Air Pollution Theory&Prac Notes

INTRODUCTION 6
The Atmosphere 9
Stratification of the Atmosphere 11
History of Air Pollution 12
Haze or Smog? 13
Factors Likely to increase the Levels of Air Pollution 13
The Protection of the Environment Operations Act 13
SOURCES, TYPES AND DISTRIBUTION OF AIR POLLUTANTS 14
Major Sources of Air Pollutants 14
Transportation-Combustion Sources 15
Stationary (Industrial) Sources 15

Solvent Evaporation 15
Stack emissions 16
Nature of the waste emission 16
Volume of the waste 16
Local topography 16
Prevailing climate 16
The Existing Atmosphere 16
Plume behaviour 17
Fugitive Emissions and Other Sources 19
Types of Air Pollutants 20
Primary and Secondary Air Pollutants 20
Particulate Pollutants 20
Particle Size 21
Particle Behavior in the Atmosphere 22
Total Suspended Particulates (PM10, PM2.5) 22
Organic Particulates 22
Lead 23
Gaseous Pollutants 24
Carbon Oxides (CO and CO2) 24

Carbon Monoxide 24
Typical Concentrations 25
Sinks 25
Carbon Dioxide 26
Sulfur Compounds 26
Sulfur Oxides 26
Air Quality & Pollution Control Introduction
Sulfur Dioxide 27
Sinks 27
Hydrogen Sulfide 28
Sinks 28
Nitrogen Compounds 28
Nitrous Oxide 28
Nitric Oxide 28
Nitrogen Dioxide 29
Sinks 30
Ammonia 31
Organic Nitrates 31
Hydrocarbons 31
Hydrocarbon Concentrations 33
Sinks 34
Methane 34
Ozone and Photochemical Smog 35

Photochemical Smog 35
Reactions Occurring in the Formation of Photochemical Smog 36
Ozone Concentrations 40
Ozone Sinks 41
Chlorofluorocarbons (CFC’s) 41
Fluoride 41
Minor Gaseous Pollutants 42

Odour Pollution 42
Odour Measurement 42
Odor Problems 44
References 44
HEALTH & ENVIRONMENTAL EFFECTS OF AIR POLLUTION 45

Effects of Air Pollution on Human Health 45
Interactions Between Pollutants and Synergism 46
Susceptible parts of the Human Body - The Respiratory System 46
Carbon Monoxide 48
Sulfur Compounds 49
Sulfur Dioxide and Particulates 49
Sulfur Dioxide 50
Oxides of Nitrogen 51
Hydrocarbons 51
Ozone & Photochemical Smog 52
Particulate Matter 53
Respiratory Deposition and Retention of Particulate Matter 53
Lead 55
Asbestos 56
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Fluoride 56
Environmental Effects of Air Pollutants 56

Effects on Plants 56
Ozone 58
Fluorides 60
Acid Deposition 62
Effects of Air Pollutants on Buildings and Materials 62

Metal Corrosion 63
Rubber and Fabrics 63
Accepted Levels of Major Air Pollutants 63
References 64
AIR QUALITY MEASUREMENT AND ASSESSMENT 65
What is Air Quality? 65
Air Sampling Techniques 66

Impingers 67
Sampling Procedures 67
Selection of Locations for Monitoring Equipment 68

General Requirements for Site Selection 68
Specific Requirements for Site Selection 68
The Importance of Meteorological Monitoring 68

Wind Direction and Velocity Measurements 69
Ambient Air Monitoring 69

Choice of Monitoring Equipment 69
Calibration and Maintenance of Monitoring Equipment 70
Data Handling and Presentation 71
Reference Methods for Measuring Air Quality 71
Measurement of Source and Stack Emissions 71

Source Sampling 72
Real Time Analysis 73
Measurement of Particulates 75
Deposit Gauges 75
High Volume Samplers 76
PM10 and PM2.5 High Volume Samplers 77
Nephelometers 78
Co-efficient of Haze - Paper Tape Samplers 78
Measurement of Gases 79
Sulfur Dioxide 79
Oxides of Nitrogen 80
Ozone 80
Carbon Monoxide 81
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Non-Methane Hydrocarbons 82
Fluoride 82
Hydrogen Sulfide 82
Questions 83
References 83
TREATMENT & CONTROL OF AIR POLLUTANTS 84

Controlling Emission of Particles 84
Process Modifications 84
Gravitational Settling and Cyclones 84
Filtration Systems 85
Wet Scrubbers 86
Electrostatic Precipitators 87
Control of Particulate Fugitive Emissions 88

Process Modifications 89
Combustion or Incineration 89
Adsorption 90
Absorption 90
Dry Scrubbing Systems 90
Control of Gaseous and Liquid Fugitive Emissions 91
Control of Vehicle Emissions 92
References 93
AIR QUALITY ANALYSIS 94

A1 - EVALUATION of LOCAL FALL-OUT by DEPOSIT GAUGE 94
A2 - DETERMINATION of METAL CONTENT of LOCAL FALLOUT by X-RAY

FLUORESCENCE SPECTROMETRY 95
A3 - DETERMINATION of IRON CONTENT of PARTICULATE FALLOUT by FLAME AAS

97
A4 - DETERMINATION of HEAVY METAL CONTENT of FALL OUT by

ELECTROTHERMAL ATOMIC ABSORPTION SPECTROPHOTOMETRY 99
NOTE 2: Electrothermal AAS is an extremely sensitive technique. Always use ultrapure
water for all solution preparation. 99
A5 - DETERMINATION of ACIDIC GASES in AMBIENT AIR by TITRIMETRY (AS 3580.3.1

- Method) 101
A6 - Determination of Total Suspended Particulates in ATMOSPHERIC GASES by High

Volume Sampler (AS 2724.3 - Method) and PM10 High Volume Sampler with Size Selective Inlet
– Gravimetric Method (AS 3580.9.6 – Method) 102
A7 - DETERMINATION of Ambient Levels of Carbon Monoxide, Sulfur Dioxide and Oxides of

Nitrogen 106
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NSW EPA MANUAL OF AIR QUALITY TESTING 107
CONTENTS 107
PART 1 - Introduction and Definitions 107
PART 2 - Stationary Sources 107
PART 3 - Mobile Sources 108
APPENDIX: Test Methods Sources 108
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Chapter
1
Introduction
The Earth is surrounded by an envelope of gases which provide many functions
including, protection from harmful radiation, moderating the surface temperature and
providing a medium (which we call air) that allows organisms to exchange gases in
order to survive (breathing). Any substantial change in the nature or contents of the
atmosphere has a direct consequence on how well the atmosphere performs these
tasks.
Air is of fundamental significance to our existence. If the quality of the air we breath
is degraded then our health will directly suffer and our standard of living decrease.
This is one of the great paradoxes of modern society. In general the higher the degree
of sophistication of society (some might call this civilisation), the lower the quality of
the air that they are exposed to. Indeed the lifestyle and extent of civilisation of
societies on the Earth directly relate to the type of atmospheric degradation which is
present.
Historically air pollutants of greatest concern have been total suspended particulates
(TSP), and oxides of sulfur, but as our processing industries become more
sophisticated the list of significant pollutants grows. Now we commonly include
oxides of nitrogen and photochemical oxidants (smog & ozone) as routine pollutants,
and often include particulate lead, asbestos, mercury, sulfuric acid and many others
that require careful monitoring.
Concern over the atmospheric concentrations of substance not normally considered

pollutants has also become much greater in the latter part of the twentieth century. A
good example of this is CO2. The levels of this gas have increased by as much as 5%
over the last two decades of the twentieth century. Most of this is thought to be due to
the combustion of fossil fuels. This has been targeted as a major environmental
problem by most of the world’s nations and strategies have been put in place to reduce
the amount being discharged into the atmosphere. It is expected that the levels of CO2
in the atmosphere will peak around 2040 – so the problems associated with
degradation of the atmosphere in general will take a long time to fix. This needs to be
considered by nations that are emerging as economic powers. Often environmental
concerns are dismissed in the interest of short-term profit – a strategy which does not
work in the long term as may be seen by the example of East Germany which required
many billions of dollars to fix up pollution problems after re-unification with West
Germany.
The Earth’s atmosphere has never been completely pure. It has always contained
waste materials from many natural sources such as bushfires, decay from plant and
animal life, and windblown dust particles to mention a few sources. Pollutants also
arise from unexpected natural sources. For example rainforests are regarded as
essential for the health of the atmosphere in that they remove CO2 and replace it with
O2. For this reason they are thought of as the Earth’s lungs. Rainforests and other
types of forests also produce natural hydrocarbon products however, which can
undergo photochemical oxidation to produce pollutant haze – which we would term
air pollution. This formation of wastes is part of the cycling and recycling of matter in
natural ecological systems. Wastes released into the atmosphere are diluted and
dispersed in the air, and are processed and recycled through a variety of natural
physical, chemical and biological mechanisms. For example, many particles of waste
are removed by settling or are washed out by rain. Many gaseous wastes are oxidised
to form particles, which then settle out or are washed out while others are converted to
other gases in the atmosphere or absorbed by plants or other soil micro-organisms. In
this way the atmosphere is continually cleaned of these substances.
Atmospheric problems are made worse when weather conditions such as a lack of rain
or wind cannot disperse pollutants. This not only holds them in the air, increasing
human exposure, but also allows them to undergo chemical reactions to produce
secondary pollutants that are often far more dangerous than those substances from
which they were made.
The residence time of waste products in the atmosphere before they are broken down
or brought back to the ground varies between a few hours and many years. Air
pollution problems occur whenever any of these normal functions of the atmosphere
are disturbed or overloaded.
Global Emissions form Natural & Man Made Sources
120
100
80
% Emissions from Natural
Sources
60
% Emissions from man made
sources
40
20
0
SOx CO NOx NH3 H/C Dust
Pollutant
Figure 1.1 - % of emissions from global and man made sources
Figure 1.1 shows that compared to natural sources, man’s activities produce a much
smaller amount of global pollution. Indeed natural pollutants may pose a serious
threat to air quality when they are generated in large amounts near human settlements.
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Examples of this include dust storms, bush fires and volcanic eruptions. Natural
pollution generally has a low impact on human wellbeing as the levels of pollutants
associated with most natural pollutants are relatively low, the sources are generally
well separated from large human populations and natural forces responsible for the
pollution occur at infrequent intervals. One major exception to this rule is the biogenic
emission of photochemically active hydrocarbons such as isoprene, α-pinene and
other terpene molecules. These natural hydrocarbons play a major role in the
formation of photochemical smogs, and are major contributors to haze. This is
especially a problem in Australia where heat produces large amounts of eucalyptus
haze from gum trees.
This does not mean that pollution from man made sources is not a problem. A closer
look at air pollution will show that dispersal of pollutants is a very important
consideration – as the atmosphere is not homogeneous. This means that pollutants
tend to concentrate in specific areas – most of which are near where large human
populations reside. This means that pollutant levels around residential areas are often
much greater than would be expected in ambient air. Natural sources on the other
hand are in general more evenly spread, but there are exceptions such as extremely
high levels of dust and acidic gases associated with volcanic activity.
Man's activities (also called anthropogenic) release heat, gases, aerosols and other
wastes into the atmosphere. These are particularly significant in that our wastes are
discharged in such high concentrations that we overload the natural dispersal, dilution
and recycling systems on a local, regional and global scale which causes damage to
plants, animal life, and materials. The ecological systems themselves are degraded,
and the services they provide are reduced. In addition to this overload due to increased
concentrations of waste products in particular areas, we are now releasing quantities
of new or previously rare substances into the environment. Very little is known about
the dispersal processes and the passage through ecological systems of these
substances. Many are resistant to degradation, some are cumulative and harmful.
Air pollution is not an easy thing to define. The World Health Organisation defines air
pollution as “Air is polluted when one or several pollutants are present in the
atmosphere at such a concentration and for so long a time that they are harmful to
man, animals, plants or material property, cause harm or reduce well-being or
disturb appreciably its application”. Whilst this is fairly complete in its cover, it is
also very complex – hence simpler definition are often used. The definition of air
pollution for legal purposes is defined in the NSW Protection of the Environment
Operations Act as “any deviation from the natural combination of gases in our
atmosphere”. What this definition fails to mention is that the natural combination of
gases in our atmosphere must be taken as dry air at sea level. This is necessary as it is
not possible to quantitatively define pure air because it will change according to
altitude and location. This also means that theoretically air pollution can also arise
from the removal of gases from the atmosphere. Neither of the definitions listed above
completely cover other factors that we might also call pollution such as the release of
energy, radiation, odour or noise.
Most air pollution concerns are associated with ambient air, that is air that is outdoors
and free flowing – hence most control programs focus on ambient air pollution, but
significant pollution now occurs in occupational environments which are indoors.
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Especially important here are the effects of cigarette smoke which may contain large
amounts of carbon monoxide and extremely toxic polycyclic aromatic hydrocarbons.
The Atmosphere
The Earth’s atmosphere is approximately 160 kilometers deep, but 95% of its air mass
lies within 20 kilometers of the surface. Moving up from the earth’s surface the
density of the atmosphere decreases rapidly and the air “thins”. Hence the atmosphere
is neither uniform, nor static in nature. Its characteristics vary widely with altitude,
season, location and solar flare activity.
Air within a few kilometers of the earth’s surface will typically contain the
components shown in table 1.2.
The most obvious conclusion that may be drawn from this table is that the pollutants
with which we have the most problems make up an extremely small part of the
atmosphere. Figure 1.1 shows sulfur dioxide to be the air pollutant produced in the
greatest amount by a long way, yet it forms an insignificant proportion of the
atmosphere (a fortunate thing from our point of view). The figures in Table 1.1 are
distorted somewhat by the fact that in polluted city areas these % concentrations will
change markedly for some pollutants.
A few other important facts should be stated about the data in Table 1.1. The
concentrations of nitrogen, oxygen, argon, neon, helium, krypton, hydrogen and
xenon remain essentially constant. These gases are fairly inert and play little or no
role in atmospheric chemistry.
Table 1.1 – Components of a normal atmosphere
Element % (by volume) in the Total Mass in the

atmosphere Atmosphere (x1012
tonnes)
nitrogen 78.08 3900
oxygen 20.95 1200
argon 0.934 67
carbon dioxide 0.035 2.5
Neon 0.0018 0.065
Helium 0.00052 0.004
Methane 0.00015 0.005
Krypton 0.0001 0.017
Carbon Monoxide 0.00001 0.0006
Ozone 0.000002 0.0003
Nitrogen Dioxide 0.0000001 0.000013
Sulfur Dioxide 0.0000001 0.000018
water 0.1 – 5 (normal range 1- Varies according to
3) location
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Even though it is the most abundant gas, nitrogen has little effect on major
atmospheric processes or to the sustenance of life forms. It does however, serve as a
precursor for other species such as NO3-, as well as amino acids and nucleic acids
(amongst others) which are essential for life.
Nitrogen reacts with oxygen – the second most abundant gas in the atmosphere to
form oxides of nitrogen (NOx). These include NO, NO2, N2O4 and N2O. The NOx
compounds in the atmosphere are found in trace levels and their concentration varies
with place and time of day. Nitrous oxide (N2O) was thought to remain constant in
atmospheric concentration, but synthetic fertiliser compounds containing nitrogen
have been found to increase the amount of nitrification by soil bacteria, which has in
turn increase the amount of N2O being generated by natural sources.
As the great majority of species on Earth use an oxidative metabolism, it comes as no

surprise that oxygen is the most important atmospheric gas for the nurturing of life. Its
significance as an atmospheric gas goes far beyond sustaining life however. Oxygen is
also present in the atmosphere as ozone (O3), which exists in high concentrations in
the upper atmosphere and acts as a heat and radiation shield for the planet –
maintaining fairly constant temperatures that allow life to exist.
At 0.035%, the concentration of carbon dioxide in the atmosphere is very low

compared to molecular oxygen or nitrogen. It is still of enormous significance
however as it is the raw material used by plants for carbon fixation to produce the
compounds used for energy by almost all forms of life. It is also a significant
greenhouse gas – which serves to keep the planet warm.
Water vapour is the most variable of all atmospheric components (varies from 0.1 –
30,000ppm), but it is also of huge significance. Water rapidly changes phase from
liquid to gas or solid in response to atmospheric conditions. This means that it allows
the transport of energy around the planet. Water vapour also condenses to form clouds
that are responsible for the Earth’s albedo – the ability of the Earth to radiate sunlight
back into space – which is another factor in controlling the Earth’s surface
temperature.
The atmosphere also contains trace gases produced from biological or geological
processes. These include ammonia, methane, hydrogen sulfide, carbon monoxide and
sulfur dioxide. Ammonia, methane and hydrogen sulfide are primarily produced by
bacterial decomposition, whilst carbon monoxide and sulfur dioxide are produced
mostly by geological processes.
To help understand the significance of air pollutants requires an analysis of what a

person breathes.
The average person breathes 20,000 litres of air per day, 995 of which is nitrogen or
oxygen. The other 1% is a mixture of gases and particulates, many of which might be
termed pollutants. This means that we breathe as much as 200litres of pollutants per
day!
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Stratification of the Atmosphere

As we move away from the Earth’s surface the temperature drops (as well as the
pressure). This causes stratification – or layering of the atmosphere The lowest layer
of the atmosphere is known as the troposphere, and extends to an area of between 10
and 16 kilometres above the earth. This is where our weather and almost all of our
pollution problems occur. Its composition fairly homogeneous due to the weather
producing circulating air masses that allow constant mixing. 95% of the atmosphere’s
air mass is found in the troposphere. The upper troposphere has a temperature of -
56ºC.
At the top of the troposphere is the tropopause layer. It serves as a barrier to prevent
water vapour rising much higher as it causes ice formation. Water vapour cannot pass
through it. If it did, it would photodissociate in contact with ultraviolet radiation, and
the hydrogen would be lost to space. The tropopause separates the stratosphere from
the troposphere.
Above the tropopause layer is the stratosphere, between 10 and 50 km above the
earth.. Moving up in this layer we find the temperature rises, and may reach up to -
2ºC., The ozone layer is within the stratosphere, and reaches levels of up to 10ppm in
the middle of the stratosphere. The stratosphere can reach temperatures of up to -2°C
due to the absorption of ultraviolet radiation by the ozone.
The mesosphere is above the stratosphere, covering an area of between 50 and 85km
above the earth. At 85km the temperature is -92°C. Above the mesosphere is an area
called the exosphere where molecules and ions can be lost to space.
An area extending far into space is called the thermosphere, an area of high
temperatures (1200°C) due to the absorption of radiation from space.
Figure 1.2 – The layers of the atmosphere
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History of Air Pollution

Air pollution probably became a serious problem from the time man discovered how
to use fire. The smoke which is associated with the incomplete combustion of
hydrocarbon materials was probably as much a problem to cave men as it is today.
Reports of air pollution and decimation of forests have been recorded since the
fourteenth century. These were mostly linked with the burning of soft coal with a high
sulfur content. This activity produces smoke, sulfur dioxide and particulate matter
containing hydrocarbons.
By the late nineteenth century London had become famous for its "pea souper" fogs.
It was around this time that the word "smog" was coined to describe the thick
combination of smoke from combustion, and fog which often rolled in from the North
Sea. These smogs were marked by extreme reductions in visibility, strong odours of
sulfurous gases and generally increase rates of illness and death. This type of smog is
grey in colour and is generally referred to as London type smog. When the term smog
is used today it is broadly applied to any pollution condition associated with a
significant reduction in visibility - it does not pollutant type, source or the inclusion
of fog.
By the mid-twentieth century the first smog related deaths were occurring. In 1930 in
the Meuse Valley of Belgium a temperature inversion trapped pollutant gases above
the deep river valley where an industrial area was housed. The excessively high
levels of air pollution resulted in 60 deaths. In 1948, 21 people were killed in Donora,
Pennsylvania, by heavy smog. A temperature inversion trapped fog and pollutants in
the basin in which the town was located for four days. Most victims died of lung and
breathing disorders. Of the survivors, 7000 of the total population of 14000 became
seriously ill. London suffered a similar disaster in 1952 when a "killer smog"
descended on the city for more than a week. In this case the smog was so heavy that
visibility during daylight hours was cut to only a few meters. SO2 concentrations were
raised to seven times their normal level, whilst CO was twice the normal level. During
this period the death rate in London soared dramatically with the number of deaths
occurring in the city closely following the concentration of sulfur dioxide in the
atmosphere. It is estimated that this event killed 4000 people. These events lead to the
development of anti-pollution regulations (such as the Clean Air Acts), which are still
being modified to this day.
There has been a great reduction in smoke in cities in the western world in the past
few decades. This is due to the replacement of coal as a source of energy by fuels
such as natural gas and oil. Smog still remains a serious problem however, as motor
vehicle and industrial emissions have pumped many tonnes of hydrocarbons into the
atmosphere and these in turn have produced photochemical smogs. These are
particularly serious in cities such as Los Angeles, Tokyo and Sydney.
Los Angeles type smogs is like the London type smog in that it produces a significant
reduction in visibility, but the conditions which produce this smog are very different
to those in London. In Los Angeles the climate is semi-arid, with many hot sunny
days. It is also part of weather system that causes air to descend over the city – greatly
restricting the dispersal and movement of air. The very large number of motor
vehicles used in the Los Angeles area produce relatively large amounts of nitrogen
page 12
dioxide and unburnt hydrocarbons, which then react in the atmosphere in the presence
of UV light and oxidants to form a brown photochemical smog.
Haze or Smog?
One term that is often used in association with air pollution is haze, but how is it
different to smog?
Both smog and haze are typified by s reduction in visibility, but the difference is the
intensity varies. Haze refers to a condition where the reduction in visibility is not
great, and is generally applied to describe the atmospheric conditions over a very
large area. Smog on the other hand is characterised by significant reductions in
visibility - generally in metropolitan areas.
Factors Likely to increase the Levels of Air Pollution

Certain conditions help make air pollution worse. Basically these are factors which
prevent air circulation, and concentrate air effluent into areas. Examples of these
include;
• calm conditions
• low level emission sources
• temperature inversions
• high buildings and narrow streets
By contrast other conditions are known to lower air pollution levels in general. These
are those conditions that encourage circulation or remove pollutants from the
atmosphere. Examples include;
• windy or turbulent conditions
• high levels of vegetation
• high level emission sources such as smoke stacks
• rain
The Protection of the Environment Operations Act

This act specifies all legal requirements for the control of air pollution in NSW. It
attempts to reduce air pollution by prescribing standards for emission of pollutants.
These are generally linked to accepted world health standards used in other countries.
Some premises are licensed under the act to pollute. This does not mean that air
pollution is encouraged, rather it is a means of controlling emission from major
sources such as power stations etc.. These premises are charged a fee for a licence to
discharge pollutants, the levels of which are carefully monitored. Any contravention
of the licence means that the company responsible will be charged in the Land &
Environment Court and generally fined.
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Chapter
2
Sources, Types and Distribution of Air
Pollutants
Major Sources of Air Pollutants

