances and mixtures of this hazard class are assigned to one of four hazard categories on the basis of the flash point and boiling point (See Table 3.3). Flash Point is determined by closed cup methods as provided in the GHS document, Chapter 2.5, paragraph 11. 3.1.7 Flammable Solids Flammable solids are solids that are readily combustible, or may cause or contribute to fire through friction. Readily combustible solids are powdered, granular, or pasty substances which are dangerous if they can be easily ignited by brief contact with an ignition source, such as a burning match, and if the flame spreads rapidly. Table 3.4 Flammable Solids
Substances and mixtures of this hazard class are assigned to one of two hazard categories (Table 3.4) on the basis of the outcome of the UN Test N.1 (UN Manual of Tests and Criteria). The tests include burning time, burning rate and behavior of fire in a wetted zone of the test sample. 3.1.8 Self-Reactive Substances Self-reactive substances are thermally unstable liquids or solids liable to undergo a strongly exothermic thermal decomposition even without participation of oxygen (air). This definition excludes materials classified under the GHS as explosive, organic peroxides or as oxidizing. These materials may have similar properties, but such hazards are addressed in their specific endpoints. There are exceptions to the self-reactive classification for material: (i) with heat of decomposition <300 J/g or (ii) with self-accelerating decomposition temperature (SADT) > 75°C for a 50 kg package. Substances and mixtures of this hazard class are assigned to one of the seven 'Types', A to G, on the basis of the outcome of the UN Test Series A to H (UN Manual of Tests and Criteria). Currently, only the transport sector uses seven categories for self-reactive substances (Table 3.5). Table 3.5 Self-Reactive Substances
Pyrophorics 3.1.9 Pyrophoric Liquids A pyrophoric liquid is a liquid which, even in small quantities, is liable to ignite within five minutes after coming into contact with air. Substances and mixtures of this hazard class are assigned to a single hazard category on the basis of the outcome of the UN Test N.3 (UN Manual of Tests and Criteria). 3.1.10 Pyrophoric Solids A pyrophoric solid is a solid which, even in small quantities, is liable to ignite within five minutes after coming into contact with air. Substances and mixtures of this hazard class are assigned to a single hazard category on the basis of the outcome of the UN Test N.2 (UN Manual of Tests and Criteria). 3.1.11 Self-Heating Substances A self-heating substance is a solid or liquid, other than a pyrophoric substance, which, by reaction with air and without energy supply, is liable to self-heat. This endpoint differs from a pyrophoric substance in that it will ignite only when in large amounts (kilograms) and after long periods of time (hours or days). Substances and mixtures of this hazard class are assigned to one of two hazard categories on the basis of the outcome of the UN Test N.4 (UN Manual of Tests and Criteria). 3.1.12 Substances which on Contact with Water Emit Flammable Gases Substances that, in contact with water, emit flammable gases are solids or liquids which, by interaction with water, are liable to become spontaneously flammable or to give off flammable gases in dangerous quantities. Substances and mixtures of this hazard class are assigned to one of three hazard categories on the basis of test results (UN Test N.5 UN Manual of Tests and Criteria) which measure gas evolution and speed of evolution. 3.1.13 Oxidizing Liquids An oxidizing liquid is a liquid which, while in itself not necessarily combustible, may, generally by yielding oxygen, cause or contribute to the combustion of other material. Substances and mixtures of this hazard class are assigned to one of three hazard categories on the basis of test results (UN Test O.2 UN Manual of Tests and Criteria) which measure ignition or pressure rise time compared to defined mixtures. 3.1.14 Oxidizing Solids An oxidizing solid is a solid which, while in itself not necessarily combustible, may, generally by yielding oxygen, cause or contribute to the combustion of other material. Substances and mixtures of this hazard class are assigned to one of three hazard categories on the basis of test results (UN Test O.1 UN Manual of Tests and Criteria) which measure mean burning time and re compared to defined mixtures. Currently, several workplace hazard communication systems cover oxidizers (solids, liquids, gases) as a class of chemicals. 3.1.15 Organic Peroxides An organic peroxide is an organic liquid or solid which contains the bivalent -0-0- structure and may be considered a derivative of hydrogen peroxide, where one or both of the hydrogen atoms have been replaced by organic radicals. The term also includes organic peroxide formulations (mixtures). Such substances and mixtures may:
Table 3.7 Organic Peroxides
3.1.16 Substances Corrosive to Metal A substance or a mixture that by chemical action will materially damage, or even destroy, metals is termed 'corrosive to metal'. These substances or mixtures are classified in a single hazard category on the basis of tests (Steel: ISO 9328 (II): 1991 - Steel type P235; Aluminum: ASTM G31-72 (1990) - non-clad types 7075-T6 or AZ5GU-T66). The GHS criteria are a corrosion rate on steel or aluminum surfaces exceeding 6.25 mm per year at a test temperature of 55°C. The concern in this case is the protection of metal equipment or installations in case of leakage (e.g., plane, ship, tank), not material compatibility between the container/tank and the product. This hazard is not currently covered in all systems. 3.2 What are the GHS Health and Environmental Hazards? The GHS health and environmental hazard criteria represent a harmonized approach for existing classification systems (see Figure 3.3). The work at the OECD to develop the GHS criteria included:
Figure 3.3 The GHS Health and Environmental Endpoints The following paragraphs briefly describe the GHS health and environmental endpoints. The criteria for classifying substances are presented first. Then the GHS approach to classifying mixtures is briefly discussed. It is recommended that the person responsible for GHS implementation consult the GHS Document or "Purple Book" for more complete information. 3.2.1 Acute Toxicity Five GHS categories have been included in the GHS Acute Toxicity scheme from which the appropriate elements relevant to transport, consumer, worker and environment protection can be selected. Substances are assigned to one of the five toxicity categories on the basis of LD50 (oral, dermal) or LC50 (inhalation). The LC50 values are based on 4-hour tests in animals. The GHS provides guidance on converting 1-hour inhalation test results to a 4-hour equivalent. The five categories are shown in the Table 3.8 Acute Toxicity. Category 1, the most severe toxicity category, has cut-off values currently used primarily by the transport sector for classification for packing groups. Some Competent Authorities may consider combining Acute Categories 1 and 2. Category 5 is for chemicals which are of relatively low acute toxicity but which, under certain circumstances, may pose a hazard to vulnerable populations. Criteria other than LD50/LC50 data are provided to identify substances in Category 5 unless a more hazardous class is warranted. 3.2.2 Skin Corrosion Skin corrosion means the production of irreversible damage to the skin following the application of a test substance for up to 4 hours. Substances and mixtures in this hazard class are assigned to a single harmonized corrosion category. For Competent Authorities, such as transport packing groups, needing more than one designation for corrosivity, up to three subcategories are provided within the corrosive category. See the Skin Corrosion/Irritation Table 3.9. Several factors should be considered in determining the corrosion potential before testing is initiated:
Table 3.9 Skin Corrosion/Irritation
3.2.3 Skin Irritation Skin irritation means the production of reversible damage to the skin following the application of a test substance for up to 4 hours. Substances and mixtures in this hazard class are assigned to a single irritant category. For those authorities, such as pesticide regulators, wanting more than one designation for skin irritation, an additional mild irritant category is provided. See the Skin Corrosion/Irritation Table 3.9. Several factors should be considered in determining the irritation potential before testing is initiated:
Several factors should be considered in determining the serious eye damage or eye irritation potential before testing is initiated:
Table 3.10 Eye Effects
Serious eye damage means the production of tissue damage in the eye, or serious physical decay of vision, following application of a test substance to the front surface of the eye, which is not fully reversible within 21 days of application. Substances and mixtures in this hazard class are assigned to a single harmonized category. Eye irritation means changes in the eye following the application of a test substance to the front surface of the eye, which are fully reversible within 21 days of application. Substances and mixtures in this hazard class are assigned to a single harmonized hazard category. For authorities, such as pesticide regulators, wanting more than one designation for eye irritation, one of two subcategories can be selected, depending on whether the effects are reversible in 21 or 7 days. 3.2.5 Sensitization Respiratory sensitizer means a substance that induces hypersensitivity of the airways following inhalation of the substance. Substances and mixtures in this hazard class are assigned to one hazard category. Skin sensitizer means a substance that will induce an allergic response following skin contact. The definition for "skin sensitizer" is equivalent to "contact sensitizer". Substances and mixtures in this hazard class are assigned to one hazard category. Consideration should be given to classifying substances which cause immunological contact urticaria (an allergic disorder) as contact sensitizers. 3.2.6 Germ Cell Mutagenicity Mutagen means an agent giving rise to an increased occurrence of mutations in populations of cells and/or organisms. Substances and mixtures in this hazard class are assigned to one of two hazard categories. Category 1 has two subcategories. See the Germ Cell Mutagenicity (Table 3.11) below. Table 3.11 Germ Cell Mutagenicity
