Lecture 3

Safety Practices in Chemical and

Nuclear Industries

Toxic Substance and Confined Spaces

Dr. Raghuram Chetty

Department of Chemical Engineering
Indian Institute of Technology Madras
Chennai- 600 036.
Contents

 Toxic substances Definition

 Entry Points for Toxic Agents
 Effects of Toxic Substance

 Relationship of Doses and Responses

 Threshold Limiting Values
 Exposure Thresholds
 Airborne Contaminants

 Confined Spaces Hazards

 Prevention and Control

Toxicology

 Because of the quantity and variety of chemicals used by

the chemical process industries, we must have knowledge
on

 The way toxicants enter biological organism

 The way toxicants are eliminated from biological
organisms
 The effects of toxicants on biological organisms
 Method to prevent or reduce entry of toxicants
Toxicology

 Long ago, toxicology was defined as the science of

poisons. Paracelsus, an early investigator of toxicology
during 1500s stated the problem: “All substances are
poisons; there is none which is not a poison. The right
dose differentiates a poison and a remedy”. Harmless
substance, such as water, can become fatal if delivered to
the biological organisms in large enough doses.

 A fundamental principle of toxicology is

‘There are no harmless substances, only harmless
ways of using substances’.
Toxicology
 Toxicology can be defined as the qualitative and
quantitative study of the adverse effects of toxicants on
biological organisms. A toxicant can be a chemical or
physical agents, including dusts, fibres, noise and
radiation.
 The toxicity of a chemical or physical agent is a
property of the agent describing its effect on biological
organisms. Toxic hazard is the likelihood of damage to
biological organisms based on exposure of usage.
 The toxic hazard of a substances can be reduced by
appropriate industrial techniques. The toxicity,
however, cannot be changed.
Toxic Substance
 A toxic substance is one that has a negative effect on
the health of a person or animal.
 Toxic effects are a function of several factors, including:
 Properties of the substances
 Amount of the dose
 Level of exposure
 Route of entry
 Resistance of the individual to the substance
 Response can vary widely and might be as little as a
cough or mild respiratory irritation or as serious as
unconsciousness and death.
Entry Points for Toxic Agents
 The development of preventive measures to protect
against the hazards associated with industrial hygiene
requires first knowing how toxic agents enter the body.
 The most common routes of entry for toxic agents are:
 Inhalation
 Entry organ: Mouth or nose

 Adsorption
 Entry organ: Skin

 Ingestion
 Entry organ: Mouth or stomach (not a major industrial concern)

 Injection
 Entry organ: Cuts in skin
 Inhalation
 Airborne toxic substances such as
gases, vapors, dust, smoke fume,
aerosols, and mists can be inhaled
and pass through the nose, throat,
bronchial tubes, and lungs to enter
the bloodstream.
 The amount of a toxic substance
that can be inhaled depends on the
 Concentration of the substances
 Duration of the exposure
 Breathing volume.
Image courtesy: Google Images
 Adsorption
 Passage through the skin and into the
bloodstream
 Organic lead compounds, nitro compounds,
organic phosphate pesticides, TNT, cyanides,
aromatic amines, amides, and phenols.
 With many substances, the rate of absorption
and in turn, the hazard levels increase in a warm
environment.
 Factors affecting absorption rate
 Molecular size
 Degree of ionization
 Lipid solubility
 Aqueous solubility
Image courtesy: Google Images
Entry Routes & Method for Control

Entry Route Entry Organ Method of Control

Enforcement of
Ingestion Mouth rules on eating and
drinking
Ventilation,
Inhalation Mouth or nose respirators, hoods,
and other PPE
Proper protective
Injection Cuts in skin clothing

Absorption Proper protective

Skin
(dermal) clothing
Effects of Toxic Substance

 The effects of toxic substance vary widely, as do the

substances themselves. However, all of the various
effects and exposure times can be categorised as being
either acute or chronic.

