Chem 310: Environmental CHEMISTRY

Course Outline
Purpose:
To learn the various chemical processes that occurs in the atmosphere and their
importance

Learning outcomes:

At the end of the course, the learner should be able to:

1. Know the various forms of pollution, sources and sinks

2. Demonstrate an understanding of the various types, sources and effects of air
pollutants.
3. Understand various methods of analyzing air pollutants
4. Understand other forms of pollution water, land, pesticides and insecticides
5. Appreciate various environmental regulations on pollution.

Course Description
Environmental pollution. Production of oxides of carbon, nitrogen and sulphur from
fossil fuel. Atmospheric photochemistry of major gaseous pollutants. Acid rain. Nature
and potential toxicity of particulate and gaseous emissions from the combustion of
petroleum based fuels. Lead fuel additives are potential health hazards. Recent
developments in emissions control. Impact of agricultural chemicals on terrestrial and
aquatic environments. Persistence of pesticide residues in tropical ecosystems and
temperate climates. Effect of pesticides residues on food chains. Eutrophication and
environmental health implications. Industrial, agricultural and domestic toxic wastes
and their environmental implications. Waste disposal methods. Environmental
regulations guiding Kenyan industries of environemental pollution.

Chapter 1
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 UNIT 1 INTRODUCTION
1.1 Background
● Nature of life depends on water and air. Water has unique properties that sustain life
● The earth has large amounts of liquid water -.75% of the earth’s surface and only 1% of
this is fresh. This makes the earth special compared to other solar planets since no other
planet has liquid water and air to sustain life(confirm)
● The two i.e. water and air must be clean
● However, natural and human activities (chemical?) affect the state of purity of these two
very much. This is the basis of environmental pollution

What then is the scope of Environmental Chemistry?

● To determine the nature and quantity of specific pollutants in the environment i.e.
To study their relative toxicities and ways of pollution control and remediation

1.2 Uniqueness of environmental chemistry

● An attempt is made to describe the topics in the light of modern developments, effects
and methods available to reduce environmental pollution and use of instruments used for
various analytical analyses
● This is so since determination of levels specific pollutants in the environment is the role
of an environmental chemist
● This process is difficult since their amounts in natural samples is appreciably small e.g.
level of air pollutants may be in microgram per cubic nature of air or for water may be
parts per million (ppm) by weight or even less. Hence need for instruments with high
sensitivity and accuracy
● Thus to grasp environmental chemistry one must understand how pollution takes place
(the nature, reactions and transport of chemical species) in the environment. In addition
one should be able use of modern instruments for analysis
● The above then equips the environmentalist to make maximum contribution to the
solution of environmental problems (see later)
1.3 Some terminologies used in the study of environmental chemistry
Names and corresponding definitions are given with examples, chemical equations or
diagrams/figures for clarity
a) Environment
● Refers to all physical and chemical, organic and non-organic components of the
atmosphere, lithosphere and oceans.
● It is the sum total of the conditions that influence life an individual or population
● It determines the quality of life of an organism and it’s in constant change
The three environments are : Atmosphere, Lithosphere and Hydrosphere
Biosphere is the right combination of the three sphere or realms – Atmosphere, Lithosphere
and Hydrosphere

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The Atmosphere is a layer of air around us. The importance of atmosphere: -
(a) It gives us life giving gases like oxygen for breathing of animal kingdom and carbon
dioxide is inhaled by plant kingdom.
(b) It has Ozone layer which protects us from the harmful ultraviolet rays of the sun.
(c) There are tiny dust particles in the atmosphere which helps in the formation of the rain
droplets.
(d) It acts as a blanket which prevents the earth from becoming too hot during day and too cold
during night.
(e) It protects us from falling meteors and other cosmic dusts. They burn when coming in
contact with the atmosphere.
(f Presence of gases, dust particles and water vapors lend colors to the sky
We, the humans are an integral part of the environment, but we are a bit different from
other creatures. Human beings adapt themselves to the natural environment by making
modifications in their food, cloth and shelter. They also modify their natural environment to suit
their social, biological, cultural and economic needs. The early human beings slept on trees and
caves, they used to roam around in search of food as that of other creatures but with the passage
of time, with the help of their mind, thinking skills, ability, knowledge, hard work, etc. they have
changed themselves drastically. Now, the modern man is far more organized, skilled, well
mannered and cultured. They live in houses, eat cooked food, travel from one place to another by
various means of transportation, etc. The biggest difference is that the humans have the ability to
create but in case of animals or other creatures, they cannot create. They must depend on
whatever is available around them to survive.

