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2.1 Terminologies
Air Pollution – any alteration of the physical, chemical, and biological properties of the
atmospheric air or discharge thereto of any liquid, gaseous, and solid substances that will or
likely to create or render the air resources of the country harmful, detrimental, or injurious to
public health, safety or welfare or which will adversely affect their utilization for domestic,
industrial, agricultural, particularly recreational and other legitimate purpose.
Air Pollutant – means any matter found in the atmosphere other than oxygen, nitrogen,
water vapor, carbon dioxide, and the inert gases in their natural or normal concentrations, that is
detrimental to health or the environment, which include but not limited to smoke, dust, soot,
cinders, fly ash, solid particles of any kind, gases, fumes, chemical mists, steam and radioactive
substances.
Droplet – a small liquid particle of such size and density as to fall under still conditions,
but which may remain in suspension in air or other gases.
Dust – a term loosely applied to solid particles predominantly larger than colloidal, and
capable of temporary suspension in air or other gases.
Fly Ash – finely divided particles of ash entrained in flue gases arising from the
combustion of fuel. The particles of ash may contain incompletely burned fuel.
Fog – loose term applied to visible aerosols in which the dispersed phase is liquid.
Formation by condensation is usually implied. In meteorology, a dispersion of water or ice.
Fume- the solid particles generated by condensation from the gaseous state, generally
after volatilization from the melted substances and often accompanied by chemical reaction such
as oxidation.
Gas- one of the three stages of aggregation of matter, having neither independent shape
or volume and tending to expand completely.
Particulate – a general term meaning “existing in the form of minute separate particles”
either as liquid or solid. It is used interchangeably with aerosol.
Vapor – the gaseous phase of matter which normally exists in a liquid or solid phase.
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Oxygen O2 20.947%
Argon Ar 0.934% 99.998%
CO2
Carbon Dioxide 0.033%
Human Respiration
The air that leaves a person's lungs during exhalation contains 14% oxygen and 4.4%
carbon dioxide. Atmospheres with oxygen concentrations below 19.5 percent can have adverse
physiological effects, and atmospheres with less than 16 percent oxygen can become life
threatening.
moving industry to the outskirts of London and establishing greenbelts in the city.
None of his proposals were implemented.
From centuries, urban air pollution has posed a problem for city dwellers. The earlier manifestation of
pollution was the smoke produced by burning poor quality coal in relatively cold climates in Northern
Europe. This caused high sulphur dioxide (SO2) and particle exposure, sometimes with serious health
impacts. The Industrial Revolution introduced point sources of larger emissions from various
processes. The most important of these was the burning of coal for energy production, resulting in SO2
and combustion particles (smoke).
Coal burning in small and large sources was allowed to continue without required abatement well into
the 20th century. Elevated stacks were the only mode of pollution abatement. Large emissions of SO2
and smoke particles overloaded the atmosphere during temperature inversions in stable high-pressure
situations with stagnant air, leading to notorious air pollution episodes. The 1952 London episode was
the worst, resulting in an estimated 4,000 deaths in five days.
Although the components of air pollution have changed over the years, with the emergence of
industrial sources like toxic gases - methyl isocyanide (CH3CN) in the case of Bhopal disaster in 1984;
coal still remains an important source of air pollution. In addition, vehicular pollution sources have
expanded rapidly in the last three decades. Traffic activity in urban areas of industrialised western
nations has witnessed a four to five fold increase over the decades. In developing nations, this increase
has been ten-fold to more. Prime examples of urban air pollution are the smog in London and
photochemical smog in Los Angeles and Mexico City. The table below shows the history of major air
pollution episodes and their effects. A brief description of these major pollution episodes and its effects
are presented.
The industrial revolution in the 19th century saw the set in of air pollution in Europe on a large scale.
The industries and the households relied heavily on coal for heating and cooking. Due to burning of
coal for heat during the winter months, emissions of smoke and sulphur dioxide were much greater in
winters than they were during the summer months. Smoke particles trapped in the fog gave it a
yellow/black colour and this smog often settled over cities for many days.
