COURSE NAME: ENVIRONMENTAL

ENGINEERING
COURSE CODE: CHE-351A
TOTAL CREDIT HOURS: 02

Dr. Muhammad Usman Rashid

Assistant Professor (ICET)
 INTRODUCTION
Technological Age: Various engineers disciplines have developed technologies for
converting/utilizing various raw materials (resources) into useful products (services) and
also worked on utilizing the earth’s resources. Mining Engineers have located, extracted,
and refined materials from mineral deposits. Petroleum and chemical engineers have
developed useful products from gas and oil fields. Mechanical and Electrical engineers
have developed technologies to convert natural resources into useful services such as
electricity. Agricultural engineers have refined methods of producing food, utilizing solar
energy, and with the application of fertilizers to enhance fertility of soils and enhance
production. Civil engineers have devised system for capturing, storing, treating and
delivering water for human uses.
These engineers have emphasized the extraction, conversion, supply and use of earth’s
resources. Less attention has been given to the generation and release to the contaminants
from these or other activities.
 INTRODUCTION

As the industrial activity has increased, utilization of earth’s resources has also increased
due to the demand for new products, therefore, the urge/necessity to mitigate(to make less)
the effect of the release of contaminants during the formation of these products in the
environment has increased. Moreover, it has been clear that the technological foundation
of modern society cannot be sustained unless we develop explicit, substantial attention to
contaminant release and their impact on the quality of the environment.
Environmental Engineering has emerged as a distinct technological discipline that
focuses on environmental contaminants and their impacts.
Role of engineer (in view of environment): Problem solver, uses science to solve problems
keeping in view the sustainability, environmental impact, cost estimation.
Solves problems with the assistance of scientific tools.
Environmental engineering is the integration of science and engineering principles to
improve the natural environment, to provide healthy water, air and land for human
habitation and for other organisms and to remediate pollution sites.
Environmental engineering is concerned with the quality and availability of environmental resources
and with the waste streams that impact them.
Environmental resources include all natural materials in those parts of the earth-atmosphere system
where life exists. However, environmental engineering focuses its greatest attention on the two major
environmental fluids-water and air. Soils also attract the attention of the env-engineers but to a
lesser extent than water and air.
Environmental Engineering deals with the pollutants getting access to different environment
dimensions (e.g., water, air) and technologies to mitigate the pollutants from these sources:
Air Pollution
Water pollution
Solid wates (Municipal, hazardous, clinical waste)
Radioactive waste
Noise pollution
MISSION/ROLE OF ENVIRONMENTAL ENGINEER
Develop and apply scientific knowledge through technology to minimize adverse effects that
are associated with contaminates in environmental media. Env-engineers conduct various
types of activities ranging from: assess level of env-contaminants, design and operate
treatment processes and emission control facility to meet env-quality standards. They devise
control strategies, deciding what sources should be reduced by what amounts to meet
environmental quality goals. Help draft env-standards.

“KUI is the Key”

Env-engineer must have knowledge of past and current engineering practices. The important
of understanding fundamentals is amplified by the fact that many control measures mimic
processes that occur in nature. Engineering solution to current and future env-problems will
also require innovation. Knowledge, understanding and inspiration are the pre-requisites for
innovation.
“Environment” includes water, air and land and the inter-relationship
which exists among and between water, air and land and human beings,
other living creatures, plants, micro-organism and property.
ENVIRONMENTAL CRISIS DUE TO INDUSTRIAL DEVELOPMENT

 Large scale contamination of water and air.

