Classification of Chemical Hazards

and their Control

CHAPTER 1: INTRODUCTION
1.1 Background and Rationale

The chemical industry has been a cornerstone of global economic development, providing
essential products that have improved quality of life, advanced technology, and revolutionized
agriculture and medicine. From fertilizers that feed the world's population to pharmaceuticals
that cure diseases and polymers that form our modern infrastructure, chemicals are ubiquitous.
However, this progress is not without its risks. Many chemical substances possess inherent
properties that can cause harm to humans, living organisms, physical property, or the
environment. These properties are known as chemical hazards.
The history of industrialization is tragically marked by incidents involving chemicals—fires,
explosions, toxic releases, and long-term environmental contamination. Events like the Bhopal
disaster in India, the Seveso disaster in Italy, and countless smaller-scale workplace incidents
have underscored the absolute necessity of a robust framework for managing chemical risks.
Effective risk management begins with understanding the hazard. Without a clear, consistent,
and universally understood method of identifying and communicating the hazards posed by a
chemical, all subsequent control measures are compromised. This fundamental need is the
rationale behind this report.

1.2 Scope and Objectives of the Project

The scope of this project is to provide a detailed and structured overview of the modern
systems used for classifying chemical hazards and the established methodologies for their
control. It primarily focuses on the United Nations' Globally Harmonized System (GHS) as the
benchmark for classification, while using the Hierarchy of Controls as the framework for
mitigation strategies.
The primary objectives of this report are:
1.​ To define what constitutes a chemical hazard and explain the critical importance of its
classification.
2.​ To describe the Globally Harmonized System (GHS), its core components, and its hazard
classes in detail.
3.​ To systematically explain the three main groups of chemical hazards: Physical, Health,
and Environmental.
4.​ To present the Hierarchy of Controls as the primary strategy for managing chemical risks,
detailing each of its five levels.
5.​ To illustrate the practical application of these principles through relevant case studies.
6.​ To provide a concluding perspective on the future of chemical safety management.

1.3 Definition of a Chemical Hazard

A chemical hazard is the intrinsic property of a chemical substance or mixture that has the
potential to cause adverse effects. It is important to distinguish a hazard from a risk.
●​ Hazard: The inherent potential to cause harm. For example, concentrated sulfuric acid
(H_2SO_4) is corrosive. This is an intrinsic property.
●​ Risk: The likelihood that a hazard will actually cause harm, combined with the severity of
that harm. The risk of being harmed by sulfuric acid depends on factors like how it's
handled, the quantity involved, and the control measures in place.
A chemical can present one or more types of hazards simultaneously. For instance, acetone
(C_3H_6O) is both a physical hazard (highly flammable) and a health hazard (causes eye
irritation and central nervous system depression).

1.4 Importance of Hazard Classification and Control

The classification and control of chemical hazards are two sides of the same coin; one is
ineffective without the other. Their combined importance cannot be overstated and spans
several key areas:
●​ Worker Safety: Provides workers with the right to know the hazards of the chemicals they
handle and ensures employers implement appropriate protective measures. This reduces
workplace injuries, illnesses, and fatalities.
●​ Public and Environmental Protection: Ensures that chemicals are transported, stored,
and disposed of in a manner that prevents catastrophic releases, fires, explosions, or
long-term environmental damage.
●​ Emergency Response: Gives firefighters, hazmat teams, and medical personnel critical
information to safely and effectively respond to incidents like spills, leaks, or fires.
●​ Global Trade: A harmonized system like GHS facilitates international trade by creating a
consistent set of rules for hazard communication, reducing the need for multiple
classifications and labels for the same product.
●​ Regulatory Compliance: Forms the basis for national and international health, safety,
and environmental regulations.

1.5 Structure of the Report

This report is organized into nine chapters.

●​ Chapter 1 provides the introduction, scope, and objectives.
●​ Chapter 2 discusses the historical and regulatory context, highlighting the need for GHS.
●​ Chapter 3 offers a detailed explanation of the GHS framework.
●​ Chapters 4, 5, and 6 are dedicated to the specific GHS classifications for Physical,
Health, and Environmental hazards, respectively.
●​ Chapter 7 comprehensively covers the Hierarchy of Controls, from elimination to PPE.
●​ Chapter 8 presents practical case studies to illustrate the concepts discussed.
●​ Chapter 9 concludes the report with a summary and a look at future trends. Appendices
are provided for quick reference.
CHAPTER 2: REGULATORY FRAMEWORK AND THE NEED FOR
HARMONIZATION
2.1 Historical Perspective on Chemical Safety

Concern for occupational health dates back centuries, with early observations on the diseases
of miners and metalworkers. However, the systematic regulation of chemical hazards is a more
recent phenomenon, largely driven by the industrial revolution and the subsequent proliferation
of synthetic chemicals in the 20th century. Early regulations were often fragmented, differing
significantly from country to country, and even from one regulatory agency to another within the
same country (e.g., transport vs. workplace vs. consumer regulations). This created confusion,
trade barriers, and inadequate protection for those exposed to chemicals.

2.2 Major Pre-GHS Classification Systems

Before the widespread adoption of GHS, several influential systems were in use. Understanding
them provides context for the improvements GHS offers.

2.2.1 NFPA 704: "Fire Diamond"

Developed by the U.S. National Fire Protection Association (NFPA), the NFPA 704 standard
provides a simple, easily recognizable system for emergency responders. The "fire diamond"
indicates the hazards of a material in a fixed facility.
●​ Blue (Health): Rated 0 (no hazard) to 4 (deadly).
●​ Red (Flammability): Rated 0 (will not burn) to 4 (rapidly vaporizes and burns).
●​ Yellow (Instability/Reactivity): Rated 0 (stable) to 4 (may detonate).
●​ White (Special Hazards): Uses symbols like 'OXY' for oxidizer or 'W' for water-reactive.
While excellent for emergencies, it is not detailed enough for comprehensive workplace safety.
Figure 2: The NFPA 704 "Fire Diamond" (A graphical representation of the four-colored
diamond, with labels for Health, Flammability, Instability, and Special Hazards.)

2.2.2 Hazardous Materials Identification System (HMIS)

Similar to NFPA 704, the HMIS uses a color and number system (0-4) but is designed for
workplace hazard communication, not emergencies. It covers Health, Flammability, and
Physical Hazard, and includes a section for recommending appropriate PPE. Its interpretation of
hazard levels can differ from NFPA 704.