 Acute effects/exposure involves a sudden dose of a

highly concentrated substance. They are usually the
result of an accident (a spill or damage to a pipe line) that
results in an immediate health problem ranging from
irritation to death.
Effects of Toxic Substance

 Acute effect/exposure are

 Sudden
 Severe
 Typically involve just one incident
 Causes immediate health problems
Effects of Toxic Substance

 Chronic effects/exposures involve limited continual

exposure over time. Consequently, the associated
health problems develop slowly.

 The characteristics of chronic effects/exposure are:

 Continual exposure over time
 Limited concentrations of toxic substances
 Progressive accumulation of toxic substance in
body
 Little of no awareness of exposures.
Effects of Toxic Substance

 When a toxic substance enters the body, It eventually

affects one or more body organs. Part of the liver’s
function is to collect such substances, convert them to
non-toxics and send them to the kidneys for elimination
in the urine
Effects of Toxic Substance
Chronic effects/exposures…

 However when the dose is more than the liver can

handle, toxics move on to the organs, producing a
variety of different effects.

 The organs that are effected by toxic substances are

the blood, kidneys, heart, brain, central nervous
system, skin, liver, lungs and eyes.
Various responses to Toxicants

 Effects that are irreversible

 Carcinogen causes cancer
 Mutagen causes chromosome damage
 Reproductive hazard causes damage to
reproductive system
 Teratogen causes birth defects
Various responses to Toxicants

 Effects that may or may not be reversible

 Dermatotoxic affects skin
 Hemotoxic affects blood
 Hepatotoxic affects liver
 Nephrotoxic affects kidney
 Neurotoxic affects nervous system
 Pulmonotoxic affect lungs
Carcinogens
 A carcinogens is any substance, that can cause a
malignant tumour or a neoplastic growth.
 Medical researchers are not sure exactly how certain
chemicals cause cancer. However, there are a number
of toxic substances that are either known or, are
strongly suspected to be carcinogens.
 Examples: coal tar, pitch, anthracene oil, soot, lamp
black, lignite, asphalt, bitumen waxes, paraffin oils,
arsenic, chromium, nickel compounds, berylium,
cobalt, benzene, and various paints, dyes, pesticides
and enamels.
Asbestos Hazards

 More than 70% of the commercial buildings in use

today contain asbestos in some form -because of its
useful characteristics such as fire resistance, heat
resistance, mechanical strength and flexibility.

 In mid-1970’s medical research tied asbestos to

respiratory cancer, scarring of lungs, etc and it was
finally banned by EPA in 1989.
Asbestos Hazards

 When asbestos becomes crumbly, it releases fibers into

the air that are dangerous when inhaled. Asbestos can
be released into the air if it is disturbed during
renovation or as a result of vandalism.

 Permissible exposure limit (PEL) is 0.2 fibers per cm3 of

air for an 8 hour time weighted average.
Toxic substances & the organs they endanger

Blood Kidneys Heart Brain

Benzene Mercury Aniline Lead
Carbon monoxide Chloroform Mercury
Arsenic Benzene
Aniline Manganese
Toluene Acetaldehyde

Eyes Skin Lungs Liver

Cresol Nickel Asbestos Chloroform
Acrolein Phenol Chromium Carbon-
Benzyl chloride Trichloroethylene Hydrogen sulfide tetrachloride
Butyl alcohol Mica Toluene
Nitrogen dioxide

Some of the widely used toxic substances and the

organs they endanger
How toxicants are eliminated?
 Toxicants are eliminated or rendered inactive by the
following routes:

 Excretion: through the kidney, liver, lungs or other

organs.
 Detoxification: by changing the chemical into
something less harmful by biotransformation.
 Storage: in the fatty tissue.
How toxicants are eliminated?
 Toxicants that are ingested into the digestive tract are
frequently excreted by the liver. In general, chemical
compounds with molecular weights >300 are excreted
by the liver into bile. Compounds with lower molecular
weights enter the bloodstream and are excreted by the
kidneys.
Animal Testing
 How is toxicity tested?

 Most toxicological data is collected using small rodents

e.g. rats, mice, Guinea pigs, as surrogates for human
beings.

 There are numerous advantages to using such animals.

