14.

0 ENVIRONMENTAL CHEMISTRY
14.1: Air Pollution and Control
 OBJECTIVES
By the end of this subtopic, you should be able to:
• Outline the main industrial methods of controlling sulphur dioxide emission
(flue gas desulphurisation, alkaline scrubbing, and use of limestone-based
fluidised beds).
• Recognise the use of lean-burn engines and catalytic converters in reducing
pollutant emissions from petrol-driven cars.
• Deduce environmental considerations related to the usage and generation
of power (with particular reference to fossil fuels and nuclear energy).
• Identify other potential power sources.
• Recognise the hazards associated with random emission from uranium-
bearing rocks and with nuclear accidents.
 INTRODUCTION
• Air pollution is defined as the presence of toxic chemicals or compounds in the air, at levels that pose
a health risk.
• It includes the presence of chemicals or compounds in the air which are usually not present and
which lower the quality of the air or cause detrimental changes to the quality of life such as the
damaging of the ozone layer or causing global warming.
• Primary pollutant - is an air pollutant emitted directly from a source.
• Examples of primary air pollutants include combustion of fuel in an engine releasing carbon
monoxide and nitrogen oxides out of the exhaust.
• Another example is sulphur dioxide released in a power plant or factory from combustion of fossil fuel.
A volcanic eruption releases smoke and ash which are considered primary pollutants.
• Nitrogen oxides are produced by combustion of fossil fuels at high temperature or by thunderstorms.
• Secondary pollutant – is an air pollutant indirectly emitted in the air and forms when other pollutants
(primary pollutants) react in the atmosphere. Examples include acid rain and smog.
• In air pollution, PM stands for particulate matter the term for a mixture of solid particles and liquid
droplets found in the air.
• Some particles, such as dust, dirt, soot, or smoke, are large or dark enough to be seen with the naked
eye.
• Others are so small they can only be detected using an electron microscope but all are particle
matter and pollute the air.
• The main culprits of air pollution are oxides of carbon, sulphur, nitrogen and also hydrofluorocarbons.
 CAUSES OF AIR POLLUTION

Fig 14.1.1: Causes of air pollution

• Sulphur dioxide(𝑆𝑂2 ) emitted from the combustion of fossil fuels like coal, petroleum is one the
major cause of air pollution.
• Manufacturing industries release large amount of carbon monoxide, hydrocarbons, organic
compounds, and chemicals into the air thereby depleting the quality of air.
• Exhaust gases emitted from vehicles including trucks, cars, trains, buses and airplanes cause
immense amount of air pollution.
• Carbon monoxide (𝐶𝑂) caused by incomplete combustion of fuels and generally emitted from
vehicles is another major pollutant along with nitrogen oxides(𝑁𝑂𝑋 ) that are produced from both
natural and man-made processes.
 Fig 14.1.2: Causes of air pollution
• Natural events that pollute the air include forest fires, volcanic eruptions, wind erosion, pollen
dispersal, evaporation of organic compounds and natural radioactivity.
• Air pollution from natural occurrences are not very often.