 Deforestation
 Increase in urban slums
 Generation of huge solid waste consisting of hazardous material.
 Water scarcity and ground water depletion.
 Global warming
 Greenhouse effect
 Ozone layer depletion
MAJOR POLLUTING INDUSTRIAL SECTORS
 OBJECTIVES OF THIS COURSE
To develop interest among Chemical Engineers regarding environment and its protection.
 To provide basic understanding of environmental engineering so that the Chemical
Engineers may meet the expectation of the Industries for pollution control in their premises
so as to comply with newer and tougher laws and acts that are being enforced in Pakistan
and globally.
 To introduce the principles and methods to control air, water and soil pollution to the
undergraduate students of chemical engineering.
 To develop basic understanding of following topics:
o sources of water, air and land pollution
o recycle and reuse of waste, energy recovery and waste utilization
o air pollution and its measurement
o design of pollution abatement systems for particulate matter and gaseous constituents
o design of waste-water and industrial effluent treatment
o hazardous waste treatment and disposal
o solid-waste disposal and recovery of useful products
 COURSE LEARNING OUTCOMES (CLOS)

Upon successful completion of the course, the students will be able to:
1. Understand the Environmental Pollution.
2. Comprehend the Air Pollution and its control by using different equipment.
3. Acquire the knowledge of effluents and waste water treatment processes.
4. Solve problems related to solid waste management and Environmental Management
Systems.
 WHY MAJOR FOCUS ON WATER-AIR?
This can be understood by considering the routes of exposure to environmental contaminants.
Exposure involve contact with an environmental fluid. There are three significant potential
ways 1) Breathing air 2) ingesting water, other fluids and foods 3)direct contact of materials
with skin.
Average adult inhales 10-20 kg of air and ingests 1-3 kg of fluids , food 1kg, while coming
into direct contact with only small quantitates of soil.
Constituents is the broadest term and includes all materials present in the fluid, including the
basic fluid molecules. E.g., water, constituents (2 hydrogen atoms and one oxygen atoms).
we will use impurities or species to refer to anything other than the dominant background
fluid. For example dissolved oxygen is generally present as species in water but not a
harmful one. Sulphur dioxide is an impurity in the air that can cause adverse health effects.
Contaminants and pollutant are used more or less interchangeably to denote that a species
ha some undesired consequences associated with its presence, Thus, all contaminants and
pollutants are considered impurities and all impurities are considered constitutes of
environmental fluids
 AIR POLLUTION
“Air pollution is the presence in the outdoor atmosphere of one or more air
contaminants (i.e., dust, fumes, gas, mist, odor, smoke, or vapor) in sufficient
quantities, of such characteristics, and of such duration as to be or to threaten to be
injurious to human, plant, or animal life or to property, or which reasonably
interferes with the comfortable enjoyment of life or property”
(Peavy et al., 1985)
 AIR POLLUTION
Air pollution is certainly not a new phenomenon. Early references date to the Middle Ages,
when smoke from burning coal was already considered such a serious problem that in 1307,
King Edward I banned its use in lime kilns in London. In more recent times, though still
decades ago, several serious episodes focused attention on the need to control the quality of
the air we breathe. The worst of these occurred in London, in 1952.
A week of intense fog and smoke resulted in over 4,000 excess deaths that were directly
attributed to the pollution. In the United States, the most alarming episode occurred during a
4-day period in 1948 in Donora, Pennsylvania, when 20 deaths and almost 6,000 illnesses
were linked to air pollution.
 CRITERIA POLLUTANTS
Much of the work on air pollution in the past few decades has centered on a small set of
six substances, called criteria pollutants (CO, NO2, O3, SO2, PM and Lead), that have
been identified as contributors to both sulfurous and photochemical smog problems.
Sulfurous smog is caused almost entirely by combustion of fossil fuels, especially coal,
in stationary sources such as power plants and smelters. In contrast, the air pollution
problem in many cities is caused by emissions of carbon monoxide, oxides of nitrogen,
and various volatile organic compounds that swirl around in the atmosphere reacting
each other in the presence of sunlight to form photochemical smog.
There are many sources of the gases and particulate matter that pollute our atmosphere.
Substances that are emitted directly into the atmosphere are called primary pollutants,
whereas others that are created by various physical processes and chemical reactions that
take place in the atmosphere are called secondary pollutants. For example, nitrogen
oxides and hydrocarbons emitted when fuels are burned are Primary pollutants, but the
ozone that is created when those chemicals react with each other in the atmosphere is a
secondary pollutant. The sources of primary pollutant emissions can be conveniently
categorized by the processes that create them.
 MAJOR SOURCE: COMBUSTION
Most primary pollutants enter the atmosphere as a result of combustion, evaporation, or
grinding and abrasion. Automobile exhaust emissions and power plant stack gases are created
during combustion; volatile substances such as gasoline, paints, and cleaning fluids enter the
atmosphere by evaporation; whereas dust kicked up when land is plowed and asbestos fibers
that flake off from pipe insulation are examples of grinding and abrasion. Of these,
combustion accounts for the great majority of emissions, and the gases and particulate
matter released when fuels are burned have been the focus of most of the technical and
legislative pollution control efforts.
 CRITERIA POLLUTANTS