2.2.3 European System (CLP Predecessor)

The pre-GHS European Union legislation (Directives 67/548/EEC and 1999/45/EC) used a
system of orange and black symbols (e.g., a skull and crossbones for toxic, a flame for
flammable) and R-phrases (Risk Phrases) and S-phrases (Safety Phrases). This system was a
direct ancestor of GHS, with many concepts being carried over and refined.

2.3 The Drive for a Globally Harmonized System (GHS)

The existence of multiple national and regional systems created significant problems:
●​ Inconsistent Protection: A chemical could be classified as 'toxic' in one country but not
another, leading to different levels of protection for workers.
●​ Barriers to Trade: Companies wishing to export chemicals had to re-classify and re-label
their products for each new market, a costly and complex process.
●​ Confusion: The sheer number of different symbols, terms, and data sheets was
confusing for users and emergency responders.
The need for a single, harmonized system was recognized at the 1992 UN Conference on
Environment and Development (the Rio Earth Summit). This led to an international mandate to
develop the GHS, a task coordinated by organizations like the ILO, OECD, and the UN
Sub-Committee of Experts on the Transport of Dangerous Goods. The GHS was not designed
to be a new regulation, but rather a "building block" system that countries could adopt into their
own regulatory frameworks.

2.4 Key International and National Bodies

2.4.1 International Labour Organization (ILO)

The ILO focuses on setting international labor standards, with a strong emphasis on
occupational safety and health. Their conventions, such as the Chemicals Convention, 1990
(C170), laid the groundwork for the worker's right to know and were a key driver for GHS
development.

2.4.2 United Nations (UN)

The UN, through its various sub-committees, coordinates the development and maintenance of
GHS (the "Purple Book") and the UN Recommendations on the Transport of Dangerous Goods
(the "Orange Book"), which governs the international transport of hazardous materials.

2.4.3 Occupational Safety and Health Administration (OSHA)

In the United States, OSHA is the primary agency for enforcing workplace safety. In 2012,
OSHA aligned its Hazard Communication Standard (HCS) with GHS, making it mandatory for
U.S. workplaces.

2.4.4 The Indian Context: MSIHC Rules

In India, the primary legislation governing hazardous chemicals is the Manufacture, Storage
and Import of Hazardous Chemicals (MSIHC) Rules, 1989, amended several times. These
rules, framed under the Environment (Protection) Act, 1986, mandate responsibilities for
importers, occupiers of facilities, and transporters. While India is moving towards GHS adoption,
the MSIHC rules remain the core legal framework and require specific safety reports, on-site
emergency plans, and public liability insurance for facilities handling specified quantities of
hazardous chemicals. The adoption of GHS in India aims to align these robust rules with
international standards for hazard communication.
CHAPTER 3: THE GLOBALLY HARMONIZED SYSTEM (GHS)
3.1 What is GHS?

The Globally Harmonized System of Classification and Labelling of Chemicals (GHS) is an

internationally agreed-upon standard managed by the United Nations. It is a logical and
comprehensive approach to:
1.​ Defining health, physical, and environmental hazards of chemicals (hazard
classification).
2.​ Creating classification processes that use available data on chemicals for comparison
with the defined hazard criteria.
3.​ Communicating hazard information and protective measures on labels and Safety Data
Sheets (SDS).
GHS is a "building block" system. Regulators in each country can choose which parts of the
GHS to implement in their own regulations. However, once a part (a hazard class or category) is
chosen, the corresponding classification criteria and communication elements must be followed.
Table 2: Comparison of Pre-GHS and GHS Approaches | Feature | Pre-GHS (Typical) | GHS
| | :--- | :--- | :--- | | Hazard Definition | Varied by country/agency | Standardized criteria | |
Communication | Multiple symbols, terms | Standardized pictograms, signal words, statements
| | Data Sheets | Varied formats (MSDS) | Standardized 16-section format (SDS) | | Global
Trade | Costly re-classification | Facilitated by consistency |

3.2 Core Elements of GHS Communication

GHS standardizes how hazard information is presented on labels and in SDSs through four key
elements.
Figure 3: Core Elements of a GHS Label (A diagram showing a sample product label with
placeholders for: Product Identifier, Supplier Information, GHS Pictograms, a Signal Word,
Hazard Statements, and Precautionary Statements.)

3.2.1 Hazard Pictograms

These are graphical symbols used to convey specific hazard information at a glance. GHS uses
nine pictograms within a red-bordered diamond shape. These pictograms represent physical,
health, and environmental hazards. (See Appendix A for a full list).
Figure 4: The Nine GHS Pictograms (An image grid showing all nine pictograms: Exploding
Bomb, Flame, Flame over Circle, Gas Cylinder, Corrosion, Skull & Crossbones, Health Hazard,
Exclamation Mark, Environment).

3.2.2 Signal Words

A signal word is used to indicate the relative level of severity of a hazard and to alert the reader
to a potential hazard on the label. There are only two signal words:
●​ Danger: Used for the more severe hazards.
●​ Warning: Used for the less severe hazards. If a chemical has both a "Danger" and a
"Warning" hazard, only "Danger" will appear on the label.
Table 1: GHS Signal Words | Signal Word | Level of Hazard | Example Hazard Class | | :--- | :---
| :--- | | Danger | Severe | Flammable Liquid Category 1/2, Skin Corrosion Cat 1 | | Warning |
Less Severe | Flammable Liquid Category 3, Skin Irritation Cat 2 |

3.2.3 Hazard Statements

These are standardized phrases assigned to a hazard class and category that describe the
nature of the hazard. For example:
●​ H225: Highly flammable liquid and vapour.
●​ H318: Causes serious eye damage.
●​ H350: May cause cancer.

3.2.4 Precautionary Statements

These are standardized phrases that describe recommended measures to minimize or prevent
adverse effects resulting from exposure to, or improper storage or handling of, a hazardous
chemical. They are grouped into four types:
●​ Prevention: "Wear protective gloves."
●​ Response: "IF IN EYES: Rinse cautiously with water for several minutes."
●​ Storage: "Store in a well-ventilated place."
●​ Disposal: "Dispose of contents/container in accordance with local regulations."