The number of different types of pollution sources in modern society is almost
endless. Hence in this chapter we will look at only the most significant sources of air
pollutants. For convenience pollutant sources can be grouped into mobile or
transportation sources, and stationary sources. Approximately 50 - 70% of all air
pollution arises from transportation-combustion sources, 15-25% from heavy
industrial stationary sources and as much as 25% from other stationary sources.
Table 2.1 lists the major sources of pollution in the USA during the late 1980’s. It
provides estimates of the amounts emitted of the five most significant air pollutants.
Levels in Australia will vary somewhat, but as our social demographics are similar to
the United States these are also a good estimate of the approximate break up of
pollutants sources. Note however that the total amount emitted in Australia will be far
less than those in the USA. One pleasing aspect is that there has been a significant
reduction in the amounts of CO and hydrocarbons when compared to the previous
decade, whilst the levels of other pollutants has been steady or shown only a slight
increase.
1
Table 2.1 – Estimated emission of 5 primary pollutants in the USA 1987
Emissions (106 tonnes / year)
Source CO Particles H/C’s NOx SOx Total %
Transport 40.7 1.4 6.0 8.4 0.9 57.4 44.9

Stationary fuel 7.2 1.8 2.3 10.3 16.4 38.0 29.7
combustion
Industrial 4.7 2.5 8.3 0.6 3.1 19.2 15.0
Processes
Solid waste 1.7 0.3 0.6 0.1 0 2.6 2.0
disposal
Miscellaneous 7.1 1.0 2.4 0.1 0 10.6 8.3
Total 61.4 7.0 19.6 19.5 20.4 127.8
% 48.0 5.5 15.3 15.3 15.9 100
Air Quality & Pollution Control Sources , Types & Distribution of Air Pollutants
Transportation-Combustion Sources
There are many different types of transportation sources, not all of which are
significant sources of pollution. Unfortunately the most important transportation
sources at present are major polluters.
Motor vehicles are a very significant source of pollution. They produce many
different pollutants including carbon monoxide, carbon dioxide, hydrocarbons, oxides
of nitrogen, lead particulates and even small amounts of oxides of sulfur. Motor
vehicle exhaust accounts for 40% of all hydrocarbon air pollutants and 90% of all
nitrogen dioxide. Additionally the pollutants from motor vehicles can react in the
atmosphere to form different and even more reactive (and dangerous) pollutants such
as photochemical smog. Many trucks run on diesel fuel. Whilst this is more
economical it is also a source of very dangerous hydrocarbons and is a major source
of the extremely carcinogenic polycyclic aromatic hydrocarbons (PAH’s).
Lead is rapidly decreasing in significance as a pollutant from motor vehicles as more

and more use unleaded fuels. IN the USA the introduction of unleaded fuel in 1978
produced a reduction in atmospheric lead over the next decade of 94%. A similar
reduction is expected in Australia. Additionally vehicles running on unleaded fuels
emit lower levels of oxides of nitrogen and sulfur as the catalytic converters in the
exhaust systems help to reduce these.
Aircraft and trains are less significant sources of pollution compared with road
transport vehicles.
Aircraft run on kerosene, which is burnt fairly efficiently, but as they fly very high in
the atmosphere the pollutants – most of which are hydrocarbons – are spread and
diluted in the upper atmosphere.
Many trains now run on electricity, and hence contribute very little to air pollution.
The discharge associated with high voltage electrical cables used to power them can
however, give off ozone, which is very toxic and a powerful oxidising agent. Despite
this electric trains are probably the most environmentally friendly forms of mass
transport systems available in modern society.
Stationary (Industrial) Sources

Again these are many and varied in nature. Some of the more important sources
include
• furnaces - and their combustion of carbonaceous fuels
• boilers
• ovens and dryers
• process systems which produce volatile chemicals, gases, etc.
Solvent Evaporation
Solvent evaporation can come from solvent-based paints, leaking pipe joints,
maintenance work involving the dismantling of pumps or breaking of pipelines, spills,
unloading /loading procedures, contaminated ground.
page 15
Solvent vapour is an important part of photochemical pollution (see photochemical

smog).
Stack emissions
The emission of waste gases. fumes, vapours and smokes to the atmosphere are
usually by the use of a smoke stack or chimney. A backyard incinerator, or even a
whole city or industrialised area could also be thought of as a stack emission to the
atmosphere. Although such emissions are usually the waste products of combustion,
many waste solvent vapours are vented to the atmosphere in this manner.
The stack emission becomes a plume in the atmosphere. The plume is an area of
concentrated waste emissions that slowly become diluted with the other atmospheric
gases.
How this dilution happens will depend on a number of factors:
Nature of the waste emission

Toxic emissions will need to be very dilute if they are allowed to be vented to the
atmosphere.
Volume of the waste

Is the emission constant or only at certain times in the process. For example, pottery
kilns will only vent waste products when the kilns are operating. Coal-fired electrical
generating plants will vent waste products all the time.
Local topography
Many cities in the world are located in delta areas surrounded by hills or mountains.
Melbourne, Sydney, Los Angeles and Mexico City are examples of cities located in
delta areas. During periods of low wind and cooler temperatures, these cities suffer
from photochemical smog.
Prevailing climate
The direction of prevailing winds is important with stack emissions. The area the
wind takes the emissions may be affected by photochemical smog, acid rain or fallout
of pollutants.
Queenstown, in the south-east of Tasmania is a famous example of the effect of stack

emissions. The smelter emissions created a "fan" of bare hills in the direction of the
prevailing wind. This fan continues for some miles beyond Queenstown.
Emissions from aluminium smelters also are linked with fluorine damage to plants
and animals in a "fan" made by the prevailing wind.
The Existing Atmosphere

In very polluted cities, the introduction of more stack emissions may not be desirable.
Large coal-fired electrical plants are built in country areas, where the waste gases can
be vented to clean air. If these plants were built in urban areas, the photochemical
smog will be much worse. If photochemical smog is already a problem, the
introduction of more waste gases must be done carefully, or where possible avoided
page 16
entirely. Any new waste gases may react strongly with the photochemical smog. An
example would be sulfur dioxide.
The effects of plumes are considered local within 500 metres of the stack, and
regional beyond this.
Plume behaviour
The mixing or dispersion of the waste gases and products into the atmosphere is
called plume behaviour. In stable air, and where the vertical movement of the plume
is slow, a fanning plume is produced. This wide, shallow, spreading plume is very
common after calm clear nights.
A temperature inversion limits the rise of the plume into the upper atmosphere. The
following diagram shows normal air movements, and a temperature inversion. A layer
of warm air limits the rise of the plume into the upper atmosphere, and creates a
higher concentration of polluted air at lower levels. This plume exists for several
hours.
2
Figure 2.1 - A Fanning Plume
In windy conditions the plume can swirl up and down. This is a looping plume, and is
common in the afternoon. Moderate and strong winds are formed on sunny days
creating unstable conditions. This plume exists for several hours.
2
Figure 2. 2 – A Looping Plume
With moderate winds and overcast days, the plume may become a coning plume. This
plume is wider than it is deep, and is elliptical in shape. This plume exists for several
hours.
page 17
Figure 2. 3 – A Coning Plume2
The fumigating plume is short-lived (fraction of an hour), but reaches the earth's
surface. Fumigating plumes occur when the conditions move from stable to more
unsettled.
A fanning plume might have developed overnight under stable conditions. As the day
heats up, unstable air is produced. This unstable air affects the fanning plume, causing
the plume to move vertically up and down. These plumes can cause localised
pollution. Fumigating plumes become looping or coning plumes as the air conditions
stabilise.
2
Figure 2. 4 – A Fanning Plume
Where the plume is above the inversion layer, it becomes a lofting plume. Normal
wind direction and speed will disperse the plume into the atmosphere without effect
from ground warming or cooling.
2
Figure 2. 5 – A Lofting Plume
page 18
A number of factors are used to establish the amount of stack emission allowed, and
its concentration to the atmosphere. These include:
• smoke stack (chimney) height,

• local topography,
• temperature,
• emission rates,
• chemical reactivity, and
• existing air pollution problems
Increasing the height of smoke stacks results in the emission of pollutants higher up in
the atmosphere. In theory this means that the pollutants will be more diluted by the
atmosphere if and when they return to the ground – hence the effect on those closer to
the stack is decreased compared to if the emission occurred at a lower height, or at
ground level. Whilst this is true it also means that the pollutants are spread over a
much greater area with taller stacks, and more individuals may be affected. In general
however, higher stacks allow emission of higher levels of pollutants.
Some types of topography harbour pollutants better than others. In general areas in
low valleys surrounded by mountains, with little wind are not conducive to natural
removal of pollutants. Hence lower pollution levels can be tolerated in these areas. By
contrast open flat areas with high levels of prevailing wind allow rapid dispersal of
pollutants.
High temperature emissions will rise to a higher level into the atmosphere. This may
mean that the pollutants will go up into the atmosphere, away from the local area
under most conditions, whilst low temperature emissions may fall rapidly, and blanket
the area surrounding the stack.
High rates of emission, or emission of highly toxic or highly reactive species require
lower limits to be set on the emission source.
Fugitive Emissions and Other Sources

Fugitive emissions are those which escape from a process rather than being
discharged. These often have serious consequences because their levels are not
monitored and they are untreated when entering the atmosphere. There are many
sources of fugitive emissions including:
• industrial sources (particulate fluorides from aluminium smelters)
• small business (e.g. dry cleaning)
• agriculture (e.g. dust from ploughing)
• natural sources (e.g. volcanoes, forest fires)
Often fugitive emissions are the result of poor maintenance of plant and equipment
and can be eliminated by standard operating procedures that involve timed
maintenance and quality control checks, but some are almost impossible to control
(such as those from natural sources). An example of the former is the particulate and
gaseous fluoride emissions from aluminium smelting. These are emitted
unintentionally when the casting areas of aluminium potlines are opened or
page 19
incorrectly sealed. Standard operating procedures that ensure that the casts are sealed
greatly reduces the problem.
Types of Air Pollutants

Essentially there are four types of air pollutants;
• particulate pollutants and
• gaseous pollutants,
• odour and
• noise.
Only the first three of these are addressed in this module. Noise is such a large area
that it is addressed in its own module, but you should be aware that the great majority
of noise pollution occurs through the atmosphere.
Primary and Secondary Air Pollutants

Not all of the pollutants found in the atmosphere are the direct result of emissions.
Many of the substances found in the atmospheres that are regarded as pollutants arise
from chemical reactions in the atmosphere with other substances or light. Chemical
reactions that require light in order to proceed are referred to as photochemical
reactions.
Pollutant substances that are directly emitted into the atmosphere are known as
primary pollutants.
Those substances that are not directly emitted into the atmosphere, but rather are
formed by chemical reactions in the atmosphere are referred to as secondary
pollutants.
Particulate Pollutants
The term particulate refers to very small solid or liquid particles. Individual particles
may vary in size, geometry, chemical composition and physical properties. They may
be of natural origin (such as pollen or sea spray) or man made (dust, fume and soot).
They provide a reactive surface for gases and vapours in the formation of secondary
pollutants. Particles also diffuse light reducing visibility. Atmospheric particles come
from stack emissions, dusty processes, unsealed roads, construction work and many
other sources.
Particulate matter may be classified under the following headings:
Dusts - large solid particles (>100um) carried into the air.
Fume - solid particles (frequently metallic oxides) formed by condensation of vapours

from a chemical reaction process or physical separation process. These particles are
quite small, typically between 0.03 - 0.3um in diameter.
Mist - liquid particles formed by condensation of vapours or chemical reaction. For

example,
SO3 + H2O H2SO4.
page 20
Typically they are 0.5 - 3.0um in diameter.
1
Figure 2.6 – the size ranges of common atmospheric particles
Smoke - solid particles formed as a result of incomplete combustion of carbonaceous

materials. Typical diameter is between 0.5 - 1.0um.
Spray - a liquid particle formed by the atomisation of a parent liquid.
Particulate matter makes up the most visible form of air pollution. Pollutant particles
in the 0.001 to 10 um range are commonly suspended as aerosols near sources of
pollution in urban atmospheres such as industrial plants, highways and power plants.
Particle Size
Atmospheric particles range in size from 0.005 - 500µm. The smallest of these are
clusters of molecules whilst the largest are easily visible with the naked eye. Note that
sizes given are not the physical size, but rather the aerodynamic equivalent diameter –
which relates the particle to the behaviour of an equivalent spherical particle.
Particles less than 1µm in diameter behave much like gases (remain suspended, may
coalesce, move in fluid streams), whilst larger particles are more like solids (affected
by gravity, don’t stay suspended long, don’t coalesce). There is a marked variation of
particle composition with size. The smaller particles generally derive from chemical
reactions and are frequently acidic, whereas the larger particles (10µm or greater) are
page 21
usually generated mechanically by bulk materials and have a tendency to be basic. It

is the former which, irrespective of chemical composition, are the most dangerous to
health, since they are not readily filtered out in the nose and throat and penetrate into
the lungs.
In urban areas there is an approximately even distribution between fine and coarse
particles, but this is weather dependent. Under calm conditions there are more fine
particles than coarse, as the coarser particles tend to settle if there is no turbulence.
Fine particulate matter also tends to be transported and spread over much greater
distances as it has a much longer residence time in the atmosphere. An extensive
analysis of suspended particles collected from a range of urban areas in the United
States showed a total concentration of 105µg/m3, and included the following
components: sulfate (10.6), organic material (6.8), nitrate (2.6), iron (1.58), lead
(0.79), zinc (0.67), arsenic (0.02) and cadmium (0.002).
Particle Behaviour in the Atmosphere

Particles in the atmosphere undergo many changes, both physical and chemical. They
may grow in size, absorb or desorb gases from their surfaces, change their electrical
charge, collide or adhere with other particles, or absorb water. These may change the
particle size and affect its atmospheric lifetime.
One of the major factors in particulate behaviour is the uptake and release of water.
This process not only dramatically changes the specific gravity of the particle, but
also them to form sulfate and nitrate aerosols. This in turn may dramatically change
their pH, chemical reactivity, toxicity and even its surface charge. Particles with a size
of greater than 3µm are generally negatively charged, whilst those less than 0.01µm
are almost always positively charged. These electrical charges have a substantial
effect on the coagulation and rates of deposition of the particles.
Total Suspended Particulates (PM10, PM2.5)

The size distribution of particles suspended in the atmosphere shows that most
particles are concentrated into three main size groups. Larger particles are most often
around 10µm in size, whilst the smaller particles occur in size groups centered around
0.2 and 0.02µm. Only particles of <10µm can penetrate into the human lung, so it is
common practice to analyse air for only this fraction to estimate its potential danger to
human health. This is called PM10 sampling. Particles <2.5µm in size can penetrate
deep into the lung tissue and are especially dangerous. For this reason a new standard
has been developed which allows testing of this very fine particulate matter. It is
referred to as PM2.5 sampling. Both PM10 and PM2.5 are discussed in the following
chapter in more detail.
Organic Particulates
Source
Organic particulate matter occurs in a vast array of compounds. When collected, they
can be fractionated into various chemical groups. Of these, the polycyclic aromatic
hydrocarbons (PAH) have received most attention. They tend to be found adsorbed
on soot and dust particles, and are formed from smaller hydrocarbons at high
temperatures. Effluent from a coal furnace may contain over 1 mg/m3 of PAH
page 22
compounds, and cigarette smoke almost 0.1 mg/m3. As a result, urban atmospheres
have shown PAH levels approaching 20 ug/m3.
PAH compounds can be synthesised from saturated hydrocarbons as small as methane
and ethane. Mixtures of ethane and ethene heated at above 500oC have yielded over
ten PAH compounds. C-H and C-C bonds are broken in the small hydrocarbons,
forming radicals. These undergo dehydrogenation and combine to form stable
aromatic rings in a process called pyrosynthesis.
Lead
Source
Currently, lead is the most serious atmospheric heavy-metal pollutant. Its primary
source is exhaust from vehicles using leaded petrol. Lead in the form of the
organometallic tetraethyl lead Pb(C2H5)4 - was included in petrol to promote more
even combustion. However, in the process, it undergoes the following reaction:
Pb(C2H5)4 + O2 + halogenated organic compounds
CO2 + H2O + PbCl2 + PbBrCl + PbBr2
The lead halides produced are sufficiently volatile to exit through the exhaust system
and condense in the atmosphere to form particles. By 1975, annual lead emissions in
the Sydney region were estimated to have reached about 1100 tonnes. As a result,
Australian governments have enforced a gradual decrease in the levels of lead added
to petrol and increased the sale of unleaded petrol. A bonus from this is that the
absence of lead in petrol makes possible further improvements in the exhaust
emissions of CO and NOx by the use of catalytic converters, which are poisoned
rapidly by lead emissions.
The American experience has shown that reducing the lead levels in petrol has a rapid
and considerable effect on atmospheric lead, and also on its rain-induced deposition.
The rate at which lead levels have decreased indicates that, unlike other pollutants
such as chlorofluorocarbons, lead has a very short atmospheric lifetime.
Australia-wide legislation has meant that all cars built after 1985 must operate on
lead-free petrol. Before the introduction of lead reduction program in New South
Wales, atmospheric lead levels in Sydney, Newcastle and Wollongong were in excess
of the recommended maximum (1.5 µg/m3 - 90-day average) at all times! In the last
three months of 1987, lead levels in the central business district exceeded the standard
on one day, but were below it on the 90-day average. However, in Port Kembla,
numerous high daily readings (peaking at 9.4 µg/m3) produced a 90-day average of
2.0 µg/m3, well in excess of the standard. This was due not to vehicle exhausts, but
base metal smelting operations. It is estimated that after the year 2000, vehicle
emissions will play a negligible role in atmospheric lead.
page 23
Gaseous Pollutants
These include substances that are gases at normal temperature and pressure as well as
vapours of substances that are liquid or solid at normal temperature and pressure. The
gaseous pollutants of greatest importance include carbon monoxide, hydrocarbons,
hydrogen sulfide, nitrogen oxides, ozone and other oxidants, and sulfur oxides.
Carbon dioxide could be added to this list as it has potential to dramatically alter our
climate. Pollutant concentrations are measured in micrograms per cubic meter (ug/m3)
or parts per million (ppm).
1 ppm = 1 volume of gaseous pollutant

106 volumes of (pollutant + air)
At 25°C and 101.3 kPa the relationship between ppm and ug/m3 is;
ug/m3 = ppm x molecular weight x 103

24.5
Carbon Oxides (CO and CO2)

Significant quantities of the carbon oxides, carbon monoxide (CO), and carbon
dioxide (CO2), are produced by natural and anthropogenic sources. Because of its
health implications, CO is considered to be a major atmospheric pollutant. Carbon
dioxide is relatively non-toxic, but it’s significant potential for causing global climatic
change makes direct and indirect emissions to the atmosphere a serious pollution
problem.
Carbon Monoxide
Carbon monoxide is a colourless, odourless and tasteless gas. The Earth's atmosphere
has an average burden of around 530 million tonnes (about 0.00001%), with an
average residence time of 36 to 100 days. Much of the CO in the atmosphere occurs
naturally as it is emitted from volcanic eruptions, photolysis of methane and terpenes,
decomposition of chlorophyll, forest fires and microbial action in oceans.
Anthropogenic sources include transportation, solid waste disposal, agricultural

burning, steel production, etc. It is also emitted directly into the atmosphere through
the inefficient combustion of fossil fuels. It is removed by reactions in the atmosphere
which change it to CO2 and by absorption by plants and soil micro-organisms. In
combustion, carbon is oxidised to CO2 in a two step process.
2C + O2 2CO
2CO + O2 2CO2
Annual global emissions are estimated to be 3 x 109 to 6.4 x 1011 tons per year for
natural and 2.75 x 108 tons per year for man made sources.
page 24
Carbon monoxide is emitted if insufficient oxygen is present for the second step to
proceed.
Typical Concentrations
Background levels of CO tend to vary greatly depending on location. Average global
levels are about 0.2ppm. Peak concentrations tend to occur during autumn months
when large volumes are generated by the decomposition of chlorophyll in leaves.
In urban areas a diurnal concentration pattern occurs (see figure 2.7). This is
associated with the daily transport cycles where most vehicles are used during the
morning and evening.
Figure 2.7 – CO levels in a typical urban area over a 24hr period1
Because the internal combustion engine contributes much of the man-generated CO