They are small and relatively easy to maintain in good
health in the laboratory. With a life expectancy of
typically 2 years, one can see the effect of a lifetime of
exposure in a relatively short time.
Designing toxicological experiments
 Manner of dosing
 There are several pathways for dosing. Most
commonly, the test substance is added to the
food or water, placed directly into the stomach by
gavage, injected into a vein, coated onto the skin,
or added to the atmosphere the animal breathes.

 The final toxicity values obtained usually differ

according to the path of entry into the body.
Designing toxicological experiments
 Manner of dosing
 The chosen path reflects the following concerns.
 What will be the manner of exposure of workers in the
plant? It should be replicated as nearly as possible in
the testing. For e.g. a solvent to be used for degreasing
parts may make contact with the skin of the worker or
its vapors may be inhaled, but it is highly unlikely that
the worker would ever swallow any. Testing should
concentrate on exposure to the skin and lungs.

 The actual design of the experiment depends on

how the dose is to be administered and what
responses are to be studied.
Designing toxicological experiments
 Manner of dosing
 Length of testing time
 When the dosing is for a limited time - acute
 The animal’s lifetime study - chronic

 Variability among animals

 The toxicity of a compound is not a constant term
for all animals. Differences are sometimes
displayed between animals of even very closely
related species.
Relationship of doses and responses

 Safety and health professionals are

interested in predictability, when it
comes to toxic substances.

 How much of a given substance is

too much?

 What effect will a given does of a

given substance produce?
Relationship of doses and responses

 These types of question concern

dose-response relationships.

 A dose of a toxic substance can be

expressed in a number of different
ways depending on the
characteristics of the substance, e.g.

 amount per unit of body weight

 amount per body surface area
Extrapolating Animal Data to Humans

 In spite of all the advantages, using mice or rats to

predict toxicity to human involves many risks.

 The difference in size between human and small

rodents is a major problem. The observation that 1 mg
of a compound makes a white rat ill dose not mean that
the same amount of would make a human ill.
Extrapolating Animal Data to Humans

 Most commonly doses are listed in milligrams of

compound given the animal per kilogram of animal
body weight. Thus the dose of 1mg per 250-g rat is a
dose rate of 4mg/kg.

 One assumes that the same dose rate should affect the
human, and that 280 mg would have roughly the same
effect on a 70-kg human. Because of difference
between rats and humans this is almost certainly not
exactly true, but it does provide a useful first
approximation of toxicity to humans.
Example

 25 mg of a narcotic substance under study causes a

200 g rat to sleep for 1 hour. What is this dose rate in
mg/kg?

25 mg 1000 g 125 mg
x =
200 g 1 kg 1 kg
Example

 As a first approximation, what dose would be needed to

produce the same effect on an 80-kg human?

125 mg 1g
x 80 kg = 10,000 mg x = 10.0 g
1 kg 1000 mg
Example

 What dose would be predicted to put a 32 kg dog to

sleep?

125 mg 1g
x 32 kg = 4,000 mg x = 4.0 g
1 kg 1000 mg
Doses

 Three important concepts to understand relating to

doses are:

 Dose Threshold

 Lethal Dose

 Lethal Concentration
 Dose Threshold

 The minimum dose required to produce a measurable

effect.
 Of course, the threshold is different for different substances.
 In animal tests, thresholds are established using methods
such as:
 Observing pathological changes in body tissues
 Observing growth rates (are they normal or retard)
 Measuring the level of food intake (has there been a
loss of appetite)
 Weighing organs to establish body weight to organ
weight ratios
Lethal Dose
 Lethal dose of a given substance is the dose that is highly
likely to cause death. Such doses are established through
experiments on animals
 When lethal doses of a given substance are established, they
are typically accompanied by information that is of value to
medical professionals and industrial hygienists.
 Such information includes:
 the type of animal used in establishing the lethal dose
 how was the dose administered
 the duration of the dose.
 Lethal doses do not apply to inhaled substances.
 Lethal Dose
 That all animals, no matter how carefully
selected, do not respond identically to a
given dosage now becomes a problem
in communications of the findings.
 Do we select the lowest dose that
caused a susceptible animal to die, the
highest necessary to kill the most
resistant animal, or an average dose?
 To resolve this, the fist step is to prepare
a dose-response curve from the data.
 Percentage mortality is plotted against
Log dose in mg/kg. This is also called as
Probit Analysis (Probit = Probability
unit).
Lethal Dose