1) Carbon monoxide: CO,

2) Nitrogen dioxide NO2,
3) Ozone: O3,
4) Sulfur dioxide: SO2,
5) Particulate Matter :PM
6) Lead: Pb
The Clean Air Act requires EPA to set National Ambient Air Quality Standards for six
common air pollutants. These commonly found air pollutants (also known as "criteria air
pollutants") are found all over the United States. The criteria air pollutants include particle
pollution, ground-level ozone, carbon monoxide, sulfur dioxide, nitrogen dioxide, and lead.
These pollutants can harm your health and the environment, and cause property damage. Of
the six pollutants, particle pollution and ground-level ozone are the most widespread health
threats. EPA calls these pollutants "criteria" air pollutants because it regulates them by
developing human health-based and/or environmentally-based criteria (science-based
guidelines) for setting permissible levels. The limits based on human health are called
primary standards. Limits intended to prevent environmental and property damage are
called secondary standards.
Greenhouse gas emissions are often considered to be interchangeable with all air pollutants.
Criteria pollutants and greenhouse gases are both major contributors to harmful emissions,
but they do so in distinctly different ways.
When we talk about global warming and pollution, most people are familiar with the term
“greenhouse gases” however, they may not be as familiar with the term “criteria
pollutants.” Both are emissions that interact in the air, contributing to the global climate
crisis with detrimental effects on both human health and the environment. But there is a
distinct difference between emissions that cause global warming versus those that cause air
pollution, and they are treated and regulated differently.
Greenhouse gases (GHG) reside in the earth’s atmosphere trapping heat and warming the planet.
These gases include carbon dioxide, methane, nitrous oxide, and fluorinated gases. Much like the
glass of a greenhouse, from which they get their name, GHGs let sunlight through the atmosphere
but prevent the heat that they generate from escaping back into space. We need these naturally
occurring gases to sustain life on Earth and help regulate global temperatures—without them the
planet would be too cold, and our oceans would freeze.

Before the industrial revolution, the global GHG balance remained essentially stable as natural
processes removed as much GHG emissions as they released. However, modern human activity
has significantly increased the level of GHGs emitted into the atmosphere, which subsequently
increases the warmth of the planet beyond sustainable levels.

Carbon Dioxide (CO2) is the primary GHG emitted through human activities, accounting for about
82% of all GHG emissions in the US, and 65% globally, according to the Environmental
Protection Agency (EPA). Today’s atmosphere contains 42% more carbon dioxide than it did at the
start of the industrial era.
Methane accounts for about 16% of the planet’s GHG emissions. Human activities are the major
driver of methane emissions including the production and use of gas and petroleum, agriculture,
waste from landfills, and treatment of wastewater. Methane is a short-lived climate pollutant
(SLCP) that is 25 times more powerful than CO2 in trapping heat in the atmosphere over a 100-
year period.
Criteria Pollutants are Responsible for Unhealthy Air Quality
Criteria pollutants are those that create poor air quality, which can damage human health as well
as the environment. These include carbon monoxide, lead, nitrogen dioxide, ozone, particulate
matter, and sulfur dioxide. Breathing in these pollutants has been linked to a significant increase
in lung and respiratory issues, heart disease, childhood development issues, cognitive
impairment, and premature death. Impacts on the environment from criteria pollutants include
dangerous levels of smog, acid rain, and water pollution.
Photochemical smog—perhaps the most commonly known and most visible form of air pollution
– forms when sunlight reacts with nitrogen oxides (commonly referred to as “NOx”) and at least
one volatile organic compound (VOC) in the atmosphere. When these chemicals react with
sunlight, they form airborne particles and ground-level ozone, otherwise known as smog.
Air pollution was responsible for an estimated 4.2 million deaths worldwide in 2015, and millions
more fell ill from breathing dirty air, according to the Global Bureau of Diseases Study. In the
same year in the US, air pollution caused more premature deaths than diabetes and the flu.