3.3 The GHS Hazard Groups

GHS organizes hazards into three main groups:

1.​ Physical Hazards: The potential for a chemical to cause physical harm to property or
people, such as through fire or explosion. (Detailed in Chapter 4).
2.​ Health Hazards: The potential for a chemical to cause adverse health effects, either
immediate (acute) or long-term (chronic). (Detailed in Chapter 5).
3.​ Environmental Hazards: The potential for a chemical to cause harm to the aquatic
environment or the ozone layer. (Detailed in Chapter 6).

3.4 The Safety Data Sheet (SDS)

The GHS specifies a standardized 16-section format for the Safety Data Sheet, which replaces
the older, often inconsistent Material Safety Data Sheet (MSDS). The SDS is a comprehensive
document containing detailed information on a chemical's hazards, handling, storage, and
emergency measures. The consistency of the format makes it easier for users to find critical
information quickly.

3.4.1 The 16-Section Format

1.​ Identification
2.​ Hazard(s) identification
3.​ Composition/information on ingredients
4.​ First-aid measures
5.​ Fire-fighting measures
6.​ Accidental release measures
7.​ Handling and storage
8.​ Exposure controls/personal protection
9.​ Physical and chemical properties
 10.​Stability and reactivity
11.​Toxicological information
12.​Ecological information
13.​Disposal considerations
14.​Transport information
15.​Regulatory information
16.​Other information
(See Appendix B for a detailed breakdown of each section's content.)

CHAPTER 4: CLASSIFICATION OF PHYSICAL HAZARDS

4.1 Introduction to Physical Hazards

Physical hazards relate to the physicochemical properties of a substance or mixture that can
lead to physical injury or property damage, typically through a sudden release of energy. The
GHS defines specific criteria for classifying chemicals into these hazard classes.
Table 3: Summary of Physical Hazard Classes under GHS | Hazard Class | GHS Pictogram |
General Description | | :--- | :--- | :--- | | Explosives | Exploding Bomb | Can explode as a result of
fire, heat, shock, or friction. | | Flammables | Flame | Can ignite and burn easily. | | Oxidizers |
Flame over Circle | Can cause or contribute to the combustion of other materials. | | Gases
Under Pressure | Gas Cylinder | Contains gas under pressure; may explode if heated. | |
Corrosive to Metals | Corrosion | Can chemically damage or destroy metals. |

4.2 Explosives

A substance or mixture which is liable to explode by a chemical reaction. This class is complex
and subdivided into six divisions based on the type of explosion hazard they present (e.g., mass
explosion hazard vs. projection hazard).
●​ Pictogram: Exploding Bomb
●​ Signal Word: Danger
●​ Examples: Nitroglycerin, TNT, Picric acid (when dry).

4.3 Flammable Gases, Aerosols, Liquids, and Solids

These substances are capable of igniting easily and burning rapidly.

●​ Flammable Liquids: Classified into 4 categories based on their flash point (the lowest
temperature at which vapors can ignite) and initial boiling point. Category 1 is the most
hazardous.
○​ Examples: Diethyl ether (Cat 1), Acetone (Cat 2), Kerosene (Cat 3).
●​ Flammable Solids: Readily combustible, or may cause or contribute to fire through
friction.
○​ Examples: Magnesium powder, Sulfur.
●​ Pictogram: Flame
●​ Signal Word: Danger (Cat 1/2), Warning (Cat 3)

4.4 Oxidizing Gases, Liquids, and Solids

These substances, while not necessarily combustible themselves, may cause or contribute to
the combustion of other materials, usually by yielding oxygen.
●​ Pictogram: Flame over Circle
●​ Signal Word: Danger
●​ Examples: Hydrogen peroxide (H_2O_2), Nitric acid (HNO_3), Potassium permanganate
(KMnO_4).

4.5 Gases Under Pressure

This class includes gases contained in a receptacle at a pressure of 200 kPa (gauge) or more,
or which are liquefied or liquefied and refrigerated. The hazard is both from the high pressure
(projectile risk if the cylinder fails) and, if the gas itself is hazardous (e.g., flammable or toxic).
●​ Pictogram: Gas Cylinder
●​ Signal Word: Warning
●​ Examples: Oxygen, Nitrogen, Acetylene, LPG.

4.6 Self-Reactive Substances

Thermally unstable liquids or solids liable to undergo strongly exothermic decomposition even
without participation of oxygen (air).
●​ Pictogram: Exploding Bomb, Flame
●​ Signal Word: Danger
●​ Examples: Dibenzoyl peroxide, certain azo-compounds.

4.7 Pyrophoric Liquids and Solids

Substances that are liable to ignite spontaneously in contact with air within five minutes.
●​ Pictogram: Flame
●​ Signal Word: Danger
●​ Examples: White phosphorus, tert-Butyllithium.

4.8 Self-Heating Substances

Substances (other than pyrophoric substances) which, in contact with air and without an energy
supply, are liable to self-heat. This occurs in large quantities and over a long period of time.
●​ Pictogram: Flame
●​ Signal Word: Danger or Warning
●​ Examples: Activated carbon, oil-soaked rags.

4.9 Substances which, in Contact with Water, Emit Flammable Gases

Solid or liquid substances which, by interaction with water, are liable to become spontaneously
flammable or to give off flammable gases in dangerous quantities.
●​ Pictogram: Flame
●​ Signal Word: Danger
●​ Examples: Sodium metal (Na), Calcium carbide (CaC_2).

4.10 Organic Peroxides

Organic liquids or solids which contain the bivalent ‘-O-O-’ structure and may be considered
derivatives of hydrogen peroxide, where one or both of the hydrogen atoms have been replaced
by organic radicals. They are thermally unstable and can be explosive, burn rapidly, and be
sensitive to impact or friction.
●​ Pictogram: Exploding Bomb, Flame
●​ Signal Word: Danger
●​ Examples: Benzoyl peroxide, Methyl ethyl ketone peroxide (MEKP).

4.11 Corrosive to Metals

A substance or a mixture which by chemical action will materially damage, or even destroy,
metals.
●​ Pictogram: Corrosion
●​ Signal Word: Warning
●​ Examples: Strong acids (Sulfuric acid) and bases (Sodium hydroxide). Note that this is
distinct from Skin Corrosion, though many chemicals have both properties.