 At the centre of this curve is found the dose that is estimated to be

fatal to half the recipient animals. This dose, the acute LD50 is
predicted to be lethal to 50% of the animals, and is the most
common value used to describe the relative toxicity of a compound.
 Once the curve is established it is possible to describe other
measures of toxicity such as LD5 (dose lethal to 5% of animal
sample) or LD95.
Toxicity class and LD50 values
Toxicity Descriptive LD50 wt/kg 4-hr inhalation Extrapolated Dose
Rating Term (single oral LC50 in Rats (g) for 70-kg
dose in Rats) (ppm) Human

1 Extremely toxic <1 mg <10 <0.07

2 Highly toxic 1-50 mg 10-100 0.07-3.5
3 Moderately toxic 50-500 mg 100-1,000 3.5-35
4 Slightly toxic 0.5-5 g 1,000- 10,000 35-350
5 Practically nontoxic 5-15 g 10,000-100,000 350-1000
6 Relatively harmless >15g >100,000 >1,000

Compounds LD50
(mg/kg, rats, oral)
Glycerol 25,200
Ethanol 10,300
Ethylene glycol 8,500
Acrylic acid 2,600
Hydroquinone 320
Acrylamide 170
Acrylonitrile 93
Nicotine 1
Dioxin 0.001 Dose-response curve for ethyl
alcohol
Lethal Concentration
 A lethal concentration of an inhaled substance is the
concentration that is highly likely to result in death.
 With inhaled substances, the duration of exposure is critical
because the amount inhaled increases with every unprotected
breath.
 In this case, the dose taken by the animal dose not have to be
adjusted to the size of the animal (e.g. when intake is through
lungs), the standards are based on the concentrations of the
substance in the environment of the animal. The toxicity is
expressed as the LC50, or concentration lethal to 50% of the
test group.
 The units in this case are usually either parts per million (ppm)
or mg/m³ of air.
Threshold Limiting Value
 The Threshold Limit Values (TLV) for chemical substances is
defined as a concentration in air, typically for inhalation or skin
exposure.
 TLV refer to airborne concentrations of substances and
represent conditions under which it is believed that nearly all
workers may be repeatedly exposed day after day without
adverse health effect.
 Its units are in parts per million parts of air (ppm) for gases and
mg/m³ for particulates such as dust, smoke and mist.
 Threshold limits are based on the best available information
from industrial experience, form experimental human and
animal studies, and when possible from a combination of the
three.
Threshold Limiting Value

Substance TLV (ppm) TLV (mg/m3)

Acetic Acid 10 25
Acetone 750 1188
Ammonia 25 17
Benzene 1 1.6
Carbon Dioxide 5000 9000
Chloroform 10 49
Ethyl Alcohol 1000 1880
Formic Acid 5 9.4
Nitric Acid 2 5.2
Toluene 50 188
TLV’s of Some Common Chemicals
 Threshold Limiting Value
 TLV (also called exposure threshold) is a specified limit on
the concentration of selected chemicals. Exposure to
these chemicals that exceed the threshold may be
hazardous to a worker’s health.
 Three types of TLVs for chemical substances are (1) time-
weighted average, (2) short-term exposure limit, and (3)
exposure ceiling.
 The Time Weighted Average (TLV-TWA) is the average
concentration of a given substance to which employees
may be safely exposed over an 8 hour work day or a 40
hour work week. Workers can be exposed without adverse
effect.
Threshold Limiting Value
 Short-Term Exposure Limit (TLV-STEL) is the maximum
concentration of a given substance to which employees
may be safely exposed for up to 15 minutes without
suffering irritation, chronic tissue change, or narcosis to a
degree sufficient to increase the potential for accidental
injury.