(the EPA estimates 90% in the Sydney region), maximum levels of this gas tend to
occur in congested urban areas at times when the maximum number of people are
exposed, such as during rush hours. At such times, CO levels in the atmosphere may
become as high as 50-100ppm. Since the introduction of the Clean Air Act in NSW
in 1972, and the control of vehicular emissions, the levels of CO in the central city
district have dropped from an average of 25ppm to around 10ppm. The accepted
standard is 9ppm over an eight-hour period. Sydney exceeds this on an average of 50
days per year.
Sinks
CO is removed from the air mostly by conversion to CO2. This may occur through
aerial oxidation or through the action of soil microorganisms. It is estimated that soil
microorganisms remove more than 5 x 108 tonnes per year in the USA alone. This is
page 25
greatly in excess of the man made emission rate. Hence we should not see great
increases in the ambient levels of CO. The reason for very high concentrations
occurring in urban areas is that high emission rates are combined with a lack of soil.
Carbon Dioxide
Carbon dioxide is produced when organic matter is combusted, weathered, or
biologically decomposed. It is removed from the atmosphere by plants in
photosynthesis and released by biological reactions.
Over hundreds of millions of years CO2 has been withdrawn from the atmosphere and
stored in coal, oil and natural gas. The intensive use of these fuels in the past century,
however, has resulted in significant CO2 emissions and an increase of atmospheric
concentrations. Base values of CO2 have reportedly increased about 25% since 1850.
Since 1958, CO2 values measured at Mauna Loa Observatory in Hawaii have
increased from 310 to more than 350ppm.
Significant seasonal variations are also observed to occur in CO2 levels, which reach a
maximum in the northern hemispheric spring and a minimum in autumn. This
seasonal variability appears to be associated with growing season photosynthetic
needs and metabolic releases of CO2 in excess of plant uptake at the end of the
growing season.
Not all CO2 emitted to the atmosphere from anthropogenic sources contributes to
increased atmospheric levels. Because of its solubility in water, the oceans are a major
sink for CO2, absorbing 50% of all man made emissions. The world's forests,
particularly tropical forests, also serve as a sink.
As a thermal absorber (read greenhouse gas), CO2 prevents some infrared emissions
from the Earth being radiated back to space. It is though that in time this may greatly
change the planet’s global heat balance – leading to global warming – the so-called
Greenhouse Effect.
Sulfur Compounds
A variety of sulfur compounds are released to the atmosphere from both natural and
anthropogenic sources. The most important of these are the sulfur oxides (SOx) and
hydrogen sulfide (H2S). Although significant SOx emissions may occur from volcanic
eruptions and other natural sources, man made emissions are responsible for much of
the atmospheric emissions.
Sulfur Oxides
These are produced by roasting metal sulfide ores and by combustion of fossil fuels
containing appreciable inorganic sulfides and organic sulfur. Of the four known sulfur
oxides, only SO2 is found at appreciable levels in the atmosphere. Sulfur trioxide
(SO3) is emitted directly into the atmosphere in ore smelting and fossil fuel
combustion and is produced by the oxidation of SO2. Because it has a high affinity for
water, it is rapidly converted to sulfuric acid.
The formation of SO2, SO3, and sulfuric acid in the atmosphere is summarised in the
following equations.
page 26
S + O2 SO2
2 SO2 + O2 2SO3
SO3 + H2O H2SO4
Sulfur dioxide may be directly absorbed by water bodies such as the oceans to form
sulfurous acid. This is one of the sources of acid rain, which has dramatically
affected the environment in Europe and North America.
Sulfur Dioxide
SO2 is an acidic colourless gas which may remain in the atmosphere for periods up to
several weeks. It can be detected by taste and odour in the concentration range of 0.38
- 1.15ppm. Above 3 ppm, it has a pungent, irritating odour.
It is estimated that 65 million tonnes of SO2 per year enter the atmosphere as a result
of man's activities, primarily from the combustion of fossil fuels. Of these, coal is by
far the greatest contributor. In the United States, it is estimated that almost 60% of
SO2 emission are the result of coal-fired power stations.
Background levels of SO2 are very low, about 1ppb. In urban areas maximum hourly
concentrations vary from less than 0.1 to more than 0.5ppm. Maximum hourly
concentrations in the range of 1.5 to 2.3ppm have been reported near large metal
smelters. Since the implementation of significant SO2 control measures in the early
1970s, many urban areas in the United States report markedly reduced ambient SO2
levels (<0.10 ppm).
Sinks
SO2 is removed from the atmosphere by both dry and wet deposition processes. It is
believed that plants are responsible for most SO2 removal that occurs by dry
deposition. SO2 can also dissolve in water to form a dilute solution of sulfurous acid
(H2SO3). This water can be in clouds, in rain droplets, or at the surface.
A major sink process for SO2 is its gas-phase oxidation to H2SO4 and subsequent
aerosol formation by nucleation or condensation. Sulfuric acid will react with
ammonia (NH3) to form salts including ammonium hydrogen sulfate (NH4HSO4),
ammonium sulfate [(NH4)2SO4] or mixed salts with ammonium nitrate (NH4NO3).
About 30% of atmospheric SO2 is converted to sulfate aerosol. Sulfate aerosols are
removed from the atmosphere by dry and wet deposition processes. In dry deposition,
aerosol particles settle out or impact on surfaces. In wet deposition, sulfate aerosol is
removed from the atmosphere by forming rain droplets (in cloud) or being captured
by falling rain droplets (below cloud). These removal processes are called rainout and
washout.
page 27
Hydrogen Sulfide
H2S is a very toxic gas with a characteristic rotten egg odour. This odour can be
detected at concentrations as low as 0.5ppb. Although H2S is quite toxic, H2S levels in
the atmosphere appear to be too low to pose a threat to human health. The principal
concerns associated with H2S are its smell and its effects causing deterioration of
lead-based paints.
Background levels of H2S are approximately 0.05ppb. Natural sources, which include
anaerobic decomposition of organic matter, natural hot springs and volcanoes,
produce approximately 100 x 106 tonnes per year world wide.. Anthropogenic
sources, which include oil and gas extraction, petroleum refining, paper mills, rayon
manufacture, and coke ovens, account for global emissions of 3 x 106 tonnes per year.
Sinks
The major sink process for H2S is its atmospheric conversion to SO2. This SO2 is then
removed from the atmosphere in the gas phase or as an aerosol by wet or dry
deposition processes.
Nitrogen Compounds
There are five major gaseous forms of nitrogen in the atmosphere. These include
molecular nitrogen (N2), ammonia (NH3), nitrous oxide (N2O), nitric oxide (NO), and
nitrogen dioxide (NO2). N2 is the major gas in the atmosphere. N2O is present in
unpolluted air as a result of microbial action, whilst NO and NO2 are significant air
pollutants. NH3 is not considered a significant man made pollutant, but enormous
quantities are generated through natural emissions.
Nitrous Oxide
Nitrous oxide is a colourless, slightly sweet, nontoxic gas. It is a natural constituent of
the atmosphere at an average concentration of 0.30ppm. It is widely used as an
anaesthetic in medicine and dentistry. It is called laughing gas because it induces a
kind of hysteria. It is a product of natural processes in the soil, produced by anaerobic
bacteria. It can photolytically dissociate in the stratosphere to produce NO.
Nitric Oxide
Nitric oxide is a colourless, odourless, tasteless, relatively nontoxic gas. It is produced
naturally by anaerobic biological processes in soil and water, by combustion
processes and by photochemical destruction of nitrogen compounds in the
stratosphere. On a global basis, natural emissions of NO are estimated to be
approximately 5 x 108 tones per year.
Major anthropogenic sources include automobile exhaust and stationary sources, such
as fossil fuel-fired electric generating stations, industrial boilers, incinerators, and
home space heaters.
Nitric oxide is a product of high-temperature combustion.
N2 + O2 2NO
page 28
As this reaction is endothermic, the equilibrium moves to the right at high

temperatures. At lower temperatures, it shifts completely to the left. If the cooling rate
is rapid, the equilibrium is not maintained and high NO emissions result. High
combustion temperatures and rapid cooling promote high NO emissions.
In 1970 combined worldwide emissions of NO and NO2 were estimated to be about

5.3 x 107 tonnes per year - about 10% of that estimated to have been produced by
natural sources.
Nitrogen Dioxide
Nitrogen dioxide is a coloured gas, which is light yellowish orange at low
concentrations and brown high concentrations. It has a pungent, irritating odour , and
is extremely corrosive especially in wet environments. It is also toxic, as it can cause
anoxia.
Some of the nitrogen dioxide in the air is produced by the direct oxidation of NO.
2NO + O2 2NO2
At low atmospheric NO levels, this occurs slow, accounting for less than 25% of all
NO conversion. Photochemical reactions involving O3, peroxy radical (RO2) and
reactive hydrogen species such as OH•, HO2, H2O2, are the primary means by which
NO is converted to NO2 in the atmosphere. Some of the more important reactions are
shown below.
NO + O3 NO2 + O2
RO2 + NO NO2 + RO
HO2 + NO NO2 + OH
NOx Concentrations
Background concentrations of NO and NO2 are approximately 0.5 and 1ppb
respectively. In urban areas, 1 hour average concentrations of NO may reach 1-2ppm,
with maximum NO2 levels of approximately 0.5ppm. The decay rate of NO is rapid as
polluted air moves away from urban to rural areas, with concentrations dropping to
near background levels.
Atmospheric levels of NO are related to the transportation/work cycle. Peak

concentrations are observed in the early morning hours, with a second smaller peak
late in the day (See Figure 2.8). Peak morning NO concentrations are followed several
hours later by peak levels of NO2 produced by the chemical and photochemical
oxidation of NO.
page 29
Atmospheric levels of NO and NO2 also show seasonal trends. Emissions of NO are
greater during winter months when there is an increased use of heating fuels. Since
the conversion of NO to NO2 is related to solar intensity, higher NO2 levels occur on
warm sunny days.
Nitrogen oxides in motor vehicles exhausts have been controlled by legislation as

with CO. In this case, the catalytic converter included in the exhaust system
encourages the reduction of NOx to N2. These catalysts include rhodium and CuO.
Australian Design Rules limit the emission of NOx from vehicle exhausts to 1.9g/km,
and authorities expect that this will continue to maintain the levels in Sydney below
the recommended standard of 0.16ppm (over a 1 hour average).
Figure 2.8 – Levels of NO, NO2, and ozone on a typical smoggy day in a large city –
1
Taken from Los Angeles
Sinks
The most significant sink for NO is its conversion by both direct oxidation and
photochemical processes to NO2. A major sink process for NO2 is its conversion to
nitric acid as is shown below.
OH• + NO2 + M HNO3 + M
where M is an energy-absorbing species (generally O2 or N2). NO2 is also converted to

nitric acid by night-time chemical reactions involving O3.
NO2 + O3 NO3• + O2
page 30
NO2+ NO3• N2O5
N 2O5 + H 2O 2HNO3
NO3• is the nitrate free radical. It is the key factor in nighttime chemistry. The
reaction product of NO2 and NO3 is dinitrogen pentoxide (N2O5). This reacts with
water rapidly to produce HNO3.
A portion of the HNO3 in the atmosphere will react with ammonia (NH3) or other
alkaline species to form salts such as NH4NO3.
Nitrate aerosol is generally removed by the dry and wet deposition processes in much
the same way as sulfate aerosol.
Ammonia
This is considered a relatively unimportant man made pollutant. Approximately 4 x
106 tons are emitted per year on a worldwide basis. This may be compared to natural
emissions, with a worldwide annual emission rate estimated to be 1.2 x 109 tonnes per
year. Most of this is comes from biological decomposition. Background
concentrations vary from 1 to 20ppb. The average atmospheric residence time is
approximately 7 days.
Ammonia has a significant effect on atmospheric sink processes of strong acids.

Reactions with sulfuric and nitric acid in the atmosphere produce ammonium salts.
Ammonium sulfate is the principal sulfate species collected on particulate sampling
devices. Ammonia itself may also be oxidised in the atmosphere in a series of
chemical reactions to produce nitrates.
Organic Nitrates
These are produced in the atmosphere by the reaction of nitrogen oxides and
hydrocarbons. Examples are the peroxyacyl nitrates (PAN’s) and peroxybutylnitrates
(PBN’s). These are discussed in more detail in the section on photochemical smog.
Hydrocarbons
These are just simple organic materials in the atmosphere. The definition is used more
broadly here than in organic chemistry where it refers simply to substances made from
carbon and hydrogen. In the atmosphere simple hydrocarbons react with substances
containing oxygen, nitrogen, sulfur, chlorine bromine and even some metals to form
hydrocarbon derivatives.
Atmospheric hydrocarbons exist in gas, liquid and solid phases. Of these the gases
and volatile liquids are the most significant pollutants. Solid hydrocarbons are
generally of higher molecular weight and exist as condensed particles in atmospheric
aerosols.
page 31
Methane (CH4) is the most common hydrocarbon in the atmosphere and it is formed
from many natural sources such as termites, cows and general decomposition of
organic matter. It and the other alkanes found in the atmosphere are fairly unreactive.
The atmospheric hydrocarbons that are the most significant in terms of chemical
reactivity are the alkenes. Many highly reactive alkene hydrocarbons are formed
naturally by plants (such as terpenes from citrus plants and eucalyptus haze). The
greatest source of these non-methane hydrocarbons are motor vehicles. Significant
quantities are also emitted from petroleum processing. Alkenes are the major air
pollutant responsible for photochemical smog and other gross oxidants in the
atmosphere. Once in the atmosphere they combine with O2 to form many different
oxygenated hydrocarbons including alkanones, alkanals, alkanoic acids, alkanols and
ethers. Some dicarboxylic acids are also formed by photochemical reactions, and are
present in the atmosphere as aerosols. An example of this is propanedioic acid (old
name malonic acid).
Some oxygenated hydrocarbons are emitted into the atmosphere directly. For example
methanal (old name formaldehyde), acrolein and some other simple alkanals are
major by-products of combustion processes and are present in significant amounts in
motor vehicle exhausts – especially those running on diesel fuel.
Aromatic hydrocarbons are not very reactive, but are important in urban atmospheric
chemistry as they undergo reactions with other very reactive chemical oxidants to
form toxic substances. Some toxic atmospheric aromatic hydrocarbons are produced
directly by combustion such as benzo[α}pyrene and other polyaromatic hydrocarbons
(PAH’s).
Benzo [α
α] pyrene
Source
Hydrocarbons are emitted from a variety of natural and man made sources. They are
important pollutants because of their role in atmospheric photochemistry. Both
biological and geological processes release hydrocarbon compounds naturally.
Sources include plant and animal metabolism, vaporisation of volatile oils from plant
surfaces, biological decomposition, and emission of volatiles from fossil fuel deposits.
U.S. emissions of natural hydrocarbons including methane are estimated to be more
than 7 x 107 tons/year, with some estimates of biogenic non-methane hydrocarbons
(especially natural alkenes such as isoprene and pinene) ranging from 3.3 to 6.6 x 107
tons/year. Man made emissions of hydrocarbons in the United States have been
estimated to be about 3 x 10' tons/year, with worldwide emissions estimated at 9 x 107
tons/year. Hence it can be seen that one country provides 33% of the worlds man
made hydrocarbon emissions.
page 32
Globally, anthropogenic emissions represent only about 5% of total hydrocarbons

emissions. In the United States, man made emissions may contribute 23-40% of the
total atmospheric load. The impact of man made emissions is particularly significant
in urban areas.
Hydrocarbons are released to the atmosphere from a variety of human activities.

Sources include transportation, petroleum refining, oil and gas production and
distribution, chemical manufacturing, industrial and commercial organic solvent use,
and food processing.
Significant portions of hydrocarbons released to the atmosphere are from mobile

sources, with light-duty motor vehicles accounting for approximately 75%.
Hydrocarbon emissions from motor vehicles result from both evaporative losses and
incomplete combustion. Controls on individual vehicles have reduced hydrocarbon
emissions in exhaust gases by about 85% since their introduction in Australia in 1985.
In the past most efforts to control hydrocarbons have focused on motor vehicles.
Stationary facilities have received less attention from regulatory authorities, although
their importance is now being recognised.
Identification of hydrocarbons species in urban atmospheres involves the use of

GC/MS techniques. Studies of atmospheric samples and emission sources, identify
hundreds of hydrocarbons and their derivatives as being present in polluted urban air.
Identification of hydrocarbons in urban atmospheres is complicated, as many

individual compounds are present in only sub-trace amounts. As a result, the likely
presence of many compounds is inferred from smog chamber studies and from
analyses of motor vehicle exhaust. Over 400 hydrocarbons and oxy-hydrocarbon
derivatives have been found in vehicle exhaust gases. Many oxygenated hydrocarbons
are found with methanal being the most significant.
Polluted ambient atmospheres contain a variety of alkane (e.g. propane, butane),

alkene (e.g. ethene, propene), polyunsaturated (e.g. ethyne, propadiene), aromatic
(e.g. benzene), and polycyclic aromatic hydrocarbons (e.g., benzo-α-pyrene).
Hydrocarbon Concentrations
Individual hydrocarbon concentrations are not routinely monitored by control
agencies. Quantitative data is based on the measurement of total non-methane
hydrocarbons. This is usually averaged over the 6-9 a.m. period. The problem with
this is that the 6-9 a.m. measurement period reflects motor vehicle emissions and
gives little indications of other sources.
Total non-methane hydrocarbon measurements show a diurnal pattern in most cities

with two peaks, one from 6-9 a.m. and another broader peak in the late afternoon.
These peaks reflect motor vehicle traffic and local meteorological dispersion
characteristics.
Total non-methane hydrocarbon concentrations in urban areas range from 1 - 10ppm.
page 33
Sinks
There is a very large number of hydrocarbons, oxy-hydrocarbons, and other
derivatives in polluted atmospheres. Information on sink mechanisms for specific
compounds is relatively limited. The most important sink processes are photochemical
conversion of hydrocarbons to CO2 and H2O or to soluble or condensable products
such as dicarboxylic acids - a major component of photochemical aerosol. These
aerosols are removed from the atmosphere by both dry and wet deposition processes.
Methane
When air pollution regulatory control first commenced, CH4 was considered to be an
unimportant hydrocarbon in polluted atmospheres. Measurements of total
hydrocarbons subtracted the concentration of CH4. Hence the ambient air quality
standard for hydrocarbons is a non-methane hydrocarbons standard.
Relative to alkenes, aromatics, and even other alkanes, CH4 is relatively unreactive
and therefore of little significance in urban photochemical reactions that produce
elevated O3 levels. The significance of CH4 is that relatively unreactive hydrocarbons
play an important role in O3 formation as polluted air masses travel long distances
downwind of urban sources. Methane has also been recognised as one of the trace
gases that may have a significant effect on global climate through the greenhouse
effect.
Methane is by far the most abundant hydrocarbon in the atmosphere, with a 1980
concentration of 1.65ppm. It has been increasing at a rate of 1.2-1.9% per year. The
rate itself is also increasing. Increases of CH4 over the last 300 years, as determined
from measurements of air bubbles trapped in Antarctic ice, can be seen in Figure 2.9.
Note the significant inflection of the curve in this century.
The increase of CH4 is due to both increased emissions and to CO-caused depletion of
OH•, which is the most important sink for CH4 in the atmosphere
Figure 2.9 – Historical global levels of methane in the atmosphere1
page 34
Ozone and Photochemical Smog

Sources
Ozone is a normal component of the Earth’s atmosphere, but most of it is found in the
middle stratosphere where it plays an important role in the controlling the amount of
UV light reaching the planet’s surface (see the Ozone Hole). This is one case where
depletion of the substance results in air pollution – as the loss of ozone is causing
deterioration in quality of life.
Ozone is not listed as a major primary air pollutant in the lower atmosphere either, but
due to its high toxicity and its involvement in the production of other pollutants it is a
very important source of atmospheric pollution. Over 90% of what is broadly referred
to as photochemical smog is ozone. Sources are electrical discharge both natural (such
as lightning) and man made (such as electric trains), and upper atmospheric chemical
reactions such as the reaction of molecular oxygen with oxygen atoms.
O2 + O + M O3 + M
In this reaction M is any third substance (usually O2 or N2) that removes the energy of
the reaction and stabilises O. In the lower atmosphere (troposphere) the only
significant source of atomic oxygen is the photolysis of NO2.
NO2 + hν NO + O*
The reaction of O* with O2 produces O3, which reacts immediately with NO to

regenerate NO2.
NO + O3 NO2 + O2
All these reactions proceed rapidly with approximate concentration of 20ppb under
solar noon conditions in mid latitudes at atmospheric NO2/NO concentration ratios
equal to 1. Hence concentrations of ozone remain low unless imbalances in the levels
of NO2 or other alternate chemical reactants are available.
Photochemical Smog
Source
This term refers to an atmosphere laden with secondary pollutants that form in the
presence of sunlight as a result of chemical reactions in the atmosphere.
Photochemical smog arises in urban areas, where there is a heavy build-up of vehicle
exhausts. It is greatly exacerbated by weather conditions.
Under normal conditions, the primary air pollutants are dispersed over a large region
or to the upper atmosphere. A good prevailing wind is important for cities and large
urban areas to help reduce smog. At certain times of the year, when the wind is very
still, the primary pollutants build up over cities. Autumn tends to be worse for
photochemical smog than other times of the year.
page 35
Figure 2.10 – Normal dispersion pattern of pollutants from a large urban area2
In autumn, the days are sunny and warm, with cool nights. Under still conditions, a
warm inversion layer forms under a layer of higher cooler air. Large urban areas store
heat, which provides the warmth for the inversion layer. The inversion layer limits air
mixing and dispersal trapping primary pollutants at lower altitudes over urban areas.
Figure 2.11 – Conditions which favour smog formation in a large urban area2
When primary pollutants such as NOx, and hydrocarbons are trapped in the lower
atmosphere and subjected to UV radiation from the sun – photochemical smog forms.
These ingredients produce the pollutants that characterise photochemical smog.
These products are termed gross photochemical oxidants, and are defined by their
ability to oxidise iodide ion to elemental iodine. They include ozone (O3), hydrogen
peroxide (H2O2), organic peroxides (ROOR'), organic hydroperoxides (ROOH)
and by far the most serious to health, peroxyacyl nitrates (RCO3NO2), known as
PAN's. The latter are formed by the irradiation of mixtures of alkanals, ozone and
nitrogen dioxide.
Reactions Occurring in the Formation of Photochemical Smog

The key chemical reactants in the formation of photochemical smog are NO2 and
hydrocarbons. The reactions undergone by these substances in the atmosphere are
many and varied. Many of the reaction mechanisms are not well understood. This
lack of knowledge has caused several control schemes to fail, but several reactions
have major roles in elevating the levels of O3.
page 36
In the lower atmosphere O3 concentrations are often much higher than those that
occur from NO2 photolysis alone. This is because there are chemical reactions that
convert NO to NO2 without consuming O3. In polluted and even weakly polluted
atmospheres, these changes in O3 chemistry can be attributed to peroxy radicals (RO2)
and other species produced by the oxidation of hydrocarbons as shown in the
reactions below. M is any species that will stabilise the molecule (generally N2).
RO2 + NO NO2 + RO
NO2 + hν NO + O*
O* + O2 + M O3 + M
Net: RO2 + O2 + hν RO + O3
This process is presented diagrammatically in Figure 2.12.
Figure 2.12 – Important reactions in the formation of photochemical smog1
page 37
The rate of O3 formation is closely related to the concentration of RO2. Peroxy

radicals are produced when hydroxy radicals OH• and HOx react with hydrocarbons.
Hydroxy radicals are produced by reactions involving the photolysis of O3, carbonyl
compounds (mostly alkanals), and nitrous acid.
In polluted atmospheres, O3 concentrations are directly related to the intensity of

sunlight, NO2/NO ratios, the hydrocarbon type and concentrations, and other
pollutants, such as alkanals and CO, which react photochemically to produce RO2.
The increase in NO2/NO ratios caused by atmospheric reactions involving RO2 results
in significant increases in lower atmosphere O3 levels.
A quick summary of the reactions involved in smog formation can be compressed

into four stages. This also explains the time variations in levels of hydrocarbons,
ozone, NO2 and NO (see Figure 2.13).
1. Primary photochemical reaction producing oxygen atoms:
NO2 + hν NO + O*
2. Reactions involving oxygen species (M is an energy-absorbing third body):
O* + O2 + M O3 + M
NO + O3 NO2 + O2
Because the latter reaction is rapid, the concentration of O3 remains low until that of
NO falls to a low value. Automotive emissions of NO tend to keep O3 concentrations
low along freeways.
3.Production of organic free radicals from hydrocarbons, RH:
O + RH R• + other products
O3 + RH R• + and/or other products