Much like GHGs, industrial activity, transportation, and agriculture are the greatest contributors of
criteria pollutants. Unlike GHGs, however, criteria pollutants typically remain in their
geographical region. Any region can experience poor air quality, but major cities experience
significantly higher levels of pollution due to increased road traffic. A region or city’s geography
— mountains, air pressure systems, lack of air flow—can also contribute to how pollution is
concentrated, making some areas, for instance, Los Angeles, especially prone to pollution.

The transportation sector—the movement of people and goods by cars, trucks, trains, ships,
airplanes, and other vehicles— is the biggest contributor to both GHG emissions and criteria
pollutants. In 2017, the transportation industry accounted for about 30% of total US GHG
emissions, over 55% of nitrous oxide emissions, and nearly 75% of carbon monoxide emissions,
according to the EPA.
Passenger cars and light-duty trucks are responsible for over half of the emissions from the
transportation sector, while the remainder of emissions come from other modes of transportation,
including freight movement and commercial transportation.

Emissions from this sector have continued to rise over the last three decades as population
growth, urban sprawl, and increased e-commerce have spurred demand for the transport of
people and goods. This trend is not expected to slow down anytime soon. Today, about 50% of
the world’s population lives in urbans areas, and that is projected to increase to 60% by 2030,
according to a McKinsey report. Following that growth, today’s 1.2 billion cars on the road are
expected to double in the same time period, while the International Transport Forum predicts
freight movement to triple by 2050.
So, the question remains, how do we reduce emissions, improve air quality, and ensure economic
growth in the face of a growing population and mobility expansion. Solving the world’s mobility
challenge requires bold, coordinated efforts by both the public and private sectors, focusing
efforts on improving both fuel and vehicle technology, freight and travel efficiency, and public
transit systems that can remove vehicles from the road altogether.
We’ve made great strides in the last few decades as today’s vehicles are far from the polluters of
years past and many US cities are experiencing greatly improved air quality from past decades.
Electric and hydrogen vehicles produce no tailpipe emissions, while others such as hybrid
electric, natural gas and propane vehicles emit significantly fewer pollutants than conventional
petroleum-powered vehicles. It is important to remember that emissions created during the fuel
production process—not just tailpipe emissions—must also be taken into account and present an
opportunity for further improvements.
States, nations, and the global community are setting aggressive zero-emission goals to guide
businesses and the public to transition to cleaner, more fuel-efficient transportation. Moving
forward, vehicle manufacturers’ advancements in implementing cleaner fuels and technology
options will get us even closer to significant emission reductions. Leadership and ambitious
commitments to sustainable manufacturing, supply chains, and transportation will also be
essential in reducing emissions at scale.
 COMBUSTION AND PRIMARY POLLUTANTS
The origins of primary pollutants is investigated by the following hydrocarbon combustion
reaction, such as methane combustion:
CH4 + 2O2 → CO2 + 2 H2O (1)

The products of combustion are simple carbon dioxide and water, neither of which had been
considered an air pollutant until we realized that the accumulation of CO2 in the atmosphere was
enhancing Earth’s natural greenhouse effect.
Two conditions: Temperature not high enough or limited/not enough oxygen supply,
the following reaction will occur leading to the formation of carbon monoxide.
So we can write the following descriptive reaction to represent incomplete combustion of our
pure hydrocarbon fuel, methane:
CH4 + O2 → mostly (CO2 + 2 H2O) + traces of [CO + (HC)] (2)