 The exposure Ceiling (TLV-C) refers to the concentration

level of a given substance that should not be exceeded at
any point during an exposure period.
TLV-Time Weighted Average
 Recommended maximum
exposures are expressed on
the basis of time-weight
averaged (TLV-TWA).

 Calculations of a TLV-TWA
assumes an 8-hr day and 40-
hr week. The exposure levels
of the compounds are
measured in regular
intervals.
TLV-Time Weighted Average

 The TWA exposure is

calculated by multiplying the
concentration of compound
in each analysis by the
length of time of exposure to
that level. These are
summed and divided by the
total time to produce an
average exposure level.
Evaluating Exposure to Volatile Toxicants

 A direct method for determining worker exposure is by

continuously monitoring the air concentration of toxicants
on-line in a work environment. For continuous
concentration data C(t) the TWA (time-weighted
averaged) concentration is computed using the equation:
tw

∫ C(t) dt
1
TWA =
8
0

where C(t) is the concentration (in ppm or mg/m3) of

the chemical in air
tw is the worker shift time in hours
Evaluating Exposure to Volatile Toxicants

 The integral is always divided by 8 hrs, independent of

the length of time actually worked in the shift. Thus, if a
worker is exposed for 12 hrs to a concentration of
chemical equal to the TLV-TWA, then the TLV-TWA has
been exceeded, because the computation is normalised
to 8 hrs.

 Continuous monitoring is not the usual situation because

most facilities do not have the necessary equipment
available.
Evaluating Exposure to Volatile Toxicants
 The more usual case is for intermittent samples to be
obtained, representing worker exposures at fixed points
in time. If we assume that the concentration Ci is fixed (or
averaged) over the period of time Ti, the TWA
concentration is computed by

TWA = C1T1 + C2T2 +… CnTn / 8 hrs

Evaluating Exposure to Volatile Toxicants
 If more than one chemical is present in the workplace,
the combined exposures from multiple toxicants with
different TLV-TWA is determined from the equation
n Ci
∑ =
i=1 (TLV-TWA)i

where n is the total number of toxicants

Ci is the concentration of chemical i with respect to
the other toxicants
(TLV-TWA) is the TLV-TWA for chemical species i.
Gas monitors & detectors

Gas Chromatogram

Image courtesy: Google Images

Sample Problem
 Given an exposure level of 2 ppm for 10 hr per week, 3
ppm for 20 hr per week and 4 ppm for 10 hr per week,
what is the TWA for this exposure?

Exposure (ppm) Time (hr) Product (ppm x hr)

2 10 20
3 20 60
4 10 40
40 120

TWA = 120 ppm x hr /40 hr = 3 ppm

Sample Problem
Determine the 8 hrs TWA worker exposure if the worker is
exposed to toluene vapour as follows:
Duration of Measured
exposure (hr) concentration
(ppm)
2 110
1 330
3 90

TWA = C1T1 + C2T2 + C3T3 / 8

= 110(2) + 330(1) + 90(3) / 8

= 102.5 ppm
Sample Problem

Because the TLV of toluene is 50 ppm, the worker is

overexposed. So additional control measure needs to be
developed. On a temporary and immediate basis all
employees working in this environment need to wear the
appropriate respirators.
Sample Problem
Air contains 5 ppm of diethylamine (TLV-TWA of 10 ppm), 20
ppm of cyclohexanol (TLV-TWA of 50 ppm) and 10 ppm of
propylene oxide (TLV-TWA of 20 ppm). Has the TLV-TWA level
been exceeded? n Ci
∑ =
i=1 (TLV-TWA)i

= 5/10 + 20/50 + 10/20

= 1.40
The sum of the fraction for the various components of the mixture are
added, and if the total is more than 1, exposure goes beyond acceptable
limit.
Because the quantity is greater than 1, the TLV-TWA has been
exceeded.
Permitted Exposure Level (PEL)
 The difference between TLV and PEL is the agencies
from which they come. TLVs are developed by the
American Conference of Governmental Industrial
Hygienists (ACGIH). PELs are developed by the
Occupational Safety and Health Administration (OSHA).
They both serve the same purpose and their values are
very similar or even identical in many cases

 The level of the chemical in the workplace should be

monitored, and the level found should be no higher than
the permitted exposure level.
Permitted Exposure Level (PEL)

 Simple formulas can be used to calculate compliance and

safety when PELs are known for all components of the
mixture.