CHAPTER 5: CLASSIFICATION OF HEALTH HAZARDS

5.1 Introduction to Health Hazards

Health hazards refer to the potential of a chemical to cause adverse health effects in people.
These effects can be acute (occurring shortly after a single exposure) or chronic (occurring after
repeated exposures over a long period of time, or with a long delay after exposure).
Table 4: Summary of Health Hazard Classes under GHS | Hazard Class | GHS Pictogram |
General Description | | :--- | :--- | :--- | | Acute Toxicity | Skull & Crossbones | Can cause death or
toxicity with short exposure to small amounts. | | Skin Corrosion/Irritation | Corrosion,
Exclamation Mark | Can cause irreversible (corrosion) or reversible (irritation) damage to skin. | |
Eye Damage/Irritation | Corrosion, Exclamation Mark | Can cause serious eye damage or
irritation. | | Carcinogenicity, etc. | Health Hazard | May cause cancer, genetic defects, or
damage to fertility/unborn child. | | Aspiration Toxicity | Health Hazard | May be fatal if swallowed
and enters airways. |

5.2 Routes of Exposure

For a chemical to cause harm, it must enter the body. The main routes of exposure are:
●​ Inhalation: Breathing in contaminated air (gases, vapors, dusts). This is the most
common route in occupational settings.
●​ Dermal Absorption: Contact with the skin. Some chemicals can pass directly through the
skin into the bloodstream.
●​ Ingestion: Swallowing the chemical, often via contaminated hands, food, or cigarettes.
●​ Injection: The chemical enters the body through a puncture wound.
Figure 5: Routes of Chemical Exposure into the Human Body (A simple diagram of a
human silhouette showing arrows pointing to the lungs (inhalation), skin (absorption), and mouth
(ingestion).)

5.3 Acute Toxicity

Refers to adverse effects occurring after a single oral or dermal dose of a substance, or multiple
doses given within 24 hours, or an inhalation exposure of 4 hours. Classification is based on
animal testing data, specifically the LD_{50} (Lethal Dose, 50%) or LC_{50} (Lethal
Concentration, 50%) values.
Table 5: Categories for Acute Toxicity (LD_{50} / LC_{50} values) | Category | Oral LD_{50}
(mg/kg) | Dermal LD_{50} (mg/kg) | Inhalation LC_{50} (ppmV) | Pictogram | | :--- | :--- | :--- | :--- |
:--- | | 1 | \le 5 | \le 50 | \le 100 | Skull & Crossbones | | 2 | > 5 and \le 50 | > 50 and \le 200 | >
100 and \le 500 | Skull & Crossbones | | 3 | > 50 and \le 300 | > 200 and \le 1000| > 500 and \le
2500| Skull & Crossbones | | 4 | > 300 and \le 2000| > 1000 and \le 2000| > 2500 and \le 20000|
Exclamation Mark |
●​ Examples: Hydrogen cyanide (Cat 1), Ammonia (Cat 3), Xylene (Cat 4).

5.4 Skin Corrosion / Irritation

●​ Skin Corrosion: The production of irreversible damage to the skin; namely, visible
necrosis through the epidermis and into the dermis, following the application of a test
substance for up to 4 hours.
○​ Pictogram: Corrosion. Signal Word: Danger.
●​ Skin Irritation: The production of reversible damage to the skin following the application
of a test substance for up to 4 hours.
○​ Pictogram: Exclamation Mark. Signal Word: Warning.
●​ Examples: Sodium hydroxide (Corrosion), Toluene (Irritation).

5.5 Serious Eye Damage / Eye Irritation

●​ Serious Eye Damage: Production of tissue damage in the eye, or serious physical decay
of vision, which is not fully reversible within 21 days.
○​ Pictogram: Corrosion. Signal Word: Danger.
●​ Eye Irritation: Changes in the eye following application of a test substance, which are
fully reversible within 21 days.
○​ Pictogram: Exclamation Mark. Signal Word: Warning.
●​ Examples: Glacial acetic acid (Damage), Acetone (Irritation).

5.6 Respiratory or Skin Sensitization

●​ Respiratory Sensitizer: A substance that will lead to hypersensitivity of the airways

following inhalation of the substance.
●​ Skin Sensitizer: A substance that will induce an allergic response following skin contact.
●​ Pictogram: Health Hazard (Respiratory), Exclamation Mark (Skin).
●​ Signal Word: Danger or Warning.
●​ Examples: Isocyanates (Respiratory), Nickel compounds (Skin).

5.7 Germ Cell Mutagenicity

A mutagen is an agent that can cause mutations (changes in the DNA of a cell). If these
mutations occur in germ cells (sperm or ova), they can be passed on to offspring.
●​ Pictogram: Health Hazard
●​ Signal Word: Danger or Warning
 ●​ Examples: Ethylene oxide, Benzene.

5.8 Carcinogenicity

A carcinogen is a substance or a mixture which induces cancer or increases its incidence.

Classification is based on evidence from human studies and animal experiments (e.g., IARC
classifications).
●​ Pictogram: Health Hazard
●​ Signal Word: Danger or Warning
●​ Examples: Formaldehyde, Asbestos, Vinyl chloride.

5.9 Reproductive Toxicity

Includes adverse effects on sexual function and fertility in adult males and females, as well as
developmental toxicity in the offspring.
●​ Pictogram: Health Hazard
●​ Signal Word: Danger or Warning
●​ Examples: Lead, Toluene, Thalidomide.

5.10 Specific Target Organ Toxicity (STOT) – Single Exposure

Covers specific, non-lethal target organ toxicity arising from a single exposure to a substance.
All significant health effects that can impair function, both reversible and irreversible, immediate
and/or delayed are included.
●​ Pictogram: Health Hazard (for organ damage), Exclamation Mark (for transient effects
like narcosis).
●​ Signal Word: Danger or Warning
●​ Examples: Methanol (causes damage to optic nerve), many solvents (cause drowsiness
or dizziness).

5.11 Specific Target Organ Toxicity (STOT) – Repeated Exposure

Covers specific target organ toxicity arising from repeated exposure to a substance.
●​ Pictogram: Health Hazard
●​ Signal Word: Danger or Warning
●​ Examples: Crystalline silica (causes silicosis in the lungs), Mercury (causes damage to
the nervous system and kidneys).