The effects of smog on human health were evident, particularly when smog persisted for several days.
Many people suffered respiratory problems and increased deaths were recorded, notably those relating
to bronchial causes. The smog-related deaths were first recorded in London in 1873, when it killed 500
people. In 1880, the toll was more than 1000. London had one of its worst experiences of smog in
December 1892. It lasted for three days and resulted in about 1000 deaths. Despite gradual
improvements in air quality during the 20th century, eight air pollution episodes occurred in London
between 1948 and 1962. The December 1952 episode is the major episode in the history of air
pollution.
The “Killer Smog” began on Thursday, Dec. 4, 1952 as a high-pressure air mass created a subsidence
temperature inversion over southern England. With the particulate and SO2 levels going up due to
extensive use of coal as fuel for space heating and electric production, the fog turned black. At the
same time the high-pressure area stalled and became stationary. The build up of pollutants combined
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with the fog resulted in essentially zero visibility. Within a matter of three days, the pollutants were
concentrated enough to cause deaths. The old and respiratory affected died first, but younger people
exposed to the outside atmosphere were also affected. The maximum daily SO2 concentration recorded
at that time was 1.34 ppm (about 4000 µg/m3, standard SO2 conc. in clean dry atmosphere is 0.0002
ppm) and smoke levels were 4.46 mg/m3. The Great London Smog lasted for five days and lifted on 9th
Dec, resulting in about 4000 deaths.
In the mid night of 2nd - 3rd December 1984, in a densely populated area of Bhopal, Central India, a
poisonous vapor burst from the tall stacks of the Union Carbide pesticide plant. About forty tons of
toxic gases had leaked from the Carbides Bhopal plant and spread throughout the city. The cause was
the contamination of Methyl Isocyanate (MIC) storage tank with water carrying catalytic material.
Residents of the city awoke to clouds of suffocating gas, unaware of the magnitude of the devastation,
which had engulfed them. The city of Bhopal was immediately turned into a city of dead bodies, and
the whole place smelled of burning chilli peppers. Of the million people living in Bhopal at that time,
more than 2,000 died immediately (one fourth of actual figures) and as many as 300,000 were injured.
In addition, about 7,000 animals were affected, of which about 1000 were killed. The precise number
of deaths still remains a mystery till date. The degree of injury was so high that about 30% of the
injured were unable to return to their jobs. Among the survivors, most of them still suffer agonizing
pain from the disastrous effects of the massive poisoning while there are still apprehensions of the
future generations being affected. The Bhopal Disaster was the worst episode in the history of
industrial air pollution.
Horror visited the US Steel company town of Donora on the Halloween night of 1948, when a
temperature inversion descended on the town. Fluoride emissions from the Donora Zinc Works
smelting operation and other sources containing sulphur, carbon monoxide and heavy metal dusts were
trapped by weather conditions, causing 20 deaths within 14 hours.
Cold ground and high-pressure conditions intensified the elevated inversion of the anticyclone that
arrived in the region. The situation was aggravated by local conditions of meteorology, industrial
pollutant emissions and peculiar terrain of the area. The meteorological conditions and the
geographical characteristics of the area produced a strong temperature inversion with a temperature
gradient as high as 33oC/km. The fog was held close to the ground by the stability of the elevated
inversion layer. During the third and fourth days of the episode, as ambient levels of pollutants
escalated, almost half of the population of 14,000 people became ill. Almost 43 % of the population in
Donora and Webster, PA experienced the effects of the smog. Most of the affected were above the age
group of 60 years and above (29% of this group were seriously affected). The health effects were
mainly symptoms affecting the lung, and in particular, upper respiratory symptoms such as nasal
discharge, constriction of the throat, or sore throat were experienced.