Of course, most combustion takes place in air, not in a pure oxygen environment, and air is
roughly 78.09 percent N2 and 21 percent O2.
When the temperature of combustion is high enough, some of that nitrogen reacts with the
oxygen in air to form various nitrogen oxides (NOx). Since this NOx is formed when
combustion temperatures are high, it is referred to as thermal NOx.
Air (N2 + O2) + Heat → Thermal NOx (3)
So far, we have assumed the fuel being burned was a pure hydrocarbon such as methane. In
reality, of course, most fuels have a number of other elements in them such as nitrogen, sulfur,
lead (in gasoline), mercury (in coal), and other unburnable materials called ash. Burning fuel
with these “impurities” in them releases additional Nox (called fuel NOx ), oxides of sulfur
(Sox) , lead (Pb), mercury (Hg) , more particulate matter, and ash.
The more general form of reaction is like that as shown below:
Fuel (H, C, S, N, Pb, Hg, ash) + Air (N2 + O2) → Emissions (CO2, H2O, CO, NOx, SOx, Pb, Hg,
particulates) + ash (4)
 PHOTOCHEMICAL SMOG

Photochemical reactions that produce ozone and other constituents of

photochemical smog. Hydrocarbons and other organic compounds that readily
vaporize are called volatile organic compounds (VOCs). VOCs react with Nox in
the presence of sunlight to produce photochemical smog:

VOCs + NOx + Sunlight → Photochemical smog (O3 + etc.)

To distinguish between the ozone that is formed near the ground by the above
reaction from the ozone that exists in the stratosphere, the designations ground-level
ozone and stratospheric ozone are sometimes used. As we shall see, ground-level
ozone is harmful to our health, whereas stratospheric ozone protects our health by
shielding us from ultraviolet radiation from the sun.
One way to approach emissions and controls of air pollutants is to categorize the sources as
being mobile sources or stationary sources. Mobile sources include highway vehicles
(automobiles and trucks), and other modes of transportation, including railroads, aircraft,
farm vehicles, and boats and ships.
Stationary sources are often categorized as stationary fuel combustion, which includes
electric power plants and industrial energy systems; industrial processes, such as metals
processing, petroleum refineries, and other chemical and allied product manufacturing; and
miscellaneous sources.