3.2.7 Carcinogenicity Carcinogen means a chemical substance or a mixture of chemical substances which induce cancer or increase its incidence. Substances and mixtures in this hazard class are assigned to one of two hazard categories. Category 1 has two subcategories. The Carcinogenicity Guidance Section in the GHS Document includes comments about IARC. Table 3.12 Carcinogenicity
3.2.8 Reproductive Toxicity Table 3.13 Reproductive Toxicity
Reproductive toxicity includeds adverse effects on sexual function and fertility in adult males and females, as well as developmental toxicity in offspring. Substances and mixtures with reproductive and/or developmental effects are assigned to one of two hazard categories, 'known or presumed' and 'suspected'. Category 1 has two subcategories for reproductive and developmental effects. Materials which cause concern for the health of breastfed children have a separate category, Effects on or Via Lactation. 3.2.9 Target Organ Systemic Toxicity (TOST): Single Exposure & Repeated Exposure The GHS distinguishes between single and repeat exposure for Target Organ Effects. Some existing systems distinguish between single and repeat exposure for these effects and some do not. All significant health effects, not otherwise specifically included in the GHS, that can impair function, both reversible and irreversible, immediate and/or delayed are included in the non-lethal target organ/systemic toxicity class (TOST). Narcotic effects and respiratory tract irritation are considered to be target organ systemic effects following a single exposure. Substances and mixtures of the single exposure target organ toxicity hazard class are assigned to one of three hazard categories in Table 3.14. Substances and mixtures of the repeated exposure target organ toxicity hazard class are assigned to one of two hazard categories in Table 3.15. Table 3.15 TOST: Repeated Exposure
In order to help reach a decision about whether a substance should be classified or not, and to what degree it would be classified (Category 1 vs. Category 2), dose/concentration 'guidance values' are provided in the GHS. The guidance values and ranges for single and repeated doses are intended only for guidance purposes. This means that they are to be used as part of the weight of evidence approach, and to assist with decisions about classification. They are not intended as strict demarcation values. The guidance value for repeated dose effects refer to effects seen in a standard 90-day toxicity study conducted in rats. They can be used as a basis to extrapolate equivalent guidance values for toxicity studies of greater or lesser duration. 3.2.10 Aspiration Hazard Table 3.16 Aspiration Toxicity
Aspiration toxicity includes severe acute effects such as chemical pneumonia, varying degrees of pulmonary injury or death following aspiration. Aspiration is the entry of a liquid or solid directly through the oral or nasal cavity, or indirectly from vomiting, into the trachea and lower respiratory system. Some hydrocarbons (petroleum distillates) and certain chlorinated hydrocarbons have been shown to pose an aspiration hazard in humans. Primary alcohols, and ketones have been shown to pose an aspiration hazard only in animal studies. Substances and mixtures of this hazard class are assigned to one of two hazard categories this hazard class on the basis of viscosity. 3.3 Environmental Hazards 3.3.1 Hazardous to the Aquatic Environment The harmonized criteria are considered suitable for packaged goods in both supply and use in multi-modal transport schemes. Elements of it may be used for bulk land transport and bulk marine transport under MARPOL (International Convention for the Prevention of Pollution from Ships) insofar as this uses aquatic toxicity. Two Guidance Documents (Annexes 8 and 9 of the GHS Document) cover issues such as data interpretation and the application of the criteria to special substances. Considering the complexity of this endpoint and the breadth of the application, the Guidance Annexes are important in the application of the harmonized criteria. 3.3.1.1 Acute Aquatic Toxicity Acute aquatic toxicity means the intrinsic property of a material to cause injury to an aquatic organism in a short-term exposure. Substances and mixtures of this hazard class are assigned to one of three toxicity categories on the basis of acute toxicity data: LC50 (fish) or EC50 (crustacea) or ErC50 (for algae or other aquatic plants). In some regulatory systems these acute toxicity categories may be subdivided or extended for certain sectors. 3.3.1.2 Chronic Aquatic Toxicity Chronic aquatic toxicity means the potential or actual properties of a material to cause adverse effects to aquatic organisms during exposures that are determined in relation to the lifecycle of the organism. Substances and mixtures in this hazard class are assigned to one of four toxicity categories on the basis of acute data and environmental fate data: LC50 (fish) or EC50 (crustacea) or ErC50 (for algae or other aquatic plants) and degradation/bioaccumulation. While experimentally derived test data are preferred, where no experimental data are available, validated Quantitative Structure Activity Relationships (QSARs) for aquatic toxicity and log KOW may be used in the classification process. The log KOW is a surrogate for a measured Bioconcentration Factor (BCF), where such a measured BCF value would always take precedence. Chronic Category IV is considered a "safety net" classification for use when the available data do not allow classification under the formal criteria, but there are some grounds for concern. Table 3.17 Acute & Chronic Aquatic Toxicity
3.4 What is the GHS approach to classifying mixtures? For consistency and understanding the provisions for classifying mixtures, the GHS defines certain terms. These working definitions are for the purpose of evaluating or determining the hazards of a product for classification and labeling. Substance: Chemical elements and their compounds in the natural state or obtained by any production process, including any additive necessary to preserve the stability of the product and any impurities deriving from the process used, but excluding any solvent which may be separated without affecting the stability of the substance or changing its composition. Mixture: Mixtures or solutions composed of two or more substances in which they do not react. Alloy: An alloy is a metallic material, homogeneous on a macroscopic scale, consisting of two or more elements so combined that they cannot be readily separated by mechanical means. Alloys are considered to be mixtures for the purpose of classification under the GHS. Where impurities, additives or individual constituents of a substance or mixture have been identified and are themselves classified, they should be taken into account during classification if they exceed the cutoff value/concentration limit for a given hazard class. Figure 3-4
As mentioned previously, the GHS physical hazard criteria apply to mixtures. It is assumed that mixtures will be tested for physical hazards. Each health and environmental endpoint chapter in the GHS contains specific criteria for classifying mixtures as well as substances. The GHS Document or "Purple Book" should be consulted for complete information on classifying mixtures. The process established for classifying a mixture allows the use of (a) available data for the mixture itself and/or (b) similar mixtures and/or (c) data for ingredients of the mixture. The GHS approach to the classification of mixtures for health and environmental hazards is tiered, and is dependent upon the amount of information available for the mixture itself and for its components. The process for the classification of mixtures is based on the following steps: (1) Where test data are available for the mixture itself, the classification of the mixture will be based on that data (See exception for carcinogens, mutagens & reproductive toxins in the GHS Document); (2) Where test data are not available for the mixture itself, then the appropriate bridging principles (as described below) in the specific chapter should be used; (3) If (i) test data are not available for the mixture itself, and (ii) the bridging principles cannot be applied, then use the calculation or cutoff values described in the specific endpoint to classify the mixture. 3.5 What are bridging principles? Bridging principles are an important concept in the GHS for classifying untested mixtures. When a mixture has not been tested, but there are sufficient data on the components and/or similar tested mixtures, these data can be used in accordance with the following bridging principles:
When the bridging principles do not apply or ca not be used, the health and environmental hazards of mixtures are estimated based on component information. In the GHS, the methodology used to estimate these hazards varies by endpoint. The GHS Document or "Purple Book" should be consulted for more complete information on classifying mixtures. Figure 3.5 summarizes the GHS mixtures approach for the various health and environmental endpoints. 3.6 What testing is required? The GHS itself does not include requirements for testing substances or mixtures. Therefore, there is no requirement under the GHS to generate test data for any hazard class. Some parts of regulatory systems may require data to be generated (e.g., for pesticides), but these requirements are not related specifically to the GHS. The GHS criteria for determining health and environmental hazards are test method neutral, allowing different approaches as long as they are scientifically sound and validated according to international procedures and criteria already referred to in existing systems. Test data already generated for the classification of chemicals under existing systems should be accepted when classifying these chemicals under the GHS, thereby avoiding duplicative testing and the unnecessary use of test animals. The GHS physical hazard criteria are linked to specific test methods. It is assumed that mixtures will be tested for physical hazards. 4. Hazard Communication Section 3, explained that classification is the starting point for the GHS. Once a chemical has been classified, the hazard(s) must be communicated to target audiences. As in existing systems, labels and Safety Data Sheets are the main tools for chemical hazard communication. They identify the hazardous properties of chemicals that may pose a health, physical or environmental hazard during normal handling or use. The goal of the GHS is to identify the intrinsic hazards found in chemical substances and mixtures, and to convey information about these hazards. The international mandate for the GHS included the development of a harmonized hazard communication system, including labeling, Safety Data Sheets and easily understandable symbols, based on the classification criteria developed for the GHS. 4.1 What factors influenced development of the GHS communication tools? Early in the process of developing the GHS communication tools, several significant issues were recognized. One of the most important was comprehensibility of the information provided. After all, the aim of the system is to present hazard information in a manner that the intended audience can easily understand and that will thus minimize the possibility of adverse effects resulting from exposure. The GHS identifies some guiding principles to assist in this process:
4.2 Labels 4.2.1 What does a label look like? Existing systems have labels that look different for the same product. We know that this leads to worker confusion, consumer uncertainty and the need for additional resources to maintain different systems. In the U.S. as well as in other countries, chemical products are regulated by sector/target audience. Different agencies regulate the workplace, consumers, agricultural chemicals and transport. Labels for these sectors/target audiences vary both in the U.S. and globally. In order to understand the value of the GHS and its benefits to all stakeholders, it is instructive to look at the different labels for one fictional product. In the U.S. the product, ToxiFlam, which has a flash point of 120°F and has an oral LD50 of 275 mg/kg, has different labels for different sectors/target audiences. Label examples as seen in the U.S.A. are shown first, followed by international examples. 4.2.2 USA Examples: Workplace and Workers Figure 4.1
In the U.S., regulatory requirements for workplace labels are 'performance oriented'. This results at a minimum in a straightforward label that has a product identity, hazard statement and supplier identification (Figure 4.1). Some products can also have additional labeling requirements depending on their end use. However, many companies follow the voluntary ANSI Z129.1 Precautionary Labeling Standard for workplace labeling and often use it also for labeling consumer products. The American National Standards Institute (ANSI) standard includes several label elements that are core to the GHS as well as other helpful elements to assist users in safe handling (Figure 4.2). Figure 4.2
Consumer Products and Consumers Figure 4.3
In several countries consumer products are regulated separately from workplace chemicals. In the U.S. the CPSC regulates consumer products. Consumer products have required label elements, but only the signal words are specified. The ANSI labeling standard is often used in developing consumer labels. Transport and Emergency Responders For hazardous products being transported, outer containers have required label elements, product identifier and hazard symbols. Transportation requirements are in addition to workplace or end use label requirements. Figure 4.4
Agricultural Chemicals and Pesticides In many systems, agricultural chemicals often have special label requirements. In the U.S. the EPA is the agency covering these chemicals. A pesticide product with the same hazards as ToxiFlam would have a label developed using FIFRA requirements. FIFRA has requirements for product identity, chemical identity, signal word, hazard statements, and precautionary measures including first aid. Figure 4.5
4.2.3 International Examples All the previous examples are specific to the U.S. Many companies do business globally. So in addition to the U.S. regulations, these companies would need to comply with the corresponding regulations in the countries to which they export products. Canada and the EU are two existing systems that were considered in the development of the GHS. To illustrate the differences in labeling, it is interesting to examine an EU and Canadian label for ToxiFlam. European Union Label Labels in the EU have chemical identity, symbols, and R/S (Risk and Safety) phrases which are hazard statements, precautionary measures and first aid. Canadian Workplace Hazardous Materials Identification System (WHMIS) Label The WHMIS label requires product identifier, hazard symbol, hazard statement, precautionary measures, first aid, MSDS statement and supplier identification. In addition to these common label elements, WHMIS requires a hatched border. Figure 4.7
4.3 What are the GHS label elements? Some GHS label elements have been standardized (identical with no variation) and are directly related to the endpoints and hazard level. Other label elements are harmonized with common definitions and/or principles. See Figure 4.8 for an illustration of the GHS label elements. The standardized label elements included in the GHS are:·
The Section numbers refer to the sections in the GHS Document or "Purple Book". 4.3.1 Symbols/Pictograms The GHS symbols have been incorporated into pictograms for use on the GHS label. Pictograms include the harmonized hazard symbols plus other graphic elements, such as borders, background patterns or colors which are intended to convey specific information. For transport, pictograms (Table 4.10) will have the background, symbol and colors currently used in the UN Recommendations on the Transport of Dangerous Goods, Model Regulations. For other sectors, pictograms (Table 4.9) will have a black symbol on a white background with a red diamond frame. A black frame may be used for shipments within one country. Where a transport pictogram appears, the GHS pictogram for the same hazard should not appear. 4.3.2 Signal Words The signal word indicates the relative degree of severity a hazard. The signal words used in the GHS are "Danger" for the more severe hazards, and "Warning" for the less severe hazards. Signal words are standardized and assigned to the hazard categories within endpoints. Some lower level hazard categories do not use signal words. Only one signal word corresponding to the class of the most severe hazard should be used on a label. 4.3.3 Hazard Statements Hazard statements are standardized and assigned phrases that describe the hazard(s) as determined by hazard classification. An appropriate statement for each GHS hazard should be included on the label for products possessing more than one hazard. The assigned label elements are provided in each hazard chapter of the Purple Book as well as in Annexes 1 & 2. Figure 4-11 illustrates the assignment of standardized GHS label elements for the acute oral toxicity categories. Other GHS label elements include:
4.3.4 Precautionary Statements and Pictograms Precautionary information supplements the hazard information by briefly providing measures to be taken to minimize or prevent adverse effects from physical, health or environmental hazards. First aid is included in precautionary information. The GHS label should include appropriate precautionary information. Annex 3 of the GHS Purple Book includes precautionary statements and pictograms that can be used on labels. Annex 3 includes four types of precautionary statements covering: prevention, response in cases of accidental spillage or exposure, storage, and disposal. The precautionary statements have been linked to each GHS hazard statement and type of hazard. The goal is to promote consistent use of precautionary statements. Annex 3 is guidance and is expected to be further refined and developed over time. 4.3.5 Product Identifier (Ingredient Disclosure) A product identifier should be used on a GHS label and it should match the product identifier used on the SDS. Where a substance or mixture is covered by the UN Model Regulations on the Transport of Dangerous Goods, the UN proper shipping name should also be used on the package. The GHS label for a substance should include the chemical identity of the substance (name as determined by IUPAC, ISO, CAS or technical name). For mixtures/alloys, the label should include the chemical identities of all ingredients that contribute to acute toxicity, skin corrosion or serious eye damage, germ cell mutagenicity, carcinogenicity, reproductive toxicity, skin or respiratory sensitization, or Target Organ Systemic Toxicity (TOST), when these hazards appear on the label. Where a product is supplied exclusively for workplace use, the Competent Authority may give suppliers discretion to include chemical identities on the SDS, in lieu of including them on labels. The Competent Authority rules for confidential business information (CBI) take priority over the rules for product identification. 4.3.6 Supplier Identification The name, address and telephone number of the manufacturer or supplier of the product should be provided on the label. 4.3.7 Supplemental Information Supplemental label information is non-harmonized information on the container of a hazardous product that is not required or specified under the GHS. In some cases this information may be required by a Competent Authority or it may be additional information provided at the discretion of the manufacturer/distributor. The GHS provides guidance to ensure that supplemental information does not lead to wide variation in information or undermine the GHS information. Supplemental information may be used to provide further detail that does not contradict or cast doubt on the validity of the standardized hazard information. It also may be used to provide information about hazards not yet incorporated into the GHS. The labeler should have the option of providing supplementary information related to the hazard, such as physical state or route of exposure, with the hazard statement. 