Fig 14.1.3: Causes of air pollution

• Clean up experts always apply the worst option in reducing the amount of
oil spilled on water bodies by burning the floating oil which results in black
carbon (soot).
• Crop dusting which involves spraying crops with crop protection products
from an agricultural aircraft, fumigating homes, household cleaning
products or painting supplies, over the counter insect killers, fertilizer dust emit
harmful chemicals into the air and cause pollution.
 EFFECTS OF AIR POLLUTION
1. Depletion of the ozone layer
• Ozone exists in earth’s stratosphere and is responsible for protecting humans from harmful
ultraviolet (UV) rays.
• Ozone depletion is due to the presence of chlorofluorocarbons, hydro chlorofluorocarbons in
the atmosphere.
• Chlorofluorocarbons were formerly used and are sometimes used in coolants, foaming agents,
fire extinguishers, solvents, pesticides, and aerosol propellants.
• As ozone layer will go thin, it will emit harmful rays back on earth and can cause skin cancers
and eye related problems.
2. Respiratory and heart problems
• A greater number of people are known to have died due to direct or indirect effects of air
pollution.
• Air pollution has both acute and chronic effects on human health, affecting a number of
different body systems and organs.
• It ranges from minor upper respiratory irritation to chronic respiratory and heart disease, lung
cancer, acute respiratory infections in children and chronic bronchitis in adults, aggravating
pre-existing heart and lung disease, or asthmatic attacks.
• Children in areas exposed to air pollutants are said to commonly suffer from pneumonia and
asthma.
3. Acid Rain
• Harmful gases like nitrogen oxides and sulphur oxides are released into the atmosphere during
the burning of fossil fuels.
• When it rains, the water droplets combines with the sulphur oxides and nitrogen oxides,
becomes acidic and then falls on the ground in the form of acid rain.
• In the environment, acid rain damages trees and causes soils and water bodies to acidify,
making the water unsuitable for some fish and other wildlife. It also speeds the decay of
buildings and statues.
4. Eutrophication
• It is a condition where in a water body, high amount of nitrogen present in some pollutants
gets settled on water`s surface and turns itself into algae
• It harmfully kills fish, plants and animal species thereby disturbing the ecosystem. The green
coloured algae present on lakes and ponds are due to presence of this chemical only.
• Air emissions of nitrogen oxides from power plants, cars, trucks, and other sources contribute to
the amount of nitrogen entering aquatic ecosystems.
5. Effect on Wildlife
• Toxic pollutants in the air, or deposited on soils or surface waters, can impact wildlife in a
number of ways.
• Like humans, animals can experience health problems if they are exposed to sufficient
concentrations of air toxics over time.
• Toxic chemicals present in the air can force wildlife species to move to new place and change
their habitat.
• The toxic pollutants deposit over the surface of the water and can also affect sea animals.
 METHODS OF CONTROLLING AIR POLLUTION
Sulphur dioxide
• Sulphur dioxide is a colourless gas with a sharp, irritating odour. It is produced by burning fossil fuels
and by the smelting of mineral ores that contain sulphur.
• Erupting volcanoes can be a significant natural source of sulphur dioxide emissions.
Environmental effects
• When sulphur dioxide combines with water and air, it forms sulphuric acid, which is the main
component of acid rain.
• Acid rain can cause deforestation, acidify waterways to the detriment of aquatic life and corrode
building materials and paints.
• Sulphur dioxide irritates the respiratory tract and increases the risk of tract infections. It causes
coughing, headaches, mucus secretion and aggravates conditions such as asthma and chronic
bronchitis.
• Once sulphur dioxide is released into the atmosphere, it can be converted to other compounds or
removed from the atmosphere by various mechanisms.
• Processes such as flue gas desulphurisation (alkaline scrubbing, use of limestone based fluidised
beds) and other processes contribute to the removal of 𝑆𝑂2 from the atmosphere.
Flue gas desulphurisation (FGD)
• Flue gas is the combustion gas exiting to the atmosphere via a flue, which is a pipe or channel or
chimney for conveying exhaust gases from fire places, furnaces, steam generators and ovens.
• Flue gas contains oxides of nitrogen, sulphur and carbon and other pollutants.
• Flue-gas desulfurization (FGD) is a set of technologies used to remove sulphur dioxide 𝑆𝑂2 from
exhaust flue gases of fossil-fuel power plants, and from the emissions of other sulphur oxide emitting
processes.
• There are two types of FGD which are wet alkaline scrubbing and dry alkaline scrubbing.
Wet alkaline scrubbing
• Sulphur dioxide is an acidic gas and therefore, the typical sorbent slurries or other materials used to
remove 𝑆𝑂2 from the flue gases are alkaline.
• The reaction that takes place in wet scrubbing is uses𝐶𝑎𝐶𝑂3 (limestone) slurry to produce𝐶𝑎𝑆𝑂3
(calcium sulphite) as shown by the equation:
𝐶𝑎𝐶𝑂3 (𝑠) + 𝑆𝑂2 (𝑔) → 𝐶𝑎𝑆𝑂3 (𝑠) + 𝐶𝑂2 (𝑔)
• Wet alkaline scrubbers help remove the sulphur dioxide from the smoke in the exhaust of a power
plant.
• The flue gas from the burning coal fuels first pass through a specific filter to get rid of soot and ash.
• The flue gas then enters a scrubber, in the scrubber, a water spray produces a cloud of fine water
droplets.
• The water is mixed with crushed limestone (𝐶𝑎𝐶𝑂3 ) , which reacts with the sulphur and pulls it out of
the exhaust as calcium sulphate.
 Fig 14.1.4: An example of a wet alkaline scrubber
• Wet calcium hydroxide and wet magnesium hydroxide can be used as well to trap sulphur dioxide giving
calcium sulphite and magnesium sulphite respectively.
• The 𝐶𝑎𝑆𝑂3 (calcium sulphite) can further be oxidized to produce𝐶𝑎𝑆𝑂4 2𝐻2 𝑂, this marketable product is known as
gypsum. This technique is also known as forced oxidation.
• Gypsum uses include manufacture of wallboard, cement, plaster of Paris and soil conditioning.
• A natural alkaline usable to absorb 𝑆𝑂2 is seawater. 𝑆𝑂2 is absorbed in the alkaline seawater, and when oxygen is