5.12 Aspiration Hazard

Aspiration means the entry of a liquid or solid chemical directly through the oral or nasal cavity,
or indirectly from vomiting, into the trachea and lower respiratory system. This is a severe
hazard, particularly with low-viscosity hydrocarbon substances.
●​ Pictogram: Health Hazard
●​ Signal Word: Danger
●​ Examples: Kerosene, Turpentine, Gasoline.
CHAPTER 6: CLASSIFICATION OF ENVIRONMENTAL HAZARDS
6.1 Introduction to Environmental Hazards

This group of hazards covers the potential for a chemical to cause damage to the environment.
The current GHS focus is primarily on the aquatic environment, but it also includes a class for
substances that harm the ozone layer.

6.2 Hazardous to the Aquatic Environment

This hazard class is intended to address the effects of chemicals on aquatic organisms (fish,
crustaceans, algae). It is divided into acute and chronic toxicity.

6.2.1 Acute Aquatic Toxicity

The intrinsic property of a substance to be injurious to an organism in a short-term exposure. It

is classified into 3 categories based on test data like LC_{50} for fish.
●​ Pictogram: Environment (for Cat 1), or none (for Cat 2/3)
●​ Signal Word: Warning (for Cat 1)
●​ Examples: Copper sulfate, many pesticides.

6.2.2 Chronic Aquatic Toxicity

The intrinsic property of a substance to cause adverse effects to aquatic organisms during
exposures which are determined in relation to the life-cycle of the organism. This considers not
just toxicity but also the potential for bioaccumulation and the substance's degradability. It is
classified into 4 categories.
●​ Pictogram: Environment (for Cat 1/2), or none (for Cat 3/4)
●​ Signal Word: Warning (for Cat 1/2)
●​ Examples: DDT, Mercury compounds.

6.3 Hazardous to the Ozone Layer

This covers substances which, on the basis of available evidence concerning their properties
and their predicted or observed environmental fate and behaviour, may present a danger to the
structure and/or the functioning of the stratospheric ozone layer. This aligns with the Montreal
Protocol.
●​ Pictogram: Exclamation Mark
●​ Signal Word: Warning
●​ Examples: Chlorofluorocarbons (CFCs), Halons.

CHAPTER 7: THE HIERARCHY OF CONTROLS

7.1 Principle of the Hierarchy of Controls

Once a chemical hazard has been identified and classified, the next step is to control the risk.
The Hierarchy of Controls is a systematic framework used in occupational safety to select the
most effective means of risk reduction. It prioritizes control measures in a "most effective" to
"least effective" order. The principle is that it is always better to remove the hazard entirely or
re-engineer the process to be safer, rather than relying on workers to follow procedures or wear
protective equipment correctly.
Figure 1: The Hierarchy of Controls Pyramid (A pyramid diagram with 5 levels. Top (most
effective): Elimination. 2nd: Substitution. 3rd: Engineering Controls. 4th: Administrative Controls.
Bottom (least effective): PPE.)

7.2 Level 1: Elimination

7.2.1 Concept and Application This is the most effective control measure. It involves
physically removing the hazard from the workplace altogether. If the hazardous chemical is not
present, it cannot cause harm. This is the first option that should always be considered in any
risk assessment.
7.2.2 Examples
●​ Designing a new process to avoid the use of a known carcinogen.
●​ Stopping the production of a product that requires a highly toxic raw material.
●​ Using mechanical joining methods (e.g., bolts) instead of solvent-based adhesives.
●​ Cleaning with steam or high-pressure water instead of caustic chemical cleaners.

7.3 Level 2: Substitution

7.3.1 Concept and Application If elimination is not feasible, the next best option is to replace
the hazardous chemical with a less hazardous one that can perform the same function. A
careful assessment is required to ensure the substitute does not introduce a new, unexpected
hazard.
7.3.2 Examples
●​ Replacing a carcinogenic benzene-based solvent with a less toxic one like cyclohexane or
heptane.
●​ Using a water-based paint instead of a solvent-based one with high volatile organic
compounds (VOCs).
●​ Switching from a powdered chemical that creates hazardous dust to a liquid or pellet
form.
●​ Using a less volatile cleaning agent to reduce inhalation risk.

7.4 Level 3: Engineering Controls

7.4.1 Concept and Application If the hazard cannot be eliminated or substituted, engineering
controls are used to isolate people from the hazard. They are physical changes to the work
environment or process that reduce or prevent exposure. They are generally more reliable than
controls that rely on human behavior.
7.4.2 Ventilation (General and Local Exhaust)
●​ General Dilution Ventilation: Uses fans or open windows to exchange air in a room,
diluting the concentration of the airborne contaminant. Less effective for highly toxic
chemicals.
●​ Local Exhaust Ventilation (LEV): Captures the contaminant at its source, before it can
escape into the workplace air. This is much more effective. Examples include fume hoods
in laboratories, snorkel extractors over welding benches, and enclosed glove boxes.
Figure 6: A Local Exhaust Ventilation (LEV) System (Fume Hood) (A simple diagram of a
laboratory fume hood, showing airflow from the room, into the hood, capturing fumes from a
container, and exhausting them out of the building.)
7.4.3 Enclosure and Isolation
●​ Enclosure: Placing the process or equipment that generates the hazard inside an
enclosure to prevent it from escaping (e.g., automated, contained chemical dosing
systems).
●​ Isolation: Placing the hazardous process in a separate room and controlling access, or
using a control room from which workers can operate the process remotely.
7.4.4 Process Automation and Modification Modifying the process to reduce exposure, for
example by reducing the temperature of a process to lower the rate of vapor generation, or
using robotic arms to handle highly corrosive materials.

7.5 Level 4: Administrative Controls

7.5.1 Concept and Application These are changes to the way people work. They are policies,
procedures, and work practices that reduce the duration, frequency, and intensity of exposure.
They are less effective than engineering controls because they rely on human behavior to be
successful.
7.5.2 Safe Work Practices and Standard Operating Procedures (SOPs) Developing and
enforcing formal procedures that detail the safest way to perform a task involving a hazardous
chemical. This includes procedures for decanting, mixing, cleaning up spills, and waste
disposal.
7.5.3 Training, Supervision, and Communication
●​ Training: Ensuring all workers who handle chemicals are trained on their specific hazards
(reading SDSs), the control measures in place, what to do in an emergency, and how to
use PPE correctly.
●​ Supervision: Monitoring work to ensure that safe work practices are being followed.
●​ Communication: Clear communication of hazards through labels and signage.
7.5.4 Work Scheduling and Job Rotation Limiting the amount of time a worker spends on a
task with high exposure potential. Job rotation moves workers between high-exposure and
low-exposure jobs to reduce their total cumulative exposure.
7.5.5 Signage and Labelling Using GHS-compliant labels on all chemical containers and
posting clear warning signs in areas where specific hazards are present (e.g., "Danger:
Carcinogen Area," "Flammable Liquid Storage").