(R• is a free radical that may or may not contain oxygen.)
4. Chain propagation, branching, and termination by a variety of reactions

such as the following:
NO + ROO• NO2 + and/or other products
NO2 + R• products (e.g. PAN)
page 38
Some of the many other reactions which are known to occur in photochemical smog
formation are listed below.
•
O + hydrocarbons HO
• •
HO + O2 HO3
•
HO3 + H alkanals, alkanones
• •
HO3 + NO HO2 + NO2
• •
HO3 + O2 O3 + HO2
•
HOx + NO2 PAN's
While all hydrocarbons can become involved in the formation of smog, there are
considerable differences in their reactivities. The simplest, methane, is very slow to
react, having an approximate atmospheric lifetime of more than 10 days. In general,
branched alkenes and alkyl aromatic compounds are the most reactive. It is
interesting to note that experiments to date have shown certain naturally-occurring
alkenes (such as d-limonene from citrus fruits) are the most reactive compounds.
Given the complex series of reactions involved and the changing levels of vehicle
emissions during a day, it is perhaps not surprising that the concentrations of the
major components vary considerably over a 24-hour period. A typical pattern of
variations is shown in the figure 2.13.
3
Figure 2.13 – Variations in smog pollutants with time of day
alkanals
page 39
As the morning rush hour begins, NO begins to rise rapidly, followed by NO2. As the
latter reacts with sunlight, ozone and other oxidants are produced. The hydrocarbon
level increases in the morning, and then decreases as the compounds are oxidised to
form PAN's and other species.
As an air mass moves toward an urban center, it picks up NO, and hydrocarbons.
Within a time scale of an hour, OH• begins to degrade hydrocarbons, producing RO2.
As the air mass moves over the urban center, O3 precursors peak and then decline
with increasing downwind distance. Ozone concentrations increase and are sustained
over a period of 1-5 hours as the more reactive alkene and aromatic hydrocarbons are
depleted by photochemical reactions.
After a 5-10 hours travel time downwind, moderately reactive hydrocarbons

increasingly play a more important role in net O3 production. Ozone levels in the air
mass subsequently decrease due to dilution, conversion of NO2 to HNO3, and surface
adsorption. Under nighttime conditions, O3 production ceases.
Protected by the inversion layer, O3 may persist aloft with a half-life of as much as 80
hours. This allows O3 to be transported over long distances giving rise to higher
concentrations at remote sites, which occur away from the normal noon maximum.
At sunrise, the inversion breaks up, bringing O3 and other products isolated aloft
during the nighttime hours to the ground, where they mix with the pollutants held in
by the inversion layer, and begin the cycle all over again.
Ozone Concentrations
In unpolluted atmospheres O3 concentrations near the ground are in the range of 10-
20ppb (0.01-0.02ppm) during the warm months of the year. O3 concentrations over
landmasses with large motor vehicle numbers are often elevated well above this even
at remote sites.
In urban areas, peak 1-hour summertime O3 concentrations are usually higher than
those reported for remote non-urban sites. Concentrations near or above the 0.3
standard of 0.12ppm have been reported for numerous cities throughout the United
States during the 1980’s, despite two decades of efforts to control O3 precursors.
It is in the precursor- and sunlight-rich Los Angeles basin that O3 concentrations reach
their highest levels. One-hour concentrations in the range of 0.20-0.40ppm are not
uncommon during the summer months. The warm, sunny summer weather of the
central coast of New South Wales has meant that the Sydney Basin has been subject
to severe photochemical smog production, particularly before the advent of motor
vehicle emission controls. The National Health and Medical Research Council
(NHMRC) has set an ozone standard of 0.12ppm (1-hour average), which should not
be exceeded on more than one day per year. In the mid- 1970's, the atmosphere in
Sydney reached levels of ozone above this standard on an average of more than 20
days per year, reaching maximum levels of 0.3ppm. Increased legislative controls on
the exhaust of NOx and H have resulted in a decrease of 80% in the levels of
hydrocarbons, and 45% in emissions of nitrogen oxides. As a consequence, days
where ozone levels are in excess of the NHMRC standard decreased to about four
within ten years, and are expected to continue falling.
page 40
Ozone Sinks
Ozone can be removed from the atmosphere in a number of ways. These include
reactions with surfaces including plants, soil, and a variety of man made materials
such as rubber. Most O3 produced in the atmosphere is removed by chemical
processes, typically involving NOx. One of the principal scavengers of O3 is NO.
Nighttime reactions with NO2 destroy O3.
Chlorofluorocarbons (CFC’s)
Source
This refers to halogenated hydrocarbon compounds which have been (and still are)
used as refrigerant gases and propellants in aerosol cans.
Many halogenated hydrocarbons released into the atmosphere as a result of human

activities. These include volatile or semi-volatile man made substances that contain
one or more halogens such as chlorine, fluorine, or bromine, in addition to hydrogen
and carbon. Halogenated hydrocarbons are unique because of their environmental
persistence. They include:
• the semi-volatile chlorinated hydrocarbons such as DDT, Chlordane, Dieldrin,
and Aldrin (widely used as pesticides)
• polychlorinated biphenyls (PCB’s) used as solvents and transformer insulators
• polybrominated biphenyls used as fire retardants
• dichloromethane, trichloroethene, perchloroethene, tetrachloroethene, and
tetrachloromethane used as solvents, and
• chlorofluorocarbons (CFC’s) used as refrigerants, degreasing agents, foaming
agents, and aerosol propellants.
Chlorofluorocarbons pose a serious atmospheric threat because of their great stability

that leads to damage the O3 layer, and their ability to absorb infrared energy and
behave as greenhouse gases. Chlorofluorocarbons represent a variety of chemical
species. The three most commonly used (making them the most common atmospheric
contaminants) are trichlorofluoromethane (CFC13), dichlorodifluoromethane
(CF2C12), and trichlorotrifluoroethane (C2C13F3). These are generally described as
CFC-11, CFC-12, and CFC-113.
Because there is no sink in the lower atmosphere, CFC concentrations in the

atmosphere increase with time. For CFC-11 and CFC-12, atmospheric lifetimes are 75
and 111 years, respectively.
Fluoride
Source
Aluminium smelters are a major source of both gaseous and particulate fluorides, as
are brick and glass works, some smelters, steel plants and coal fired power stations.
Fluoride is very much a localised problem, of little significance outside the Hunter
region in Australia.
page 41
Minor Gaseous Pollutants

These include hydrogen sulfide, odours and noise. They emanate from many different
sources. A major source of H2S is swamps. It is extremely dangerous if inhaled in
large quantities, but this is unlikely unless you live in a swamp or sewage treatment
works.
Odour Pollution
Though unpleasant odours may cause symptoms in some individuals, the problem of
odour or odour air pollution is usually viewed as being one of annoyance. Odour,
from a regulatory point of view, is seen as a welfare not a health issue.
Scientists define odour as when a substance is detected by the human olfactory

system. The olfactory function in humans consists of two different organs in the nose.
The olfactory epithelium (found in the highest part of the nose) consists of millions of
yellow-pigmented bipolar receptor cells that connect directly to the olfactory bulbs of
the brain. The free endings of trigeminal nerves distributed throughout the nasal
cavity serve as another olfactory organ. Trigeminal nerves respond to odouriferous
substances that cause irritation, tickling, or burning. The chemical senses that
correspond to these two olfactory organs are not easily separated, with many
odouriferous substances or odourants stimulating both systems. They stimulate
different parts of the brain and, therefore, may have different effects. The major
function of the trigeminal nerve system is to stimulate reflex actions such as sneezing
or the interruption of breathing when the body is being exposed to potentially harmful
odour-producing substances1.
Odour Measurement
The perception of odour is a physio-psychological response to the inhalation of an
odouriferous chemical substance. Odours cannot, therefore, be measured by chemical
means. However, some of the sensory attributes of odours can be measured by
exposing individuals under controlled conditions. Elements of odour subject to
measurement are:
• detectability
• intensity
• character (quality), and
• hedonic tone (pleasantness, unpleasantness)1.
The limit of detection is called the odour threshold. It may be characterized in one of
two ways. The threshold may be that concentration of an odouriferous substance
where there is a detectable difference from the background. Alternatively, the
threshold may be defined as the first concentration at which an observer can positively
identify the quality of the odour. The former would be best described as a detection
threshold, the latter as a recognition threshold.
Though the olfactory sense in humans is not as acute as it is in many animals, it still
has the ability to detect many substances at very low concentrations. Odour thresholds
for a variety of chemicals are given in Table 2.2. Note that humans can detect H2S at
approximately 0.5ppb.
page 42
Odours differ in their character or quality. This odour parameter allows us to

distinguish odours of different substances by prior odour associations. The characters
of a variety of selected chemicals are summarised in Table 2.2. For example,
dimethylamine is described as fishy, phenol as medicinal, 1,4-dihydroxybenzene
(paracresol) as tar-like.
Table 2.2 – Odour thresholds and characteristics of selected chemical compounds1
Chemical Odour Threshold (ppm) Odour Character
ethanal (acetalydehyde) 0.21 Green, sweet

propanone (acetone) 100.0 Chemical sweet, pungent
dimethylamine, 0.047 Fishy
ammonia 46.8 Pungent
benzene 4.68 Solvent
butanoic acid 0.001 Sour
dimethylsuffide 0.001 Vegetable sulfide
ethanol 10.0 Sweet
ethyl mercaptan 0.001 Earthy, sulfide
formaldehyde 1.0 Hay, straw-like, pungent
hydrogen sulfide 0.00047 Egg like sulfide
methanol 100.0 Sweet
2-butanone (methylethylketone 10.0 Sweet
or MEK)
1,4-dihydroxybenzene 0.001 Tar-like, pungent
(paracresol)
perchloroethene 4.68 Chlorinated solvent
phenol 0.047 Medicinal
sulfur dioxide 0.47 Pungent Sulfur
toluene 2.14 Moth balls, rubbery
Related to the character/quality aspects of an odour is hedonic tone or the degree of

pleasantness or unpleasantness. The character of an odour may, in many cases, be the
primary determinant of whether it is pleasant or unpleasant. The olfactory sense is
highly subjective, with some odours being pleasant to some and unpleasant to others.
The difficulty of defining some odour problems lies in part with the lack of
objectivity.
The olfactory response to an odourant decreases as the odourant concentration

decreases. This decrease is nonlinear. For a substance such as pentyl butanoate, the
perceived odour intensity decreases by 50% for a tenfold reduction in concentration.
This relationship is common for many other odourants.
The perceived intensity of an odour rapidly decreases after initial exposure. Generally
within a few minutes, the odour may not be perceived at all. This phenomenon is
called adaptation. Within minutes after the exposure ceases, sensitivity to the odour is
page 43
restored. A person may also become habituated to an unpleasant odour – this

generally occurs over a long time.
Unpleasant odours may affect our sense of wellbeing. Responses to a variety of

malodours can include nausea, vomiting, headaches, coughing, sneezing, induction of
shallow breathing, disturbed sleep, appetite disturbance, sensory irritation, annoyance,
and depression. Effects may be physiological, psychological, or both1.
Odour Problems
Bad odours emanating from a nearby source result in more complaints to regulatory
agencies than any other form of air pollution. Likely sources of bad odours are soap-
making facilities, petrochemical plants, refineries, pulp and paper mills, fish-
processing plants, diesel exhaust, sewage treatment plants, and agricultural operations
including feedlots, poultry houses, and abattoirs. Bad odours associated with such
sources include a variety of amines, sulfur gases (such as H2S, methyl and ethyl
mercaptan, and carbon disulfide), phenol, ammonia, alkanals, alkanoic acids, etc.
References
1
Godish, T., Air Quality, 2nd Ed., Lewis, Michigan, 1991.
2
ACTRAC, Environmental Control- Unit 2 Air Pollution, Cert. In Chem. Plant Skills Resource, 1998.
3
Manahan, S.E., Environmental Chemistry, 6th Ed., Lewis, Boca Raton, 1994.
page 44
Chapter
3
Health & Environmental Effects of Air
Pollution
There have been many reports of death, illness and environmental damage caused by
air pollution. This chapter describes the more important effects of major air pollutants
and explains how they interact with each other and the environment.
Effects of Air Pollution on Human Health

In general specific sections of the public are most affected by air pollution. Those
individuals already suffering from diseases of the cardiorespiratory system such as
asthmatics and smokers are far more likely to be affected than those individuals who
are healthy.
Figure 3.1 – The effect of smoking and pollution levels on the occurrence of
cardiorespiratory disease in humans1
Pollutants generally act on the surfaces of the respiratory system, causing chronic
respiratory and cardiovascular disease. They may also alter important body functions
such as oxygen exchange in the lungs, or oxygen transport in the blood. Irritant
pollutants may lead to irritation and long term damage to eyes, nose, throat and other
wet surfaces of the body. Deposition of particulate matter in the alveoli of the lung is
quite serious as removal can be slow. Soluble particles will be transferred to the
blood. One of the most important particles man encounters in the atmosphere is
H2SO4, which irritates the mucous membranes and leads to bronchial constriction.
Air Quality & Pollution Control Health & Environmental Effects of Air Pollution
Most of the gaseous effects are more acute than chronic (as opposed to the particulate
pollutants). SO2, O3 and NO2 are all pulmonary irritants, and may lead to congestion,
oedema and even haemorrhage. NO, H2S and CO are asphyxiant gases. These
combine with haemoglobin molecules to prevent oxygen transfer around the body.
These molecules bind far more successfully to haemoglobin than does O2. Many of
the organic gas pollutants such as acrolein (1-propenal) as well as those gaseous
pollutants mentioned above produce eye irritation.
Other chronic diseases related to air pollution include lung cancer, emphysema,
chronic bronchitis and asthma. In addition air pollution can have serious effects on
acute diseases such as the common cold
In the following sections each major pollutant’s specific effects on human health and
is examined. Synergistic effects are also considered.
Interactions Between Pollutants and Synergism

Ambient air is a complex mixture of gases and particulate matter. In such a mixture it
is likely that there will be interaction between the components to modify the
physiological effects of others. This may occur in several ways. For example, one
pollutant may affect the site of deposition of another as is the case with sulfur dioxide.
Due to its great solubility in water, sulfur dioxide is normally be removed in the upper
respiratory system – where it has a corrosive effect. When sulfur dioxide is
adsorbed/absorbed onto particles, it can however, be transported deep into the
pulmonary system, where irritation and corrosion may occur. Thus, the particles may
amplify the effect of sulfur dioxide. Also, harmful aerosols such as sulfuric acid can
be produced by the interaction of gaseous pollutants in the warm moist environment
of the lung.
Interaction between pollutants may result in effects that may be additive, synergistic,
or antagonistic. Additive effects are those which occur when the exposure to several
pollutants produces an effect equal to the sum of the effects of the pollutants acting
alone. Synergistic effects are those where the sum of the effects of two or more
pollutants is greater than the combined effect. Antagonistic effects refer to the
situation where one pollutant lessens the effect of another pollutant. The great
majority of pollutant effects are additive.
Susceptible parts of the Human Body - The Respiratory System

All forms of air pollution (gases, liquids and particulates) can damage human health.
There are three main routes by which they enter the body:
• absorption through the skin
• ingestion, and
• inhalation.
Of these the latter is by far the most important as we exchange large amounts of
atmospheric gas every day through our lungs. All forms of air pollutants can enter the
lungs, but at this point it is probably appropriate to describe the structure of the human
respiratory system, which allows us to exchange air with the atmosphere.
page 46
Figure 3.2 shows the details of the respiratory system. During breathing air is passed
through the nose, then down the nasopharynx (a space at the back of the nose) and
into the Trachea (windpipe). From here it is passed into the lungs which consist of a
series of pipes ( the bronchi and bronchioles) which become thinner and thinner until
they reach the small air sacs where gas exchange takes place. These are the alveoli,
which appear like a bunch of microscopic grapes. They have a very fine membrane
that separates the blood from the air, which is where gas exchange (O2 uptake and
expulsion of CO2) occurs.
All of the air passages have a coating of mucus and are also lined with tiny branch
like structures called cilia, which constantly move in an upward fashion to remove
any solid material that enters the lungs.
1
Figure 3.2 – Details of the human respiratory system
Figure 3.2 – Details of the human respiratory system
page 47
Injury to the respiratory tract occurs when chemicals enter the lungs and cause direct
damage to the lung tissue, or when the lungs trap material and allow it to be
transferred to the bloodstream where it may affect any organ in the body.
Carbon Monoxide
High levels of carbon monoxide are a major concern, since the gas preferentially and
irreversibly binds to haemoglobin in the blood forming carboxyhaemoglobin. The net
effect is thus a reduction in the blood's capacity to carry oxygen. Carbon monoxide
has a higher affinity (200 times greater) for haemoglobin than O2, and also tends to
remain more tightly bound.
The first discernible effect of CO at around 10ppm is a reduction in awareness, a

probable cause of many car accidents. At around 100ppm, headaches and drowsiness
set in. Loss of consciousness and death require levels of 250ppm and over. There is
now also some medical evidence to suggest that continued exposure to low levels of
CO may cause nervous disorders and be a factor in the cause of heart disease.
Carbon monoxide is highly toxic at concentrations in excess of 1000ppm. Death

results from anoxia since body tissues, especially the brain, are deprived of an
adequate O2 supply. Because it is colourless, odourless and tasteless, individuals
exposed to toxic concentrations are unaware of its presence. Since elevated CO levels
are produced in a variety of circumstances or activities, CO deaths are not uncommon.
The concentrations of CO normally encountered in urban environments are usually

only a fraction of those levels that cause asphyxiation.
When a human or animal is exposed to CO, the amount of carboxyhaemoglobin

produced in the blood is directly related to the CO dose. For example, exposure to
35ppm CO for 1 hr, or 9ppm for 8 hr, will result in 1.3% carboxyhaemoglobin
saturation. These exposure levels represent the air quality standards for CO. No
adverse biological effects have been shown for such exposure levels, and as a
consequence they are assumed to be safe.
The effects of CO exposures can be related to carboxyhaemoglobin levels. Table 3.1

shows the response to different levels of CO. Most low level effects are central
nervous system (CNS) related, such as behavioural changes, decreased time interval
discrimination, impairment of brightness discrimination, increased reaction time to
visual stimuli, and lowered performance in driving simulations. It is thought that the
latter may be the cause of many motor vehicle accidents in peak hour traffic of cities
where peak hour CO levels may rise above 50ppm.
page 48
Table 3.1 – The effects of CO on human health
Concentration of CO (ppm) Physiological Effect
10 Lowered awareness and driving

performance
50 - 100 Headaches and drowsiness, changes in

driving performance and increased
reaction time to visual stimulation
>250 Death
In addition to CNS effects, CO exposures have the potential for contributing to or

exacerbating cardiovascular disease. Animal studies indicate that CO exposures may
be related to arteriosclerotic heart disease (AHD), or hardening of the arteries.
Arteriosclerotic heart disease accounts for about 35% of all deaths and is a major
cause of morbidity (illness) as well. It is characterised by a severe diffuse narrowing
of the coronary arteries.
Ambient exposures to CO may be a direct cause of increased blood
carboxyhaemoglobin levels. It may also elevate levels that are already high from other
exposures (e.g. cigarette smoking, cooking and heating, seepage into motor vehicle
interiors during normal driving, etc.). The health effects of ambient CO cannot be
dissociated from the effects of other CO exposures. For cigarette smokers, CO
exposures are far more significant (an average 3 – 8% carboxyhaemoglobin
saturation) than those experienced under urban ambient conditions. Additive effects of
ambient CO could further exacerbate this considerable health burden.
Reduction in the levels of CO in car emissions have been associated with changes in
the design of the exhaust system, whereby oxidation catalysts, such as Pd and Ru,
promote further reaction with excess air to carbon dioxide. Uncontrolled emissions
average 3.5% CO: current design rules limit emission to 1.0%. Under specified
testing procedures, this is equivalent to 24.2 g/km.
Sulfur Compounds
Sulfur compounds include the very corrosive sulfur dioxide and sulfur trioxide, and
hydrogen sulfide.
Sulfur dioxide and sulfur trioxide produce very similar effects as both are very
corrosive, whilst hydrogen sulfide produces similar effects to CO in that it can lead to
anoxia when present in high concentrations – a situation which is very rare in ambient
air.
Sulfur Dioxide and Particulates

Analysis of the effects of sulfur dioxide are complicated by the fact that it is often
associated with particulate pollutants – so the direct effects of each individual
pollutant are difficult to separate. They are often produced by a common source, such
page 49
as the combustion of coal, hence high SO2 levels are often associated with high
particulate matter levels often forming sulfate aerosols.
Sulfate aerosols present a more significant threat to health than do sulfur dioxide
emissions alone. These are produced when acidic particles are formed by the reaction
of water with ash and SO2, to give SO42- and H+. Particles from aerosols are just the
right size to be retained in the lungs so cause maximum physiological damage.
There is also some scientific evidence to suggest that particulate matter exacerbates
the toxic response to SO2. Studies of acute air pollution episodes in the United States
and Great Britain have indicated an association between increased mortality and
elevated levels of combined SO2 and particulate matter. Epidemiological studies of
longer-term, lower-level exposures have also shown an association with certain
adverse health effects, such as significantly higher mortality from bronchitis and lung
cancer.
Sulfur Dioxide
Sulfur dioxide in the atmosphere has its primary effect on the respiratory tract,
producing irritation and difficulty in breathing. It affects most strongly those people
who already have respiratory problems. Children are known to suffer increased
frequency of infection upon prolonged exposure to sulfur dioxide – but true long term
effects of exposure are not well understood. The acute effects of sulfur dioxide on
humans are listed in Table 3.2.
Table 3.2 – Acute effects on humans of different atmospheric SO2 levels
[SO2] in ppm Effect

500 Lowest level of human sensation
800 Threshold of taste
1400 Threshold of odour
4400 Threshold for reversible bronchial
constriction
20000 Immediate throat irritation
30000 Immediate eye irritation
50000 Immediate coughing
To put this in perspective, the London smog of 1952 averaged about 4000-5000ppm.
Street levels in Wollongong in the late 1970’s recorded values of 2250 ppm –
probably due to smelting operations in the area.
Because of its solubility in water, SO2 is almost entirely removed in the mouth, throat,
and nose through normal breathing. Less than 1% of inspired SO2 reaches the lung
tissue (alveoli). Although exposure of the lower airways and alveoli to SO2 increases
considerably during exercise, the principal effect of SO2 exposure is to alter the
mechanical function of the upper airway.
Laboratory animal exposures at very high concentrations indicate that SO2 has the
potential for causing chronic bronchitis.
page 50
Studies on humans and animals report an exaggerated air flow resistance in response
to short-term acute exposures in about 10% of the apparently normal population under
test. Human challenge studies have further demonstrated that SO2 exposures at
relatively low levels (0.25 and 0.5ppm) could produce acute bronchoconstriction on
inhalation by strenuously exercising asthmatic subjects. The mechanism of these
apparently non-allergenic hypersensitive responses is unknown.
The health consequences of ambient SO2 exposures may only partly lie in the direct
effects of this gas on the human respiratory system. It is more likely that health effects
attributed to SO2 are due to the highly irritant effects of sulfate aerosols, such as
sulfuric acid, which are produced from SO2.
Oxides of Nitrogen
Nitric oxide is a relatively nonirritating gas and is thought to pose little threat to health
at normal ambient levels. Its importance lies in the fact that it is rapidly oxidised to
NO2, a gas of much greater toxicity.
Whilst SO2 is rapidly absorbed in the fluids in the upper respiratory tract, NO2 is less
soluble and generally penetrates deep into the lung leading to tissue damage.
Exposure to acute high levels leads to effects such as pulmonary oedema.
The lowest NO2 exposure level shown to cause physiological change is 0.5ppm at
which adverse effects included the destruction of cilia, alveolar tissue disruption, and
obstruction the respiratory bronchioles. Exposures at higher levels can lead to severe
tissue damage. Minor respiratory problems are caused by brief exposures at levels
below 5ppm. At levels below 100ppm, exposure leads to prolonged, but non fatal
inflammation of lung tissue. Higher levels are generally toxic. There is also evidence
that NO2, can damage respiratory defence mechanisms, allowing bacteria to
proliferate and invade lung tissues.
Another health problem linked to nitrogen oxides is that they are precursors for
pollutants that form photochemical smog.
Hydrocarbons
Most hydrocarbons are relatively nontoxic at the ambient levels found in normal
atmospheres. They are however key reactants in photochemical smog formation.
Where they undergo complicated reactions in the atmosphere with O2, O3, NOx, SOx
and other components to form photochemical smog (see following section) which is
very deleterious to human health. They reduce visibility, have unpleasant odours and
cause skin and eye irritation at higher levels. Some are carcinogenic, such as
benzo[α]pyrene.
Hydrocarbon air quality standards are not based on the health effects of hydrocarbon
chemicals, but rather an attempt to reduce photochemical smog formation.
Hydrocarbons that may be of concern to human health include the carcinogenic

polycyclic aromatic hydrocarbons (PAH), such as benzo(α)pyrene (BaP), and the eye
irritants, including HCHO (methanal), acrolein, and peroxyacyl nitrate (PAN). The
page 51
PAHs are produced as a result of the incomplete combustion of high-molecular-

weight hydrocarbon species. Benzo(α)pyrene is the most abundant PAH in urban air.
It is normally found adsorbed on aerosol particles. Controlled animal studies indicate
that exposures in excess of ambient levels may be required to induce tumours.
The PAH levels of urban areas in the United States have been reduced by a factor of
three since the mid- 1950s. This decrease has been due to a change of fuel usage from
coal to natural gas and oil for home heating. If the PAHs in urban areas were
contributing to the urban excess of lung cancer, then the decrease in PAH should have
resulted in a decrease in lung cancer attributed to the "urban factor." There is no
evidence that this has occurred.
Hydrocarbon derivatives such as HCHO, acrolein, and PAN are of interest because
they contribute to the eye irritation experienced in photochemical smog. The threshold
for HCHO-induced eye irritation is in the range 0.1 to 1ppm; for acrolein, moderate
eye irritation can be detected at 0.25ppm for PAN, 20ppb. In general, eye irritation
experienced in urban areas is likely to be produced by the combined effects of these
substances and other hydrocarbon derivatives.
Ozone & Photochemical Smog

