1.
Definitions
2.
Hazards and Risks Arising from Chemicals
3.
Risk Assesment of Chemicals
- Labelling of Chemicals
- Material Safety Data Sheets
4. Principles for Eliminating or Reducing Risks
5. Application of the Principles for Prevention
6.
Safe Storage of Chemicals
7.
Implementing Regulations on EU

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 and Safety
Measures from the Risks Related to Chemical Agents at Work ( based on the
Directive 1998/24/EC )

Chemical Agents
 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 above but 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.

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.

(in EU)
• Construction and associated activities (carpentry, painting, water, gas and electrical installations, etc.);
• Professional cleaning,
• Hospitals,
• Waste –processing industry,
• Agriculture,
• Metalworking and mechanical industries,
• Mechanical workshops,
• Printing works,
• Chemists’ shops,
• Laboratories,
• Restoration of works of art,
• Hairdressing salons.

E Explosive T+ Highly toxic C Corrosive O Oxidising T Toxic
Xi Irritant F+ Highly flammable
Xn Harmful F
Flammable
N Nature polluting

Compressed gas Flammable solid Organic Peroxides
Toxic Toxic gas
Flammable gas
Flammable Liquid
Spontaneously combustible
Dangerous when wet
Oxidising agent
Corrosive

– 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, and environmental relevant properties ...
• classification and labeling ...
• harmonized hazard communication ...
(e.g. harmonized label statements and harmonized safety data sheets)
... of chemicals.

– 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. In many Asian countries, for example, GHS has already been introduced.

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 placed on the market shall be notified to the European Chemicals Agency
(ECHA) for inclusion in the classification and labeling inventory.

– 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.

– 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.

– GHS introduces globally harmonized criteria for the classification of physical, toxicological, and environmental relevant properties.
– GHS establishes globally harmonized criteria for hazard communication. In the overview, 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 health and the environment on a global scale.

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

Physical Hazards
Health Hazards Env. hazards

Compressed gas Flammable solid
Toxic gas
Flammable gas
Flammable Liquid
Spontaneously combustible
Dangerous when wet
Oxidising agent
Organic Peroxides
Toxic
Corrosive

A hazard statement is a phrase , assigned to a hazard class and category that describes the nature / intrinsic property of a hazardous product as well as the hazard level .
Hazard statement group
2 Physical hazards
3 hazards
4 al hazards
H 3 00 – Fatal if swallowed
Sequence in the group

A hazard statement is a phrase , assigned to a hazard class and category that describes the nature / intrinsic property of a hazardous product as well as the hazard level .
Precautionary statement group
2 Prevention
3 Response
4 Storage
Precautionary statement
5 Disposal
P 3 80 – Evacuate area
Sequence in the group

Chemical agents can cause harm;
1. either directly,
2. or by producing some form of energy (such as fire or explosion).

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 body Local Effect
 Or if may appear following a process of absorption and distribution through the body Systemic Effect

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.
.

Chemical agents present in workplace may pose risks to health and safety on account of;
1.
Their hazardous properties (physico-chemical or toxicological) (e.g. explosive or sensitiser)
2.
The temperature or pressure at which they occur in the workplace (e.g. water vapor at
150 ° C)
3.
Their capacity to displace the atmospheric oxygen from the workplace (e.g.
pressurized inert gas)
4.
The manner in which they are present in the workplace (e.g. inert solid in the form of a breathable powder)

Risks to be assessed;
1.
The risk of fire and/or explosion,
2.
Risk generated due to the hazardous chemical reactions which may affect the health and safety of workers,
3.
Risk due to inhalation,
4.
Risk due to absorption through the skin,
5.
Risk due to contact with skin or eyes,
6.
Risk due to ingestion,

 To determine the risks of a chemical agent; the hazardous properties of these chemicals and the way in which they are present and are used must be known.
 To assess the risks first be informed about the hazardous properties of chemicals.
(Directive 2000/39/EC)
 Labelling
 Material Safety Data Sheets (MSDS)
 Occupational Exposure Limit Values and Biological Limit Values

1. Identification of substance/preparation and company
2. Composition/information of ingredients
3. Hazard identification
4. First-aid measures
5. Firefighting measures
6. Accidential spillage measures
7. Handling and storage
8. Exposure controls/personal protection
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

 General Information
Chemical Composition
Physico-chemical Properties
 Use
Recommended uses and restrictions
Handling and Storage
User Protection
Exposure Limit Values
Section 2
Section 9
Section 16
Section 7 and 15
Section 8
Section 8 and 15

 Hazards
Safety: Flammability, explosiveness, reactivity
Health: Toxicity
Environment: Ecotoxicity
 Emergencies
First aid
Fire
Leaks/releases
Section 3,9,10
Section 3 and 11
Section 3 and 12
Section 4
Section 5
Section 6

 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.

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.

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.

Action Diagram for Risk Assesment and Resulting Actions

• 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

Risk Level Acute Health
Risk
Chronic
Health Risk
Fire and
Explosion Risk
Exposure
Potential
Very High Benzen (R45)
Hazards
Associated with Process
High Benzen (R25) Benzen
Toluen (R11)
Benzen
(VP.101 hPa)
Medium Toluen
(R20)
Toluen
(VP.29 hPa)
Benzen
Toluen
Low
Negligible

napo\napo-sgh-03-flammable-eng.avi

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,
 Avoid the combined storage of incompatible or highly reactive chemicals,
 Provide secure containers (sufficient physical resistance, automatic closure, appropriate for the type and quantity of chemical stored etc.).