added reacts to form sulphate ions and free hydrogen ions.
• The surplus of hydrogen ions is offset by the carbonates in seawater pushing the carbonate equilibrium to release
carbon dioxide gas.
• The advantages of using wet alkaline scrubbers is that they have relatively high removal efficiency (90-95%) and
low cost of operation.
• They are less hazardous in terms of causing explosions and fires and they collect both gas and particulate
matter.
Dry alkaline scrubbing
• A dry or semi-dry scrubbing system, unlike the wet scrubber, does not saturate the
flue gas stream that is being treated with moisture.
• In other setups no moisture is added, while in others small amount of moisture that
can be evaporated in the flue gas without condensing is added.
• Dry scrubbing systems use quicklime (𝐶𝑎𝑂) to remove acid gases such as 𝑆𝑂2
primarily from combustion sources.
3
𝐶𝑎𝑂(𝑠) + 𝑆𝑂2 (𝑔) → 𝐶𝑎𝑆(𝑠) + 𝑂 (𝑔)
2 2
• There are different types of dry scrubbing system designs and all consist of two main
sections:
• A section to introduce the acid gas sorbent material into the gas stream.
• A particulate matter control section to remove reaction products, excess sorbent
material as well as any particulate matter already in the flue gas.
• The calcium oxide produced is less hazardous, it can be easily disposed and does
not produce corrosive material or waste water.
• However, use of dry scrubbers is less efficient (70%) than wet scrubbing.
Limestone-based fluidised beds
• Low-rank coals like lignite and brown coals
account for approximately 50% of global coal
reserves.
• Such coals contain high sulphur content which
is a pollutant if released into the atmosphere.
• The most important use of coal is in
combustion for power generation and during
combustion various compounds are released
which include sulphur dioxide.
• Therefore to prevent sulphur from polluting the
environment after combustion, it requires the
application of additional technologies for its
capture and limestone based fluidised beds
are used during combustion.
• In fluidised bed combustion, a bed of crushed
solid particles is made to behave like a fluid by
an airstream passing from the bottom of the
bed at sufficient velocity to suspend the
material in it.
• The bed contents is a mixture of coal
and limestone (𝐶𝑎𝐶𝑂3 ) whichpossesses many Figure 14.1.5: Setup of a limestone based fluidised bed
of the properties of a fluid and behaves like a
fluid.
• The crushed coal is fed into the bubbling bed together with limestone which is preheated to about
850– 950 °C. Coal particles are heated at approximately 1,000 °C per second and are devolatilised.
• Since the bed is continuously bubbling and mixing like a boiling liquid, transfer of heat to and from
the bed is very efficient and, hence, uniform temperatures can be achieved throughout the bed.
• Due to this efficient heat transfer, less surface area is required to remove heat from the bed.
Therefore, there are lower total capital costs associated with a given heat load.
• Limestone based fluidized bed combustion systems are predominantly suitable for coals of low
quality and high sulphur content because of their ability to retain sulphur dioxide within the bed.
• When limestone (𝐶𝑎𝐶𝑂3 ) is introduced into the bed along with the coal, the limestone decomposes
to lime, calcium oxide (𝐶𝑎𝑂) according to the reaction below;
𝐻𝑒𝑎𝑡
𝐶𝑎𝐶𝑂3 𝐶𝑎𝑂 + 𝐶𝑂2 (𝑔) ↑
• Calcinations reaction occurs at 600 °C to 750°C temperature.
• The 𝐶𝑎𝑂reacts in the bed with most of the SO2 released from the burning coal to produce calcium
sulphate (𝐶𝑎𝑆𝑂4 ).
1 𝐻𝑒𝑎𝑡
𝐶𝑎𝑂 + 𝑆𝑂2 + 𝑂
2 2
𝐶𝑎𝑆𝑂4
• Desulfurization reaction occurs at 700 °C to 850 °C temperature.
• The 𝐶𝑎𝑆𝑂4 can be removed as a solid by-product (bottom ash on the diagram) for use in a variety
of applications.
• In addition, partially spent calcium can be recycled by a variety of techniques.
• Limestone based fluidized bed combustors are usually connected to additional equipment such as
cyclone separators to separate fines containing a high amount of combustibles and recycle them
back into the system.
Lean-burn engines and catalytic converters
• If internal combustion engines were 100 percent efficient, the fuel would burn and produce just carbon dioxide
and water.
• However, in reality, engines are far less efficient and the combustion process produces harmful substances like
carbon monoxide (CO), oxides of nitrogen (NOx) and unburned hydrocarbons in addition to carbon dioxide
and water.
• In order to reduce these harmful exhaust emissions, there are two basic methods used to reduce these harmful
exhaust emissions.
• Use of lean-burn engines
• Use of catalytic converters to the exhaust system.
Lean – burn engines
• Petrol burns best in a standard car engine when it is mixed with air in the proportions 14.7:1 - nearly 15 parts of air
to every one part of petrol.
• In practice the mixture strength varies between about 13:1 and 16:1, depending on the speed of an engine and
its load at the time.
• At these mixtures, engines produce fairly high levels of harmful exhaust gas emissions, particularly during initial
acceleration.
• Lean-burn engines are designed to produce a lower level of harmful emissions by better combustion control and
more complete burning inside the engine cylinders.
• The engine operates with excess air in the fuel-air mixture, resulting in the presence of relatively high oxygen
concentration in the exhaust stream.
• The excess of air in a lean-burn engine combusts more of the fuel and emits fewer hydrocarbons.
• The current generation of lean-burn engines run on stoichiometric ratios of around 17:1 or 18:1
• The main drawback of lean-burning is that a complex catalytic converter system is required to reduce NOx
emissions.
Catalytic converters
• Catalytic converters in a car are fitted downstream of the engine in the exhaust system.
• A catalytic converter is designed like a slightly swollen silencer and contains a fine metal or ceramic
honeycomb, coated with platinum or a similar, platinum-like metal such as palladium or rhodium.
• The platinum catalyst initiates a chemical reaction in which the harmful exhaust constituents such as carbon
monoxide and nitrogen oxides are converted into harmless nitrogen, carbon dioxide and water vapour.