7.6 Level 5: Personal Protective Equipment (PPE)

7.6.1 The Last Line of Defense PPE is equipment worn by a worker to minimize exposure to
hazards. It is considered the last line of defense because it does not eliminate the hazard; it only
places a barrier between the worker and the hazard. If the equipment fails or is used incorrectly,
the worker is exposed. PPE should only be used when higher-level controls are not feasible or
to supplement other controls.
7.6.2 Respiratory Protection
●​ Air-Purifying Respirators: Use filters or cartridges to remove specific contaminants from
the air (e.g., particulate masks, chemical cartridge respirators). They do not supply
oxygen.
●​ Supplied-Air Respirators: Provide clean breathing air from an independent source (e.g.,
 an airline respirator or a Self-Contained Breathing Apparatus - SCBA). Used in
oxygen-deficient or highly toxic atmospheres.
7.6.3 Eye and Face Protection
●​ Safety Glasses: Protect against flying particles.
●​ Goggles: Provide a tighter seal to protect against chemical splashes.
●​ Face Shields: Protect the entire face from splashes, but must be worn with glasses or
goggles.
7.6.4 Skin and Body Protection
●​ Gloves: Must be selected based on the specific chemical being handled, as no single
glove material protects against all chemicals. Common materials include nitrile, neoprene,
and butyl rubber.
●​ Aprons, Coveralls, and Full-Body Suits: Used to protect the body from splashes and
contact. The material must be chemically resistant.
7.6.5 PPE Program Management An effective PPE program requires careful selection of the
right equipment, training on how to use and maintain it, proper fit-testing (especially for
respirators), and regular inspection and replacement.

CHAPTER 8: CASE STUDIES IN HAZARD CONTROL

8.1 Case Study 1: Ammonia (NH_3) Management in an Industrial Refrigeration
Plant

8.1.1 Hazard Identification (Classification)

●​ Chemical: Anhydrous Ammonia (NH_3)
●​ Physical Hazards: Gas Under Pressure (liquefied gas).
●​ Health Hazards:
○​ Acute Toxicity (Inhalation), Category 3 (Toxic if inhaled).
○​ Skin Corrosion, Category 1B (Causes severe skin burns and eye damage).
○​ Serious Eye Damage, Category 1.
●​ GHS Pictograms: Gas Cylinder, Skull & Crossbones, Corrosion.
●​ Signal Word: Danger.
8.1.2 Control Measures Implementation (Hierarchy of Controls)
1.​ Elimination/Substitution: Not feasible in this case, as ammonia is a highly efficient and
widely used refrigerant. Substituting with less efficient or more environmentally harmful
refrigerants (like older Freons) is not a preferred option.
2.​ Engineering Controls:
○​ Isolation: The entire refrigeration system (compressors, condensers, vessels) is
located in a dedicated, restricted-access machine room.
○​ Ventilation: The machine room is equipped with a dedicated LEV system, including
ammonia gas detectors linked to an emergency ventilation mode that activates at a
set concentration (e.g., 25 ppm).
○​ Process Integrity: All piping is designed to relevant pressure vessel codes, made
of compatible materials (no copper or brass), and subject to regular integrity testing
(e.g., ultrasonic thickness testing). Pressure relief valves are installed and vented to
a safe location.
3.​ Administrative Controls:
○​ SOPs: Detailed procedures exist for startup, shutdown, maintenance, and
 emergency response.
○​ Training: Operators are extensively trained on ammonia hazards, the plant's
systems, and emergency procedures.
○​ Signage: The machine room is clearly marked with "DANGER: AMMONIA," GHS
pictograms, and access restrictions.
○​ Monitoring: An ammonia detection and alarm system is in place.
4.​ PPE:
○​ Routine Tasks: Workers entering the machine room must wear safety glasses and
have quick access to escape respirators.
○​ Maintenance/Emergency: For tasks involving opening the system or for
emergency response, a full-face respirator with an ammonia-specific cartridge or a
SCBA is required, along with chemical-resistant gloves and a full-body suit.
Emergency eyewash stations and safety showers are strategically located.
8.1.3 Lessons Learned A multi-layered control strategy, heavily reliant on robust engineering
controls and strict administrative procedures, is essential for safely managing highly hazardous
chemicals like ammonia.

8.2 Case Study 2: Toluene (C_7H_8) Handling in a Research Laboratory

8.2.1 Hazard Identification (Classification)

●​ Chemical: Toluene (C_7H_8)
●​ Physical Hazards: Flammable Liquid, Category 2 (Highly flammable liquid and vapour).
●​ Health Hazards:
○​ Skin Irritation, Category 2.
○​ Reproductive Toxicity, Category 2 (Suspected of damaging the unborn child).
○​ STOT - Single Exposure, Category 3 (May cause drowsiness or dizziness).
○​ STOT - Repeated Exposure, Category 2 (May cause damage to organs through
prolonged or repeated exposure).
○​ Aspiration Hazard, Category 1 (May be fatal if swallowed and enters airways).
●​ GHS Pictograms: Flame, Exclamation Mark, Health Hazard.
●​ Signal Word: Danger.
8.2.2 Control Measures Implementation (Hierarchy of Controls)
1.​ Elimination: The research protocol specifically requires toluene as a solvent, so
elimination is not possible.
2.​ Substitution: Researchers evaluated replacing toluene with a less toxic solvent like
heptane. While possible for some procedures, it was not suitable for all due to different
solvency properties. Where possible, heptane is used.
3.​ Engineering Controls:
○​ LEV: All work involving open containers of toluene is performed inside a certified
chemical fume hood to capture vapors at the source.
○​ Storage: Toluene is stored in a dedicated, ventilated, and grounded flammable
liquid storage cabinet, away from ignition sources.
4.​ Administrative Controls:
○​ Quantity Limitation: Only the minimum necessary quantity of toluene is brought
into the lab; bulk storage is kept elsewhere.
○​ SOPs: Lab protocols clearly define handling procedures, including prohibiting open
flames and requiring grounding straps when transferring large volumes to prevent
static discharge.
 ○​ Training: All lab personnel are trained on the specific hazards of toluene, proper
fume hood use, and emergency procedures. Female researchers of child-bearing
age are specifically counselled on the reproductive hazards.
5.​ PPE:
○​ Nitrile gloves (checked for toluene compatibility and breakthrough time), chemical
splash goggles, and a lab coat are mandatory when handling toluene.
8.2.3 Lessons Learned For laboratory settings, the combination of substitution (where
feasible), primary reliance on fume hoods (engineering control), and strict administrative rules
(small quantities) is a highly effective control strategy.

