RISKS , CONTROL MEASURES , APPLICATIONS IN CHEMICAL INDUSTRY

1. RISKS, CONTROL MEASURES, APPLICATIONS IN CHEMICAL INDUSTRY

2. Content • Definitions • HazardsandRisksArisingfromChemicals • Risk Assesment of Chemicals • Labelling of Chemicals • MaterialSafety Data Sheets 4. PrinciplesforEliminatingorReducingRisks 5. Application of thePrinciplesforPrevention • SafeStorage of Chemicals • Implementing Regulations on EU

3. 1. Definitions Chemical agent: Means any chemical element, compound or a mixture of them, as it occurs in the natural state or as produced, used or released by any work activity or come about as waste or produced unintentionally. Implementing Regulation on the Protection of the Health andSafety Measures from the Risks Related to Chemical Agentsat Work(based on the Directive 1998/24/EC)

4. Definitions ChemicalAgents • Any substance that has one or more of characteristics that are toxic for reproduction and dangerous for the environment like being explosive, oxidizing, easily flammable, flammable, toxic, very toxic, hazardous, corrosive, irritating, allergic, carcinogen, mutagen. • Any chemical agent that is not mentioned in the classifications abovebut due to its chemical, physico-chemical, or toxicological properties, and the way it is used or present in the workplace, present a risk to the safety and health of workers. • Chemical agents with established occupational exposure limit value.

5. Definitions Hazard is the intrinsic capacity of a chemical agent to cause harm. Risk is the likelihood that the potential for harm will be attained under the conditions of use and/or exposure. Exposure to chemical agents is any work situation in which a chemical agent is present and the worker comes into contact with this agent, normally through the skin or via inhalation.

6. Use of Chemical Agents in the Last 5 Years (in EU) • Construction andassociatedactivities (carpentry, painting, water, gasandelectricalinstallations, etc.); • Professional cleaning, • Hospitals, • Waste –processingindustry, • Agriculture, • Metalworkingandmechanicalindustries, • Mechanicalworkshops, • Printing works, • Chemists’ shops, • Laboratories, • Restoration of works of art, • Hairdressingsalons.

7. Classifications according to 67/548/EEC (published in December 2008in Official Paper in Turkey) E Explosive T+ Highly toxic C Corrosive O Oxidising T Toxic Xi Irritant F+Highlyflammable Xn Harmful F Flammable N Nature polluting

8. Classificationsaccording to Globally Harmonized System(GHS) Compressed gas Flammable solid Organic Peroxides Toxic gas Spontaneously Toxic combustible Flammable gas Dangerous Corrosive when wet Flammable Liquid Oxidising agent

9. Globally Harmonized System(GHS) Overview – The UN-developed system „GHS“ standarts for "Globally Harmonized System of Classification and Labeling of Chemicals" – With GHS, globally harmonized criteria have been created for the classification and labeling of chemicals. GHS wants to ensure internationally comparable high standards for health and consumer protection, occupational health and safety, and environmental protection. – GHS regulates ... • criteria for the classification of physical, toxicological, andenvironmental relevant properties ... • classification and labeling ... • harmonized hazard communication ... (e.g. harmonized label statements and harmonized safety data sheets) ... of chemicals.

10. GHS Overview – GHS affects manufacturers, suppliers, and users of chemicals – The global implementation of GHS should take place during 2008. The registration phase of REACH, the uniform chemical law applicable within the EU, also begins in 2008. – Because of the numerous interconnections between GHS and REACH, the European Commission has scheduled the implementation of the two regulations to follow each another in quick succession. – The implementation of GHS is progressing at different paces around the world. Inmany Asian countries, for example, GHS has already been introduced.

11. What must be done? The conversion to GHS has significant effects on the handling of chemicals. – All products have to be checked to be in line with the requirements of GHS. – Within the transition periods, • labeling shall be adapted to the new requirements. • safety data sheets shall be correspondingly changed. – All substances which meet the criteria for classification as hazardous and are placedon the market shall be notified to the European Chemicals Agency (ECHA) for inclusionin the classification and labeling inventory.

12. The Timeline – The implementation timeline provides the following critical milestones: • On January 1, 2009, GHS enters into force • By December 1, 2010, all substances shall be classified and labeled in accordance with GHS criteria • By June 1, 2015, all mixtures shall be classified and labeled in accordance with GHS criteria.

13. The Timeline – The implementation timeline provides the following critical milestones: • On January 1, 2009, GHS enters into force • By December 1, 2010, all substances shall be classified and labeled in accordance with GHS criteria • By June 1, 2015, all mixtures shall be classified and labeled in accordance with GHS criteria.