Figure 14.1.6: A catalytic converter

• Hydrocarbons and carbon monoxide are present in car exhausts gases in the form of unburnt petrol or diesel.
• Nitrogen oxides are created when the heat in the engine forces nitrogen in the air to combine with oxygen.
• Carbon monoxide is a poison for any air-breathing animal, nitrogen oxides lead to smog and acid rain, and
hydrocarbons produce smog.
• As the gases from the engine fumes blow over the catalyst, chemical reactions take place on its surface,
breaking apart the pollutant gases and converting them into other gases that are safe enough to blow
harmlessly out into the air.
• The following reactions shows how the pollutants are removed:
Carbon monoxide + oxygen → carbon dioxide
Hydrocarbons + oxygen → carbon dioxide + water
Nitrogen monoxide + carbon monoxide → nitrogen + carbon dioxide
Air pollution in Zimbabwe
• Zimbabwe has experienced a rapid expansion in the national vehicle population on its road largely due to the
import of second hand vehicles from countries like Japan.
• The main problem associated with this rapid growth in vehicle population especially in the major cities is the
increased concentration of line and area emission sources due to road congestion at peak hours.
• As a result there are high emission rates of major air pollutants from vehicle emissions resulting in a deterioration
of the ambient air quality especially in the major cities of Harare, Bulawayo, Gweru, Mutare and Kwekwe.
• The Environmental Management Agency of Zimbabwe (EMA) conducts programs of vehicle emissions tests
during random road blocks within these high traffic prone areas of the country, to help curb the environmental
emissions pollution from vehicles.
• Vehicle test kits are used during these road blocks to determine the level of emissions from motor vehicles.
• Failure by the vehicle to release the levels that are within the permissible limits will attract a fine to the motorist.
• The environmental management agency urges all vehicle owners to ensure that their vehicles are well
conditioned and run efficiently to reduce levels of pollution.
• Vehicle emissions testing are designed to identify such vehicles in order to make necessary repairs to reduce
emissions below the applicable pollution control standards.
• Another contribution to air pollution in Zimbabwe comes from the use of old technology and equipment by the
industries.
• Companies cannot replace old technologies due to the economic down-turn or do not have abatement
equipment to control emissions into the atmosphere.
Alternative power sources to fossil fuels
• Generating electricity from renewable energy sources rather than fossil fuels offers significant environmental and public health benefits.
• Replacing fossil fuels with renewable energy has been found to reduce environmental degradation, mortality and healthcare costs.
• Wind, solar, and hydroelectric systems generate electricity with no associated air pollution emissions.
• While geothermal and biomass energy systems emit some air pollutants, total air emissions are generally much lower than those of coal- and
natural gas-fired power plants.
• Motor vehicles driven by fossil fuels, a key factor in urban air pollution, can be replaced by electric vehicles though the technology is still being
implemented.