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 b) Environmental Chemistry
● Refers to the study of the sources, reactions, transport, effects and fates (end up) of
chemical species in the water, soil and air environment.
● It is a multidisciplinary science
The Science with studies the relationship between living and non-living environment is termed
as Ecology.
The Interrelation between plants and animals in the natural environment is called Ecosystem.

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 c) Environmental pollution
Refers to unfavorable alteration of our surroundings, wholly or largely as a by-product of man’s
actions, through direct or indirect effects of change in energy patterns, radiation levels, chemical
and physical constitution and abundances of organisms.

The determination of unfavorable vs. favorable effects or of benefits verses costs has been
difficult –subjective. Example
● Man made alteration of the environment will probably have unfavorable effects to others
e.g. cutting down trees helps man economically while this will affect rain, increases soil
erosion
● Effluents: Rich societies of developed countries may be concerned more about basic
needs e.g. employments. This makes poor nations not about pollution
Pollution is usually classified according to the environment (air, water, soil) in which it occurs or
according to type of pollutant (lead, Hg, CO2, solid waste, noise) by which pollution has been
caused include the listed below: -
● Air pollution
● Water pollution
● Solid wastes land pollution
● Marine pollution
● Noise pollution
● Radiation pollution
● Thermal pollution
Sometimes, can be broadly classified as:
● Natural pollution- which originates from natural processes
● Artificial pollution-it originates due to activities of man
Class activity: Use the list above to classify each as either natural or artificial or both
1.3.1 Pollutants:
● Defined as anything, living or non living, or any physical agent that in excess makes any
part of the environment undesirable. These affect life of man directly or indirectly e.g.
water –not good for drinking or air – not good for breathing
Unserviceable machines, electronic gadgets
● Agricultural and other biological products are affected

Concentration of pollutants can be expressed by fractions

Symbol Definition Fraction
ppm parts per million 10-6
ppb parts per billion 10-9
ppt parts per trillion 10-12
● For particulate matters in the atmosphere, they are expressed in density units of
micrograms per cubic meter (µg/m3 at a given pressure and Temp. Specific or common
pollutants include:
Gaseous pollutants
● Oxides of Nitrogen (NO, NO2)
● Oxides of Sulphur (SO2, H2S)
● Oxides of Carbon (CO, CO2)
● Halogens –Cl2, Br2, I2

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 ● Fluoride compounds
Solid pollutants
Metals: Hg, Pb, Fe, Zn, Ni, Sn, Cd
● Complex organic pollutants –Benzene, benzpyrene, acetic acid, ether
Photochemical oxidants: ozone, NOX, CH3 C (O) OONO2, Peroxy acetylnitrate (PAN),
aldehyde, PBzNx
Other pollutants are
● Deposited matter – sort, smoke, tar, dust
● Solid waste/domestic e.g. dust, animal fur etc
● Economic poisons- herbicides, fungicides, pesticides etc
● Fertilizers/Agricultural e.g. nitrates, phosphates
● Radioactive wastes
● Noise
● Heat
● Industrial wastes e.g. Cr3+ ions from tanneries (how is this treated to acceptable levels?)
1.3.2 Micotoxins and Microbial contamination
Examples of these are afflatoxins which can be carcinogenic
Are be classified into two basic types
Non-degradables
● Are heavy metals and their salts, DDT, long chain phenolic compounds
● These can accumulate and are biomagnified(could be stored in body tissues and food
chains)
● They react with other compounds in the environment to produce more toxins referred to
as 2o pollutants
Biodegradables
Domestic sewage, herbicides and some pesticides
1.3.3 Contaminant: Something which causes a deviation from the normal composition of an
environment. Contaminants are not classified as pollutants unless they have some detrimental
effects e.g. Oil spill, Gas leaks.
1.3.4 Threshold Limit Value (TLV)
It refers to the permissible level of toxic pollutant in atmosphere to which a healthy industrial
worker gets exposed during an eight hour day without getting any adverse effects. E.g. TLV, Be
& Zn=0.002 and 1.000mg/m3 respectively. Radiation also has its limits
1.3.5 Source- Logical place from which the pollutant originates from e.g. industries,
agricultural activities, domestic and natural sources
Self Assessment Question: Why is Knowledge of sources important to an environmental
chemist?
Receptor- Refers to anything which is affected by the pollutant e.g. ourselves
Sink- it is the medium which is able to retain and interact with a long lived pollutant, though not
necessarily indefinitely. Can be –soil, water atmosphere.
An illustrated example is limestone which is a sink for atmospheric H2SO4