14. What essential changes does GHS involve? – GHS introduces globally harmonized criteria for the classificationof physical, toxicological, and environmental relevant properties. – GHS establishes globally harmonized criteria for hazard communication. In theoverview, this relates to the introduction of new or modified: • hazard classes, • hazard categories, • hazard pictograms, • signal words, • hazard statements, • precautionary statements. – GHS offers the opportunity to bring product safety to a high level all over the world. GHS will thus contribute to improving measures for protecting human healthand the environment on a global scale.

15. New Labeling Elements Signal word The signal word on the label gives information about the relative hazard level of a substance or mixture and alerts the reader to a potential hazard. Hazard pictogram • Square set on a point, • Red border, • White background, • Black symbols. Danger Warning

16. New pictograms – the most striking GHS feature Physical Hazards Health Hazards Env. hazards

17. Classificationsaccording to GHS Compressed gas Flammable solid Organic Peroxides Toxic gas Spontaneously Toxic combustible Flammable gas Dangerous Corrosive when wet Flammable Liquid Oxidising agent

18. Hazard statements, definition and coding A hazard statement is a phrase, assigned to a hazard class and category that describesthe nature / intrinsic property of a hazardous product as well as the hazard level. Hazard statement group 2 Physical hazards 3 hazards 4 al hazards H300 – Fatal if swallowed H300 – Fatal if swallowed Hazard statement Hazard statement Sequence in the group

19. Precautionary statements, definition and coding A hazard statement is a phrase, assigned to a hazard class and category that describesthe nature / intrinsic property of a hazardous product as well as the hazard level. Precautionary statement group 2 Prevention 3 Response 4 Storage 5 Disposal Precautionary statement P 380 – Evacuate area Sequence in the group

20. The labeling must be adapted to the new regulations

21. 2. The Hazard Associated with Chemicals Chemicalagents can causeharm; • eitherdirectly, • orbyproducingsome form of energy (such as fire orexplosion).

22. The Hazard Associated with Chemicals For the 1st case; • Harm can become apparent rapidly or even immediately after contact(Acute Effect) • Or appear in the long term due to repeated exposure over time (Chronic Effect) • If the harm is apparent at the point of the contact of chemical and the bodyLocal Effect • Or if may appear following a process of absorption and distribution through the bodySystemic Effect

23. The Harm Caused by Chemicals For the 2nd case; • The harm is caused by the energy produced by the fire or explosion of chemical agents. • Explosions occur when a sudden oxidation or decomposition reaction occurs producing a temperature and pressure rise or both simultaneously. .

24. The Hazard Posed by Chemicals Chemical agents present in workplace may pose risks to healthand safety onaccount of; • Their hazardous properties (physico-chemical or toxicological) (e.g. explosive or sensitiser) • The temperature or pressure at which they occur in the workplace (e.g. water vapor at 150°C) • Their capacity to displace the atmospheric oxygen from the workplace (e.g.pressurized inert gas) • The manner in which they are present in the workplace (e.g. inert solid in the form of a breathable powder)

25. 3. Risk Assesment of Chemicals Risks to be assessed; • The risk of fire and/orexplosion, • Risk generatedduetothehazardouschemicalreactionswhichmayaffectthehealthandsafety of workers, • Risk duetoinhalation, • Risk duetoabsorptionthroughtheskin, • Risk duetocontactwith skin oreyes, • Risk duetoingestion,

26. To Assess the Risks of Chemicals • Todeterminetherisks of a chemicalagent; thehazardousproperties of thesechemicalsandtheway in whichtheyarepresentandareusedmust be known. • Toassesstherisksfirst be informedaboutthehazardousproperties of chemicals. (Directive 2000/39/EC) • Labelling • MaterialSafetyData Sheets (MSDS) • OccupationalExposure Limit ValuesandBiological Limit Values

27. Labelling

28. Material Safety Data Sheets (MSDS) 9. Physical/Chemical properties 10. Stability and reactivity 11. Toxicological information 12. Ecological information 13. Disposal considerations 14. Transport information 15. Regulatory information 16. Other information • Identification of substance/preparation and company • Composition/information of ingredients • Hazard identification • First-aid measures • Firefighting measures • Accidential spillage measures • Handling and storage • Exposure controls/personal protection

29. Application of MSDS • General Information ChemicalCompositionSection 2 Physico-chemicalPropertiesSection 9 • Use RecommendedusesandrestrictionsSection 16 Handling and Storage Section 7 and 15 User ProtectionSection 8 Exposure Limit ValuesSection 8 and 15

30. Application of MSDS • Hazards Safety: Flammability, explosiveness, reactivitySection 3,9,10 Health: ToxicitySection 3 and 11 Environment: EcotoxicitySection 3 and 12 • Emergencies First aidSection 4 Fire Section 5 Leaks/releasesSection 6

31. Occupational Exposure Limit Value • Specific reference parameters used in assessing risks due to exposure to chemical agents in the workplace. • All EU Member States must have their own national list of exposure limits and biological limits in accordcance with Directive 98/24/EC. • According to Community Legislation (Directive 98/24/EC), any substance which has an exposure limit value must be regarded as hazardous substance.