 A fraction is made of the actual level of a chemical divided

by the PEL, where both values must be in the same units.
The sum of the fraction for the various components of the
mixture are added, and if the total is more than 1,
exposure goes beyond acceptable limit.
Airborne Contaminants

 It is important to understand the different types of

airborne contaminants that may be present in the
workplace.

 Each type of contaminants has a specific definition that

must be understood in order to develop effective safety
and health measures to protect against it.
Airborne Contaminants

 The most common types of airborne contaminates are:

 Dusts
 Fumes
 Smoke
 Aerosols
 Mists
 Gases
 Vapours
Airborne Contaminants

 Dusts
 Dusts are various types of solid particles that are
produced when a given type of organic or inorganic
material is scraped, sawed, ground, drilled, handled,
heated, crushed, or otherwise deformed.

 The degree of hazard represented by dust depends

on the toxicity of the parent material and the size and
level of concentration of the particles.
Airborne Contaminants

 Fumes
 The most common causes of fumes in the workplace
are such manufacturing processes as welding, heat
treating, and metalizing, all of which involve the
interaction of intense heat with a parent material.
 The heat volatizes portions of the parent material,
which then condenses as it comes in contact with
cool air. The result of this reaction is the formation of
tiny particles that can be inhaled.
Airborne Contaminants

 Smoke
 It is the result of the incomplete combustion of
carbonaceous materials. Because combustion is
incomplete, tiny soot and/ or carbon particles remain
and can be inhaled.
Airborne Contaminants

 Aerosols
 Aerosols are liquid or solid particles that are so small
they can remain suspended in air long enough to be
transported over a distance. They can be inhaled.
 Mists
 Mists are tiny liquid droplets suspended in air. Mists
are formed in two ways:
 when vapours return to a liquid state through
condensation,
 when the application of sudden force or pressure
turns a liquid into particles.
Airborne Contaminants

 Gases
 Unlike other airborne contaminants that take the form
of either tiny particles or droplets, gases are formless.
 Gasses are actually formless fluids. Gases become
particularly hazardous when they fill a confined
unventilated space.
 The most common sources of gases in an industrial
setting are from welding and the exhaust from internal
combustion engines.
Airborne Contaminants

 Vapours
 Certain materials that are solid or liquid at room
temperature and at normal pressure turn to vapour
when heated or exposed to abnormal pressure.
Evaporation is the most common process by which a
liquid is transformed into a vapour.
Effects of airborne toxics
 Airborne toxic substances are also classified according to the
type of effect they have on the body. The primary
classifications are:
 Irritants
 Asphyxiant
 Narcotics/Anesthetic
 For reporting the toxicity of airborne toxicants, no adjustment
is necessary for the ratio of animal to human size. One
assumes that the rat and human each breath an amount of air
that is in proportion to the size. The dose is therefore listed in
terms of the concentration in the air, with no reference to
animal size.
Effects of airborne toxics

 Irritants
 Irritants are substances that cause irritation to the
skin, eye and the inner lining of the nose, mouth,
throat and upper respiratory tract.

 Asphyxiants
 Asphyxiants are substances that can disrupt breathing
so severely that suffocation results.

 Asphyxiants may be simple or chemical in nature.