Very roughly speaking, mobile sources are responsible for most of the CO and almost half of
the NOx , whereas stationary sources are responsible for most of the SOx, Hg, particulates,
and VOCs, along with a bit more than half of the NOx. As we shall see, regulatory
approaches to controlling emissions, as well as technologies used to do so, are quite different
for mobile and stationary sources.
 CRITERIA POLLUTANTS
Given the ongoing focus of the Clean Air Act, most of the monitoring of emissions,
concentrations, and effects of air pollution has been directed toward the six criteria pollutants:
ground-level ozone (O3) , carbon monoxide (CO), sulfur dioxide (SO2) , small particulates
( PM10 and now PM2.5 ), nitrogen dioxide ( NO2), and lead (Pb).
Carbon Monoxide
Over two-thirds of the mass of all the pollutant emissions in the United States is the colorless,
odorless, tasteless, poisonous gas, carbon monoxide (CO). It is produced when carbonaceous
fuels are burned under less than ideal conditions. Incomplete combustion, yielding CO instead
of CO2, results when any of the following four variables are not kept sufficiently high:
(1) oxygen supply,
(2) combustion temperature,
(3) gas residence time at high temperature,
(4) combustion chamber turbulence.
 These parameters are generally under much tighter control in stationary sources
such as power plants than in motor vehicles, and CO emissions are correspondingly
less. For example, power plants, which are designed and managed for maximum
combustion-efficiency, produce less than 1 percent of all CO emissions in spite of the
fact that they consume about 30% of our fossil fuel.
Over 80 percent of total CO emissions are from the transportation sector, and almost
all of the CO in urban areas comes from motor vehicles. Hourly atmospheric
concentrations of CO over our cities often reflect city driving patterns: peaks occur on
weekdays during the morning and late afternoon rush hours, while on weekends
there is typically but one lower peak in the late afternoon.
Carbon monoxide is an asphyxiant; 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, in
fact, has a much greater affinity for carbon monoxide than it does for oxygen, so that
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 offset the oxygen deficit.
EFFECT OF EXPOSURE TO CARBON MONOXIDE
 OXIDES OF NITROGEN
Although 7 oxides of nitrogen are known to occur, NO, NO2, NO3, N2O, N2O3
N2O4 and N2O5 , the only two that are important air pollutants are nitric oxide (NO) and
nitrogen dioxide (NO2). As mentioned earlier, there are two sources of nitrogen oxides (or
NOx) when fossil fuels are burned.
Thermal NOx is created when nitrogen and oxygen in the combustion air are heated to a high
enough temperature (about 1,000 K) to oxidize the nitrogen.
Fuel NOx results from the oxidation of nitrogen compounds that are chemically bound in the
fuel molecules themselves. Both thermal NOx and fuel NOx can be significant contributors to
the total NOx emissions, but fuel NOx often is the dominant source.
In 2003, transportation accounted for 57% of emissions, whereas stationary fuel combustion
emitted 37%.
About 95% of anthropogenic emissions of NOx are in the form of NO, which is a colorless gas
that has no known adverse health effects at concentrations found in the atmosphere.
However, NO readily oxidizes to NO2, and NO2 can irritate the lungs, cause bronchitis and
pneumonia, and lower resistance to respiratory infections.

Nitrogen dioxide has other environmental consequences besides those directly associated
with human health. It reacts with the hydroxyl radical (OH.) in the atmosphere to form
nitric acid that corrodes metal surfaces and contributes to the acid rain problem.
Reductions in NOx emissions have been harder to come by than reductions in other criteria
pollutants. In fact, emissions increased for several decades after the original Clean Air Act
was passed, due in part to early automobile emission controls that focused on reducing CO
emissions at the expense of increasing NOx.
Since then, better technology and more stringent standards applied to new cars and light
duty trucks are beginning to turn the corner.
 VOLATILE ORGANIC COMPOUNDS (VOCS)
This class of compounds consists of volatile compounds that enter the atmosphere when
solvents, fuels, and other organics evaporate, along with unburned and partially burned
hydrocarbons that are emitted from tailpipes and smoke stacks when fossil fuels are not
completely combusted.

" Volatile organic compounds (VOC) means any compound of carbon, excluding carbon
monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, and ammonium
carbonate, which participates in atmospheric photochemical reactions”.

Regulation of VOCs is based on their role as precursors to the formation of photochemical

smog.

Maintaining good indoor air quality (IAQ) is critical for health and safety. However, this can
be a challenge due to the presence of volatile organic compounds (VOCs).
Industrial sources account for almost all of the other half of VOC emissions,
with much of that again being caused by vaporization of hydrocarbons.
Volatile organic emission are found in many common household items, and they
vaporize at room temperature. Because of this, concentrations are usually much
higher in the home than elsewhere
Organic chemical compounds are everywhere in both indoor and outdoor
environments because they have become essential ingredients in many products and
materials.
•Outdoors, VOCs are volatized or released into the air mostly during manufacture or
use of everyday products and materials.
•Indoors, VOCs are mostly released into the air from the use of products and
materials containing VOCs.
VOCs are of concern as both indoor air pollutants and as outdoor air pollutants.
However, the emphasis of that concern outdoors is different from indoors. The main concern
indoors is the potential for VOCs to adversely impact the health of people that are exposed.
While VOCs can also be a health concern outdoors,
EPA regulates VOCs outdoors mainly because of their ability to create photochemical smog
under certain conditions.
List of VOCs:
Acetone
Acetic acid
Butanal
Carbon disulfide
Ethanol
Formaldehyde
Methylene chloride
A VOC is any organic compound having an initial boiling point less than or equal
to 250° C measured at a standard atmospheric pressure of 101.3 kPa