4.4 How are multiple hazards handled on labels? Where a substance or mixture presents more than one GHS hazard, there is a GHS precedence scheme for pictograms and signal words. For substances and mixtures covered by the UN Recommendations on the Transport of Dangerous Goods, Model Regulations, the precedence of symbols for physical hazards should follow the rules of the UN Model Regulations. For health hazards the following principles of precedence apply for symbols: (a) if the skull and crossbones applies, the exclamation mark should not appear; (b) if the corrosive symbol applies, the exclamation mark should not appear where it is used for skin or eye irritation; (c) if the health hazard symbol appears for respiratory sensitization, the exclamation mark should not appear where it is used for skin sensitization or for skin or eye irritation. If the signal word 'Danger' applies, the signal word 'Warning' should not appear. All assigned hazard statements should appear on the label. The Competent Authority may choose to specify the order in which they appear. 4.5 Is there a specific GHS label format / layout? The GHS hazard pictograms, signal word and hazard statements should be located together on the label. The actual label format or layout is not specified in the GHS. National authorities may choose to specify where information should appear on the label or allow supplier discretion. Figure 4.12 shows an example of a GHS label for the fictional product 'ToxiFlam'. The core GHS label elements are expected to replace the need for the array of different labels shown earlier for ToxiFlam. (Figure 4.8 also illustrates the GHS label elements.) Figure 4.12 Example GHS Inner Container Label (e.g., bottle inside a shipping box)
There has been discussion about the size of GHS pictograms and that a GHS pictogram might be confused with a transport pictogram or "diamond". Transport pictograms (Table 4.10) are different in appearance than the GHS pictograms (Table 4.9). Annex 7 of the Purple Book explains how the GHS pictograms are expected to be proportional to the size of the label text. So that generally the GHS pictograms would be smaller than the transport pictograms. Figure 4.13 Combination Packaging (Outer box with inner bottles)
Several arrangements for GHS labels are also provided in Annex 7 of the Purple Book. Figure 4.13 shows an arrangement for a combination packaging with an outer shipping box and inner bottles. The shipping box has a transportation pictogram. The inner bottles have a GHS label with a GHS pictogram. Figure 4.14 Combination Packaging (Outer box with inner bottles)
For a container such as a 55 gallon drum, the transport required markings and pictograms may be combined with the GHS label elements or presented separately. In Figure 4.14 a label arrangement for a single packaging such as a 55 gallon drum is shown. Pictograms and markings required by the transport regulations as well as GHS label and non-duplicative GHS pictogram are shown on the drum. A label merging the transportation requirements and the GHS requirements into one label for the fictional product "ToxiFlam" is shown in Figure 4.15. This combined type label could also be used on a 55 gallon drum. Figure 4.15 Example GHS Outer Container Label (55 gallon/200 liter drum)
4.6 What about risk? Competent Authorities may vary the application of the components of the GHS by the type of product (industrial, pesticide, consumer, etc.) or the stage in the lifecycle (workplace, farm, retail store, etc.). Once a chemical is classified, the likelihood of adverse effects may be considered in deciding what informational or other steps should be taken for a given product or use setting. Annex 5 of the GHS Purple Book includes a discussion of an example of how risk-based labeling could be considered for chronic health effects of consumer products in the consumer use setting. 4.7 Are workplace containers covered in the GHS ? Products falling within the scope of the GHS will carry the GHS label at the point where they are supplied to the workplace, and that label should be maintained on the supplied container in the workplace. The GHS label or label elements can also be used for workplace containers (e.g., storage tanks). However, the Competent Authority can allow employers to use alternative means of giving workers the same information in a different written or displayed format when such a format is more appropriate to the workplace and communicates the information as effectively as the GHS label. For example, label information could be displayed in the work area, rather than on the individual containers. Some examples of workplace situations where chemicals may be transferred from supplier containers include: containers for laboratory testing, storage vessels, piping or process reaction systems or temporary containers where the chemical will be used by one worker within a short timeframe. 4.8 What is the GHS Safety Data Sheet (SDS)? The (Material) Safety Data Sheet (SDS) provides comprehensive information for use in workplace chemical management. Employers and workers use the SDS as sources of information about hazards and to obtain advice on safety precautions. The SDS is product related and, usually, is not able to provide information that is specific for any given workplace where the product may be used. However, the SDS information enables the employer to develop an active program of worker protection measures, including training, which is specific to the individual workplace and to consider any measures that may be necessary to protect the environment. Information in a SDS also provides a source of information for other target audiences such as those involved with the transport of dangerous goods, emergency responders, poison centers, those involved with the professional use of pesticides and consumers. The SDS should contain 16 headings (Figure 4.14). The GHS MSDS headings, sequence and content are similar to the ISO, EU and ANSI MSDS/SDS requirements, except that the order of sections 2 and 3 have been reversed. The SDS should provide a clear description of the data used to identify the hazards. Figure 4.14 and the GHS Purple Book provide the minimum information that is required in each section of the SDS. Examples of draft GHS SDSs are provided in Appendix B of this guidance document. The revised Purple Book contains guidance on developing a GHS SDS (Annex 4). Other resources for SDSs include:
4.9 What is the difference between the GHS SDS and existing MSDSs/SDSs? SDSs are in use globally. So it is useful to have an understanding of the similarities and differences in the existing MSDS/SDS content and format and the GHS SDS content and format. A table comparing MSDS/SDS content/format is provided in Appendix A of this guidance document. 4.10 When should SDSs and labels be updated? All hazard communication systems should specify a means of responding in an appropriate and timely manner to new information and updating labels and SDS information accordingly. Updating should be carried out promptly on receipt of the information that necessitates the revision. The Competent Authority may choose to specify a time limit within which the information should be revised. Suppliers should respond to "new and significant" information they receive about a chemical hazard by updating the label and safety data sheet for that chemical. New and significant information is any information that changes the GHS classification and leads to a change in the label information or information that may affect the SDS. 4.11 How does the GHS address Confidential Business Information (CBI)? Confidential business information (CBI) will not be harmonized under the GHS. National authorities should establish appropriate mechanisms for CBI protection. The GHS established CBI principles which include:
The GHS states in Chapter 1.4, Section1.4.9, the importance of training all target audiences to recognize and interpret label and/or SDS information, and to take appropriate action in response to chemical hazards. Training requirements should be appropriate for and commensurate with the nature of the work or exposure. Key target audiences include workers, emergency responders and also those responsible for developing labels and SDSs. To varying degrees, the training needs of additional target audiences have to be addressed. These should include training for persons involved in transport and strategies required for educating consumers in interpreting label information on products that they use. 5. References References for Section 1. ANSI Z129.1: American National Standard for Hazardous Industrial Chemicals-Precautionary Labeling. Australia: Australia Worksafe, National Occupational Health and Safety Commission, Approved Criteria for Classifying Hazardous Substances (1994). CPSC FHSA: U.S. CPSC, 16 CFR 1500, FHSA regulations. DOT: U.S. DOT, 49 CFR Part 173, Subpart D. EPA FIFRA: U.S. EPA, 40 CFR Part 156, FIFRA regulations. EU: Council Directive 92/32/European Economic Community, amending for the 7th time, Directive 67/548/European Economic Community, approximation of the laws, regulations and administrative provisions on the classification, packaging and labeling of dangerous preparations. GHS: Globally Harmonized System of Classification and Labelling of Chemicals, United Nations, 1st Revised Edition 2005. IATA: International Air Transport Association's Dangerous Goods Regulations. ICAO: International Civil Aviation Organization's Technical Instructions for the Safe Transport Of Dangerous Goods By Air. IMO: International Maritime Organization's International Maritime Dangerous Goods (IMDG) Code. Japan: Japanese Official Notice of Ministry of Labor No. 60 "Guidelines for Labeling of the Danger and Hazards of Chemical Substances". Korea: Korean Ministry of Labor Notice 1997-27 "Preparation of MSDS and Labelling Regulation". Malaysia: Malaysian Occupational Safety and Health Act (1994), Act 514 and Regulations (1994). Mexico: Dario Oficial (March 30, 1996) NORMA Oficial Mexicana NOM-114-STPS-1994. NFPA: National Fire Protection Association, 704 Standard, System for the Identification of Fire Hazards of Materials, 2001. NPCA HMIS: National Paint and Coatings Association, Hazardous Materials Identification System, 2001. OSHA HCS: U.S. DOL, OSHA, 29 CFR 1910.1200. WHMIS: Controlled Products Regulation, Hazardous Products Act, Canada Gazette, Part II, Vol. 122, No. 2, 1987. References for Section 2.0: GHS Chapter 1.1 Purpose, Scope and Application of the GHS. GHS Chapter 1.3 Classification of Hazardous Substances and Mixtures. References for Section 3.0: GHS Chapter 1.3. Classification of Hazardous Substances and Mixtures. GHS Part 2. Physical Hazards. GHS Part 3. Health Hazards. GHS Part 4. Environmental Hazards GHS Annex 8. An Example of Classification in the GHS. GHS Annex 9. Guidance on Hazards to the Aquatic Environment. GHS Annex 10. Guidance on Transformation/Dissolution of Metals and Metal Compounds in Aqueous Media References for Section 4: GHS Chapter 1.4. Hazard Communication: Labelling. GHS Chapter 1.5. Hazard Communication: Safety Data Sheets. GHS Annex 1 Allocation of Label Elements. GHS Annex 2 Classification and Labelling Summary Tables. GHS Annex 3 Precautionary Statements and Precautionary Pictograms. GHS Annex 4 Guidance on the preparation of Safety Data Sheets GHS Annex 5 Consumer Product Labelling Based on the Likelihood of Injur. GHS Annex 6 Comprehensibility Testing Methodology. GHS Annex 7 Examples of Arrangements of GHS Label Elements. References for Government and Private Standards: Canada Hazardous Products Act: Controlled Products Regulations; Consumer Chemical and Container Regulations, 2001 Pest Control Products Act; Transportation of Dangerous Goods Act. European Union (EU) Directive 67/548/EEC (consolidated, 7th revision). Directive 2001/59/EC adapting to technical progress for the 28th time Council Directive 67/548/EEC. Manual of decisions, implementation for the sixth and seventh amendments to Directive 67/548/EEC on dangerous substances. Directive 1999/45/EC of the European Parliament and of the Council of 31 May 1999 related to the classification, packaging and labelling of dangerous reparations. Commission Directive 91/155/EEC defining and laying down the detailed arrangements for the system of specific information relating to dangerous preparations (SDS.) Directive 2001/58/EC (amending Directive 91/155/EEC) defining and laying down the detailed arrangements for the system of specific information relating to dangerous preparations (SDS). Standards American National Standard for Hazardous Industrial Chemicals - Precautionary Labeling (ANSI Z-129.1-2000). American National Standard for Hazardous Industrial Chemicals - MSDS Preparation (ANSI Z400.1-2004). ISO 11014-1:2003 DRAFT Safety Data Sheet for Chemical Products. UN TRANSPORT UN Recommendations on the Transport of Dangerous Goods, Model Regulations (14th Revised Edition 2005). UN Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria, 4th Revised Edition USA OSHA Hazard Communication Standard 29 CFR 1910.1200. CPSC Consumer Product Safety Act (15 U.S.C. 2051 et seq.) and Federal Hazardous Substances Act (15 U.S.C. 1261 et seq.). (FIFRA) Federal Insecticide, Fungicide, and Rodenticide Act (7 U.S.C. 136 et seq.). US EPA Label Review Manual (3rd Edition, August 2003) EPA 735-B-03-001. Federal Hazardous Materials Transportation Law (49 U.S.C. 5101 et seq.). 6.0 GLOSSARY Aerosols means any non-refillable receptacles made of metal, glass or plastics and containing a gas compressed, liquefied or dissolved under pressure, with or without a liquid, paste or powder, and fitted with a release device allowing the contents to be ejected as solid or liquid particles in suspension in a gas, as a foam, paste or powder or in a liquid state or in a gaseous state. Aerosol includes aerosol dispensers. Alloy means a metallic material, homogeneous the naked eye, consisting of two or more elements so combined that they cannot be readily separated by mechanical means. Alloys are considered to be mixtures for the purpose of classification under the GHS. Aspiration means the entry of a liquid or solid chemical product into the trachea and lower respiratory system directly through the oral or nasal cavity, or indirectly from vomiting; ASTM means the "American Society of Testing and Materials". BCF means "bioconcentration factor". BOD/COD means "biochemical oxygen demand/chemical oxygen demand". CA means "competent authority". Carcinogen means a chemical substance or a mixture of chemical substances which induce cancer or increase its incidence. CAS means "Chemical Abstract Service". CBI means "confidential business information". Chemical identity means a name that will uniquely identify a chemical. This can be a name that is in accordance with the nomenclature systems of the International Union of Pure and Applied Chemistry (IUPAC) or the Chemical Abstracts Service (CAS), or a technical name. Competent authority means any national body(ies) or authority(ies) designated or otherwise recognized as such in connection with the Globally Harmonized System of Classification and Labelling of Chemicals (GHS). Compressed gas means a gas which when packaged under pressure is entirely gaseous at ‑50°C; including all gases with a critical temperature £ ‑50°C. Contact sensitizer means a substance that will induce an allergic response following skin contact. The definition for "contact sensitizer" is equivalent to "skin sensitizer". Corrosive to metal means a substance or a mixture which by chemical action will materially damage, or even destroy, metals. Criteria means the technical definition for the physical, health and environmental hazards; Critical temperature means the temperature above which a pure gas cannot be liquefied, regardless of the degree of compression. Dermal Corrosion: see skin corrosion; Dermal irritation: see skin irritation. Dissolved gas means a gas which when packaged under pressure is dissolved in a liquid phase solvent. EC50 means the effective concentration of a substance that causes 50% of the maximum response. EC Number or (ECN°) is a reference number used by the European Communities to identify dangerous substances, in particular those registered under EINECS. ECOSOC means the "Economic and Social Council of the United Nations". EINECS means "European Inventory of Existing Commercial Chemical Substances". End Point means physical, health and environmental hazards; ErC50means EC50 in terms of reduction of growth rate. EU means "European Union". Explosive article means an article containing one or more explosive substances. Explosive substance means a solid or liquid substance (or mixture of substances) which is in itself capable by chemical reaction of producing gas at such a temperature and pressure and at such a speed as to cause damage to the surroundings. Pyrotechnic substances are included even when they do not emit gases. Eye irritation means the production of changes in the eye following the application of test substance to the front surface of the eye, which are fully reversible within 21 days of application. Flammable gas means a gas having a flammable range with air at 20°C and a standard pressure of101.3kPa. Flammable liquid means a liquid having a flash point of not more than 93°C. Flammable solid means a solid which is readily combustible, or may cause or contribute to fire through friction. Flash point means the lowest temperature (corrected to a standard pressure of 101.3 kPa) at which the application of an ignition source causes the vapors of a liquid to ignite under specified test conditions. Gas means a substance which (i) at 50 °C has a vapor pressure greater than 300 kPa; or (ii) is completely gaseous at 20 °C at a standard pressure of 101.3 kPa. GESAMP means "the Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection of IMO/FAO/UNESCO/WMO/WHO/IAEA/UN/UNEP." GHS means "the Globally Harmonized System of Classification and # Labeling of Chemicals". Hazard category means the division of criteria within each hazard class, e.g., oral acute toxicity includes five hazard categories and flammable liquids includes four hazard categories. These categories compare hazard severity within a hazard class and should not be taken as a comparison of hazard categories more generally. Hazard class means the nature of the physical, health or environmental hazard, e.g., flammable solid carcinogen, oral acute toxicity. Hazard statement means a statement assigned to a hazard class and category that describes the nature of the hazards of a hazardous product, including, where appropriate, the degree of hazard; IARC means the "International Agency for the Research on Cancer". ILO means the "International Labor Organization". IMO means the "International Maritime Organization". Initial boiling point means the temperature of a liquid at which its vapor pressure is equal to the standard pressure (101.3kPa), i.e., the first gas bubble appears. IOMC means the "Inter-organization Program on the Sound Management of Chemicals". IPCS means the "International Program on Chemical Safety". ISO means International Standards Organization. IUPAC means the "International Union of Pure and Applied Chemistry". Label means an appropriate group of written, printed or graphic information elements concerning a hazardous product, selected as relevant to the target sector(s), that is affixed to, printed on, or attached to the immediate container of a hazardous product, or to the outside packaging of a hazardous product. Label element means one type of information that has been harmonized for use in a label, e.g., pictogram, signal word. LC50 (50% lethal concentration) means the concentration of a chemical in air or of a chemical in water which causes the death of 50% (one-half) of a group of test animals. LD50 means the amount of a chemical, given all at once, which causes the death of 50% (one half) of a group of test animals. L(E)C50 means LC50 or EC50. Liquefied gas