An episode occurred in the first week of December 1930, when a thick mist lay over large parts of
Belgium. On December 3rd, 4th and 5th, several thousand cases of acute pulmonary attacks occurred in
the densely populated valley of the Meuse, east of Liege, resulting in 60 deaths. Post episode
investigations led to the conclusion that the cause was poisonous products in the waste gas of the many
factories in the valley, in conjunction with unusual climatic conditions. During that time, the day
temperature was a little above freezing point while at night it measured up to 10oC below, while the
wind speed was only 1-3km/hr. It was impossible to indicate any definite substance or chemical
compound as the cause, but the investigators were of the opinion that the disaster in all probability had
been brought about by sulphur dioxide (SO2) or oxidation products of that compound, of which
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quantities were found in the factory smoke. The investigation also looked into the question of fluorine
intoxication, however its role is doubtful.
The cases of illness were reported after the mist had lasted about 2 days. It was estimated that the total
number of cases was several thousands. In three days, there were 60 deaths, of which fifty-six were in
the eastern half of the valley and only four deaths were reported from the west of Engis. The area
around Engis was the worst affected.
A catastrophic exposure episode involving the release of large quantities of hydrogen sulfide occurred
in Poza Rica, Mexico in November 1950. Poza Rica, a city of 22,000 people located about 210 km
northeast of Mexico City, was then the centre of Mexicos leading oil-producing district and the site of
several oil field installations, including a sulphur-recovery plant. An early morning malfunction of the
waste gas flare resulted in the release of large quantities of unburned hydrogen sulfide into the
atmosphere. The unburned gas, aided by a low-level temperature inversion and light early morning
breezes, was carried to the residential area adjacent to the plant area. Residents of the area succumbed
while attempting to leave the area and assisting stricken neighbors. Within a matter of 3 hours, 320
persons were hospitalized and 22 were killed.
A. According to Origin
Primary Pollutants – substances that are emitted directly into the atmosphere. Most of these are
harmful components of fuel combustion such as sulfur oxides (SOx), nitrogen oxides (Nox), particulate
matter (PM), hydrocarbons (Hcs), and heavy metal particles.
Secondary Pollutants – substances that are created by various physical processes and chemical
reaction that takes place in the atmosphere. An example is ozone, which results from the
photochemical reaction NOx of with sunlight.
Criteria Pollutants - Criteria pollutants are pollutants for which there are already a set of national
ambient air quality guideline values, or standards that need to be met to protect the environment
and human health.
These pollutants are also the most wide-spread and have serious impacts. These are: TSP, particulate
matter with a diameter of 10microns and smaller (PM 10), sulfur dioxide (SO2), nitrogen dioxide (NO2),
carbon monoxide (CO), lead (Pb), and ozone (O3).
A. Area Sources – pollution coming from residential, construction, and other related activities.
B. Mobile Sources – those from vehicular emissions.
C. Stationary Sources – those coming from industrial, commercial, and utilities smokestacks.
D. Natural Sources – examples include volcanoes, forest fires, pollens, spores, and dust springs.
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In the Philippines, the alarming rate of increase in air pollution-related diseases especially
in urban areas like Metro Manila has prompted the government to enact the most comprehensive
legislation to address air pollution – the Philippine Clean Air Act of 1999 (RA 8749).
The Philippines has two types of standards that directly regulate air pollution as provided
in the DENR Administrative Order (DAO) 14:
1. National Emission Standards for Source Specific Air Pollutants (NESSAP), and
2. National Ambient Air Quality Standards (NAAQS) for criteria pollutants from
industrial sources/operations
1.1 The standards listed in NESSAP are the source emission standards that establish the
legal ceiling on the total quantity or concentrations of a pollutant discharged from a pollution
source. Source emission standards are to be complied through application of control technologies
that reduce continuously and result in improved air quality.