Hazards associated with uranium bearing rocks and nuclear accidents

• The presence of certain naturally occurring elements, such as uranium can make exposure to the rocks that contain them hazardous.
• The radioactive element uranium exists in very small amounts (parts per million) in rocks, soils, and water.
• The half-life of uranium`s most common isotope, 238U is approximately 4.5 billion years, making it ideal for radiometric dating of the oldest rocks on
earth.
• Radon is produced by natural radioactive decay of uranium. Radon is carcinogenic and a prominent cause of lung cancer.
• Radon is colourless, odourless, and tasteless, making it exceptionally hazardous, as its presence is revealed only by specific detectors.
• Structures built over radon-emitting granites can trap and concentrate the gas, putting the inhabitants at extreme risk.
• If inhaled or ingested uranium, however, its radioactivity poses increased risks of lung cancer and bone cancer.
• Uranium is also chemically toxic at high concentrations and can cause damage to internal organs, notably the kidneys.
• Fissile isotopes of uranium have the ability to cause a nuclear chain reaction making the metal important for generating heat in nuclear power
reactors and producing fissile material for nuclear weapons.
• A nuclear and radiation accident is defined by the International Atomic Energy Agency (IAEA) as an event that has led to significant
consequences to people, the environment or the facility.
• Examples include lethal effects to individuals, large radioactivity release to the environment, or reactor core melt.
• The prime example of a major nuclear accident is one in which a reactor core is damaged and significant amounts of radioactivity are released,
such as in the Chernobyl disaster in 1986.
Serious nuclear accidents: Case Study
Fukushima, Japan, March 2011
• The earthquake and tsunami that struck eastern Japan on March 11, 2011, caused a serious
accident at the Fukushima Dai-ichi nuclear power plant on the north-eastern coast of Japan.
• The earthquake cut off external power to the reactors. Tsunami, which reached levels more than
twice as high as the plant was designed to withstand, disabled backup diesel generators, crippling
the reactor cooling systems.
• Battery power was quickly exhausted, and overheating fuel in the plant's operating reactor cores
led to hydrogen explosions that severely damaged three of the reactor buildings.
• Fuel in three of the reactor cores melted, and radiation releases from the damaged reactors
contaminated a wide area surrounding the plant and forced the evacuation of nearly half a
million residents.

Chernobyl, Ukraine, April 26, 1986

• Chernobyl is considered the world’s worst nuclear disaster to date. It occurred on April 26, 1986,
when a sudden surge in power during a reactor systems test resulted in an explosion and fire that
destroyed Unit 4.
• Massive amounts of radiation escaped and spread across the western Soviet Union and Europe.
• As a result of the disaster, approximately 220,000 people had to be relocated from their homes.
• In the case of Chernobyl, 31 people died as a direct result of the accident, two died from blast
effects and a further 29 firemen died as a result of acute radiation exposure in the days which
followed.
 ASSESSMENT EXERCISE 14.1 AIR POLLUTION
1. The most important use of coal is in combustion for power generation and
during combustion various compounds are released which include sulphur
dioxide which is a pollutant.
a. Explain why 𝑆𝑂2 is considered to be an environmental hazard.[4]
b. Name any two processes that can be used to prevent emission of sulphur
dioxide into the atmosphere.[2]
c. Outline how wet alkaline scrubbing is used to control the release of 𝑆𝑂2 .[5]
d. State a use of the product obtained after the process in (c). [2]
2. Mr Nhamo wanted to buy a Mercedes Benz 300E at ZIMOCO car
sales. During the negotiations with the sales man, he discovered that
the vehicle`s engine was not fitted with a lean burn engine and he
declined to buy.
a. Give an explanation why Mr Nhamo preferred a vehicle fitted with a lean burn
engine over one fitted with a standard engine. [2]
b. Outline how a lean burn engine operates.[3]
c. Outline the limitation of using a lean burn engine. [1]