32. Risks Arising from Hazardous Chemicals

33. Risks Arising from Hazardous Chemicals

34. General Principles for Eliminating/Reducing Risks 1. Design and organisation of systems of work at the workplace. 2. Provision of suitable equipment for work with chemical agents and maintenance procedures which ensure the health and safety of workers at work. 3. Reducing to a minimum the number of workers exposed or likely to be exposed. 4. Reducing to a minimum the duration and intensity of exposure.

35. General Principles for Eliminating/Reducing Risks 5. Appropriate hygiene measures. 6. Reducing the quantity of chemical agents present at the workplace to the minimum required for the type of work concerned. 7. Suitable working procedures including arrangements for the safe handling, storage and transport within the workplace of hazardous chemical agents and waste containing such chemical agents.

36. Application of the Principles for Prevention

37. Specific Prevention Measures & Prioritisation

38. Action Diagram for Risk Assesment and Resulting Actions

39. An Example: Substitution of the Chemical Agent • In accordance with the Directive 98/24/EC, substitution of hazardous chemical agent shall be preferred as a specific measure for eliminating or reducing the chemical risk. • Example: In a process, benzene is being used, which has a IARC classification of 1, carcinogenic to humans. Occupational Hygienist want to substitute benzene with toluene. • Before the substitution the hazards of toluene and benzene should be evaluated in order to decide whether toluene is less hazardous than benzene. • In order to assess the substitution, first we examine the risk phrases of benzene and toluene; R-phrases of benzene: R11, R23, R24,R25, R45, R48 R-phrases of toluene: R11, R20

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42. 6. Safe Storage of Chemicals Main Principle: In terms of prevention, the main measure is to maintain the hazardous chemical stocks at the lowest possible level or to change chemicals used with less dangerous ones. Then maintain; • Safe storage area away form process area or other hazardous areas, • Avoidthe combined storage of incompatible or highly reactive chemicals, • Provide secure containers (sufficient physical resistance, automatic closure, appropriate for thetype and quantity of chemical stored etc.).

43. Safe Storage of Chemicals • To a large extent, how the chemical groups are dividedand assigned, willdepend largely upon the amount ofspace available. • The risk associated with incompatible chemicalscominginto contact must be avoided wherever chemicals arehandledorstored. • The common features uniting all these plans is theseparation ofincompatible materials. • The ten most commonly cited groups are: • flammables, oxidants, reducers, concentrated acids,concentrated bases, water reactives, extreme toxics,peroxide formers, pyrophorics and gas cylinders.

44. Examples of; • Incompatible Agents • Oxidising Agents with; inflammable substances, nitrides, hydrides, sulphides, alkylmetals • Reducing Agents with: nitrates, chlorates, oxides, peroxides, fluoride • Strong Acids with Strong Bases • Sulphuric acid with: cellulose, perchloric acid, potassium permanganate, chlorate

45. Examples of; • Unstable Substances • Products that may decompose when stored long periods: alkaline anhydrides • Substances that readily peroxidise: allylic compounds, styrene • Compounds that react violently on contact with air: phosphides, hydrides • Monomers that polymerise rapidly: styrene, acrylonitrile

47. Safe Storage of Chemicals • Violent reactions occur when the following chemicalsfrom different Storage Groups are mixed: – Corrosives + Flammables = Explosion/Fire – Corrosive + Poisons = PoisonGas (ToxicGas) – Flammables + Oxidizers = Explosion/Fire – Acids + Bases = CorrosiveFumes/Heat

49. Safe Storage of Chemicals • Basic Storage Requirements: • Label storage areas according to the type of chemicalfamily or hazard classification found there, • Inspect storage areas at least annually, • Keep aisles, hallways, doorways, exits, and entryways clear, • Keep storage areas well lit, appropriately ventilated, and ata consistent, cooltemperature.

50. Safe Storage of Chemicals • Basic Storage Requirements (Cont’d) • Eliminate ignition sources such as open flames, heat sources,or direct sunlight. • Keep emergency equipment such as fire extinguishers handyand in good working order. • Confine chemical storage areas so that leaks or spills arecontrolled. Preventchemicals from running down sink, floor,or storm water drains. Clean up spills and drips immediately.