means a gas which when packaged under pressure, is partially liquid at temperatures above-50°C. A distinction is made between. (i) High pressure liquefied gas: a gas with a critical temperature between -50°C and+65°C; and (ii) Low pressure liquefied gas: a gas with a critical temperature above +65°C. Liquid means a substance or mixture which at 50°C has a vapor pressure of not more than 300kPa (3bar), which is not completely gaseous at 20 °C and at a standard pressure of 101.3kPa, and which has a melting point or initial melting point of 20°C or less at a standard pressure of 101.3 kPa. A viscous substance or mixture for which a specific melting point cannot be determined shall be subjected to the ASTM D 4359-90 test; or to the test for determining fluidity (penetrometer test) prescribed in section 2.3.4 of Annex A of the European Agreement concerning the International Carriage of Dangerous Goods by Road (ADR). MARPOL means the "International Convention for the Prevention of Pollution from Ships". Mixture means a mixture or a solution composed of two or more substances in which they do not react. MSDS means "Material Safety Data Sheet" and in this document is used interchangeably with Safety Data Sheet (SDS). Mutagen means an agent giving rise to an increased occurrence of mutations in populations of cells and /or organisms. Mutation means a permanent change in the amount or structure of the genetic material in a cell; NGO means "non-governmental organization". NOEC means the "no observed effect concentration". OECD means "The Organization for Economic Cooperation and Development". Organic peroxide means a liquid or solid organic substance which contains the bivalent -0-0- structure and may be considered a derivative of hydrogen peroxide, where one or both of the hydrogen atoms have been replaced by organic radicals. The term also includes organic peroxide formulation (mixtures). Oxidizing gas means any gas which may, generally by providing oxygen, cause or contribute to the combustion of other material more than air does. Oxidizing liquid means a liquid which, while in itself not necessarily combustible, may, generally by yielding oxygen, cause, or contribute to, the combustion of other material. Oxidizing solid means a solid which, while in itself not necessarily combustible, may, generally by yielding oxygen, cause, or contribute to, the combustion of other material. QSAR means "quantitative structure-activity relationships". Pictogram means a graphical composition that may include a symbol plus other graphic elements, such as a border, background pattern or color that is intended to convey specific information. Precautionary statement means a phrase (and/or pictogram) that describes recommended measures that should be taken to minimize or prevent adverse effects resulting from exposure to a hazardous product, or improper storage or handling of a hazardous product. Product identifier means the name or number used for a hazardous product on a label or in the SDS. It provides a unique means by which the product user can identify the substance or mixture within the particular use setting (e.g. transport, consumer or workplace). Pyrophoric liquid means a liquid which, even in small quantities, is liable to ignite within five minutes after coming into contact with air. Pyrophoric solid means a solid which, even in small quantities, is liable to ignite within five minutes after coming into contact with air. Pyrotechnic article means an article containing one or more pyrotechnic substances; Pyrotechnic substance means a substance or mixture of substances designed to produce an effect by heat, light, sound, gas or smoke or a combination of these as the result of non-detonative, self-sustaining exothermic (heat-related) chemical reactions. Readily combustible solid means powdered, granular, or pasty substance or mixture which is dangerous if it can be easily ignited by brief contact with an ignition source, such as a burning match, and if the flame spreads rapidly. Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria means the latest revised edition of the United Nations publication bearing this title, and any published amendment thereto. Recommendations on the Transport of Dangerous Goods, Model Regulations means the latest revised edition of the United Nations publication bearing this title, and any published amendment thereto. Refrigerated liquefied gas means a gas which when packaged is made partially liquid because of its low temperature. Respiratory sensitizer means a substance that induces hypersensitivity of the airways following inhalation of the substance. RID means The Regulations concerning the International Carriage of Dangerous Goods by Rail [Annex 1 to Appendix B (Uniform Rules concerning the Contract for International Carriage of Goods by Rail) (CIM) of COTIF (Convention concerning international carriage by rail)], as amended. SAR means "Structure Activity Relationship". SDS means "Safety Data Sheet" and in this document is used interchangeably with Material Safety Data Sheet (MSDS). Self-Accelerating Decomposition Temperature (SADT) means the lowest temperature at which self-accelerating decomposition may occur with substance as packaged. Self-heating substance means a solid or liquid substance, other than a pyrophoric substance, which, by reaction with air and without energy supply, is liable to self-heat; this substance differs from a pyrophoric substance in that it will ignite only when in large amounts (kilograms) and after long periods of time (hours or days). Self-reactive substance means a thermally unstable liquid or solid substance liable to undergo a strongly exothermic decomposition even without participation of oxygen (air). This definition excludes substances or mixtures classified under the GHS as explosive, organic peroxides or as oxidizing. Serious eye damage means the production of tissue damage in the eye, or serious physical decay of vision, following application of a test substance to the front surface of the eye, which is not fully reversible within 21 days of application. Signal word means a word used to indicate the relative level of severity of hazard and alert the reader to a potential hazard on the label. The GHS uses 'Danger' and 'Warning' as signal words. Skin corrosion means the production of irreversible damage to the skin following the application of a test substance for up to 4 hours. Skin irritation means the production of reversible damage to the skin following the application of a test substance for up to 4 hours. Skin sensitizer means a substance that will induce an allergic response following skin contact. The definition for "skin sensitizer" is equivalent to "contact sensitizer". Solid means a substance or mixture which does not meet the definitions of a liquid or gas. SPR means "Structure Property Relationship". Substance means chemical elements and their compounds in the natural state or obtained by any production process, including any additive necessary to preserve the stability of the product and any impurities deriving from the process used, but excluding any solvent which may be separated without affecting the stability of the substance or changing its composition. Substance which, in contact with water, emits flammable gases means a solid or liquid substance or mixture which, by interaction with water, is liable to become spontaneously flammable or to give off flammable gases in dangerous quantities. Supplemental label element means any additional non-harmonized type of information supplied on the container of a hazardous product that is not required or specified under the GHS. In some cases this information may be required by other competent authorities or it may be additional information provided at the discretion of the manufacturer/distributor. Symbol means a graphical element intended to succinctly convey information. Technical name means a name that is generally used in commerce, regulations and codes to identify a substance or mixture, other than the IUPAC or CAS name, and that is recognized by the scientific community. Examples of technical names include those used for complex mixtures (e.g., petroleum fractions or natural products), pesticides (e.g., ISO or ANSI systems), dyestuffs (Color Index system) and minerals. UNCED means the "United Nations Conference on Environment and Development". UNCETDG/GHS means the "United Nations Committee of Experts on the Transport of Dangerous Goods and on the Globally Harmonized System of Classification and Labelling of Chemicals". UNITAR means the "United Nations Institute for Training and Research"; UNSCEGHS means the "United Nations Sub-Committee of Experts on the Globally Harmonized System of Classification and Labelling of Chemicals". UNSCETDG means the "United Nations Sub-Committee of Experts on the Transport of Dangerous Goods". 7.0 Appendices A. Comparison of MSDS/SDS Elements B. GHS MSDS Examples Appendix A Comparison of MSDS/SDS Elements The following tables provide a comparison of MSDS elements for the following:
1. Globally Harmonized System of Classification and Labelling of Chemicals (GHS), United Nations, 2005. 2. ISO 11014-1:2003 DRAFT Safety Data Sheet for Chemical Products. 3. American National Standard for Hazardous Industrial Chemicals-MSDS Preparation (ANSI Z-400.1-2004). 4. U.S. DOL, OSHA, 29 CFR 1910.1200, HAZCOM. Appendix B MSDS Examples (Fictional Products) B-1: Bondit B-2: Chemical Stuff Appendix B-1 Bondit (GHS MSDS Example) 1. Identification Name of the product: Bondit Recommended use: General adhesive. Producer: GHS Ltd., UK - London, SE, Southwarkbridge 1 Telephone no. +44 171717 555.555 5, Emergency no. +44 171717 333 333 3 2. Hazard(s) identification Classification: Flammable liquid, Category 2 Eye irritation, Category 2A Hazardous to the aquatic environment, Acute Category 3 Labelling: Symbol: Flame, Exclamation mark Signal word:Danger Hazard statement: Highly flammable liquid and vapour. Causes severe eye irritation. Harmful to aquatic life. Precautionary statements: Keep container tightly closed. Keep away from heat/sparks/open flame. - No smoking. Wear protective gloves and eye/face protection. Ground/Bond container and receiving equipment. Use explosion-proof electrical/ventilating/lighting/ equipment. Take precautionary measures against static discharge. Use only non-sparking tools. Store in cool/well-ventilated place. Avoid release to the environment. 3. Composition / Information on ingredients Chemical identity: Component A 70-80% Common name: Solvent A Numbers of identity: CAS-Nr.:111111-11-1 Impurities: None Chemical identity: Component C 20-25% Common name: Not applicable Numbers of identity: CAS-Nr.: 44444-44-4 Impurities: none 4. First-aid measures Inhalation: Remove person to fresh air. If respiratory irritation, dizziness, nausea, or unconsciousness occurs, seek immediate medical assistance. If breathing has stopped, give artificial respiration. Skin contact: Wash the contaminated area with soap and water. Remove contaminated clothing and wash before reuse. If irritation develops, get medical attention. Eye contact: Hold eyelids apart and flush eyes with plenty of water for at least 15 minutes. Get medical attention. Ingestion: If swallowed, do NOT induce vomiting. Seek immediate medical attention. 5. Firefighting measures Suitable extinguishing media: Foam, extinguishing powder, carbon dioxide, water fog. In case of fire, cool endangered containers with water fog. Unsuitable extinguishing media: High pressure water jet. Specific hazards in case of fire: None are known. Special protective equipment and precaution for fire fighters: For fires in enclosed areas, wear self-contained breathing apparatus. Do not inhale combustion gases. 6. Accidental release measures Personal precautions: Depending on extent of release, consider the need for fire fighters/emergency responders with adequate personal protective equipment for cleaning up. Do not eat, drink or smoke while cleaning up. Use a self-contained respirator, a mask with filter (type A class 3) or a filtering mask (e.g., EN 405). Wear protective clothing, safety glasses and impervious gloves (e.g., neoprene gloves). Ensure adequate ventilation. Avoid all sources of ignition, hot surfaces and open flames (see also Section 7). Environmental precautions: Prevent spills from entering storm sewers or drains and contact with soil. Methods and materials for containment and cleaning up: Eliminate all ignition sources. Runoff may create fire or explosion hazard in sewer system. Absorb on fire retardant, liquid-absorbing material (treated sawdust, diatomaceous earth, sand). Shovel up and dispose of at an appropriate waste disposal facility in accordance with current applicable laws and regulations, and product characteristics at time of disposal (see also Section 13). 7. Handling and storage Precautions for safe handling: Avoid contact with eyes. Avoid prolonged repeated skin contact and breathing mists/vapours. Use in well-ventilated area away from all ignition sources. Switch off all electrical devices such as parabolic heaters, hotplates, storage heaters etc. in good time for them to have cooled down before commencing work. Do not smoke; do not weld. Do not empty waste into sanitary drains. Take measures to prevent the build up of electrostatic charge. Conditions for safe storage, including incompatibilities: Storage containers must be grounded and bonded. Store away from all ignition sources in a cool area equipped with an automatic sprinkling system. Ensure adequate ventilation. Store at temperatures between +5 and +50°C. Store only in the original container. 8. Exposure controls / personal protection Information on the system design: Draw off vapours directly at the point of generation and exhaust from the work area. In the case of regular work, provide bench-mounted extraction equipment. Ventilation: Use in well-ventilated area with local exhaust. Respiratory protection: Approved respiratory equipment must be used when airborne concentrations are unknown or exceed the exposure limits. When processing large amounts, use a light duty construction compressed air line breathing apparatus (e.g., in accordance with EN1835), a mask with filter (type A class 3, colour brown) or a filtering half mask (e.g., in accordance with EN 405) when there is inadequate ventilation. Eye protection: Safety glasses with side shields or chemical goggles must be worn. Skin protection: If prolonged or repeated skin contact is likely, neoprene gloves should be worn. Good personal hygiene practices should always be followed. 9. Physical and chemical properties Physical state: Liquid Colour: Colourless, transparent Odour: Solvent, ester-like Odour threshold:Not available pH-value: Not applicable Melting point: Not available Freezing Point: Not available Initial boiling point: 56°C Flash point: - 22°C DIN 51755 Evaporation rate: Not available Flammability (solid, gas): Not applicable Explosion limits: lower limit = 1.4 Vol%; upper limit 13.0 Vol% (literature) Vapour pressure: 240 mbar (highest partial vapour pressure) at 20°C Vapour density: Not available Relative density: 0.89 g/cm3 at 20°C Solubility: Partially soluble in water at 20°C Partition coefficient: Log Kow = 3.3 Auto-ignition temperature: Not available Decomposition temperature: Not available 10. Stability and reactivity Chemical stability: No decomposition, if used according to specifications. Possibility of hazardous reactions: None are known. Conditions to avoid: Heat, sparks, flame and build up of static electricity. Materials to avoid: Halogens, strong acids, alkalies and ozidizers. Hazardous decomposition products: None are known. 11. Toxicological information Summary Comments: Component A may have a drying effect on the skin; frequent or prolonged contact may cause flaking or cracking of the skin. 12. Ecological information Persistence and degradability: The total of the organic components contained in the product is not classified as "readily biodegradable" (OECD-301 A-F). However, this product is expected to be inherently biodegradable. Bio-accumulative potential: There is no evidence to suggest bioaccumulation will occur. Mobility: Accidental spillage may lead to penetration in the soil and groundwater. However, there is no evidence that this would cause adverse ecological effects. 13. Disposal considerations Waste Disposal: Product is suitable for burning in an enclosed, controlled burner for fuel value or disposal by supervised incineration. Such burning may be limited by local regulation. The product is suitable for processing at an appropriate government waste disposal facility. Use of these methods is subject to user compliance with applicable laws and regulations and consideration of product characteristics at time of disposal. Recommended European waste code (EWC): 080406 14. Transport information UN-number: 1993 UN proper shipping name: Flammable Liquid, N.O.S. (Contains Component C) Transport hazard class: 3 Packing group: II Marine Pollutant: No 15. Regulatory information Inventory Status: All components are on TSCA, EINECS/ELINCS, AICS, and DSL. German: Regulations governing combustible liquids (German-VbF) class: AI German water endangering class (WGK) = 1, slightly water-endangering product (manufacturer classification.) Australian Regulations: AS 1940 Class: PGII Poisons Schedule: S5 U.S. Regulations: U.S. Superfund Amendments and Reauthorization Act (SARA) Title III: SARA (311/312) HAZARD CATEGORIES: FIRE, ACUTE 16. Other information Abbreviations and acronyms: UK OES = United Kingdom Occupational Exposure Standards German MAK = Germany Maximum Allowable Concentration MSDS Prepration date: July 1, 2005 The information contained herein is accurate to the best of our knowledge. My Company makes no warranty of any kind, express or implied, concerning the safe use of this material in your process or in combination with other substances. Appendix B-2 Chemical Stuff (GHS MSDS Example) GHS SAFETY DATA SHEET 1. Identification Product Name: Chemical Stuff Synonyms: Methyltoxy Solution CAS Number: 000-00-0 Product Use: Organic Synthesis Manufacturer/Supplier: My Company Address: My Street, Mytown, TX 00000 General Information: 713-000-0000 Transportation Emergency Number: CHEMTREC: 800-424-9300 2. Hazards Identification 3. Composition / Information on Ingredients Component CAS Number Weight % Methyltoxy 000-00-0 80 (See Section 8 for Exposure Limits) 4. First Aid Measures Eye: Eye irritation. Flush immediately with large amounts of water for at least 15 minutes. Eyelids should be held away from the eyeball to ensure thorough rinsing. Get immediate medical attention. Skin: Itching or burning of the skin. Immediately flush the skin with plenty of water while removing contaminated clothing and shoes. Get immediate medical attention. Wash contaminated clothing before reuse. Inhalation: Nasal irritation, headache, dizziness, nausea, vomiting, heart palpitations, breathing difficulty, cyanosis, tremors, weakness, red flushing of face, irritability. Remove exposed person from source of exposure to fresh air. If not breathing, clear airway and start cardiopulmonary resuscitation (CPR). Avoid mouth-to-mouth resuscitation. Ingestion: Get immediate medical attention. Do not induce vomiting unless directed by medical personnel. 5. Fire Fighting Measures Suitable Extinguishing Media: Use dry chemical, foam, or carbon dioxide to extinguish fire. Water may be ineffective but should be used to cool fire-exposed containers, structures and to protect personnel. Use water to dilute spills and to flush them away from sources of ignition. Fire Fighting Procedures: Do not flush down sewers or other drainage systems. Exposed firefighters must wear NIOSH-approved positive pressure self-contained breathing apparatus with full-face mask and full protective clothing. Unusual Fire and Explosion Hazards: Dangerous when exposed to heat or flame. Will form flammable or explosive mixtures with air at room temperature. Vapor or gas may spread to distant ignition sources and flash back. Vapors or gas may accumulate in low areas. Runoff to sewer may cause fire or explosion hazard. Containers may explode in heat of fire. Vapors may concentrate in confined areas. Liquid will float and may reignite on the surface of water. Combustion Products: Irritating or toxic substances may be emitted upon thermal decomposition. Thermal decomposition products may include oxides of carbon and nitrogen. 