Table 2.1 National Emission Standards for Source Specific Air Pollutants (NESSAP)
Notes:
a- all new geothermal power plants starting construction by 01 January 1994 (DAO 14) and 01
January 1995 (RA 8749) shall control H2S emissions to not more than 150 g/GMW-Hr.
b- All existing geothermal power plants shall control H2S emissions to not more than 200
g/GMW-Hr
c- Best practicable control technology for air emissions and liquid discharges. Compliance with
air and water quality standards is required.
d- Emissions limit of Nickel Carbonyl shall not exceed 0.5 mg/Ncm.
DAO No. 14
Industry RA 8749 New SOurce Existing source
1993 After 1978 Before 1978
Fuel Burning System
1. Urban or industrial 150 150 300 500
Areas
2. Other areas 200 200 300 500
Incinerators - 200 300 -
Cement Plants (Kilns, etc.) 150 150 300 500
Smelting Furnaces 150 150 300 500
** other stationary sources 200 200 300 500
Sources: Section 19, RA 8749 and Table 2, DAO No. 14
Notes: * - incinerators are prohibited by the Clean Air Act.
** - Other stationary sources means trade, process, industrial plant, or fuel burning equipment other
than thermal plants, industrial boilers, cement plants, incinerators, and smelting furnaces.
** - Other stationary sources means trade, process, industrial plant, or fuel burning equipment other
than thermal plants, industrial boilers, cement plants, incinerators, and smelting furnaces.
2.1 NAAQS for Source specific Air Pollutants from industrial sources/operations.
Ambient Air Quality – refers to the atmosphere’s average purity in broad area as
distinguished from discharge measurements taken at the source of pollution or the present
characteristic or nature of the surrounding atmosphere.
Are required to be set at levels that will protect public health and include an
“adequate margin of safety”, regardless of whether the standards are economically
or technologically achievable.
Must protect even the most sensitive individuals, including elderly and those
already suffering from respiratory and cardiopulmonary disorders.
Table 3 National Ambient Air Quality Standards for Source Specific Air Pollutants from
Industrial Sources/Operation (NAAQS)
The values in the NAAQG refer to the concentrations of air over specified periods
classified as short-term and long-term.
They are intended to serve as goals or objectives for the protection of health and/or public
welfare. These values are for air quality management purposes such as determining time
trends, evaluating stages of deterioration or enhancement of air quality.
Table 4 national Ambient Air Quality Guidelines (NAAQG) for Criteria Pollutants
Suspended particulate
Matter (c)
TSP
Sulfur Dioxide
Nitrogen Dioxide
Photochemical Oxidant
(Ozone)
RA 8749 140 0.07 1 hr
60 0.03 8 hr
DAO No. 14 60 0.07 1 hr
60 0.03 8 hr
Carbon Monoxide
35 0.07 1 hr
RA 8749 10 0.03 8 hr
35 0.07 1 hr
DAO No. 14 10 0.03 8 hr
Lead (d)
CO emissions from stationary source are lesser compared to vehicular emissions which
account for 70% of CO emissions. About 77% of total CO emissions are from mobile
sources, mostly in urban areas.
Environmental fate
CO can persist in the atmosphere for one to two months before it is converted to CO2 –
thus CO contributes to CO2 in the atmosphere.
Concentrations:
1. 5 to 10 ppm – busy roadways/congested highways
2. More than 400 ppm of CO – from cigarette smoke
3. 20 to 30 ppm – tobacco smokes in bars and restaurants
4. 5 to 10% COHb – smoking
Significant Effects:
1. Physiological – affecting the elderly, fetus and individual who suffer from cardiovascular
disease.
2. The reduction of oxygen in the bloodstream also affects the brain’s ability to perceive and
react.
Interferes with the blood’s ability to carry oxygen throughout the body.
The effect of CO inhalation on human health is directly proportional to the quantity of
CO bound to hemoglobin as shown in Table 2.
Since CO is an asphyxiant (induces the state of not being able to breathe), it interferes
with the blood’s ability to carry oxygen from the lungs to the body’s organs and tissues.
When inhaled, it readily binds to hemoglobin in the bloodstream to form
carboxyhemoglobin (COHb).