8.3 Case Study 3: The Bhopal Gas Tragedy (1984) – A Failure of Controls

8.3.1 The Chemical: Methyl Isocyanate (MIC)

●​ Hazards: Extremely toxic (Acute Toxicity Cat 1/2), Flammable, highly reactive with water
(exothermic reaction).
8.3.2 Catastrophic Failure of Multiple Control Layers The 1984 disaster at the Union Carbide
plant in Bhopal, India, is the world's worst industrial disaster and a tragic textbook example of
the failure of every single layer of the Hierarchy of Controls.
●​ Elimination/Substitution (Failed): The plant was designed to produce pesticides using a
highly hazardous MIC-based process. Safer alternative production chemistries existed but
were not used.
●​ Engineering Controls (Failed):
○​ Refrigeration System: A system designed to keep the MIC storage tank cool (to
reduce reactivity) was shut down to save costs.
○​ Vent Scrubber: A system designed to neutralize any released MIC gas with caustic
soda was not operational.
○​ Flare Tower: A system designed to burn off any released gas was out of service for
maintenance.
○​ Water Curtain: Water sprays intended to knock down the gas cloud were not
designed to reach the height of the release.
●​ Administrative Controls (Failed):
○​ SOPs: Unsafe practices, such as using water to flush pipes connected to the MIC
tank, were allowed. This water ingress is believed to have initiated the runaway
reaction.
○​ Training & Staffing: The plant was reportedly understaffed, with reduced training
standards compared to its U.S. counterpart.
○​ Alarms: The public warning siren was initially turned off and then only sounded
briefly, causing confusion rather than effective warning.
●​ PPE (Irrelevant): The scale of the uncontained release was so massive that PPE
became entirely irrelevant for the surrounding community and most plant workers.
8.3.3 Enduring Lessons for Chemical Safety Bhopal demonstrated that safety systems are
interdependent. Relying on a single control is insufficient. Multiple, redundant layers of
protection are necessary (defense-in-depth). It also highlighted the critical importance of a
strong "safety culture," where cost-cutting is never prioritized over the integrity of critical safety
systems, and the need for robust regulatory oversight and community emergency planning.

CHAPTER 9: CONCLUSION AND FUTURE SCOPE

9.1 Summary of Key Findings

This report has established the foundational principles of modern chemical safety management.
The key findings can be summarized as follows:
1.​ Systematic classification is the starting point: Before any risk can be managed, it
must be understood. The GHS provides a comprehensive, logical, and internationally
recognized framework for classifying chemical hazards, facilitating clear communication
through standardized labels and SDSs.
2.​ Hazards are diverse: Chemicals can pose a wide array of physical (e.g., flammability),
health (e.g., carcinogenicity), and environmental (e.g., aquatic toxicity) hazards, often in
combination.
3.​ The Hierarchy of Controls is the roadmap for action: Effective risk reduction prioritizes
permanent solutions. Eliminating or substituting hazards is always preferable to relying on
procedural controls or personal protective equipment, which are more susceptible to
human error.
4.​ Safety is a multi-layered system: As tragically demonstrated by the Bhopal case study,
relying on a single control measure is a recipe for disaster. Robust safety depends on
multiple, redundant layers of controls (engineering, administrative, PPE) working in
concert.

9.2 The Interdependence of Classification and Control

The two main themes of this report—classification and control—are inextricably linked. Hazard
classification directly informs the selection of control measures.
●​ A "Flammable Liquid, Category 1" classification demands controls like flammable
storage cabinets, grounding and bonding, and prohibition of ignition sources.
●​ A "Carcinogen, Category 1B" classification demands the most stringent controls,
prioritizing elimination, substitution, or complete enclosure (engineering controls) over
reliance on PPE.
●​ An "Acute Toxicity, Category 3" classification necessitates emergency response plans,
access to specific first-aid measures (listed in the SDS), and potentially specialized PPE
like supplied-air respirators.
Without accurate classification, the basis for selecting appropriate controls is lost, leading to
either inadequate protection or unnecessarily burdensome and costly measures.

9.3 Challenges in Implementation

Despite the clear benefits, implementing comprehensive chemical safety programs faces
challenges:
●​ Cost and Resources: Smaller enterprises may struggle with the cost of implementing
engineering controls or comprehensive training programs.
●​ Complacency and Culture: A weak safety culture can undermine the best-designed
systems, as procedures are ignored and shortcuts are taken.
●​ Data Gaps: For some new or less common chemicals, complete hazard data may not be
available, making classification difficult.
●​ Global Adoption: While GHS is widely adopted, the pace and specifics of
implementation still vary between countries, creating lingering inconsistencies.
9.4 Future Trends in Chemical Safety

9.4.1 Green Chemistry

One of the most promising future directions is the rise of Green Chemistry, also known as
sustainable chemistry. This is a design philosophy that seeks to reduce or eliminate the use and
generation of hazardous substances at the source. It is, in essence, applying the principle of
Elimination at the molecular design level. By creating inherently safer chemicals and
processes, the need for complex and costly downstream controls is greatly reduced.

9.4.2 Nanomaterials and Emerging Risks

The rapid development of nanomaterials presents new challenges. The properties of materials
at the nanoscale can be vastly different from their bulk counterparts, leading to novel
toxicological profiles that are not yet fully understood. Future work in hazard classification will
need to develop standardized methods for assessing and communicating the risks of these
emerging technologies.

9.4.3 Automation and Data Analytics

Increased automation and robotics can further reduce worker exposure by physically removing
them from hazardous processes (an engineering control). Furthermore, the use of sensors, IoT
devices, and big data analytics can allow for real-time monitoring of chemical exposures and
process parameters, predicting potential failures before they occur and enabling more proactive
safety management.