Ozone is one of the most toxic pollutants regulated under ambient air quality
standards. It may cause significant physiological and pathological changes in both
animals and humans at exposure concentrations that are within the range of those
measured in polluted ambient environments. The ambient air quality standard for O3 is
0.12ppm (235mg/m3) averaged over 1 hour. The short exposure duration for this
standard is based on the historical regulatory assumption that O3 levels have a
tendency to peak at mid-day and that these peaks are primarily responsible for health
risks associated with ambient O3 exposures.
O3 may cause significant lung function changes even with exposures in the 0.10-
0.40ppm range of for 1-2 hours The changes are transient; and lung function appears
to return to normal after the exposure is stopped. Lung function changes are
concentration dependent and increase with increasing depth of breathing. Such
changes have been reported for healthy adolescents and young adults. There is no
evidence, however, that smokers, older adults (over 55), asthmatics, or individuals
with chronic obstructive lung disease are more responsive to O3 exposures.
Exposure to O3 levels above 0.12ppm, may lead to a variety of symptoms including

throat dryness, chest tightness, coughing, pain whilst deep breathing, shortness of
breath, lassitude, malaise, headache, and nausea. O3 exposures also cause decreases in
athletic performance.
O3 exposures may inhibit the immune system's ability to defend the body against
infection. A single 3-hour exposure at concentrations of 0.08-0.10ppm has been
reported to increase the susceptibility of mice to bacterial infection, and increased O3 -
associated mortality occurred at the elevated levels commonly reported in Los
Angeles.
page 52
Studies of prolonged exposures to O3 indicate progressive changes in respiratory

function, a marked increase in nonspecific airway reactivity, and progressive changes
in symptoms. Repetitive daily exposures can also have significant effects. Repetitive
exposures result in an enhanced response on the second day with diminishing
responses on days 3 and 4 and virtually no response on day 5. This apparent
adaptation persists about a week after exposure ceases. Animal exposure studies
indicate that despite the fact that functional adaptation takes place, progressive and
persistent damage to lung tissue continues to occur. Damage may include necrosis of
cilia cells, cilia shortening and damage to the bronchioles1.
Studies of chronic human exposures to ambient air indicate that there appears to be a
functional adaptation that persists several months after the O3 season, returning to
normal by the following spring. Other studies indicate that chronic exposures to O3 in
community air may result in a premature aging of the lungs1.
Studies on microorganisms, plant root tips, and tissue cultures indicate 03 is

mutagenic, that is, it can cause heritable changes in genes. Mutagenic substances have
a high probability of being carcinogenic as well.
Particulate Matter
Particulate matter exhibits toxic effects due to the direct irritant action of particles
(such as sulfuric acid) and substances that are readily adsorbed to the large surface
area of small particles. The concentration of adsorbed substances may be considerably
greater than in the ambient atmosphere. Adsorbed substances of particular concern
include SOx, polycyclic aromatic hydrocarbons (PAH), and heavy metals such as lead,
cadmium, zinc and mercury. The PAH and heavy metals tend to predominate in the
small respirable particles.
Respiratory Deposition and Retention of Particulate Matter

The health consequences of atmospheric particulate matter depend on its ability to
penetrate respiratory defence mechanisms. These are adequate to remove inhaled
particles in excess of 10µm, but particles smaller than can enter and be deposited in
the respiratory system. These are described as "inhalable particles". Particles less than
2.5µm are called "respirable"; they can enter pulmonary tissue and be deposited there.
Particles larger than 2.5µm are removed in the upper respiratory system. Deposition
of particles as a function of particle size is illustrated in Figure 3.31.
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Figure 3.3 – Deposition of particles in respiratory tract according to particle size1.
Because of changes in flow patterns in the tracheobronchial zone, particles tend to be

deposited at or near airway intersections. As nerve endings are concentrated at these
sites, the mechanical stimuli of deposited particles often lead to reflex coughing and
bronchoconstriction. This leads to an increased breathing rate.
The deposition of particles is not only influenced by particle size but also by mass
concentration, molecular composition, pH and solubility. Deposition also varies
among non-smokers, smokers, and individuals with lung disease. Tracheobronchial
deposition is slightly higher in smokers and greatly increased in individuals with lung
disease1.
After particles have been deposited, their retention may be a function of the rate of
clearance, which varies greatly among the different regions of the respiratory tract. In
the ciliated airways of the nose and upper tracheobronchial zone, clearance in healthy
individuals is achieved in less than a day. As the site of deposition becomes deeper in
the lungs the time required for clearance greatly increases. Clearance of particles in
the alveolar region may take weeks to months. Slow clearance of particles from the
respiratory system of humans is generally considered to be detrimental since toxic
substances are in contact with sensitive tissue for longer periods of time.
Alveolar deposition of particles is most efficient in the range of 0.1 to 2.5µm. The
effective toxicity of these small particles may be greater than that of larger particles
since the concentrations of toxic substances such as lead, zinc, chromium, mercury,
sulfates, nitrates, etc., increase with decreasing particle size. Additionally, the
enormous surface area of small particles allows for higher reaction and dissolution
rates for toxic chemical species. Their relatively long retention in the alveolar region
page 54
permits substances such as lead to be extracted and transported to other parts of the
body1.
Particulate matter may contribute to the development of chronic bronchitis and may
be a predisposing factor to acute bacterial and viral bronchitis, especially in smokers
and children. It may also aggravate bronchial asthma and the late stages of chronic
bronchitis and pulmonary emphysema. Health effects of particulate matter may also
depend in large measure on synergistic effects with pollutants such as SO21.
Studies of the effects of particulate materials in the atmosphere are shown in Table
3.3.
Table 3.3 – The effect of levels of TSP on human health
3 1
Total Suspended Particulate Level (ug/m ) Effect
1000 Increased mortality
250 – 500 Aggravation of bronchitis
200 Small reversible changes in lung function
of children
There is now strong evidence that acid aerosols composed of H2SO4 and HNO3, have
significant health effects. Exposures to these at concentrations slightly above ambient
levels significantly decrease the ability of the upper respiratory tract to remove
potentially harmful particles. Acid aerosols also appear to be able to induce asthmatic
attacks in exercising asthmatic adolescents at near-ambient concentrations.
Lead
Depending on the level of exposure, individuals may develop symptoms of acute or
chronic lead poisoning. The most affected organs are the blood, the brain, the kidney,
the nervous system and the reproductive system.
Symptoms of acute lead poisoning include shock, anaemia, nervousness, and

irreversible kidney and brain damage.
Episodes of acute lead poisoning are rarely associated with ambient atmospheric lead
levels – even in lead smelters. Atmospheric lead is normally a chronic cumulative
poison, mostly affecting the central nervous system. Lead is found at highest
concentrations in particles of 0.2µm or less, which increases its access to animals by
allowing access to the deep lung tissue where it is readily absorbed into the blood and
transferred to other organs. In growing children, lead affects intelligence, length of
concentration and activity. Pregnant women are also especially susceptible to the
effects of the metal. This is because lead crosses the placenta, resulting in high lead
levels in the foetus, which may lead to mental retardation.
Lead has been shown to interfere with the maturation and development of red blood
cells. It does so by inhibiting enzymes involved in haemoglobin synthesis. Blood lead
page 55
is much higher in smokers than non-smokers. Atmospheric lead does not lead to acute
intoxication, but rather is a chronic problem.
Asbestos
The name asbestos refers to number of minerals which are compressed together to
form fibrous materials. Particulate asbestos is a considerable community health
problem due to its past use as a construction and insulating material. Medical
evidence suggests that inhalation of the fibres causes the lung disease asbestosis –
which is characterised by scarring of the lower lungs and lowered breathing function.
It is a common disease in those exposed to asbestos for long periods. Some forms of
asbestos are responsible for causing lung cancer and mesothelioma (cancer of the
lining of the body cavity). Asbestos fibres are chronic toxins with very long latency
periods. Once the fibre is inhaled it has the potential to cause cancer for the rest of the
individuals life. It is estimated that between 25-50% of all individuals have asbestos
in their bodies.
Fluoride
Gaseous fluorides damage vegetation and if ingested in sufficient quantities the bones
and teeth of animals eating these plants.
Environmental Effects of Air Pollutants

When developing standards for the assessment of air pollution the emphasis has
always been on controlling the effects on human beings, with all other effects being
treated as of much lesser importance. Air pollutants do have significant effects on
plants, buildings and other animals and these should also be considered when
developing standards to assess environmental harm from air pollution.
Effects on Plants
Plants are often the first to show damage associated with increased ambient levels of
air pollution. The effects of SO2, HCl and HF have been reported as early as the
middle of the 19th century. The most severe damage seems to have been associated
with high levels of SO2 and heavy metal particulates associated with mining and
smelting, but many other pollutants such as NO, Cl and NH3 are now know to cause
direct toxic effects on plant tissue.
The problems of acid rain and photochemical smog were first suggested as major
environmental problems by their actions on plants.
Air pollutants may injure plants in several ways– with some effects being subtle, but
others clearly visible. Visible effects normally involve identifiable changes in the leaf
structure such as chlorophyll destruction (chlorosis), tissue death (necrosis) and
pigment formation. Subtle effects include inhibition of growth and lowered rates of
photosynthesis.
Plant tissue damage may be either acute or chronic. Acute exposures to high levels of
pollutants generally lead to necrosis. Chronic injuries result from intermittent or long
term exposures to lower levels of pollutants, with chlorophyll destruction or chlorosis
being the most common symptoms of injury.
page 56
Different pollutants produce differing symptomatic effects on plants and this can be
used as an indicator as to the possible presence raised levels of certain pollutants.
These are discussed in more detail in the paragraphs below.
Sulfur Dioxide
Atmospheric sulfur dioxide is harmful to certain plants at levels below 1ppm, causing
tissue damage and destruction of chlorophyll. However, it is through chemical
reactions in the atmosphere which produce sulfuric acid, that sulfur dioxide emissions
have caused their most significant damage. In conjunction with the nitric acid
produced from nitrogen oxide emissions, the phenomenon known as acid rain has
transformed ecosystems throughout Europe and North America, destroying forests
and increasing acidity levels in lakes by several pH units.
Sulfur dioxide causes damage to plant tissues by entering through stomates where it
immediately comes into contact with the spongy mesophyll cells of the leaf. Initially
the damage is restricted to the near vicinity of the pore, but as exposure continues,
there is a progressive expansion of injury and tissue collapse (see Figure 3.4). As the
injury develops, affected tissue may have a greyish green water-soaked appearance,
which on drying becomes ivory-to-white, red, brown or even black, depending on the
species. The injury extends from the bottom to the top of the leaf and is visible on
both surfaces.
The severity of the injury, that is, the amount of leaf tissue affected, is dependent on
the dose to which the plant has been exposed. The greater the dose or exposure, the
more severely injured are individual leaves as well as the whole plant. The entire leaf,
or in some extreme cases the entire plant, may be killed.
The severity of observed injury on individual leaves is also dependent on leaf

maturity. Young, fully expanded leaves are most sensitive to SO2. Older leaves and
those not fully expanded are much less sensitive.
In dicots, acute SO2 injury is usually manifested as an interveinal necrosis, although

necrosis in some species may appear on the margins. In some instances, chlorosis may
be associated with the necrotic areas. In monocots, such as grains, lilies, and gladioli,
injury may appear as irregular necrotic streaks between the larger veins on both
surfaces of the leaf. At low to moderate concentrations, SO2 may cause leaf tip injury
on monocots. Sulfur dioxide injury on conifers is observed as reddish brown to brown
tip necrosis that may have a banded appearance from repeated exposures.
Different species and varieties vary in their sensitivity to SO2 exposure. Alfalfa is the
most sensitive species, with acute injury observed at a dose of 1ppm for 1hr. Because
of its hypersensitivity, alfalfa has been used as a bioindicator of SO2levels in the
ambient atmosphere.
page 57
1
Figure 3.4 – Tissue injury symptoms associated with exposure to high levels of SO2
Ozone
Ozone also enters the leaf through the stomates on the lower leaf surface. In dicots it
bypasses the spongy cells and injures the palisade mesophyll cells preferentially (see
Figure 3.5). Due to this the symptoms of acute injury are visible on the upper leaf
surface. In monocots, conifers, and dicots without a palisade mesophyll, cells near the
stomates are injured, with symptoms appearing on either or both surfaces. Developing
leaves ranging from 65-90% of their full size are most sensitive to O3 injury. As with
SO2 the maturity of the plant determines sensitivity, with younger plants being more
sensitive and older plants more resistant.
Figure 3.5 – Leaf tissue injury associated with ozone exposure1
The most common O3-induced symptom patterns observed on dicots are upper surface
flecks (see Figure 3.6). These flecks are produced when groups of palisade cells are
killed or injured, resulting in chlorotic or necrotic lesions. The adjacent epidermal
page 58
cells may in some cases also collapse. The flecks may be white, tan or yellow in color.
If flecking is extensive the upper leaf surface may appear bronzed or chlorotic. A
variation of this symptom is called stipple. In stipple, the injured palisade cells may
become intensely pigmented, giving the leaf surface a red to purple to black to brown
appearance. The collapse of the overlying epidermal cells is generally not observed
with the stipple symptom. Flecking is generally a more severe reaction than stipple,
but it is apparent that these symptoms are more related to plant species than to ozone
dose. In both the fleck and stipple symptom patterns, injury is confined to the
interveinal tissues, the veins being uninjured.
1
Figure 3.6 – Fleck injury associated with ozone exposure
Ozone sensitivity varies from species to species and from variety to variety within
species. Ozone is more toxic to plants than SO2. Symptoms may be observed on
sensitive plants from exposures of as little as 0.10 - 0.30ppm for a few hours.
Ozone is considered by plant scientists to be the most important of all of the

phytotoxic air pollutants. It has been estimated to be the cause of over 90% of all plant
injury due to air pollution in North America.
Peroxyacyl Nitrate (PAN)

Peroxyacyl nitrate is the causal agent of "smog injury" observed on vegetable crops.
PAN enters the leaf through the stomate, then reacts immediately with the spongy
mesophyll around the stomate. This causes the stomate to collapse, forming large air
pockets that lead to a glazing/browning appearance on the lower surface of the leaf.
Patterns of banding may also be observed with PAN exposures. These bands occur in
the same location on leaves of the same age. PAN injury often appears as bands at the
apex of the youngest sensitive leaf, the middle of an intermediate-aged leaf and the
base of the oldest sensitive leaf. Young, rapidly developing leaves on young rapidly
growing plants are most sensitive to PAN.
page 59
In monocots, such as grasses, glazing and bronzing rarely occur. PAN injury usually
appears as distinct bands several millimeters to 2 cm wide across the leaf blade. If the
injury is slight the injured tissue may be chlorotic. Severe injury results in tissue
collapse and bleaching of the necrotic tissue.
1
Figure 3.7 – Tissue damage and symptoms associated with leaf exposure to PAN’s
Peroxyacyl nitrate is more toxic to plants than O3. Sensitive plants such as petunia,
tomato, and lettuce may be injured by an exposure to as little as 15-20ppb for a few
hours1.
Fluorides
Fluoride can have substantial effects on growing plant tissue. Injury may result from
the uptake of gaseous hydrogen fluoride through the stomates or from soluble
particulate fluorides absorbed through the leaves and/or roots. Regardless of the
means of entry, fluorides enter the veins and are transported to leaf margins and/or the
leaf tip, where they accumulate. Fluoride injury generally results from the
accumulation of small quantities of fluoride over long periods. The severity of the
injury is directly related to the dose absorbed / level of exposure.
page 60
1
Figure 3.8 – Tissues of a leaf affected by fluoride exposure
Fluoride injury normally appears as a marginal or tip necrosis (commonly called “tip
burn”). The injury occurs in both the mesophyll and the epidermis. There is often a
narrow reddish band between the living and dead tissue.
Typical fluoride-induced injury on selected species is illustrated in Figures 3.8 and

3.9. Some sensitive plant species (such as iris, wheat, tulip and gladiolus) can be
injured by fluoride exposures of only a few ppb for a 1 week period.
Figure 3.9 – Symptoms of a typical leaf exposed to fluoride for an extended period1
page 61
Particulate Materials
Particulate dusts may cause injury to vegetation both directly and indirectly.
Direct effects such as those for cement kiln dust include a variety of plant responses,
such as
• reduction in yield and growth without visible injury,
• increase in disease incidence,
• severe injury to leaf cells,
• suppression of photosynthesis, and
• death of trees.
The injury may result from the deposition of a thick crust that suppresses
photosynthesis and/or alkaline toxicity when alkaline solutions are produced when
dusts are present in free moisture. Ecological studies of forest communities affected
by the deposition of limestone dusts have shown significant changes in tree growth
and species composition. Changes in dominant tree species and the decrease in
herbaceous vegetation are particularly evident.
There are indirect beneficial effects from soil neutralisation by alkaline dusts.
Atmospheric aerosols near urban areas may significantly elevate lead levels in both
soil and vegetation. The uptake of lead by roadside plants results in no apparent
visible injury. Heavy metal aerosols generated by nonferrous metal smelters may,
however, have significant plant effects. The severe devastation of vegetation and
denudation of the landscape around smelters is likely due to aerosol-derived heavy
metal contamination of the soil and subsequent accumulation of phytotoxic levels by
plants. There is evidence of this in the hills around Queenstown in Tasmania. This
heavy metal problem is exacerbated by high concentrations of SO2, which occur
simultaneously with metal aerosol emissions. Growth of vegetation around smelters
that have ceased operation is still suppressed for many years after their closure
Acid Deposition
Acidic particles which fall onto plants or soil in which they grow can cause significant
changes in plant wellbeing. These can result in necrotic lesions of the upper leaf
surface, which is followed on subsequent exposures by tissue collapse on both
surfaces.
An indirect effect is the deposition onto soil, which affects soil pH. The effects here
may be positive or negative depending on the make up of the soil.
Effects of Air Pollutants on Buildings and Materials

Air pollution is renowned for soiling building surfaces, clothing and other articles.
This is generally a result of smoke particles adhering to the surface in question, but
their are many other more sinister effects.
Air pollutants significantly affect many non-biological structures and materials. These
effects cause economic losses in billions of dollars each year. Most important are
effects on metals, carbonate building stones, paints, textiles, fabric dyes, rubber,
leather, and paper. In Western Europe, which is a repository for many monuments of
history and fine works of art, air pollutant-induced damage has been incalculable.
page 62
Because these cultural treasures are irreplaceable, their preservation from the
destructive effects of airborne contaminants poses a significant challenge to scientists.
Materials can be affected by both physical and chemical mechanisms. Physical

damage may result from the abrasive effect of wind-driven particulate matter
impinging on surfaces and the soiling effect of passive dust deposition. Chemical
reactions may result when pollutants and materials come into direct contact. An
example of this the reaction of lead in older paint materials with sulfurous materials
(particularly H2S) from air pollution to produce the unsightly lead sulfide black
streaks on buildings.
Metal Corrosion
Metal corrosion in industrialised areas represents one of the most costly effects of
atmospheric pollutants. Since corrosion is natural we tend not to recognise the role
that pollutants play in accelerating this process. As the ferrous metals, iron and steel,
account for about 90% of all metal usage, pollution-induced corrosion on these metals
is of particular significance. The acceleration of corrosion in industrial environments
is associated with high levels of atmospheric SO2 and particulate matter pollution is
very significant. Oxidants, such as ozone, inhibit the effects of SO2 by producing a
more corrosion-resistant product.
Rubber and Fabrics

Another important material damaged by pollution is rubber, which is attacked by
ozone. This leads to cracking, which is an economically significant problem. Fabrics
such as nylon are also affected by air pollution. These tend to disintegrate upon
prolonged exposure to the air. Bleaching and discolouration may also occur.
Accepted Levels of Major Air Pollutants

These vary significantly from country to country, so the values listed in Table 3.4
should only be used as guidelines. For the most up to date information on accepted
pollutant levels you should consult the NSW EPA.
page 63
Table 3.4 – Accepted levels of major air pollutants2
Air Pollutant Acceptable Level
CO 1 hour ave. 30ppm (60ppm detrimental)

8 hour ave. 9ppm (20 ppm detrimental)
1 hour alert level 150ppm
NO2 1 hour ave. 0.12ppm (0.25ppm detrimental)

8 hour ave. 0.06ppm (0.15 ppm detrimental)
1 hour alert level 0.50ppm
1 year 0.03ppm
NH3 Ground level conc. 0.83ppm (0.6 mg/m3)
HNO3 Ground level conc. 0.067ppm (0.17 mg/m3)
SO2 1 hour ave. 0.20ppm (0.34ppm detrimental)

1 day ave. 0.08ppm
1 year ave. 0.02ppm
H2S Ground level conc. 0.0001ppm (0.00014 mg/m3)
Photochemical oxidants 1 hour ave. 0.10ppm (0.15ppm detrimental)

(as O3) 4 hour ave. 0.08ppm (0.15ppm detrimental)
Respirable particles 24 hour ave. 120 mg/m3 (240mg/m3 detrimental)

1 year ave. 40 mg/m3 (80mg/m3 detrimental)
PM10 Respirables 1 day ave. 50µg/m3
Atmospheric Lead 3 month ave. 1.0 µg/m3

1 year ave. 0.50µg/m3
Benzo[α
α]pyrene 1 year ave. 5.0ng/m3
Benzene 1 year ave. 10.0ng/m3
Fluorine Ground level conc. 0.033ppm (0.067 mg/m3)
References
1
2
ACTRAC, Environmental Control- Unit 2 Air Pollution, Cert. In Chem. Plant Skills Resource, 1998.
page 64
Chapter
4
Air Quality Measurement and Assessment
What is Air Quality?

