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RISKS, CONTROL MEASURES, APPLICATIONS IN
CHEMICAL INDUSTRY
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Content

• Definitions
• Hazards and Risks Arising from Chemicals
• 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
• Safe Storage of Chemicals
• Implementing Regulations on EU

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

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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.

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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.

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Use of Chemical Agents in the Last 5 Years (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.

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

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

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

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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.

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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.

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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.

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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.

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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.

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New pictograms the most striking GHS feature
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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

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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 group
• 2 Physical hazards
• 3 hazards
• 4 al hazards

H300 Fatal if swallowed
Hazard statement
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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 group 2
  Prevention
• 3 Response
• 4 Storage
• 5 Disposal

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The labeling must be adapted to the new
regulations
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2. The Hazard Associated with Chemicals

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

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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

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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. .

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The Hazard Posed by Chemicals

• Chemical agents present in workplace may pose
  risks to health and safety on account 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 150C)
• 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)

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3. Risk Assesment of Chemicals Risks to be
assessed

• The risk of fire and/or explosion,
• Risk generated due to the hazardous chemical
  reactions which may affect the health and safety
  of workers,
• Risk due to inhalation,
• Risk due to absorption through the skin,
• Risk due to contact with skin or eyes,
• Risk due to ingestion,

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To Assess the Risks of Chemicals

• 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

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Labelling
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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

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

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Application of MSDS

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

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Application of MSDS

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

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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.

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Risks Arising from Hazardous Chemicals
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Risks Arising from Hazardous Chemicals
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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.

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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.

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Application of the Principles for Prevention
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Specific Prevention Measures Prioritisation
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Action Diagram for Risk Assesment and Resulting
Actions
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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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Risk Level Acute Health Risk Chronic Health Risk Fire and Explosion Risk Exposure Potential Hazards Associated with Process
Very High Benzen (R45)
High Benzen (R25) Benzen Toluen (R11) Benzen (VP.101 hPa)
Medium Toluen (R20) Toluen (VP.29 hPa) Benzen Toluen
Low
Negligible
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• napo\napo-sgh-03-flammable-eng.avi

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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,
• 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.).

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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.

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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

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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

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Safe Storage of Chemicals

• 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

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

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Safe Storage of Chemicals

• Basic Storage Requirements (Contd)
• 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.

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Safe Storage of Chemicals

• Storage Donts !
• Dont 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.
• Dont store chemicals on dirt or grass, near a
  creek or storm drain entrance, where they could
  contaminate the environment.
• Dont store chemicals on the floor, window
  ledges, or balconies.

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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.

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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)

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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.

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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.

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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

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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.
• Izmir Yüksek Teknoloji Enstitüsü, Mühendislik
  Fakültesi, Kimya Mühendisligi, Kimyasal Hijyen
  Plani, 2007.
• Finnish Institute of Occupational Health, Pirjo
  Irmeli Korhonen, 2010
• Arme Istisnai Egitim ve Danismanlik Hiz. Ltd.
  Sti, Endüstriyel Tesislerde Tehlikeli Kimyasal
  Yönetiminin Ilkeleri, Adana, 2007.
• Pirjo I Korhonen, Dangerous interactions between
  stored chemicals, INT MARKT IND/EXP 34794, 2010,
  Ankara

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Thanks