Self Assessment Question: Write equations to show how water is a sink

1.3.6 Pathway of a pollutant-

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Refers to the mechanism by which the pollutant gets distributed from its source into the
environmental segments e.g.

Self Assessment Question: State any three sources of lead commonly found in the environment
1.4 Other terminologies
a) Speciation
● Is a term used for the analysis of different chemical forms or species of inorganic or
organ metallic compounds which are present in the environment. (toxicology of any
compound depends on its form) E.g. To determine Methyl mercury CH3Hg+. (more toxic
that Hg)
● Important when considering toxicological studies and ways of their/waste removal from
environment. E.g. Cr2+ is more toxic while Cr3+ is essential element
b) Dissolved Oxygen (DO)
● Amount of oxygen dissolved in water. Optimum value for good quality of water 4-6
mg/liter of DO. Anything below mean the water is polluted
c) Biochemical Oxygen Demand (BOD)
● Refers to a standardized measurement of the amount of oxygen that would be required by
microorganisms to cause the decomposition of certain organic and inorganic matter in
water in 5 days. It is a quality parameter for organic matter in water. Good drinking water
should have 0.7 to 1.5 mg/l. It is an indicator of pollution
Self Assessment Question: Read on how this is done??
d) Chemical Oxygen Demand (COD)
● Is a measure of the concentration in a water supply of substances that can get attacked by
a strong chemical oxidizing agent in a standardized analysis? It is an index of the organic
content of water oxygen demanding substances in water. Potassium dichromate and
potassium permanganate are used to measure COD and results expressed as amount (in
ppm) oxygen needed to oxidize the contaminants
Self Assessment Question:
1) Read and explain how above parameters are measured
2) What is the difference between COD and BOD?
3) What are the factors that influence BOD?
e) Eutrophication
Is a process by which pollution from such sources as sewage effluent or leachate from fertilized
fields causes a lake, pond, or fen to become over rich in organic and mineral nutrients, so that
algae and cyanobacteria grow rapidly and deplete the oxygen supply (DO)
f) Synergism and Antagonism
Synergism

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 ● In many cases the combined effects of two or more pollutants are more severe or even
qualitatively different from the individual effects of separate pollutants –synergism or
sometimes called potentiation e.g. studies show that sometimes the particulate matter
such as soluble salts of Fe, V, Mn, can increase the toxicology of SO2
Antagonism
● Sometimes the combined effects of two or more pollutants are less than more severe.
Than the effect of individual pollutants. This effect is called antagonism e.g. cyanide is
very poisonous but in presence of Ni, Zn, Cd is less severe due to complex formation.
Self Assessment Question: Explain using examples the differences between synergism and
antagonism
NB
Other terms will be defined at the relevant sections
1.5 Role of an Environmental Chemist [discuss each using specific examples]
● Involvement in environmental health to improve standard and quality of life
● Conservation of resources
● Development of non-polluting recycling processes with zero material loss.
● Monitoring pollution sources in the environment
● Pollution control
● Engage and implement government policy on environmental issues e.g. National
Environment Monitoring Agency (NEMA-covered in details later) e.g. non pollutant
products (any example?)
● Sectors of the economy must adhere to set rules and regulations on environmental safety.
( Public Health Safety Act)
2.0 AIR POLLUTION
2.1 Composition of clean dry air and the atmosphere
Component Volume (%)
Nitrogen (N2) 78.1
Oxygen (O2) 21.0
Argon (Ar) 0.9
Carbon dioxide (CO2) 0.03
Neon (Ne) 0.002
Helium (He)
Methane (CH4)
Krypton (Kr)
Xenon (Xe)
Traces of Hydrogen
-Oxides of N2
- Ozone
- Oxides of S
- Other gases
2.2 Classification of Pollutants
(1) Sources – Man-made (Anthropogenic)
- Natural pollution
Primary pollution
● Emitted directly into the atmosphere e.g.
Secondary pollution