6: Accidental Release Measures Keep unnecessary people away; isolate hazard area and deny entry. Stay upwind; keep out of low areas. (Also see Section 8). Vapor protective clothing should be worn for spills and leaks. Shut off ignition sources; no flares, smoking or flames in hazard area. Small spills: Take up with sand or other noncombustible absorbent material and place into containers for later disposal. Large spills: Dike far ahead of liquid spill for later disposal. Do not flush to sewer or waterways. Prevent release to the environment if possible. Refer to Section 15 for spill/release reporting information. 7. Handling and Storage Handling Do not get in eyes, on skin or on clothing. Do not breathe vapors or mists. Keep container closed. Use only with adequate ventilation. Use good personal hygiene practices. Wash hands before eating, drinking, smoking. Remove contaminated clothing and clean before re-use. Destroy contaminated belts and shoes and other items that cannot be decontaminated. Keep away from heat and flame. Keep operating temperatures below ignition temperatures at all times. Use non-sparking tools. Storage Store in tightly closed containers in cool, dry, well-ventilated area away from heat, sources of ignition and incompatibles. Ground lines and equipment used during transfer to reduce the possibility of static spark-initiated fire or explosion. Store at ambient or lower temperature. Store out of direct sunlight. Keep containers tightly closed and upright when not in use. Protect against physical damage. Empty containers may contain toxic, flammable and explosive residue or vapors. Do not cut, grind, drill, or weld on or near containers unless precautions are taken against these hazards. 8. Exposure Controls / Personal Protection Exposure Limits Component, Methyltoxy - TWA: 3 ppm (skin) - STEL: C 15 ppm (15 min.) Engineering Controls: Local exhaust ventilation may be necessary to control air contaminants to their exposure limits. The use of local ventilation is recommended to control emissions near the source. Provide mechanical ventilation for confined spaces. Use explosion-proof ventilation equipment. Personal Protective Equipment (PPE) Eye Protection: Wear chemical safety goggles and face shield. Have eye-wash stations available where eye contact can occur. Skin Protection: Avoid skin contact. Wear gloves impervious to conditions of use. Additional protection may be necessary to prevent skin contact including use of apron, face shield, boots or full body protection. A safety shower should be located in the work area. Recommended protective materials include:Butyl rubber and for limited contact Teflon. Respiratory Protection: If exposure limits are exceeded, NIOSH approved respiratory protection should be worn. A NIOSH approved respirator for organic vapors is generally acceptable for concentrations up to 10 times the PEL. For higher concentrations, unknown concentrations and for oxygen deficient atmospheres, use a NIOSH approved air-supplied respirator. Engineering controls are the preferred means for controlling chemical exposures. Respiratory protection may be needed for non-routine or emergency situations. Respiratory protection must be provided in accordance with OSHA 29 CFR 1910.134. 9. Physical and Chemical Properties Flashpoint: 2oC (35oF) Autoignition Temperature: 480oC (896oF) Boiling Point: 77oC (170.6oF) @ 760 mm Hg Melting Point: -82oC Vapor Pressure: 100.0 mm Hg @ 23oC Vapor Density(Air=1): 1.7; air = 1 % Solubility in Water: 10 @ 20ºC Pour Point: NA Molecular Formula: Mixture Odor/Appearance: Clear, colorless liquid with mild, pungent odor. Lower Flammability Limit: >3.00% Upper Flammability Limit: <15.00% Specific Gravity: 0.82g/ml @ 20oC % Volatile: 100 Evaporation Rate (Water=1): 5(Butyl Acetate =1) Viscosity: 0.3 cP @ 25oC Octanol/Water Partition Coefficient: log Kow: 0.5 pH: 7, 8% aqueous solution Molecular Weight: Mixture 10. Stability and Reactivity Stability/Incompatibility: Incompatible with ammonia, amines, bromine, strong bases and strong acids. Hazardous Reactions/Decomposition Products: Thermal decomposition products may include oxides of carbon and nitrogen. 11. Toxicological Information Signs and Symptoms of Overexposure: Eye and nasal irritation, headache, dizziness, nausea, vomiting, heart palpitations, difficulty breathing, cyanosis, tremors, weakness, itching or burning of the skin. Acute Effects: Eye Contact: may cause severe conjunctival irritation and corneal damage. Skin Contact: may cause reddening, blistering or burns with permanent damage. Harmful if absorbed through the skin. May cause allergic skin reaction. Inhalation: may cause severe irritation with possible lung damage (pulmonary edema). Ingestion: may cause severe gastrointestinal burns. Target Organ Effects: May cause gastrointestinal (oral), respiratory tract, nervous system and blood effects based on experimental animal data. May cause cardiovascular system and liver effects. Chronic Effects: based on experimental animal data, may cause changes to genetic material; adverse effects on the developing fetus or on reproduction at doses that were toxic to the mother. Methyltoxy is classified by IARC as group 2B and by NTP as reasonably anticipated to be a human carcinogen. OSHA regulates Methyltoxy as a potential carcinogen. Medical Conditions Aggravated by Exposure: preexisting diseases of the respiratory tract, nervous system, cardiovascular system, liver or gastrointestinal tract. Acute Toxicity Values Oral LD50 (Rat) = 100 mg/kg Dermal LD50 (Rabbit) = 225-300 mg/kg Inhalation LC50 (Rat) = 200 ppm/4 hr., 1100 ppm vapor/1 hr 12. Ecological Information LC50 (Fathead Minnows) = 9 mg/L/96 hr. EC50 (Daphnia) = 8.6 mg/L/48 hr. Bioaccumulation is not expected to be significant. This product is readily biodegradable. 13. Disposal Considerations As sold, this product, when discarded or disposed of, is a hazardous waste according to Federal regulations (40 CFR 261). It is listed as Hazardous Waste Number Z000, listed due to its toxicity. The transportation, storage, treatment and disposal of this waste material must be conducted in compliance with 40 CFR 262, 263, 264, 268 and 270. Disposal can occur only in properly permitted facilities. Refer to state and local requirements for any additional requirements, as these may be different from Federal laws and regulations. Chemical additions, processing or otherwise altering this material may make waste management information presented in the MSDS incomplete, inaccurate or otherwise inappropriate. 14. Transport Information U.S. Department of Transportation (DOT) Proper Shipping Name: Methyltoxy Hazard Class: 3, 6.1 UN/NA Number: UN0000 Packing Group: PG 2 Labels Required: Flammable Liquid and Toxic International Maritime Organization (IMDG) Proper Shipping Name: Methyltoxy Hazard Class: 3 Subsidiary 6.1 UN/NA Number: UN0000 Packing Group: PG 2 Labels Required: Flammable Liquid and Toxic 15. Regulatory Information U.S. Federal Regulations Comprehensive Environmental Response and Liability Act of 1980 (CERCLA): The reportable quantity (RQ) for this material is 1000 pounds. If appropriate, immediately report to the National Response Center (800/424-8802) as required by U.S. Federal Law. Also contact appropriate state and local regulatory agencies. Toxic Substances Control Act (TSCA): All components of this product are included on the TSCA inventory. Clean Water Act (CWA): Methyltoxy is a hazardous substance under the Clean Water Act. Consult Federal, State and local regulations for specific requirements. Clean Air Act (CAA): Methyltoxy is a hazardous substance under the Clean Air Act. Consult Federal, State and local regulations for specific requirements. Superfund Amendments and Reauthorization Act (SARA) Title III Information: SARA Section 311/312 (40 CFR 370) Hazard Categories: Immediate Hazard: X Delayed Hazard: X Fire Hazard: X Pressure Hazard: Reactivity Hazard: This product contains the following toxic chemical(s) subject to reporting requirements of SARA Section 313 (40 CFR 372) Component CAS Number Maximum % Methyltoxy 000-00-0 80 State Regulations California: This product contains the following chemicals(s) known to the State of California to cause cancer, birth defects or reproductive harm: Component CAS Number Maximum % Methyltoxy 000-00-0 80 International Regulations Canadian Environmental Protection Act: All of the components of this product are included on the Canadian Domestic Substances list (DSL). Canadian Workplace Hazardous Materials Information System (WHMIS): Class B-2 Flammable Liquid Class D-1-B Toxic Class D-2-A Carcinogen Class D-2-B Chronic Toxin Class E Corrosive This product has been classified in accordance with the hazard criteria of the Controlled Products Regulations and the MSDS contains all the information required by the Controlled Products Regulations. European Inventory of Existing Chemicals (EINECS): All of the components of this product are included on EINECS. EU Classification: F Highly Flammable; T Toxic; N Dangerous to the Environment EU Risk (R) and Safety (S) Phrases: R11: Highly flammable. R23/24/25: Toxic by inhalation, in contact with skin and if swallowed. R37/38: Irritating to respiratory system and skin. R41: Risk of serious damage to eyes. R43: May cause sensitization by skin contact. R45: May cause cancer. R51/53: Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment. S53: Avoid exposure - obtain special instructions before use. S16: Keep away from sources of ignition - No Smoking. S45: In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible). S9: Keep container in a well-ventilated place. S36/37: Wear suitable protective clothing and gloves. S57: Use appropriate container to avoid environmental contamination. 16. Other Information National Fire Protection Association (NFPA) Ratings: This information is intended solely for the use of individuals trained in the NFPA system. Health: 3 Flammability: 3 Reactivity: 0 | |
OSHA Labeling
Labeling Requirements for OSHA compliance
Occupational Health & Safety Administration Labeling
