RISKS , CONTROL MEASURES , APPLICATIONS IN CHEMICAL INDUSTRY

RISKS, CONTROL MEASURES,

APPLICATIONS IN CHEMICAL INDUSTRY

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

Content

Chemical agent: Means any chemical element, compound or amixture of them, as it occurs in the natural state or as produced, used or released by any work activity or come about as waste orproduced unintentionally.

Implementing Regulation on the Protection of the Health and SafetyMeasures from the Risks Related to Chemical Agents at Work (based on the Directive 1998/24/EC)

1. Definitions

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.

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.

Definitions

• 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.

Use of Chemical Agents in the Last 5 Years (in EU)

Classifications according to 67/548/EEC (published in December 2008 in Official Paper in

Turkey)

E Explosive T+ Highly toxic C Corrosive O Oxidising T Toxic

Xi Irritant F+ Highly flammable

Xn Harmful F Flammable

N Nature polluting

Classifications according 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

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 classificationand labeling of chemicals. GHS wants to ensure internationally comparable highstandards 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 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 withinthe EU, also begins in 2008.– Because of the numerous interconnections between GHS and REACH,the European Commission has scheduled the implementation ofthe 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.

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

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 labeledin accordance with GHS criteria

• By June 1, 2015, all mixtures shall be classified and labeledin accordance with GHS criteria.

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 labeledin accordance with GHS criteria

• By June 1, 2015, all mixtures shall be classified and labeledin accordance with GHS criteria.

What essential changes does GHS involve?– 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.

New Labeling Elements

Signal word

The signal word on the label gives informationabout the relative hazard level of a substanceor mixture and alerts the reader to apotential hazard.

Hazard pictogram• Square set on a point,• Red border,• White background,• Black symbols.

Danger

Warning

New pictograms – the most striking GHS feature

Physical Hazards

Health Hazards Env. hazards

Classifications according to GHS

Compressed gas Flammable solid Organic Peroxides

Toxic gas Spontaneously Toxic combustible

Flammable gas Dangerous Corrosive when wet

Flammable Liquid Oxidising agent

Hazard statements, definition and coding

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 group2 Physical hazards3 hazards4 al hazards

H300 – Fatal if swallowedHazard statement

Sequence in the group

H300 – Fatal if swallowedHazard statement

Precautionary statements, definition and coding

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 group2 Prevention

3 Response4 Storage5 Disposal

P 380 – Evacuate areaPrecautionary statement

Sequence in the group

The labeling must be adapted to the new regulations

Chemical agents can cause harm;

1. either directly,

2. or by producing some form of energy (such as fire or explosion).

2. 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 body Local Effect

Or if may appear following a process of absorption and

distribution through the body Systemic Effect

The Hazard Associated with 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. .

The Harm Caused by Chemicals

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)

The Hazard Posed by Chemicals

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,

3. Risk Assesment of ChemicalsRisks to be assessed;

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

To Assess the Risks of Chemicals

Labelling

Material Safety Data Sheets (MSDS)

1. Identification of substance/preparation and company

2. Composition/information of ingredients

3. Hazard identification4. First-aid measures5. Firefighting measures6. Accidential spillage measures7. Handling and storage8. Exposure controls/personal

protection

9. Physical/Chemical properties10. Stability and reactivity11. Toxicological information12. Ecological information13. Disposal considerations14. Transport information15. Regulatory information16. Other information

Application of MSDS

General Information

Chemical Composition Section 2Physico-chemical Properties Section 9

Use

Recommended uses and restrictions Section 16Handling and Storage Section 7 and 15User Protection Section 8Exposure Limit Values Section 8 and 15

Application of MSDS

Hazards

Safety: Flammability, explosiveness, reactivity Section 3,9,10Health: Toxicity Section 3 and 11Environment: Ecotoxicity Section 3 and 12

Emergencies

First aid Section 4Fire Section 5Leaks/releases Section 6

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.

Risks Arising from Hazardous Chemicals

Risks Arising from Hazardous Chemicals

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.

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.

General Principles for Eliminating/Reducing Risks

Application of the Principles for Prevention

Specific Prevention Measures & Prioritisation

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

An Example: Substitution of the Chemical Agent

Risk Level Acute Health Risk

Chronic Health Risk

Fire and Explosion Risk

Exposure Potential

Hazards Associated

with ProcessVery High Benzen (R45)

High Benzen (R25) BenzenToluen (R11)

Benzen (VP.101 hPa)

Medium Toluen(R20)

Toluen (VP.29 hPa)

BenzenToluen

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.).

6. Safe Storage of Chemicals

Safe Storage of Chemicals

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.

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

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

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

Safe Storage of Chemicals

Safe Storage of Chemicals

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.

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 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.

Safe Storage of Chemicals

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.

Safe Storage of Chemicals

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)

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.

Implementing Regulations on the Protection of the Health and Safety Measures from the Risks Related to Chemical Agents at Work

Conclusions• 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

References

• 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