 To a large extent, how the chemical groups are divided and assigned, will depend largely upon the amount of space available.
 The risk associated with incompatible chemicals coming into contact must be avoided wherever chemicals are handled or stored.
 The common features uniting all these plans is the separation of incompatible 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.

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

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

 Violent reactions occur when the following chemicals from different
Storage Groups are mixed:
– Corrosives + Flammables = Explosion/Fire
– Corrosive + Poisons = Poison Gas (Toxic Gas)
– Flammables + Oxidizers = Explosion/Fire
– Acids + Bases = Corrosive Fumes/Heat

Highly flammable
-
-
+
-
+
Explosive
-
-
-
+
-
Toxic
-
-
+
-
+
Oxidising
-
-
-
+
0
Harmful
+
-
+
0
+

Basic Storage Requirements:
 Label storage areas according to the type of chemical family 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 at a consistent, cool temperature.

Basic Storage Requirements (Cont’d)
 Eliminate ignition sources such as open flames, heat sources, or direct sunlight.
 Keep emergency equipment such as fire extinguishers handy and in good working order.
 Confine chemical storage areas so that leaks or spills are controlled.
Prevent chemicals from running down sink, floor, or storm water drains.
Clean up spills and drips immediately.

Storage Don’ts !
 Don’t store chemicals in a sink or fume hood, except for certain toxic gases that are so dangerous they can only be stored in a gas cabinet or fume hood.
 Don’t store chemicals on dirt or grass, near a creek or storm drain entrance, where they could contaminate the environment.
 Don’t store chemicals on the floor, window ledges, or balconies.

To avoid explosion;
 Store two incompatible chemicals at least 3 m. apart.
 Where the goods could react violently, store them at least 5 m. apart.
 Consider storing some chemicals especially unstable chemicals in separate fire rated enclosures or separate buildings with appropriate fire suppression equipment.

Implementing Regulations on the Protection of the
Risks Related to Chemical Agents
Identification of HCAs (Hazard Chemical Agents)
• Council Directive 67/548/EEC, as amended and adapted to technical progress, on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling substances;
• Directive 1999/45/EC of the European Parliament and of the Council, as subsequently adapted to technical progress, relating to the classifcation, packaging and labelling of dangerous preparations;
• Commission Directive 91/155/EEC , as amended, by Directive 2001/58/EC defining and laying down the detailed arrangements for the system of specific information relating to the dangerous preparations and substances(MSDS)

Implementing Regulations on the Protection of the
Health and Safety Measures from the Risks Related to
Chemical Agents at Work
Chemical Safety
• Council Directive 96/82/EC on the control of major-accident hazards involving dangerous substances, and subsequent Commission decisions on its application;(SEVESO-II)
• Directive 94/9/EC of the European Parliament and the Council on the approximation of the laws of the Member States concerning equipment and protective systems intended for use in potentially explosive atmospheres;
• Directive 1999/92/EC on minimum requirements for improving the safety and health protection of workers potentionally at risk from explosive atmospheres.

Implementing Regulations on the Protection of the
Health and Safety Measures from the Risks Related to
Chemical Agents at Work
Work with particular HCAs
• Directive 2003/18/EC of the European Parliament and of the Council Directive
83/477/EEC on the protection of workers from the risks related to exposure to asbestos at work,
• Council Directive 98/24/EC on the protection of the health and safety of workers from the risks related to chemical agents at work,
• Council Directive 90/394/EC, as amended (Directive 97/42/EC and Directive
1999/38/EC), on the protection of workers from the risks related to exposure to carcinogens at work.

• All substances must be stored in securely closed containers designed for the purpose
• All substances must be clearly labelled in ordered to determine the hazards on the material
• Read always MSDS in order to acquiring understanding of all hazardous properties of a specific substance
• Careful analysis of substance properties will curtail adverse reactions involving intentional mixing of chemicals or malfunction at storing

• Articles 3, 4, 5 and 6, and Annex II, Section I, of Directive 98/24/EC
• European Commission, Employment, Social Affairs and Equal Opportunities, Particle
Guidelines of a Non-binding Nature on the protection of the Health and Safety of Workers
from the Risks Related to Chemical Agents at Work , June 2005
• Safe Storage of Hazadous Chemicals, University of California, Berkeley, Office of
Environment, Health & Safety.
• İzmir Yüksek Teknoloji Enstitüsü, Mühendislik Fakültesi, Kimya Mühendisliği, Kimyasal
Hijyen Planı, 2007.
• Finnish Institute of Occupational Health, Pirjo Irmeli Korhonen, 2010
• Arme İstisnai Eğitim ve Danışmanlık Hiz. Ltd. Şti, Endüstriyel Tesislerde Tehlikeli Kimyasal
Yönetiminin İlkeleri, Adana, 2007.
• Pirjo I Korhonen, Dangerous interactions between stored chemicals, INT MARKT IND/EXP
34794, 2010, Ankara