Air quality measurement, like water quality measurement is complicated by a lack of
knowledge as to what is "clean" and what we mean by quality. It is fairly obvious
from the human perspective that the air during the London smog episodes of the
1950’s or the Los Angeles air of today would not be defined as high quality. This is
because of the health risks associated with breathing this air, but just what makes air
of poor or good quality?
Pure air has been defined as containing only naturally occurring gases, hence pure air
never exists in nature as air always contains pollen, dusts and fog. No attempt has
been made to differentiate between natural and man-made pollutants and air quality
measurements are designed to measure all types of pollutants.
The main reason for air pollution control programs is to protect public health. At first
therefore it would seem best to define air quality based on its effects on people and
the environment. Unfortunately many of the effects of air pollution are chronic and so
are not immediately obvious. For this reason air quality is normally measured by real
time or average measurable conditions, which through experience can be related to
potential effects on human beings and the environment.
In order to implement an air pollution control program it is necessary to have systems

in place that will monitor the levels of air pollutants and relate the levels of pollutants
to effects on the environment. Such a system requires that appropriate air quality
surveillance be carried out in areas that are particularly sensitive to raised levels of air
pollutants. This may include the monitoring of potential emission sources (such as
stacks), and ambient air monitoring in appropriate locations, but other factors such as
weather conditions also play a large part in determining the level of pollutants in air at
any particular location. The latter is very important as generally the level of emission
of most pollutants varies little from day to day, but the air quality as measured by
ambient levels of pollutants varies enormously. This can be attributed almost entirely
to meteorological conditions.
Measurements of air quality generally fall into three classes:
1. Measurements of Emissions - also called source sampling. Refers to when a

particular emission source is measured, generally by on the spot tests.
2. Meteorological Measurement - Measures meteorological factors that show how

pollutants are transferred from source to recipient.
Air Quality & Pollution Control Air Quality Measurement
3. Ambient Air Quality - Measures the quality of all the air in a particular place.
Almost all the evidence of health effects is based on these measurements.
The latter two methods are referred to as atmospheric sampling.
Two other categories have recently been added in the USA. These are:
4. Industrial Hygiene sampling - for testing the air quality inside of factories and
places of work
5. Residential Indoor sampling - to evaluate the quality of air in living spaces.
Air Sampling Techniques

As is the case with aquatic systems, it is always better if possible to evaluate pollutant
levels in the atmosphere in situ. On some occasions however, it may become
necessary to obtain an ambient air sample.
Any sampling process has limitations, but provided standard techniques are followed
the data obtained from analysis of air samples should be a reasonable reflection of
ambient air.
Most air pollution monitoring equipment performs the act of sampling and analysis in
one action. This is because most modern equipment is capable of so called real time
measurement – whilst older equipment had to perform intermittent sampling where
there was a time lag between when the sample was obtained and when data from it
was available. This type of system provides average data (not real time). Today
almost all gaseous pollutants are monitored by real time analysis. Particulate
pollutants on the other hand are still mostly monitored by intermittent sampling, even
though real time methods are available.
When obtaining a sample for air pollution analysis a number of considerations should
be kept in mind.
• The sample should be of sufficient quantity to allow analysis. Most pollutants are
present in very low levels and require a large volume of gas for accurate
measurement.
• When pollutants are present in very small quantities it is very easy to contaminate
them. For this reason great care should be taken to purge sampling containers if
grab samples are used.
• Collection and analysis limitations may require collection over extended periods
which means that air quality data may often only be a 24 hour average (depends
on sampling and analysis time). This is not necessarily as great a limitation as it
might first seem as many real time measuring instruments produce so much data
that they are often set to give hourly averages to make the data more
understandable.
Air pollutant sampling systems require gases or particles to be drawn to the surface of
a collecting medium or a sensor. These functions are usually accomplished by
sampling trains, which may include a vacuum pump, vacuum trap, a flow regulator
and a collecting device or sensing unit. A bubbler-type gas sampling train used to
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collect samples on an intermittent basis is illustrated in Figure 4.1. Sampling trains for
gases may also utilize filters to present particles from entering the collection unit.
1
Figure 4.1 – A typical gas sampling train
Impingers
Many air pollutants emitted from stationary sources such as stacks may be sampled
via gas absorption. This generally involves the collection of a gas sample via a
sampling train into a series of gas bubblers. These are commonly referred to as
impingers. The impingers may vary considerably in size and the type of absorbent
they contain. This may be water or a water-soluble substance that will react and
dissolve the pollutant (such as limewater), or they may be organic materials, such as
methylbenzene or benzeneamine.
Sampling Procedures
Depending on the type of information required and limitations of collection and
analysis, sampling may be conducted by static, grab, intermittent or continuous
procedures. These sampling procedures provide air quality data representing a range
of averaging times, from instantaneous (for continuous monitoring instruments) to a
30-day average (for some static samplers).
Static or passive sampling may involve the collection of contaminants by the diffusion
of gases to a collection medium, the sedimentation of heavy particles into a container,
or the impact of particles on sticky paper.
In the early days of air pollution monitoring static sampling was commonly used. It
had the advantage of simplicity and low cost. However, because of the long averaging
times (a week to 30 days), static sampling data were limited in use for ambient air
pollution control. Some examples of static sampling devices include deposit gauges
and lead candles. Static sampling is widely employed for personal monitoring in
industrial environments and for measurement of indoor air quality parameters such as
HCHO (methanal) and radon.
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Grab sampling is not commonly used to monitor ambient air quality. It is generally
used as a tool for control personnel and researchers to identify problem pollutants. In
grab sampling a small volume of air is collected in a matter of seconds or minutes
using sampling containers such as evacuated bottles, gas syringes and bags made of
synthetic materials (such as wine bladders). Gas syringes can also be used in
conjunction with sampling tubes that contain dry chemicals that react with specific
pollutants, combining sampling and analysis in one manual operation. These gas
syringe/sampling tube systems are commonly used in industrial hygiene and chemical
emergency response episodes. They have relatively poor precision and accuracy and
are primarily used to provide a rough estimate of pollutant concentration.
Selection of Locations for Monitoring Equipment

In order to obtain meaningful and useful data it is not only important to use the correct
sampling procedures, but also to choose an appropriate position to sample from. In
order to do this the objectives of the air monitoring program must be considered. For
example a site next to a high stack would not be suitable to determine the level of
stack emissions as the emissions would be carried far away from the sampling point.
Such an analysis would require in stack monitoring.
General Requirements for Site Selection

A number of factors such as the purpose of monitoring, number and type of
instruments required, and duration of measurements ultimately determine the choice
of a suitable site2. There are few reliable guidelines for selecting suitable monitoring
sites. Probably the best available general guide comes from AS29223.
Monitoring sites should be easily accessible (as difficult access lead to data loss), but
it should not be easily vandalised – as this is a major source of data loss.
Specific Requirements for Site Selection

For all air quality measurements it is recommended that the following steps be taken
when determining a suitable monitoring site:
• determine the purpose(s) of the site(s) and ensure that data obtained will be:
- relevant to the stated objectives or goals, and
- representative of the local, urban or regional air
• optimise location choice based on published guideline criteria to generally suit the
purpose(s) of the monitoring site(s)
• use scientific judgement, past experience and common sense in precisely siting
instrumentation or monitoring stations ensuring that there are no local
interferences (chemical or physical) which could cast doubt on the validity of the
data obtained2.
The Importance of Meteorological Monitoring

Meteorological conditions play a large part in determining air quality at any particular
place and time. Emission levels may be fairly constant in most ambient air, but
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changing weather conditions can produce dramatic changes in air quality and ambient
pollution levels. Factors such as:
• wind dispersion rates (velocity and direction)
• temperature inversions
• photochemical reactions, and
• rain.
Wind Direction and Velocity Measurements

These should be available whenever possible for each sampling site. Wind sensors
(anemometers) should be installed to measure the general winds of the local urban or
regional area under investigation and should not be influenced by physical
obstructions. The standard exposure of anemometers over level open terrain is 10
metres above the ground. Any obstructions to the airflow, such as buildings, hills or
tall trees, should be distant by at least five, and preferably ten, times their height.
In some cases rough guides to general wind direction can be provided by double sided
adhesive tapes on the outside of devices such as deposit gauges.
Ambient Air Monitoring
Choice of Monitoring Equipment

For almost every type of air pollutant there are several different acceptable methods of
analysis. The type of equipment and methodology used for analysis may be
determined by many factors such as:
• cost
• the number of data points required
• the purpose for which the data are being used
• the time interval required between data points
• the devices power requirements
• the type of air pollutant, and
• the environment in which the monitoring equipment is being placed.
Cost is probably the most important factor for many monitoring programs. Obviously
everyone would prefer to have all monitoring stations of the real time continuous
analysis type – but the cost of this would in many cases be prohibitive. Hence less
expensive alternatives must be found. For example a deposit gauge may be used
instead of a gravity microbalance for particulate matter.
If data are being used for a rough estimate then much less expensive (and reliable)
methods may be used. If data are being used for EPA monitoring or legal purposes to
determine emission levels, then much more expensive accredited methods are
required.
If only a few data points per week are required, then a different type of monitoring
may be used than if continuous monitoring is required. For example a high volume
particulate sampler may be used instead of a microbalance.
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If a piece of monitoring equipment is to be placed in a harsh environment (as is often

the case with air pollution monitoring) then robust equipment or suitable protective
shielding must be used. Some forms of equipment are more robust than others, and as
this affects reliability it may influence the choice of monitoring equipment. For
example a dust deposit gauge is more robust than a high volume particulate sampler,
and it does not require power. Hence it might be a suitable choice for examining
fallout levels at a remote site where conditions are harsh and power is not available.
This is provided of course that one datum per 28 days is acceptable.
Calibration and Maintenance of Monitoring Equipment

As is the case with all other forms of scientific analysis, data is of little use if the
equipment used to obtain it is not calibrated, and suitable quality assurance standards
are not used whenever possible.
When a device uses airflow input, it is necessary to calibrate the airflow system. This
involves using a device or a pre-calibrated gas flow meter to check on the ambient
airflow into the device. Examples of devices used to measure airflow input include:
• spirometers
• displacement bottles
• soap bubble meter
• mercury sealed piston
• Roots meters
• wet test gas meters and
• dry test gas meters.
More details of these are found in texts such as Fundamentals of Air Sampling4
All devices should be calibrated according to the manufacturer’s specifications as

outlined in their maintenance manuals. The times and results of these calibrations
should be kept in the instrument logbook.
Standard (certified) gas calibration mixtures are available from several chemical
manufacturers. These may be used for both quality assurance checks and in some
cases primary calibration of the instrument.
There are two types of calibration procedures commonly used on air monitoring
equipment – static methods and dynamic methods.
Static methods generally involve a simple one point electrical or chemical test. The
electronic test generally involves bypassing the air sampling system and checking the
detector or instrument response to a known electrical signal. This does not generally
suffice for a full instrument calibration. Chemical procedures generally involve the
use of a chemical to simulate a known level of pollutant, or a sample of the pollutant
may be used in some circumstances.
Dynamic methods of calibration are based on generating a flowing stream of

calibration gas – which is used to calibrate the whole instrument. This is the preferred
method for calibration of air monitoring equipment.
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Data Handling and Presentation

There are many acceptable methods for storing data from monitoring equipment.
These range from the simplest manual methods to very sophisticated electronic
devices.
Manual methods involve the use of field data sheets or log books, where all
parameters are entered manually by the technician. Examples of this are provided in
the Aquatic Systems resource package. Manual methods are generally not suitable for
any devices that are remotely situated, or are required for continuous monitoring.
Dataloggers are electronic devices that store many data points in an electronic
memory. They can be attached to a device and accumulate the data for long periods
of time if required. The data is usually collected by connection to a computer, which
downloads it into an appropriate data processing program. New data loggers are now
available which are equipped with solar powered modems. These enable remote
monitoring of many sites from a central laboratory. In this instance the central
computer automatically dials up the datalogger by mobile phone and requests that it
down load the data via satellite. This minimises the need for technicians to travel to
very remote sites, with only regular maintenance being required. These systems can
even be calibrated by satellite when required. The satellite system has another
advantage in that data is downloaded more often meaning that in the event of failure
less is lost, and also environmental problems may be detected earlier.
Reference Methods for Measuring Air Quality

Because of the great number of methods available for measuring air pollutants, we
will consider only those which are Australian Standards or where no Australian
Standards exists US EPA Methods. It must be realised that new more refined (and
accurate) techniques are continually being developed, and these will in time replace
current standard methods.
In general devices used to determine the levels of pollution in the atmosphere are
classified into three categories;
• first generation devices - these are low cost unpowered devices which require
long time frames to accumulate data e.g. deposit gauge
• second generation devices- which are powered and require small amounts of time
to produce data e.g. high volume sampler
• third generation devices - these produce instant (continuous data) e.g.
nephelometer, gravimetric microbalance, remote UV-visible detectors and remote
infra red sensors.
Measurement of Source and Stack Emissions

In addition to ambient air quality monitoring, surveillance programs may need to
assess emissions from sources within an area or region in which an air pollution
control program is being conducted. An program of ambient air quality monitoring is
of little benefit if the pollutant sources and knowledge of what and how much they
emit is not available. For a variety of complex reasons, including cost, the assessment
of source emissions receives less attention than it deserves.
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Source Sampling
A variety of approaches may be used to determine emission rates for a pollutant
source such as a stack. The most desirable means is to actually measure emissions by
source sampling. For some sources, emissions are monitored continually with
automated instruments (real time analysers). Where automated systems are not
available, expensive manual sampling techniques and testing are often required.
Source sampling in many cases requires that a sampling team collect samples from the
emission stream of a source. This usually involves climbing a stack to a sufficient
height to collect representative samples of emissions. Such work contains practical
access limitations, technical difficulties, and an element of physical danger. Stack
sampling is often carried out once a day for several days. From this sampling,
inferences are made as to the level of continuous emissions. Depending on a variety of
plant operating factors, these might be subject to considerable error. Nevertheless, a
case can be made that some quantitative data based on actual measurements is better
than no data at all or emission assessments based on calculations or generic
extrapolation.
Source sampling consists of introducing a probe into a waste gas stream flowing up a
smokestack. This probe must then withdraw a sample of waste gas, which will be
analysed in the laboratory. Gaseous pollutants may be collected by absorption in
impingers, adsorption on charcoal or other media, or condensation in collecting traps.
Particulate matter may be collected by a variety of techniques including wet
scrubbing, filtration, impaction, and electrostatic precipitation. Cascade impactors are
used in source sampling when characterisation of particle size is desired, a fact which
may determine the selection of control equipment.
Source sampling represents unique conditions of airflow and temperature. When

emissions are associated with combustion systems, the velocity and temperature may
be considerably higher than ambient conditions. Consequently, temperature and
pressure must be measured to correct the sample volume to standard conditions (20'C
and 760 mm Hg). Velocity data determined from pressure measurements utilising a
pitot-tube (see Figure 4.2) are also necessary to calculate mass loading to the
atmosphere, i.e., plant emission rates.
Because particulate matter comprises a range of inertial and other flow characteristics,
such sampling requires that airflow through the sampling probe be at the same rate as
that flowing in the waste gas stream. Such sampling is described as being isokinetic.
If sampling is conducted where flow rates through the sample probe are less than or
greater than the emission source (non-isokinetic), substantial error in emission
measurement will occur.
A typical stack sampling set up is illustrated in Figure 4.4. This shows the sampling
train used for analysis of volatile organic materials.
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Figure 4.2 – A Pitot probe for manual sampling of stack emissions (from Wright4)
Real Time Analysis

Many gaseous pollutants may be monitored using real time (continuous) measuring
devices. These provide a continuous readout of emission levels of the pollutant gas.
Several methods are used to provide real time analysis, with the most popular being
remote UV detection.
Sulfur dioxide is a stack gas that is routinely monitored on a continuous basis using
real-time analysers. All of the power stations in NSW and many other private
companies have real time SO2 monitors on their stacks. This is essential, as
continuous data is required to allow calculation of emission levels for load base
licensing.
page 73
5
Figure 4.3 – Effects of isokinetic and non-isokinetic sampling (from Lodge
Figure 4.4 – A train for stack sampling of gaseous organic material (US EPA)
page 74
Measurement of Particulates
Particulate matter may be sampled by a variety of techniques including gravitational
settling, filtration, electrostatic precipitation, light scattering and impact. Of these
settling, filtration and light scattering are the most commonly used, although impact
techniques such as cascade impactors are used in stack sampling.
Deposit Gauges
Also known as dust gauges these were the earliest devices for measuring particulate
pollution. The technique involves simple collection of dust that settles to the earth by
gravitation (collection of settleable particles). Here the dust is collected in open jars
partially filled with a copper sulfate solution (to prevent mould growth) generally over
a period of 30 days. Sticky tapes are often wrapped around jars and read every 7 days
to give qualitative indications of the direction of particulate pollution. The dust fall
jars are dried at the end of the collection period, the contents poured through screens
of standard size, then the contents weighed to determine the amount of dust in the jar,
which is commonly reported as tons of dust settled per square mile in 30 days.
Deposit gauges suffer from many problems (not the least of which is uncooperative
pigeons and drunks who can’t find anywhere else to go), and only one data point per
month is obtained. This is a static (passive) method which requires no power or pump
equipment. For more details you should consult Australian Standard AS3580.9. -
1990. Additionally Australian Standard AS2922 - 1987 should be consulted with
regard to where to place sampling equipment.
Figure 4.4 – A typical deposit gauge
page 75
High Volume Samplers

This is the most commonly used particle sampling method. The high volume sampler
has been developed to overcome many of the problems of the deposit gauge. This
operates much like a vacuum cleaner by simply forcing up to 2000 m3 of air through a
250 x 200mm glass fibre filter in 24 hours (at a rate of 1.0 – 1.6m3/min.). The filter is
securely clamped so that no particles can by-pass the filter through leaks. The analysis
is gravimetric in that the filter is weighed before and after the analysis on an analytical
balance, and the difference is the particulates collected. The sampler is mounted in a
shelter with the filter placed parallel to the ground. The covered housing protects the
filter from wind and other debris that might otherwise be blown onto or off the filter
and from direct precipitation. A standard high volume sampler collects particles in the
size range from 0.1 - 100µm.
The airflow is measured by a small flow meter (calibrated in cubic meters of air per
minute). This is necessary because airflow rates change as the filter becomes more
clogged. The particulate concentration measured by this device is referred to as the
Total Suspended Particles (TSP), which is a combination of settleable particles and
suspended particles. The mass concentration of total suspended particulates is
expressed as µg/m3 for a 24hour period. High volume sampling is an intermittent
method, which is generally operated on a 6-day cycle. In NSW all high volume
samplers are operated on the same day in the 6-day cycle.
Regular flow calibration is essential for the operation of all high volume samplers –
even those with automatic flow control. The procedure is set out in AS3580.10, but
some key points are:
• check the flow measuring system for correct operation
• ensure that their are no leaks between the filter and the filter holder
• allow 5 minutes warm up time before calibration
• perform the calibration when wind speed is < 1m/sec.
Figure 4.5 – A typical high volume sampler (from Godish1)
More information and the correct operating procedures on high volume samplers is
available in Australian Standard AS3580.10 - 1990. Once again Australian
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Standard AS2922 - 1987 should be consulted with regard to where to place sampling
equipment.
PM10 and PM2.5 High Volume Samplers

Some particles are particularly important with regard to human health as their size
allows them to be carried into deep into the lungs and cause maximum damage. This
refers to those particles with a size of 10µm or less. Specially adapted high volume
samplers are used to check on the concentration of these particles in the atmosphere.
They are known as PM10 high volume samplers – they only collect those particles
with aerodynamic sizes of 10µm or less – all other particles are trapped and removed
by a special type of impaction chamber before they arrive at the collection filter. They
may be recognised by their PM10 head, which looks like a cross between a flying
saucer and an overgrown wok!
A newer standard employs a sampling head that only allows even finer particles –
those of 2.5µm or less to strike the sampling paper. This new standard is used as it
gives an indication of the amount of respirable particles in the air that will reach all
the way into the alveoli of the lung and therefore cause maximum problems in the
respiratory system.
4
Figure 4.6 – A typical PM10 high volume sampler (from Wright )
page 77
For more information on these refer to Australian Standards AS3580.9.6 and

AS3580.9.7 - 1990.
Nephelometers
These are devices which use the scattering of light to measure the size and number of
particles in a given air sample. Normally a red helium neon laser is used for the light
source, and a computer determines the interference patterns produced from the
interaction of the particles with the light. Air is drawn into the optical chamber by a
centrifugal fan at about 100L/min. A photomultiplier tube is used to detect the
scattered light. The intensity of scattered light increases with increasing fine
particulate concentration. Nephelometers are best used to determine the amount of
particulate matter in different size fractions. They are usually used to examine the
amount of particulate material in the 0.1 – 2.5µm size range – that which presents the
greatest risk to human health.
This device has the distinct advantage of being able to produce an almost instant
readout of data. More information on nephelometers is provided in Australian
Standard AS3580.10.1 - 1990. Figure 4.7 illustrates the normal construction of the
device.
Figure 4.7 - Schematic diagram of a typical nephelometer (from Air Pollution