Hemoglobin has much greater affinity for CO than it does for oxygen, so even small
amounts of CO can seriously reduce the amount of oxygen conveyed throughout the
body.
With the bloodstream carrying less oxygen, brain function is affected and heart rate
increases in an attempt to affect the oxygen deficit.
Hemoglobin has greater affinity for CO than for molecular oxygen. A person breathing a
mixture of CO and O2 will carry equilibrium of COHb and HbO2 is given by:
Example:
Estimate the saturation value of HbCO in the blood if the CO content of the air
breathed is 100 ppm. Assume that the CO in the blood is at equilibrium. Assume a value of
210 M, air is 21% oxygen.
The percentage of carbon monoxide in the blood may also be computed using the formula
developed by Master’s (1988):
Where:
% of HbCO = Carboxyhemoglobin as % saturation
(CO) = carbon monpxide concentration, ppm
£ = physical activity coefficient
= 1 for sedentary activity
= 3 for heavy work
t = exposure time in minutes
Example:
Estimate the % HbCO expected for a 1-hour exposure to 35 ppm for sedentary
activities and for heavy work.
2. Lead (Pb)
Cumulative poison; emitted into the atmosphere in the form of inorganic particulates
Ingested in food and water as well as being inhaled.
Sources:
Effects:
1. Can cause aggressive, hostile and destructive behavioral changes as well as learning
disabilities, seizures and severe permanent brain damage and death
Two important air pollutants, Nitric Oxide (NO) and Nitrogen dioxide (NO2)
Nitrogen Dioxide is reddish brown in concentrated form while brownish yellow tint at
lower concentrations.
1. Thermal NOx
Created when nitrogen and oxygen in the combustion air are heated to a high
enough temperature (about 1000K) to oxidize the nitrogen.
2. Fuel NOx
Results from the oxidation of nitrogen compounds that are chemically bound
in the fuel molecules themselves.
Dominant source of NOx emissions.
Effects:
Almost all Nox emissions are in the form of NO, which is a colorless gas that has no
known adverse effects at concentration found in the atmosphere.
However, NO can oxidize to NO2 and NO2 can irritate the lungs, causing bronchitis and
pneumonia and lower resistance to respiratory infection.
NOx can also react with VOC in the presence of sunlight to form photochemical
oxidants that have adverse effects as well.
NO2 reacts with hydroxyl radical (OH) in the atmosphere to form nitric acid (HNO3),
which corrodes metal surfaces and contributes to the acid rain problem.
It can also cause damage to terrestrial plants and is a significant cause of euthrophication.
3. Thermal NOx
Created when nitrogen and oxygen in the combustion air are heated to a high
enough temperature (about 1000K) to oxidize the nitrogen.
4. Fuel NOx
Results from the oxidation of nitrogen compounds that are chemically bound
in the fuel molecules themselves.
Dominant source of NOx emissions.
Effects:
Chest constriction and irritation of the mucous membrane of people (coughing).
Cracks rubber products and damages vegetation.
ENT irritation.
4. Photochemical Oxidants
When oxides of nitrogen, VOCs and sunlight come together, they can initiate a complex
set of reactions that produce a number of secondary pollutants known as photochemical
oxidants.
Ozone (O3) is the most abundant of the photochemical oxidants and reason why ambient
air quality standards was written.
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Unlike atmospheric oxygen (O2), ozone (O3) has three oxygen atoms. And, although O2
is reactive, O3 is more reactive. Many of us know the odor of ozone from hot summer
days in the city, lightning storms, or improperly maintained electrical equipment such as
a photocopier.
The word, smog refers to photochemical smog because sunlight plays a major role in its
formation. Ozone is a major component of smog, but smog contains other photochemical
oxidants too including peroxyacyl nitrates (PAN) and nitrogen dioxide. And smog
contains particulate matter making it “air you can see.”
Ground-level ozone is a serious pollutant, but in the atmospheric layer above the
troposphere (the stratosphere), ozone performs a vital function. It absorbs the sun’s
harmful ultraviolet rays, thereby protecting life on Earth.