9.5 Concluding Remarks

The management of chemical hazards is a dynamic and essential field. The journey from
fragmented, localized rules to a globally harmonized system represents a major step forward for
the safety of workers, the public, and the environment. However, the work is never finished. A
label or an SDS is not the end of the process; it is the beginning of a continuous cycle of risk
assessment, control implementation, and review. By embracing the principles of the GHS and
the Hierarchy of Controls, and by looking forward to innovations like Green Chemistry, we can
continue to harness the immense benefits of chemicals while responsibly managing their
inherent risks.

REFERENCES
1.​ United Nations. (2023). Globally Harmonized System of Classification and Labelling of
Chemicals (GHS) (Ninth revised ed.).
2.​ Occupational Safety and Health Administration (OSHA). Hazard Communication
Standard, 29 CFR 1910.1200.
3.​ National Fire Protection Association (NFPA). NFPA 704: Standard System for the
Identification of the Hazards of Materials for Emergency Response.
4.​ International Labour Organization. C170 - Chemicals Convention, 1990.
5.​ Government of India, Ministry of Environment and Forests. The Manufacture, Storage
And Import Of Hazardous Chemical Rules, 1989.
 6.​ Goetsch, D. L. (2019). Occupational Safety and Health for Technologists, Engineers, and
Managers. Pearson.
7.​ DiNardi, S. R. (Ed.). (2003). The Occupational Environment: Its Evaluation, Control, and
Management. AIHA Press.
8.​ Eckerman, I. (2005). The Bhopal Saga: Causes and Consequences of the World's
Largest Industrial Disaster. Universities Press.

APPENDIX A: GHS PICTOGRAMS AND HAZARDS

Pictogram Name Hazard(s) Represented
Exploding Bomb Explosion Hazard Explosives, Self-Reactives,
Organic Peroxides
Flame Fire Hazard Flammables, Pyrophorics,
Self-Heating, Emits Flammable
Gas, Self-Reactives, Organic
Peroxides
Flame Over Circle Oxidizing Hazard Oxidizers
Gas Cylinder Gas Under Pressure Gases Under Pressure
Corrosion Corrosion Hazard Skin Corrosion/Burns, Eye
Damage, Corrosive to Metals
Skull & Crossbones Acute Toxicity (Fatal or Toxic) Acute Toxicity (Categories 1-3)
Health Hazard Chronic Health Hazard Carcinogen, Mutagen,
Reproductive Toxicity,
Respiratory Sensitizer, Target
Organ Toxicity, Aspiration
Toxicity
Exclamation Mark Acute/Less Severe Hazard Irritant (skin and eye), Skin
Sensitizer, Acute Toxicity
(harmful, Cat 4), Narcotic
Effects, Respiratory Tract
Irritant
Environment Environmental Hazard Hazardous to the Aquatic
Environment
APPENDIX B: STRUCTURE OF A 16-SECTION SAFETY DATA SHEET
(SDS)
●​ Section 1: Identification - Product identifier, manufacturer/supplier details, emergency
phone number.
●​ Section 2: Hazard(s) Identification - All GHS hazards, label elements (pictograms,
signal word, hazard/precautionary statements).
●​ Section 3: Composition/Information on Ingredients - Chemical ingredients,
concentrations, CAS numbers.
●​ Section 4: First-Aid Measures - Necessary first-aid instructions by route of exposure.
●​ Section 5: Fire-Fighting Measures - Suitable extinguishing techniques, equipment,
chemical hazards from fire.
●​ Section 6: Accidental Release Measures - Emergency procedures, protective
equipment, proper methods of containment and cleanup.
 ●​ Section 7: Handling and Storage - Precautions for safe handling and storage, including
incompatibilities.
●​ Section 8: Exposure Controls/Personal Protection - Exposure limits (e.g., PEL, TLV),
appropriate engineering controls, and personal protective equipment (PPE).
●​ Section 9: Physical and Chemical Properties - The chemical's characteristics
(appearance, odor, pH, flash point, etc.).
●​ Section 10: Stability and Reactivity - Chemical stability and possibility of hazardous
reactions.
●​ Section 11: Toxicological Information - Routes of exposure; related symptoms, acute
and chronic effects; numerical measures of toxicity (LD_{50}).
●​ Section 12: Ecological Information - Ecotoxicity, persistence and degradability,
bioaccumulative potential.
●​ Section 13: Disposal Considerations - Description of waste residues and information
on their safe handling and methods of disposal.
●​ Section 14: Transport Information - UN Number, proper shipping name, transport
hazard class(es), packing group.
●​ Section 15: Regulatory Information - Safety, health, and environmental regulations
specific for the product.
●​ Section 16: Other Information - Date of preparation or last revision.

APPENDIX C: NFPA 704 HAZARD DIAMOND

The NFPA 704 diamond is designed for emergency responders to quickly identify the hazards of
materials stored in a fixed facility.
●​ Blue Diamond (Left) - Health Hazard:
○​ 4: Deadly (e.g., Hydrogen Cyanide)
○​ 3: Extreme Danger (e.g., Ammonia)
○​ 2: Hazardous (e.g., Chloroform)
○​ 1: Slightly Hazardous (e.g., Turpentine)
○​ 0: Normal Material (e.g., Water)
●​ Red Diamond (Top) - Flammability Hazard:
○​ 4: Flash Point below 23°C (73°F) (e.g., Propane)
○​ 3: Flash Point below 38°C (100°F) (e.g., Acetone)
○​ 2: Flash Point below 93°C (200°F) (e.g., Diesel Fuel)
○​ 1: Flash Point above 93°C (200°F) (e.g., Canola Oil)
○​ 0: Will Not Burn (e.g., Argon)
●​ Yellow Diamond (Right) - Instability/Reactivity Hazard:
○​ 4: May Detonate (e.g., Nitroglycerin)
○​ 3: Shock and Heat May Detonate (e.g., Ammonium Nitrate)
○​ 2: Violent Chemical Change (e.g., Calcium)
○​ 1: Unstable if Heated (e.g., Acetylene)
○​ 0: Stable (e.g., Liquid Nitrogen)
●​ White Diamond (Bottom) - Special Hazards:
○​ OXY: Oxidizer
○​ W: Reacts with water in an unusual or dangerous manner (e.g., Sodium metal)
○​ SA: Simple Asphyxiant gas (e.g., Nitrogen, Helium)
Note: The NFPA system and GHS are not interchangeable. GHS is for comprehensive
workplace, transport, and consumer communication, while NFPA 704 is specifically for
emergency response at fixed facilities.