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 ● Occurs when primary pollutants reacts in the atmosphere to produce other pollutants e.g.

Natural pollutants arise from:

● Volcanic activity or forest fires
● The effects of solar radiation or electric discharge
● Natural disturbances can also lead to presence of tiny particles of solids or liquid matter
(particulate matter) in the air e.g. Tornados.
Primary pollutants
● The major pollutants however arise from man’s activities
● Five types of substances accounts for over 90% of air pollution
They include:
Oxides of carbon (CO)
Nitrogen oxides
Sulphur oxides
Hydrocarbons
Particles
2.2.1 Carbon monoxide
● Is a colorless, odorless, tasteless and non-irritating gas
● It is generated by incomplete combustion processes mainly from motor-vehicle exhausts,
stoves
● It is slightly lighter than air and insoluble in water
Effect on blood
● It is poisonous to human and animal life. It forms carboxyhaemoplobin (COHb) which
prevents blood haemoglobin from performing its function of transporting oxygen from
lungs to body tissues and taking CO2 from these organs to the lungs.
● The affinity of CO for haemoglobin is 320 times that of oxygen. However, the body is
slow to absorb (and desorbs) CO at low CO levels. I.e. it takes some time for the inhaled
CO to equilibrate with the circulating blood.
● Equilibrium is not established until after 4 to 12 hours depending on the physical activity
of the individual. (For a person involved in strainous activity equilibrium is reached more
quickly).

Observations
● When COHb in blood is less than 0.7% there No apparent effects
● 1-2.0% - some evidence of behavioral performance
● 2.0 -5.0 –central nervous system effects. Impairment of time intervals, discrimination of
visual acuity, brightness discrimination and other psychomotor functions
● 5.0 cardiac and pulmonary functional changes
● 10-80 – Headaches, fatigue, drowsiness, coma, respiratory failure and Death.
Note

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Normal levels of COHb in blood is 0.5% as a result of CO produced during destructive
metabolism of Hb
2.2.2 Sources of CO
Natural
● Vegetation- mainly produced by oxidation of the methane by OH present in the
atmosphere. ( a gas released in copious amounts in swamps, bogs and rice paddies)
● Ocean- oceans are usually saturated with CO from marine algae and jellyfish. It therefore
diffuses from ocean to the atmosphere.
Anthropogenic
● Combustion – from combustion of coal, stoves, furnaces etc

The sec. reaction is 10 times slower than the first one, hence CO still observed even in
presence of sufficient oxygen

● Vehicular emission – it is estimated that for every 7 liters of petro about 370g of CO is
produced/emitted.
● During peak hrs, levels of CO2 could as high as 100ppm (Correlates with that of CO)
● Cigarette smoking- cigarette smoke contains about 2% CO due to incomplete combustion
of tobacco.

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Sources of CO in the atmosphere

2.2.2 Fate of Carbon monoxide in the atmosphere – CO sinks (End up, or how it’s
removed)
● Residence of CO in atmosphere is in the order of 0.03 yrs(work out how many d,Hor m)
● It is basically acted on by the following:
i) Hydroxyl radicals important in the generation of CO from methane are similarly are
instrumental in removing CO from the atmosphere by oxidizing it to CO2

ii) The CO may be transported from troposphere to stratosphere, where it is rapidly oxidized to
carbon dioxide by oxygen free radicals.
ii) Soils acts as an important sink for carbon monoxide. e.g. Methanosarcina barkerii of
methanobacteria formicum by oxidation to CO2 or Reduction to