Boiling Point Range

Description Abbreviation Example Compounds
(°C)
Very volatile (gaseous) Propane, butane,
VVOC <0 to 50-100
organic compounds methyl chloride

Formaldehyde,
toluene, acetone,
Volatile organic
VOC 50-100 to 240-260 ethanol (ethyl alcohol)
compounds
2-propanol (isopropyl
alcohol), hexanal
In terms of direct human health effects of VOCs, it is our exposure to a long list of volatile
and toxic compounds inside our buildings that provides our greatest risk.
When NOx, 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 it is the one for which
an ambient air quality standard has been written.
Although it is responsible for many of the undesirable properties of photochemical smog,
from chest constriction and irritation of the mucous membrane in people to the cracking of
rubber products and damage to vegetation, it is not a cause of the eye irritation that is our
most common complaint about smog.

Eye irritation is caused by other components of photochemical smog, principally

formaldehyde (HCHO), peroxybenzoyl nitrate (PBzN), peroxyacetyl nitrate (PAN), and
acrolein (CH2CHCOH).
In the very simplest of terms, we can express the formation of photochemical
smog as:
 PARTICULATE MATTER

Particulate matter is the sum of all solid and liquid particles suspended in air
many of which are hazardous. This complex mixture includes both organic
and inorganic particles, such as dust, pollen, soot, smoke, and liquid droplets.
These particles vary greatly in size, composition, and origin.
 PARTICULATE MATTER
Atmospheric particulate matter consists of any dispersed matter, solid or liquid, in which the
individual aggregates range from molecular clusters of 0.005 micrometers (µm) diameter to
coarse particles up to about 100 µm (roughly the size of a human hair). As a category of criteria
pollutant, particulate matter is extremely diverse and complex since size and chemical
composition, as well as atmospheric concentration, are important characteristics.
A number of terms are used to categorize particulates, depending on their size and phase (liquid or
solid).
The most general term is aerosol, which applies to any tiny particles, liquid or solid, dispersed in
the atmosphere. An aerosol (abbreviation of "aero-solution") is a suspension of fine solid particles
or liquid droplets in air or another gas. Aerosols can be natural or anthropogenic. Examples of
natural aerosols are fog, mist, dust, forest exudates and geyser steam.
Solid particles are called dusts if they are caused by grinding or crushing operations.
Solid particles are called fumes if they are formed when vapors condense.
Liquid particles may be called mist, or more loosely, fog.
Smoke and soot are terms used to describe particles composed primarily of carbon that result from
incomplete combustion.
Smog is a term that was derived from smoke and fog, originally referring to particulate matter
but now describing air pollution in general.
Particulate matter (PM) can be emitted directly as carbonaceous soot particles from incomplete
combustion, or it can be formed in the atmosphere, as, for example, when gaseous and
emissions are transformed into liquid droplets of sulfates (sulfuric acid) and nitrates (nitric
acid).
The original NAAQS for particulates did not take size into account. Larger particles could
dominate the mass per unit volume measure but be unimportant in terms of human health risk.
In 1987, however, the PM10 standard was introduced, and in 1997 the PM2.5 standard was
added. Particles smaller than 2.5 µm (i.e., PM2.5) are referred to as fine particles, whereas those
between 2.5 µm and 10 µm are the coarse fraction of PM10.
Coarse particles tend to settle quickly, so their spatial impact is limited to areas near their
source, but fine particles have longer atmospheric lifetimes and are capable of traveling vast
distances.
Equivalent aerodynamic diameter determined by comparing them with perfect
spheres having the same settling velocity.
The particles of most interest have aerodynamic diameters in the range of 0.1 µm to
10 µm.