Effects of airborne toxics
 Simple asphyxiant
 is an inert gas that dilutes oxygen in the air to the point
that the body cannot take in enough air to satisfy its
need for oxygen.
 CO2, ethane, helium, hydrogen, methane and nitrogen.
 Chemical asphyxiant
 by chemical interfere with the passage of oxygen into
the blood or the movement of oxygen from lungs to
body tissues.
 CO, hydrogen cyanide, hydrogen sulfide.
 Either way, the end result is suffocation due to insufficient
or no oxygenation.
 Effects of airborne toxics
 Narcotics/Anesthetic
 Are similar in the meaning carefully controlled dosages
can inhibit the normal operation of the central nervous
system without causing serious or irreversible effects.
 This make them particularly valuable in a medical setting.
 However if the concentration of the dose is too high,
narcotics and anesthetics can cause unconsciousness
and even death.
 Examples: methyl-ethyl-ketone, acetylene, ether,
hydrocarbons and chloroform.
Confined Space Hazards

 Confined space means a space that has any of the

following characteristics:
 limited openings for entry and exit;
 unfavorable natural ventilation;
 not designed for continuous worker occupancy.
 It includes, but is not limited to, boilers, manholes,
furnace, pressure vessels, cargo tanks, ballast tanks,
sewage-tanks, bins, pits, tunnels, pipes, pump-rooms,
compressor rooms, cofferdams, void spaces, duct
keels, inter-barrier spaces and engine crankcases.
Confined space e.g. cargo tanks

Image courtesy: Google Images

 Confined Space

Image courtesy: Google Images

Confined Spaces Hazards

 Atmospheric hazards
 Oxygen Deficiency
 Oxygen Enriched
 Flammable atmosphere
 Toxic or Irritating Atmosphere
Confined Spaces Hazards

 Physical hazards
 Fixed & portable mechanical equipment
 Electrically energized conductors
 Fluids: Liquids, powders & gases
 Thermal Condition : Hot or Cold
 Engulfment by finely divided material
 Ionizing and non-ionizing radiation
 Contact with corrosive substances
 Confined Spaces Hazards
 To evaluate the confined spaces, the following limit values
should be used.
 Testing for oxygen
 Any atmosphere with less than 20.8% (± 0.2%) oxygen
by volume should not be entered. Oxygen
measurements should be carried out immediately
before entry into the confined space.
 Testing for flammable atmosphere
 A space with an atmosphere with more than 5% of the
“Lower Flammable Limit” (LFL) or “Lower Explosive
Limit” (LEL), on a combustible gas indicator should not
be entered.
Confined Spaces Hazards
 Toxic gases/ vapours must be less than the
Permitted Exposure Level (PEL).
 carbon monoxide (PEL <35 ppm)
 or any other hazardous materials as determined by
the use of the space.
 Confined Spaces Hazards

Image courtesy: Google Images

Test the Atmosphere

Always test the

air at various levels Good Air
to be sure that the
entire space is safe.

Good air near the

opening does Poor Air

NOT mean there

is good air at the
bottom! Deadly Air
Oxygen Scale
Toxic atmosphere: Toxins
Oxygen Enriched are measured in parts per
21 % million (ppm). Under no
Minimum for circumstances should
19.5%
safe entry
anyone enter a confined
16% Impaired judgment space exceeding the limits
& breathing specified below.
14% Faulty judgment
Rapid Fatigue

Difficult breathing
6%
Death in minutes

Oxygen Scale
Confined Spaces Hazards
 An oxygen deficient atmosphere has less than 19.5%
available oxygen (O2). Any atmosphere with less than
19.5% O2 should not be entered without an approved
self-contained breathing apparatus (SCBA).

 The oxygen level in a confined space can decrease

because of work being done, such as welding, cutting or
brazing, or even corrosion.

 The O2 level is decreased if oxygen is displaced by

another gas, such as CO2 or N2. Total displacement of O2
will result in unconsciousness, followed by death.
Oxygen toxicity
 Oxygen toxicity is caused by exposure to oxygen at
partial pressures greater than those to which the body is
normally exposed.

 Exposures to partial pressures of oxygen above 1.6 bars

(160 kPa) are usually associated with central nervous
system oxygen toxicity. Since atmospheric pressure is
about 1 bar (100 kPa), central nervous system toxicity
can occur where ambient pressure is above normal.

 Severe cases can result in cell damage and death.