2
Measurement Manual - Clean Air Society of Australia )
Co-efficient of Haze - Paper Tape Samplers

In contrast to the high volume samplers, paper tape samplers (see Figure 4.5) are
continuous sampling devices. They do not, however, provide instantaneous data as do
most continuous gas monitoring instruments, as averaging times of two hours are the
norm. Paper tape samplers draw ambient air through a cellulose tape filter. After a 2-
hour sampling period, the instrument automatically advances to a clean piece of tape
and begins a new sampling cycle.
Advanced paper tape samplers are equipped with densitometers for optical density
measurements during the sampling period. These instruments record changes in light
transmission which can be converted into COH (Coefficient of Haze) units. Simpler
instruments without built-in densitometers necessitate manual determination of optical
density in the laboratory.
COH units are based on light transmission through the soiled filter area. The higher
the ambient particle loading, the more soiled the filter. The subsequent increase in
optical density can in most instances be directly related to mass concentration.
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In the early 70s, paper tape samplers were widely used for continuous monitoring of
particulate matter concentrations. Because of difficulties in relating data acquired by
this optical method to the gravimetric data of the high volume sampler reference
method, most paper tape sampling has now been discontinued. Paper tape samplers
are still used on a standby basis in metropolitan areas where rapid data acquisition is
essential.
Figure 4.8 – A typical paper tape sampler (from Godish1)
Measurement of Gases
Sampling of Gases
It is often necessary to collect a sample of gas for later analysis in the laboratory and
this is not an easy process if a true representative sample is to be obtained.
One method is to use evacuated containers, drawing a vacuum in a glass jar and
releasing it when the air is to be sampled. Unfortunately it is impossible to obtain a
perfect vacuum and so some contamination always results from this method.
Another method involves bubbling gas into a container with water in it and displacing
the water. This is an effective method only if the gases being sampled are totally
insoluble in water.
Plastic and aluminium bags have been used extensively. Usually the gas is pumped in
and allowed to escape through a hole. The displacement of two or three volumes of
the bag generally avoids contamination problems.
Sulfur Dioxide
There are many methods available for the determination of SO2. These range from
simple titrimetric procedures (Australian Standard 2509 - 1981), to colourimetric
tests such as the West & Gaeke Method (US EPA method), to direct reading
instrumental methods.
For the sake of brevity we will consider only the relevant Australian Standard
AS3580.4.1 - 1990. This method is appropriate for SO2 concentrations within the
range of 0-5ppm. It permits the use of any of the following detection methods;
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• UV fluorescence analyser
• flame photometric detector (with or without gas chromatograph)
• electrochemical (coulimetric detector)
Probably the most widely used method in this country is the UV fluorescence
analyser. The air sample is drawn into a scrubber chamber which removes polynuclear
aromatic hydrocarbons (which would interfere with the analysis), and then on into an
irradiation chamber where it is exposed to UV light. SO2 absorbs in several regions of
the UV spectrum, but in the band from 190-230nm it is not quenched by other
pollutants. When the SO2 in an air sample is exposed to this light it forms a high
energy molecule which returns to the ground state with emission of light. The amount
of fluorescent radiation is directly proportional to the concentration of SO2. This is
shown in the reaction scheme below.
SO2 + UV SO2*
SO2* SO2 + light
Oxides of Nitrogen
These are generally determined using a method as described in Australian Standard
AS 2447 - 1981. The method is suitable for ambient air containing levels of NOx (NO
and NO2) at levels less than 1 mL/m3. The method is specific for NO, but total oxides
of nitrogen may be determined by passing the sample over a catalyst to convert NO2
to NO. The NO2 may then be calculated as the difference between NO and NOx.
The levels of NO are determined using chemiluminescence techniques. This

involves the reaction of NO with ozone in a darkened enclosed chamber to produce
light near the infra red region of the spectrum. This is detected by a photomultiplier
tube. A reaction scheme for the process is given below.
NO + O3 NO2* + O2
NO2* NO2 + hν
ν (light)
Provided the ozone is present in excess the light output is directly proportional to the
concentration of NO.
Ozone
Ozone is generally determined either by chemiluminescence methods or direct
reading UV detectors. Both of these are covered in Australian Standard AS3580.6 -
.6.1 - 1990. This method is suited to determination of these pollutants in the range
from 0 - 0.5ppm.
The chemiluminescence method requires the sample to by drawn into a mixing

chamber where it is mixed with a stream of ethene gas. This causes a
chemiluminescent reaction and the subsequent emitted light at about 430nm. The
page 80
amount of light emitted is directly proportional to the concentration of ozone in the

sample. A photomultiplier tube is used to detect the light.
The direct reading UV method is even simpler. Here the stream of gas in the sample is
drawn through a flow cell where it is irradiated with UV light at 254nm. The amount
of light absorbed is detected by a photomultiplier tube (in exactly the same fashion as
a UV-visible spectrophotometer). The amount of absorption is directly related to the
number of molecules in the path length only and is not affected by flow rates. A zero
value is obtained by examination of an ozone free gas sample.
Carbon Monoxide
This is normally determined using methods described in Australian Standard
AS3580.7-7.1 - 1990. These involve the use of non-dispersive infra red (NDIR)
devices, and are suitable for detection from 0-500ppm by volume.
The method involves drawing the sample through a flow cell in the instrument where
it is irradiated with infra red radiation. A carbon monoxide free cell is located in the
reference beam that is irradiated at the same time. The difference in intensity between
the two beams is directly proportional to the concentration of carbon monoxide in the
sample.
The instrument used in this analysis is very simple and contains four parts. An infra
red source, a sample flow cell, a reference flow cell, and a detector. It is essentially
just a modified dual beam infra red spectrophotometer, as shown in Figure 4.9.
IR source
Chopper
CO free air in
Ambient sample in
Reference cell Sample cell
CO free air out Ambient sample out
IR transmitting windows
0.12 Detector
diaphragm & capacitance plate
Figure 4.9 - A typical non-dispersive infra red CO monitor
page 81
Non-Methane Hydrocarbons
A number of instruments are now available which allow the determination of total
hydrocarbons and non-methane hydrocarbons. It is essential to discriminate between
methane and other hydrocarbons, as it is the only hydrocarbon that naturally occurs in
large amounts in the atmosphere - remember those cows & termites!
The principle for determination of non-methane hydrocarbons relies on feeding a

continuous stream of gas sample into a gas chromatograph with a flame ionisation
detector. Even simpler instruments are available which simply use the detector, with
the methane being removed by a scrubber before the gas gets to the detector. The
instrument must be carefully calibrated before use as not all hydrocarbons respond
equally to the detector. The gas chromatography system has the advantage over this
method in that it allows identification of individual hydrocarbons in the mixture if
required, although the latter method is less expensive and faster.
Hand held field gas chromatographs are know available which allow sampling and
analysis to be done in the field – eliminating any sampling error.
Fluoride
Gaseous and particulate fluorides may be released to the atmosphere from a number
of industrial sources. Gaseous fluorides such as hydrogen fluoride, silicon
tetrafluoride and fluorosilicic acid are more highly toxic to vegetation than are
particulate forms of fluoride.
Fluorides concentrations in the atmosphere are determined using the method

described in Australian Standard AS2618.2-1984 which is suitable for determining
levels of 0.1µg/m3 or greater. In this procedure an automatic sampler draws ambient
air through an inlet tube which passes it through an acid impregnated paper tape
(initial filter tape) to collect particulate fluorides and then through an alkali-
impregnated paper tape (final filter tape) to collect acidic gaseous fluorides. The
sampler is programmed to collect and store samples over selected time periods up to
seven days. The fluorides from the exposed filter tapes are then extracted into aqueous
solution and the electrochemical response (fluoride activity) determined using a
fluoride ion sensitive electrode.
Hydrogen Sulfide
Ambient air determination of H2S is best determined using the Automatic Intermittent
Sampling Gas Chromatographic Method as outlined in Australian Standard
AS3580.8.1 - 1990. The method is applicable to ambient air with H2S concentrations
in the range 0.003 - 2ppm and is totally specific.
In this method measured test portions of sampled air are drawn off at regular intervals
into a gas chromatographic system. H2S is separated from the other sulfur compounds
and is detected and measured flame photometrically at a wavelength specific for
sulfur. The GC is designed to sample air automatically at least ten times per hour.
page 82
Questions
Class Discussion: A company wishes to develop an air monitoring program for its particulate
emissions. EPA requirements mean that they are required to provide daily data on 24hour
levels. What type of monitoring system would be the most appropriate?
References
1
2
Clean Air Society of Australia & New Zealand, Air Pollution Measurement Manual, 1994.
3
Standards Australia, AS2922 – A Guide for the Siting of Sampling Units, 1987.
4
Wright, G.D., Fundamentals of Air Sampling, Lewis, Boca Raton, 1994.
5
Lodge, J.P., Methods of Air Sampling & Analysis, Lewis, Chelsea, 1989.
page 83
Chapter
5
Treatment & Control of Air Pollutants
Air Quality Standards
Air quality standards are provided by many groups and organisations such as:
• National Environment Protection Council Standards
• WHO
• US EPA
• NSW EPA standards
• Standards Australia
These have been discussed in detail in other modules. All are used to some extent in
air quality monitoring in NSW, but those provided by the NSW EPA and Standards
Australia are the most significant.
Controlling Emission of Particles

Particulate matter leads to the most obvious forms of air pollution – therefore it is the
form that receives the most effort in pollution reduction measures. Many devices and
practices that vary greatly in cost and effectiveness are used throughout industry and
society to reduce the number of particles that are poured into the atmosphere. The
more important of these are discussed in the following chapter.
Process Modifications
Sometimes it is possible to reduce the level of particulate pollutants by simply
changing a procedure or a part of the manufacturing process. Probably the simplest of
these is fuel substitution. From the middle ages to the mid-twentieth century most of
the homes in Britain had wood or coal fires as their main heating source. These were
an enormous source of particulate pollution, and probably greatly contributed to the
countries smog problems. The British Government realised this and banned the use of
coal and wood in home heating – forcing all private citizens to change their heating
over to oil or gas. This dramatically reduced the level of particulate pollutants in the
atmosphere in subsequent years.
Other process modifications such as encapsulation and wet operation can also greatly
reduce the amount of fugitive particles emanating from a potential pollutant source.
Gravitational Settling and Cyclones

This is the simplest way of controlling particulate emissions. This includes several
systems. One of the simplest is the gravitational settling chamber, where particles are
allowed to drop out of the air by sedimentation in a still environment. This method is
not so common, but separation by centrifugation is probably the most common form
of particulate removal. Here the gas is spun rapidly, which causes the heavier
particulate matter to collect on the outside of the separator by centrifugal force, where
Air Quality & Pollution Control Treatment & Control of Air Pollutants
it is collected and removed. This device is called a cyclone separator, and is

demonstrated in Figure 5.1.
cleaned gas
outlet
dirty
gas inlet
particulate outlet
Figure 5.1 – A typical cyclone separator
Filtration Systems
Collection of particles by filtration systems such as fibre bags or beds of small
particles are becoming increasingly popular due to their ease of use and low cost.
Fabric filters are the most common of these devices. These are made of material that
allows gas molecules to pass through, but prevents the much larger particulate matter
from passing. The bags are normally open tubes, manufactured from material with
small pores and many fibrous hairs that stick out from the main membrane. The small
particulates adhere to these hairs, which causes them to coagulate into larger particles.
The bags are periodically shaken to remove the accumulated particles, which fall
down into a collector and are removed.
Fibre bags are commonly used for the control of particulate emissions with very high
dust loadings and smaller particles.
In the typical baghouse unit (figure 5.2) waste gas enters from the side and flows
downward toward a hopper, where the flow is reversed upward into the array of bags.
As the gas changes direction, large particles are removed by inertial separation and
collected in the hopper. As gas passes through the tubular bags, dust is collected on
the inside of the bag surface and the filtered gas is discharged to the atmosphere.
page 85
Fabric filtration has a collection efficiency of >99%, making it the most efficient
method of particulate removal. Limitations of the method include high initial costs,
flammability problems with some dusts, large size requirements for the baghouse unit,
limitation on flue gas temperatures to <300°C, and possible compromises on
efficiency with large changes in gas moisture content.
Figure 5.2 – Filtration bag for collection of particulate matter1
Wet Scrubbers
These devices consist of spray systems where fine water droplets are sprayed at high
velocity at right angles to the emerging gas. Most of the particles in the gas stream are
scavenged by the water droplets, which fall and are collected along with the particles.
One example of a wet scrubber is the open spray tower (see Figure 5.3). In these
devices a scrubbing liquid is sprayed downward through low-pressure nozzles. The
dust-laden waste gas enters from the side and moves downward toward the liquid pool
at the bottom of the tower. Large particles are removed by impingement on the liquid
surface. The waste air then changes direction and moves in the opposite direction to
the flow of the scrubbing liquid and is discharged at the top. Dust particles are
captured by the falling droplets. The liquid-particle agglomerate is collected in the
liquid pool at the bottom of the tower.
Wet scrubbers such as spray towers are limited to low gas flows to prevent liquid drop
entrainment in the scrubbed gas stream. This scrubber attains relatively low
efficiencies (80-90%) and is usually employed as a pre-cleaner to remove particles
larger than 5µm. Other forms of wet scrubbers such as the venturi scrubber are used if
greater collection efficiencies are required. These are also more effective at collecting
fine particles.
Scrubbers are relatively inexpensive to set up, but have high maintenance costs due to
corrosion by acidic flue gases and abrasion of fine particles.
page 86
1
Figure 5.3 – A spray type wet scrubber
Electrostatic Precipitators
These pass the dirty gas through a series of fine wires (called coronas). These wires
support a DC current and are either positively or negatively charged. They work by
relying on the fact that many suspended particles (particularly in smoke) are charged
and will be attracted to the oppositely charged wire, causing them to coalesce and fall
out by precipitation. Alternatively the corona produces negative ions that cause the
particles in the gas stream to become negatively charged, and therefore attracted to the
positive terminal – where they also coalesce and fall into a collection hopper.
The collection efficiency of these devices is greatly affected by the size of the
precipitation field and the gas velocity. Large precipitators and low gas flow rates
give better results. Figure 5.4 shows a typical electrostatic precipitator.
page 87
soot free gas escape
charged electrodes
soot laden smoke

inlet
earth point
removal of soot particles
Figure 5.4 – A typical electrostatic precipitator
Control of Particulate Fugitive Emissions

As is the case with most fugitive emissions, modifications to process and procedures
generally provide the greatest improvement in decreasing the level of fugitive
particulate emissions. Their are some simple steps however which can greatly
decrease the amount of emissions when process errors occur.
The use of ventilation and collection hoods over parts of the process reduces
emissions by sucking particulate matter into filters that are located in the hood. A
simple example of this is the common kitchen range hood.
Other methods such as wet suppression and chemical or physical stabilisation are also
used. Wet suppression involves spraying the work or process at regular intervals in
order to wet any particulate matter. Provided the area is not too hot this means that the
particles are adsorbed onto water, increasing their mass and/or adhesion to the ground
and preventing them from entering the atmosphere.
Control of Gaseous Pollutants

Even though the health effects of gaseous pollutants have been known for a long time,
public concern has in the past always been focused on particulate pollutants due to
their visibility. Gaseous pollutants were largely ignored because they were invisible.
As a consequence the methods for control of gaseous pollutants is nowhere near as
advanced, as is that for particulate pollutants. Additionally in particulate control,
specific techniques can be utilised for a variety of dust collection problems and
sources. The major consideration in selecting such equipment is the performance
required. The application of control technology for gaseous pollutants cannot be as
page 88
Generically applied. Gas cleaning equipment must be developed/designed to control

specific gaseous pollutants or pollutant categories that vary considerably in their
chemical and physical properties. The control of gaseous pollutants is an inherently
more complex technological problem. It is also an inherently more expensive one, as
both capital and operating costs for control equipment are often high.
Major physical and/or chemical principles used in removing gaseous contaminants

from effluent gas streams include combustion, adsorption, and absorption. These
principles and their applications are described below.
Process Modifications
As was the case with particulate pollutants some of the simplest and least expensive
methods for the control of gaseous pollutants are the most obvious. Modifications to
manufacturing processes can often lead to substantial reductions in gas emissions and
pollutants. As was the case with particulates fuel substitution can greatly reduce
pollution levels. For example the use of low sulfur coal, or fuel oils in place of
cheaper coal can greatly reduce the amount of SO2 emissions at the source. Another
example of a process modification is the maintenance of correct combustion ratio for
fuel and air in a furnace. Ensuring the oxygen concentration stays high (through air
injection processes) not only increases the heat output, but also ensures that
combustion is complete and CO2 is generated rather than the far more dangerous CO.
This type of source control is always the best approach wherever possible.
Combustion or Incineration
Combustion involves a series of complex chemical reactions in which oxygen is
combined with organic molecules, to form CO2 and H2O. Although combustion
releases considerable quantities of heat energy, the process requires a flame or high
temperature for its initiation.
The use of combustion processes for control of effluent gases is commonly referred to
as incineration or afterburning. The term afterburning is applicable when the
treatment process is located downstream of a primary combustion process.
Incineration is often applied to effluent streams containing combustible gases in

which the volume flow rate of gas is large and the concentration of the combustible
contaminant is relatively low. Incineration can be used to eliminate;
• malodourants such as mercaptans and H2S
• organic aerosols and visible plumes such as those produced by coffee roaster and
enamel bake ovens
• combustible gases produced by refineries, and
• solvent vapours produced by a variety of industrial processes.
There are three types of combustion systems commonly utilised for pollution control,
These include;
• direct flame,
• thermal, and
• catalytic incineration systems.
page 89
The use of any of these for air pollution control requires a knowledge of the
flammability range of the pollutant gas-air mixture. The concentration of combustible
contaminants and oxygen relative to the flammability range may determine the type of
incineration system used and requirements for supplemental fuel and/or air.
Thermal incineration is used in a large number of industrial processes to reduce

gaseous emissions such as enamel baking ovens and coke ovens. Due to the need for
fuel and/or catalysts the cost of this type of pollution control is high.
Adsorption
Some contaminant gases can be removed from effluents by their physical adsorption
to solid surfaces. The solid collecting media are called adsorbents, the collected gases
or vapours, the adsorbate. The adherence of adsorbate to adsorbents results from the
intermolecular attractive (Van der Waals) forces between them. Adsorption is
reversible; the adsorbate can be removed from the adsorbent by increasing
temperature or lowering pressure. Because of this reversibility, adsorption is widely
used for solvent recovery in dry cleaning, metal degreasing operations, surface
coating, and rayon, plastic, and rubber processing. The application of adsorption
technology has received only limited. use in solving ambient air pollution problems –
with its main use involved in the reduction of odour.
Adsorbents that have a very large surface area to volume ratio such as activated
carbon are the preferred agents for this type of gaseous pollutant control. Efficiencies
may be as high as 99% if the operating parameters are optimised.
Absorption
Control systems that employ liquid media to remove gases are called scrubbers.
Scrubbers remove gases by chemical absorption in a medium that may be a liquid or a
liquid-solid slurry. Because of its low cost, water is the most commonly used
scrubbing medium. Additives, however, are commonly employed to increase
chemical reactivity and absorption capacity. For example, lime or ethanolamine is
added to scrubbing media for the control of acidic gases.
Scrubbers must be designed to provide maximum contact between the gas phase and
the scrubbing medium. Significant gas-media contact can be achieved by employing
mixing mechanisms such as spraying, atomisation, and agitation. Gas-media contact
can also be enhanced by the use of column/tower packing materials. These are usually
ceramic and made in a variety of configurations designed to provide a large amount of
surface area
The most widely used scrubbing system has been the fixed bed packed tower (see
Figure 5.5). The scrubbing medium is introduced at the top and flows downward,
against the flow of the effluent gas. The efficiency of absorption is affected by the
height of the packed tower since the longer the gas path through the scrubber, the
greater the chance of the gas being absorbed.
Dry Scrubbing Systems

This process is used to remove large amounts of SOx from flue gases. This dry flue
gas desulfurisation is achieved by using a dry alkaline absorbent (usually lime or
page 90
sodium carbonate) into contact with the flue gases. These absorbents can also be
applied on a spray, where the heat vapourises the liquid, and the mixture of flyash,
sulfates and dry absorbent is collected and removed by standard dust collectors. Dry
scrubbers have several advantages over wet scrubbers. These include:
• they do not suffer from scaling or residue build up
• they do not require elaborate sludge handling systems for waste materials
• they require less maintenance as there is less corrosion
• they use up to 50% less power, and
• they use less water.
1
Figure 5.5 – A fixed bed tower absorption scrubber
Control of Gaseous and Liquid Fugitive Emissions

Most effort in reducing the level of gaseous pollutants involves reduction of the
pollutant at the source – which is most often a stack or emission valve. Much of the
polluted gaseous material released into the atmosphere does not come through
deliberate emission, but rather fugitive emission.
As is the case with all fugitive emissions, control is normally associated with
improved maintenance and procedures. Routine checking of small sources such as
seals, pumps and valves for leaks normally completely eliminates them as fugitive
emission sources. Large sources such as solvent baths generally need to be enclosed
or at least adequately ventilated with appropriate fume hoods or other ventilation
techniques that fed the exhaust gas through appropriate treatment systems.
page 91
Wet suppression methods are also used to scrub effluent gases from fugitive
emissions – such as those used in the analytical chemistry laboratory in Block E at
Hunter Institute of Technology.
Odour Control
The human nose is a very sensitive organ. This means that it will detect many gaseous
pollutants that are odorous at very low concentrations. Hence it is often necessary to
control the level of substances which although not toxic or directly harmful to health,
smell repulsive. This is the case with many sulfur containing organic materials.
The main approaches used to remove odorous materials from gas emission include
wet scrubbing, charcoal filtration and incineration.
Wet scrubbing is useful for the removal of many water-soluble materials. Here the
pollutant is trapped in mist, absorbed and then collected in a waste stream in exactly
the same fashion as with removal of other undesirable gaseous material.
An alternative method relies on the fact that many of the materials which cause strong
odours are strongly adsorbed onto materials with high surface areas (this is the case
with most organic materials). Hence a charcoal filter (or a series of filters) can be used
to remove odour. Often for strong odours, or in the case when there are higher
concentrations of odorous material in the emission gas, both processes will be utilised
with the effluent gas stream being passed through a charcoal filter on the way to a
scrubber.
Charcoal filters are generally not placed in stacks as they are combustible – hence
they are used in lower temperature environments.
The incineration process used to remove other undesirable air pollutants is also very
effective at removing those substances that cause bad odours. The substances are
generally combusted into other inorganic odourless gases.
Control of Vehicle Emissions

There has been considerable effort in reducing the amount of gaseous materials which
emanate from motor vehicles due to the considerable number which are used world
wide – hence making these a great contributor to air pollution in general. Motor
vehicle emissions produce large amounts of unburnt hydrocarbons, carbon monoxide
and oxides of nitrogen. Older vehicles also produce large amounts of lead, but there
are now very few of these on the load and so these will not be considered here in any
detail.
Reduction in motor vehicle exhaust emissions generally involves simple procedures

such as maintaining the correct tuning for the engine, or more complex processes such
as the use of catalytic converters.
When a hydrocarbon fuel is burnt in air there is an optimum ratio of fuel to air which
produces maximum power and minimum unburnt fuel. The carburettor or fuel
injections system is responsible for maintaining the correct fuel to air ratio. As with
page 92
all mechanical devices it comes out of adjustment with time and so needs regular
tuning to maintain optimum performance. If the vehicle is not tuned it wastes fuel
which is voided with other exhaust gases, and produces much higher levels of CO –
particularly if the engine is running too fuel rich (insufficient oxidant).
Most modern motor vehicles that run on gasoline use a catalytic converter to help the
conversion of unburnt hydrocarbons and CO into CO2 and water. These catalytic
converters use platinum and palladium attached to some form of ceramic material.
They have an extremely high surface area (in hundreds of square meters) which
allows the catalytic materials to come into contact with the exhaust gases, oxidising
them to CO2 and water vapour. Platinum and palladium are used because they are
inert to the sulfur materials also found in exhaust gas streams, but they are rendered
inactive if they come into contact with leaded fuels – a process which is referred to as
catalyst poisoning.
1
Figure 5.6 – A typical catalytic converter (from Godish )
One other major pollution product from motor vehicles is NOx. Unfortunately all the
measures which decrease CO and hydrocarbon emissions, increase NOx emissions.
Measures such as changing engine spark plug timing and reduction of compression
ratios have allowed NOx emissions to be lowered without greatly increasing other
pollutant emissions.
References
1
page 93
Appendix
1
Air Quality Analysis
A1 - EVALUATION of LOCAL FALL-OUT by DEPOSIT GAUGE
This experiment will be conducted as a class experiment with all data points being
pooled to evaluate the area in question. Each pair of students will set up and monitor
their own deposit gauge.
1.1 Prework (this MUST be completed before beginning the practical

session)
Consult Australian Standard AS3580.9 & .10, 1990 and Australian Standard
AS2922 - 1987, and propose a scheme for the evaluation of the levels of fall-out in the
local area.
1.2 Procedure
Use the procedure devised in your prework to set up and monitor your deposit gauge.
Positions for setting of the gauge will be advised by the teacher, but you must be
aware of correct placement for these devices according to Australian Standard
AS2922 - 1987.
1.3 Results
All results are to be recorded on the group data board so that all members of the class
may use them. Your report should use all of the relevant class data for the purpose of
evaluation of particulate pollution levels in the area. Levels of pollution should be
reported in the appropriate units as indicated in Australian Standard AS3580.9. -
1990.
1.4 Questions
1. Describe other alternate procedures for the evaluation of fall out in the atmosphere
and compare and contrast them to the method you have used.
1.5 References
1. Standards Australia, Australian Standard AS3580.9. - 1990.
2. Standards Australia, Australian Standard AS2922 - 1987.