Particles smaller than these undergo random (Brownian) motion and, through
coagulation, generally grow to sizes larger than 0.1 µm. Particles larger than 10 µm
settle quickly; a 10 µm particle, for example, has a settling velocity of approximately
20 centimeters per minute
 OXIDES OF SULFUR
About 86 % of the 15 million tons per year of anthropogenic sulfur oxide emissions are
the result of fossil fuel combustion in stationary sources, and most of that is emitted by
coal-fired power plants.
Only about 5 percent comes from highway vehicles. The only significant non combustion
sources of sulfur emissions are associated with petroleum refining, copper smelting, and
cement manufacture.
All fossil fuels as they are extracted from the ground contain some sulfur. Coal, which has
the most, typically contains from 1 to 6% sulfur. About half of that is organic sulfur that is
chemically bound to the coal.
The other half is simply physically trapped in the noncarbon portion of coal, and much of
that half can be removed by pulverizing and washing the coal before combustion.
The amount of sulfur in petroleum tends to be less than a few percent, and if refined,
almost all of that sulfur is removed during processing.
Gasoline, for example, has much less than 1 ppm sulfur.
Natural gas as it leaves the wellhead contains a considerable amount of sulfur in the
form of highly toxic hydrogen sulfide (H2S) that must be removed before the gas can
be used.

After natural gas is cleaned, however, negligible amounts of sulfur remain, which
makes it a highly desirable replacement fuel for coal.
When these fuels are burned, the sulfur is released mostly as sulfur dioxide (SO2) but also
with small amounts of sulfur trioxide (SO3) . Sulfur dioxide, once released, can convert to
SO3 in a series of reactions, which, once again, involve a free radical such as

The HO2. radical can then react with NO to return the initial OH. radicals . Sulfur trioxide
reacts very quickly with H2O to form sulfuric acid, which is the principal cause of acid rain

Sulfuric acid molecules rapidly become particles by either condensing on existing particles in
the air or by merging with water vapor to form H2O-H2SO4 droplets.
Often, a significant fraction of particulate matter in the atmosphere consists of such sulfate
(SO4) aerosols. Sulfate particles in urban air typically have an effective size of less than 2 µm ,
with most of them being in the range of 0.2 to 0.9 µm . Their size is comparable to the
wavelengths of visible light, and their presence greatly affects visibility. Their size also allows
deep penetration into the respiratory system.

ACID DEPOSITION
The transformation from gas to sulfate particles is gradual, taking a matter of days. During that
time, sulfur pollution may be deposited back onto the land or into water, either in the form of
SO2 or sulfate.
In either form, sulfur pollution can be deposited by removal during precipitation (wet
deposition), or by slow, continuous removal processes that occur without precipitation (dry
deposition). Natural rainfall would have a pH value between 5 and 5.6, and anything less is
loosely called “acid rain.”
 HEALTH AND WELFARE IMPACTS

Sulfur dioxide is highly water soluble, much more so than any of the other criteria
pollutants. As a result, when inhaled, it is most likely to be absorbed in the moist
passages of the upper respiratory tract, the nose and upper airways, where it does less
long-term damage.
Other gases, being less soluble, are more likely to reach the more critical terminal air
sacs of the lungs.
When sulfur is entrained in an aerosol, however, the aerodynamic properties of the
particles themselves affect the area of deposition, and it is possible for sulfur oxides to
reach far deeper into the lungs.
Sulfur oxides can damage trees, especially when trees are bathed in acid fog or clouds
that tend to have very low pH levels.

Prolonged exposure to sulfates causes serious damage to building marble, limestone, and
mortar, as the carbonates (e.g., limestone, ) in these materials are replaced by sulfates.
The reaction between limestone and sulfuric acid shows such a replacement:

The calcium sulfate (gypsum, ) produced by this reaction is water soluble and
easily washes away, leaving a pitted, eroded surface. Many of the world’s
historic buildings and statues are rapidly being degraded due to this exposure
e.g., Taj Mahal white marble changing color to yellowish due to sulfur dioxide,
NOx and carbon based pollutants and emissions