O2 Sunlight O2
O3 NO
AT early morning traffic emits NO, then as the morning a progress, No is converted to
NO2 (oxidize). As the sun’s intensity increases towards noon, the rate of photolysis of
NO2 increases. Thus NO2 begins to drop while O3 rises. O3 is so effective in its reaction
with NO, that as long as there is O3 present, No concentrations do not rise through the
rest of the afternoon even though there may be new emissions.
Includes unburnt hydrocarbons that are emitted from tailpipes and smoke stacks when
fossil fuels are completely combusted along with gaseous hydrocarbons that enter the
atmosphere, when solvents, fuels and other organics evaporate.
Natural sources of reactive hydrocarbons such as deciduous trees and shrubs that emit
isoprene, conifers that emit pinene and limonene (aromatics).
Anthrtopogenic sources of 1/3 of VOC emissions is the transportations.
Industrial sources account for 2/3 of VOC emission, which much of it caused by
vaporization of hydrocarbons.
Less than 2% of VOCs result from fossil-fuel combustion in power plants and industrial
boilers.
5. Photochemical Smog
Photochemical smog involves the interactions of primary pollutants, Nitric Oxide, and
hydrocarbons in the presence of sunlight.
1. High temperature inside car engines causes the combination of N and O2 in the air
forming Nitric Oxide.
N2 + O2 2NO
2. Gasoline vapors and car exhaust may contain a combustion of hydrocarbon, ketone
and aldehydes. These molecules are excited as they absorb UV from the sun. They
then transfer the extra energy to O2 molecules in air, which also become excited (O2).
Excited molecules then react with NO, forming NO2 and atomic O2. Atomic O2
reacts with ordinary O2 forming O3.
NO + 2O2 NO2 + O3
3. Ozone can react with NO to form ordinary O 2 and more NO2. CO which by
incomplete combustion also participate in generating NO2.
O3 + NO O2 + NO2
4. Atomic O2 can react with hydrocarbon forming free radicals. The reaction may
continue producing more radicals which can react with ordinary O2, other
hydrocarbon and NO.
6. Particulate Matter
Consists of any dispersed matter, solid or liquid, in which the individual aggregates range
from molecular clusters of 0.00µ5 m diameter to coarse particles up to about 100µ m
(size of human hair).
Sources:
45% fuel combustion, 33% industrial processing, 22% transportation
Effects:
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Aggravate existing respiratory and cardio vascular disease and damage lung tissues and
some are carcinogenic.
Upper respiratory infections, cardiac disorders, bronchitis, asthma, pneumonia.
7. Oxides of Sulfur
Almost 90% of anthropogenic SO emissions are the result of fossil fuel combustion in
stationary sources, 8% of that is emitted from electric utility power plants, 3% comes
from highway vehicles.
Sulfur dioxide (SO2) is a corrosive acid gas, colorless with a sharp irritating odor. It
accounts for about 18% of all air pollution, making it second only to CO as the most
common urban air pollutant. It is converted in the atmosphere into substances, which
form aerosols.
Sulfuric acid and sulfate are the major aerosols formed.
Non-combustion sources of sulfur emissions are asssoicated with petroleum refinery,
copper smelting, and cement manufacture.
Effects:
SO2 is highly water soluble, it is most likely to be absorbed in the moist passage of the
upper respiratory tract, the nose and upper airways, when it does less long-term damage.
Combustion of SO damage trees, causes leaf injury and suppresses growth and yield.
Acidification also damages plants by affecting their ability to extract nutrients from the
soil.
Sulfurous pollutants can discolor paint, corrode metals and cause organic fibers to
weaken.
Airborne sulfates significantly reduces visibility and discolor the atmosphere.
So like NO are soluble in water and may be washed down by the rain.
This has beneficial results since sulfur is one of the essential elements for plants. An
excess, however, can be harmful to the soil which is low in alkali.