Air Quality & Pollution Control Practical Exercises
A2 - DETERMINATION of METAL CONTENT of LOCAL FALLOUT by X-

RAY FLUORESCENCE SPECTROMETRY
Prework
1. Briefly explain how an X-ray fluorescence spectrometer works, and why it is
suitable for general analysis of elements in a fallout sample.
2. Consult an appropriate reference and outline which elements are suitable for
analysis by XRF analysis.
2.1 Introduction
X-ray fluorescence is a very useful method of qualitative identification (and semi-
quantitative if standards are used) of the elemental components of a particulate
pollutant sample. It is extremely rapid as it is capable of multi-element analysis (all
elements are analysed in the one spectrum).
In this experiment you will examine the fallout sample obtained from your deposit
gauge. You will identify the main metallic components of the fallout and also make an
estimate of the approximate concentration of the more important ones.
2.2 Procedure
Part 1 - Qualitative Analysis
1. Obtain a dried (oven for 1 hour at 105°C) portion of your fallout sample from the
deposit gauge. If a deposit gauge sample is not available, obtain a sample from the
laboratory staff.
2. Grind the sample thoroughly with a mortar and pestle until it is completely
homogeneous (at least 10 minutes).
3. Place the sample on a mylar film sample container and ensure that it is evenly
distributed across the film.
4. Follow the instruction sheet provided (next to the instrument) to scan your sample.
5. Obtain your XRF spectrum and discuss how you will analyse it with your teacher.
6. With the aid of a teacher, identify as many of the elements in the sample as
possible.
7. List the elements in approximate order of importance (from amount and toxicity
of substance) in a table, and propose possible sources of each of these pollutants.
Part 2 - Semi-quantitative Analysis
1. Consult the teacher for a suitable method to prove identity and estimate
concentration of two of the components of your fall out sample.
Note: This method must be approved by the teacher before commencing this
section of the practical.
page 95
2.3 Questions
1. List an alternate method that might allow the same rapid multi-element analysis as
XRF.
2. What are the disadvantages of the XRF method?
3. State the concentration range for which XRF is suited for quantitative analysis.
2.4 References
1. Fullick, G., & Barker, D., Advanced Instrumentation Theory notes, Hunter
Institute of Technology Students Association, 1995.
page 96
A3 - DETERMINATION of IRON CONTENT of PARTICULATE FALLOUT by

FLAME AAS
Prework
Consult a suitable reference1 and outline suitable AAS conditions for the
determination of iron in a particulate fall out sample.
3.1 Introduction
Iron is one of the most common elements on Earth and is a major component of soils,
and dust. It is particularly significant in the Newcastle area as there are major heavy
industries that produce iron and hence it would be expected that some of their waste
products and raw materials might be carried into the atmosphere and deposited in the
local area.
As iron is a major constituent of fall out it is not necessary to resort to trace analysis
to analyse the iron content of a fallout sample. Hence we can employ simple
techniques such as flame atomic absorption spectroscopy which are far less expensive
and easier to operate than trace analysis techniques involving inductively coupled
plasma and electrothermal atomic absorption spectrophotometry.
In this experiment you will determine the amount of iron in your fall out sample, and
compare it to other methods of analysis performed in this module.
3.2 Procedure
NOTE: If you have already performed practical A4 then your sample
preparation is completed – see the teacher.
1. Obtain a fall out sample which has been dried in an oven for at least an hour at
105°C.
2. Carefully weigh approximately 0.1g of your sample on an analytical balance in

duplicate into a platinum crucible.
3. Wet the sample with a few drops of ultrapure water, then add 72% perchloric acid
(0.5mL) and 48% hydrofluoric acid (5mL), place the lid on top, and heat at
approximately 200°C until the sample is digested (consult the teacher here).
4. Add 5M Aristar HNO3 (5mL), and ultrapure water (10mL), then boil until the
solution is homogeneous.
5. Transfer the contents of the crucible to a 100mL volumetric flask, ensuring that
the lid is washed into the flask as well.
6. Make up standards containing 2, 5 and 8mg/L Fe using a 100mg/L stock Fe

solution. Each standard MUST contain 5mL of HNO3 (use normal HNO3 – do not
waste Aristar!) and be prepared in a 100mL volumetric flask.
7. Perform the analysis using the AAS.
page 97
3.3 Report
1. Prepare a calibration graph from the data obtained by the AAS.
2. Use the calibration graph to deduce the concentration of iron in the fall out
sample.
3. Report your answer as Fe content in mg/Kg.
3.4 References
1. Varian Instruments, Methods for Flame Atomic Absorption Analysis, (available

in the laboratory).
page 98
A4 - DETERMINATION of HEAVY METAL CONTENT of FALL OUT by

ELECTROTHERMAL ATOMIC ABSORPTION SPECTROPHOTOMETRY
4.1 Prework
Consult the MSDS for perchloric acid and hydrofluoric acid and list the appropriate
safety procedures for their use.
NOTE 1: Perchloric acid and hydrofluoric acid must only be used under
strict teacher supervision – they are extremely dangerous.
NOTE 2: Electrothermal AAS is an extremely sensitive technique.

Always use ultrapure water for all solution preparation.
4.1 Introduction
Heavy metals are a major health problem, particularly when they are associated with
airborne particulates, as this means they can be readily transported into the lungs and
stomach and directly absorbed into the body. These substances accumulate in the
body and eventually may lead to severe health problems such as dementure and
growth retardation, even at relatively low doses. For this reason health authorities are
continually revising the acceptable level of lead particulates in the atmosphere and
reducing the value.
In this experiment we will use the electrothermal atomic absorption

spectrophotometer to determine the level of lead in our fall out sample. Other methods
such as conventional atomic absorption spectroscopy do not normally provide the
sensitivity to conduct successful determinations of lead as the levels are too low.
4.2 Procedure
1. Obtain a fall out sample which has been dried in an oven for at least an hour at
105°C.
2. Carefully weigh approximately 0.1g of your sample on an analytical balance in

duplicate into a platinum crucible.
3. Wet the sample with a few drops of ultrapure water, then add 72% perchloric acid
(0.5mL) and 48% hydrofluoric acid (5mL), place the lid on top, and heat at
approximately 200°C until the sample is digested (consult the teacher here).
4. Add 5M Aristar HNO3 (5 mL), and ultrapure water (10mL), then boil until the
solution is homogeneous.
5. Transfer the contents of the crucible to a 100mL volumetric flask, ensuring that
the lid is washed into the flask as well.
6. Obtain a 10ppb sample of Pb standard and place it in the autosampler as instructed

by the teacher.
7. Obtain the chemical modifier and place it in the autosampler.
page 99
8. Place your sample in the autosampler (in duplicate) as instructed by the teacher.
9. Run the analytical procedure on the EAAS instrument.
NOTE: Do not discard your sample at the end of the practical as it is also
used in A3. Store in a safe place until you attempt A3.
4.3 Report
1. Use the spreadsheet provided in the laboratory to calculate the concentration of
lead in the fall out sample.
2. Comment on the significance of the lead levels that you have found with regard to
their dangers to human health.
4.4 Questions
1. This procedure uses the method of standard addition. What is the standard
addition method, and why is it appropriate for use on a sample such as the one
used in this practical?
2. Explain the function of the chemical modifier in this method.
3. List the advantages of EAAS compared to normal AAS. Could this analysis be
performed on a normal AAS?
4.4 References
1. Varian Instrument Co., Methods for Graphite Tube Atomic Absorption Analysis -
(available in the laboratory).
2. Fullick, G., & Barker, D., Advanced Instrumentation Theory notes, Hunter
Institute of Technology Students Association, 1995.
page 100
A5 - DETERMINATION of ACIDIC GASES in AMBIENT AIR by

TITRIMETRY (AS 3580.3.1 - Method)
Prework
Consult Australian Standard AS 3580.3.1 and devise a method for the evaluation of
sulfur dioxide (acid gases) in ambient air.
5.1 Introduction
Sulfur dioxide is an important atmospheric pollutant normally associated with the
burning of fossil fuels. It is the cause of the so-called acid rain effect, which seriously
damages plants, structures and human health. The levels of SO2 can be easily
evaluated over a 24hr period using titrimetric methods. This method is not specific for
SO2 however, as it will determine ALL acidic atmospheric gases. As SO2 is normally
by far the most concentrated of the acidic gases in a normal polluted atmosphere, we
will assume that the test is for it alone.
The method involves the collection of a sample of gas over a 24hr period by pumping
ambient air into a chemical trap that accumulates the acid gases. These are then
titrated using suitable indicators to pH 4.5 using standard alkaline solutions. The
concentration of SO2 is then reported in ppm.
5.2 Procedure
1. Use the method devised in the prework to determine the concentration of SO2 in
ambient air over the previous 24hrs.
2. Report your results as the average concentration of SO2 in the air over the past
24hrs in ppm. To do this you will need to estimate the volume of gas pumped
through your trap in the previous 24hr period.
5.3 Questions
1. Is it entirely valid to assume all of the acidic gas in the Tighes Hill area is SO2? If
no, explain why not.
2. Why is it necessary to carefully measure the amount of gas pumped through the
trap?
3. Describe at least two other methods that are suitable for the determination of SO2
in ambient gas mixtures. Compare and contrast these to the method used in this
experiment (state advantages and disadvantages of each).
5.4 References
1. Standards Australia - Australian Standard AS 3580.3.1, 1990.
page 101
A6 - Determination of Total Suspended Particulates in ATMOSPHERIC

GASES by High Volume Sampler (AS 2724.3 - Method) and PM10 High
Volume Sampler with Size Selective Inlet – Gravimetric Method (AS
3580.9.6 – Method)
Prework
1. Consult Australian Standard AS 2724.3 and AS 3580.9.6. Produce a point form
summary of the method for preparation of filters for this procedure.
2. Outline the procedures for setting up and calibrating the sampler prior to
measurement. Point form is acceptable.
6.1 Introduction
There are several accepted methods for the determination of the levels of particulate
matter in the atmosphere. The simplest and least expensive of these is the deposit gauge
(see A1), but it has many limitations. A more convenient method which provides data
much more rapidly (typically one point every 24hours) is the high volume sampler –
which measures suspended particles (not settleable particles as for the deposit gauge).
In order to provide reliable and reproducible data these devices must be very carefully set
up and calibrated before use, and the filters treated by strict handling procedures before
and after use.
In this exercise you will set up and calibrate a high volume sampler and set it to sample
the atmospheric particles in the local area for 24 hours on the prescribed day of the NSW
6-day sampling cycle.
Some suspended particles are far more dangerous to human health than others. One of the
key factors in determining the hazard posed by atmospheric particles is their size. Those
with equivalent aerodynamic diameters (EAD) of less than 10µm may be carried into the
lungs as they are not filtered out in the nose and throat. This means that they are
respirable, and may lodge in the lower lungs to cause respiratory disease.
In order to measure the amount of these respirable particles in the atmosphere a high
volume sampler fitted with a size selective inlet (PM10 head) is used. This size selective
inlet only allows those particles with EAD’s of 10µm or less to be carried onto the filter
and their mass evaluated.
You will set up and calibrate the PM10 head and use it to assess the amount of respirable
particles in ambient air in Tighes Hill.
Finally you will compare the amount of respirable and non-respirable particles in ambient
air through difference calculations.
page 102
6.2 Calibration of Air Samplers

The high volume sampler comes Factory Calibrated. It is necessary however to regularly
check the accuracy of the system. This is done using the procedure below.
1. Placing 'Calibration Flow Head' (see Figure 6.2.1) squarely on top of the Filter Paper
Cassette, with a clean Filter Paper in it.
2. Connect a manometer that reads in either inches or millimetres of water to the

Calibration Flow Head.
3. Place the machine in constant speed mode and adjust speed of motor until desired
flow rate is achieved according to Manometer reading. See Flow Rate Vs Manometer
Chart that is supplied with the Calibration Flow Head.
4. Use the 'Calibration Adjust' Screw (see Figure 6.2.2) to adjust the Flow Rate reading
until it is correct, wait 30 seconds between each tum of the screw for reading to settle
down.
Figure 6.2.1
Figure 6.2.2
page 103
6.3 Determination of Total Suspended Particulates

Note: You must not attempt this step without approval from the teacher.
1. Using the method outlined in your pre-work set up the filter in the filter cassette.
Make sure that you have pre-weighed your paper before placing it on the cassette.
2. Set the timer for the appropriate day of the state wide six day cycle as instructed by
the teacher.
3. In the next practical session - or after the sampling has been completed, retrieve
your paper, allow it to equilibrate in the laboratory (as per pre-work) then weigh it to
the nearest milligram on the same balance used to obtain the initial paper weight.
4. Determine the mass of particles by difference between the initial and final weights.
6.4 Determination of PM10 Suspended Particulate Matter

Note: You must not attempt this step without approval from the teacher.
1. Using the method outlined in your pre-work set up the filter in the filter cassette.
Make sure that you have pre-weighed your paper before placing it on the cassette.
2. Set the timer for the appropriate day of the state wide six day cycle as instructed by
the teacher.
3. In the next practical session - or after the sampling has been completed, retrieve
your paper, allow it to equilibrate in the laboratory (as per pre-work) then weigh it to
the nearest milligram on the same balance used to obtain the initial paper weight
.
6.5 CALCULATIONS.
Volume of air sampled. Calculate the volume of air sampled from the following
expression:
V = (Qi + Qf)t x 273 x P1

2 T 101.3
where
V = air volume sampled, in cubic metres corrected to 0°C and 101.3 kPa
Qi = initial flow rate, in cubic metres per minute
Qf = final flow rate, in cubic metres per minute
T = sampling time, in minutes
T = estimated mean, ambient temperature, in kelvins
P1 = estimated mean, ambient barometric pressure, in kilopascals.
page 104
Calculate the TSP concentration for each sample from the mass of particles collected on
the filter and the respective volume of air sampled, from the following expression:
C = (Wf - Wi) x 103

V
where
C = mass concentration of total suspended particulates, in micrograms per

cubic metre
Wi = initial mass of filter, in milligrams
Wf = final mass of filter, in milligrams.
6.6 Report
The following information should be reported:
1. Reference to the Australian standard, i.e. AS 2724.3.
2. Reporting authority (Hunter Institute of Technology CFET)
3. The concentration of TSP in air in micrograms per cubic metre at 0°C and 101.3 kPa
and the related time averaging periods.
4. Location of the sample-all relevant details, e.g. location on Australian Map Grid* or
GPS, height above ground level, classification of area (industrial, residential,
agricultural, urban etc).
5. The dates and time of day (state whether local or standard time).
6. Any other relevant data, e.g. meteorological conditions.
6.7 References
1. Standards Australia, Australian Standard AS 2724.3, 1984.
2. Standards Australia, Australian Standard AS3580.9.6, 1990.
page 105
A7 - DETERMINATION of Ambient Levels of Carbon Monoxide, Sulfur

Dioxide and Oxides of Nitrogen
7.1 Introduction
There are several methods for the monitoring of ambient levels of pollutant gases such as
CO, SO2 and NO. Most involve expensive real time analysers, which are very accurate,
but are heavy and delicate to set up. An alternative to these is the much smaller and
convenient, but less accurate portable air monitoring meters. These are so small that they
are hand held, but they still provide reliable results and full data logging capability.
In this practical session you will be assigned one or more ambient gas monitoring meters
which you will use to examine the levels of pollutant gases around the nearest busy
roadway. After recording the data you will be required to downland the data into a
computer using a special interface then graph and interpret the results. Finally you will
compare these to historical records of the level of these gases which will be available in
the laboratory.
7.2 Method
1. Obtain an ambient air-monitoring meter from the teacher or laboratory staff.
2. Consult the supplied how to use guide and explain to the teacher how you intend to
use the meter to monitor the ambient levels of this gas at the nearest busy road.
3. Record at least 90 minutes of data in the data logger, ensuring that the meter is used
correctly as per the guide.
4. Connect the meter to the interface and transfer the data to a file in the computer as
per the supplied instructions.
5. Plot the data using an appropriate spreadsheet.
7.2 Report
Provide details of all your data in spreadsheet form and provide a plot of ambient level of
gas versus time.
Comment on the significance of the levels with reference to time of day, health effects,
and previous data.
page 106
Appendix
2
NSW EPA Manual Of Air Quality Testing
CONTENTS
PART 1 - Introduction and Definitions

1.1 Introduction
1.2 Definitions
PART 2 - Stationary Sources

2.1 Sampling
Test Method 1 Selection of sampling positions
Test Method 2 Isokinetic sampling method
2.2 Sulfur (sulfuric acid, sulfur trioxide, sulfur dioxide, hydrogen sulfide)
Test Method 3 Determination of sulfuric acid mist and/or sulfur trioxide
Test Method 4 Determination of sulfur dioxide
Test Method 5 Determination of hydrogen sulfide
Test Method 6 Determination of sulfur content of fuel oil
2.3 Halogens
Test Method 7 Determination of chlorine
Test Method 8 Determination of acids and acid gases (hydrogen chloride)
Test Method 9 Determination of fluorine, hydrofluoric acid and inorganic fluorine
compounds
Test Method 10 Determination of rate of emission of fluoride from aluminium smelters
2.4 Oxides of Nitrogen

Test Method 11 Determination of oxides of nitrogen
2.5 Hazardous Substances

Test Method 12 Determination of metals emissions
Test Method 13 Determination of tin emissions
Test Method 14 Determination of vanadium emissions
2.6 Solid Particles

Test Method 15 Determination of total particulate matter
2.7 Smoke
Air Quality & Pollution Control NSW EPA Air Quality Manual
Test Method 16 Monitoring smoke emissions

Test Method 17 Determination of soot
2.8 Dioxins and Furans

Test Method 18 Determination of polychlorinated dibenzo-p-dioxins (PCDD) and
polychlorinated dibenzofurans (PCDF) from stationary sources
2.9 Volatile Organic Liquids

Test Method 19 Determination of total mass of unburnt organic vapours
Test Method 20 Determination of total mass of unrecovered organic vapours
Test Method 21 Calculation of vapour pressure
2.10 Miscellaneous
Test Method 22 Determination of moisture content in stack gases
Test Method 23 Determination of dry gas density in stack gases
Test Method 24 Determination of carbon dioxide in stack gases
Test Method 25 Determination of oxygen in stack gases
PART 3 Mobile Sources

Test Method 26 (a) Exhaust emission and evaporative emission testing procedure
(b) Determination of H (SHED test)
Test Method 27 Determination of lead concentration in petrol
Test Method 28 Determination of phosphorus concentration in unleaded petrol
Test Method 29 Determination of research octane number of unleaded petrol
Test Method 30 Determination of motor octane number of unleaded petrol
Test Method 31 Observation procedure for excessive air impurities:visible emissions
APPENDIX: Test Methods Sources
page 108

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INTRODUCTION 6

History of Air Pollution 12

Factors Likely to increase the Levels of Air Pollution 13

The Protection of the Environment Operations Act 13

SOURCES, TYPES AND DISTRIBUTION OF AIR POLLUTANTS 14

Major Sources of Air Pollutants 14

Stationary (Industrial) Sources 15

Fugitive Emissions and Other Sources 19

Types of Air Pollutants 20

Primary and Secondary Air Pollutants 20

Particle Behavior in the Atmosphere 22

Total Suspended Particulates (PM10, PM2.5) 22

Carbon Oxides (CO and CO2) 24

Ozone and Photochemical Smog 35

Minor Gaseous Pollutants 42

HEALTH & ENVIRONMENTAL EFFECTS OF AIR POLLUTION 45

Interactions Between Pollutants and Synergism 46

Susceptible parts of the Human Body - The Respiratory System 46

Ozone & Photochemical Smog 52

Environmental Effects of Air Pollutants 56

Effects of Air Pollutants on Buildings and Materials 62

Accepted Levels of Major Air Pollutants 63

AIR QUALITY MEASUREMENT AND ASSESSMENT 65

What is Air Quality? 65

Air Sampling Techniques 66

Selection of Locations for Monitoring Equipment 68

The Importance of Meteorological Monitoring 68

Ambient Air Monitoring 69

Reference Methods for Measuring Air Quality 71

Measurement of Source and Stack Emissions 71

Co-efficient of Haze - Paper Tape Samplers 78

TREATMENT & CONTROL OF AIR POLLUTANTS 84

Control of Particulate Fugitive Emissions 88

Control of Gaseous and Liquid Fugitive Emissions 91

Control of Vehicle Emissions 92

AIR QUALITY ANALYSIS 94

A2 - DETERMINATION of METAL CONTENT of LOCAL FALLOUT by X-RAY

A3 - DETERMINATION of IRON CONTENT of PARTICULATE FALLOUT by FLAME AAS

A4 - DETERMINATION of HEAVY METAL CONTENT of FALL OUT by

A5 - DETERMINATION of ACIDIC GASES in AMBIENT AIR by TITRIMETRY (AS 3580.3.1

A6 - Determination of Total Suspended Particulates in ATMOSPHERIC GASES by High

A7 - DETERMINATION of Ambient Levels of Carbon Monoxide, Sulfur Dioxide and Oxides of

NSW EPA MANUAL OF AIR QUALITY TESTING 107

Concern over the atmospheric concentrations of substance not normally considered

Global Emissions form Natural & Man Made Sources

Figure 1.1 - % of emissions from global and man made sources

Table 1.1 – Components of a normal atmosphere

Element % (by volume) in the Total Mass in the

As the great majority of species on Earth use an oxidative metabolism, it comes as no

At 0.035%, the concentration of carbon dioxide in the atmosphere is very low

To help understand the significance of air pollutants requires an analysis of what a

Stratification of the Atmosphere

Figure 1.2 – The layers of the atmosphere

History of Air Pollution

Factors Likely to increase the Levels of Air Pollution

The Protection of the Environment Operations Act

Major Sources of Air Pollutants

Emissions (106 tonnes / year)

Source CO Particles H/C’s NOx SOx Total %

Transport 40.7 1.4 6.0 8.4 0.9 57.4 44.9

Lead is rapidly decreasing in significance as a pollutant from motor vehicles as more

Stationary (Industrial) Sources

Solvent vapour is an important part of photochemical pollution (see photochemical

Air Pollution Theory&Prac Notes

Air Pollution Theory&Prac Notes