Vessel Entry Requirement
Entry permit system
 Permit elements
 Identification & job description
 Description of the hazard
 Precautions already taken while preparation
 Isolations
 Gas test results
 Communications
 Special equipment or precautions
 Identify entrants and stand by rescue
 Hot-work permit involved
 Any other relevant information
 Issue, authorization and acceptance
 Competing the permit procedure
Respiratory Protection
When effective engineering controls are not feasible to control
breathing contaminated air, appropriate respirators shall be used.

 Air-Purifying Respirator (APR)  Supplied Air

 Dust Mask Respirator (SAR)
 Half Face  Air-line
 Full Face
 Hood style
 Powered Air-Purifying Respirators
(PAPR)  Facepiece style
 Self Contained
Breathing
Apparatus (SCBA)
Dust Mask
Image courtesy: Google Images
Tight -Fitting Coverings

Quarter Mask Half Mask

Mouthpiece/Nose Clamp
Full Facepiece
Image courtesy: Google Images
Loose-Fitting Coverings

Hood Helmet

Loose-Fitting
Full Body Suit
Facepiece
Image courtesy: Google Images
Self-Contained Breathing Apparatus (SCBA)

 An atmosphere-supplying respirator for which the

breathing air source is designed to be carried by the
user.

Image courtesy: Google Images

Positive & Negative Pressure SCBA

An action conducted by the respirator user to determine if the respirator is

properly seated to the face.

Negative Pressure Check

SCBA will be either "positive pressure" or "negative pressure" operation.

In negative pressure SCBA air is delivered to the wearer when he
breathes in, or in other words, reduces the pressure in the mask to less
than outside pressure, hence the name "negative pressure". Any leaks in
the device or the interface between the mask and the face of the wearer
would reduce the protection offered.
Image courtesy: Google Images
 Positive & Negative Pressure SCBA

Positive Pressure Check

Positive pressure SCBA addresses this limitation. By careful design, the

device is set to maintain a small pressure inside the facepiece. Although
the pressure drops when the wearer breathes in, the device always
maintains a higher pressure inside the mask than outside of the mask.
Thus, even if the mask leaks slightly, there is a flow of clean air out of the
device, automatically preventing inward leakage under most
circumstances.
Image courtesy: Google Images
Prevention and Control

 Most preventive and control strategies can be placed in

one of the following four categories:

 Personal protective equipment (PPE)

 PPE imposes a barrier between the worker and the
hazard but dose nothing to eliminated or reduce the
hazard, e.g. safely goggles, face shields, gloves,
boots, full-body clothing, respirators.
Prevention and Control
 Engineering controls
 Strategies for replacing a toxic material with one that
is less hazardous or redesigning a process to make it
less stressful. Isolating a hazardous process to
reduce the number of people exposed & introducing
moisture to reduce dust.
 Ventilation
 Exhaust ventilation involves trapping and removing
contaminated air. Typically used in processes such as
abrasive blasting, grinding, polishing, buffing, and
spray painting/finishing.
Prevention and Control

 Administrative controls
 Involves limiting the exposure of the employees to
hazardous conditions using strategies such as,
rotating schedules, required breaks, work shifts.
Summary
 Definition of toxic substances
 Entry Points (Inhalation/ Adsorption/ Ingestion/
Injection
 Effects (acute / chronic)

 Relationship of Doses and Responses

 Dose Threshold/ Lethal Dose/Concentration
 Threshold Limiting Value
 Airborne Contaminants (Dusts/ Fumes /Smoke /
Aerosols/ Gases/ Vapours)
Summary

 Confined Spaces Hazards

 Oxygen scale
 Respiratory protection

 Prevention and Control

 Engineering controls/ ventilation/ PPE/
administrative.
References & Further Reading

 David.L. Goetsch, “The Safety and Health Handbook”

Prentice Hall, 2000.

 D.A. Crowl and J.F. Louvar, Chemical Process Safety:

Fundamentals with Applications, 2001 (2nd Edition).

 R.G. Smith and J.B. Olishifski, “Industrial Hygiene”

Chicago National Safety Council, 1988.