● The soil is able to remove about 5 times the discarded CO in the atmosphere, It is a major
sink since
● Most CO remain in the atmosphere since the sink not evenly distributed
2.2.3 Analysis of Carbon Monoxide
● The concentration of CO in the atmosphere is determined by non-dispersive infrared
analysis.
Principles:
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 ● CO has a dipole moment hence can absorb IR unlike other gases (IR in
Control measures for CO
Mainly production of CO is through vehicular automobiles (space flights/submarines
● Thus these have been fitted with catalytic burners/converters to oxidize CO to harmless
CO2.
● These catalytic converters not only reduce CO but also nitrogen oxides.
● Modification of internal engines to burn efficiently
● Use of alternative fuel e.g. hydrogen
● Use lean air fuel mixture
2.3 Nitrogen oxides and their sources
These are primary oxides involved in urban pollution
● Nitrogen combines with oxygen to form a family of oxides: Nitrous oxide (N2O), Nitric
oxide (NO), Nitrogen dioxide (NO2), Dinitrogen trioxide (N2 O3), Dinitrogen tetroxide
(N2 O4) and dinitrogen pentoxide (N2O5).

Of the oxides the most important pollutants environmentally are

● Nitrous oxides, N2O, Nitric oxide NO, Nitrogen dioxide, NO2. (Or Collectively Nitrogen
Oxides; NOx)
● At primary level, they elicit several toxic effects
● At secondary level, they enter into chemical reactions with other constituents of the
atmosphere producing acid rain, photochemical Smog and aerosols.
2.3.1 Sources of NOx
● Naturally during thunders storms
● When the temperature are high.
● Also by micro-organism in soil on aerobic + anaerobic nitrate base
● Anthropogenically –by fossil fuel based power plants and automobiles.
● High temperature and pressure in the combustion chamber provide suitable conditions for
the production of oxides of nitrogen.
● NO, NO2 enter in the atmosphere through natural processes as illustrated below
Nitrogen combines with oxygen to give nitric oxide only at high temperature

In the atmosphere it is converted to nitrogen dioxide by aerial oxidation

Ozone can also oxidize nitric oxide to NO2

2.3.2 Concentration and distribution of NOx in the atmosphere

(Use reactions above to explain)
● Before daylight, NO and NO2 levels is fairly constant
● As human activity increases, levels of NO increases (due to combustion of fuel)
● Sunrise provides UV radiation and NO2 go up as levels of NO go down (Why?)
● As O3 begins to accumulate as NO goes down (Why?)
● As solar intensity goes down and traffic increases in the evening (5-8pm), conc. Of NO
increases (no solar energy to convert NO to NO2) but O3 built up during day reacts with
NO to form NO2
● Thus increase in NO2 but decrease in O3
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 2.3.3 Harmful effects of NOx
● NOx are potential health hazards
● NO2 is 4 times more toxic than NO
● NO not harmful but reacts to form NO2
● Like CO it has similar effects on human but at higher doses
Self Assessment Question:
i) Explain the effect of NOs on human beings in a similar way CO was done
ii) What is the effect of NO2 on plants? Materials e.g. textiles?
2.3.4 Fate of Nitrogen oxides in the Environment
In the atmosphere NOx/NO2 are relatively inert
In the stratosphere NOx undergoes photolysis producing either nitric oxide (a) or free oxygen
atoms (b)

Free oxygen atoms interact with nitrous oxide producing nitric oxide

Nitrogen dioxide react with water vapors producing nitric acid

Nitric acid is either washed as rain or combines with atmosphere ammonia producing ammonium
nitrate aerosols.

2.3.5 Photochemical smog

● Oxides of nitrogen may also interact with hydrocarbons in presence of sunlight to
produce photochemical smog (later).
● Here when sunlight falls on air with a mixture of NOx and hydrocarbons + other
pollutants it leads to formation of a mixture of pollutants called photochemical smog
(smoke +fog)
Self Assessment Question:
i) Write a summary of chemical equations to show formation of photochemical smog
ii) How are peroxy acetylnitrates (PAN) formed
2. 3.2 Analysis of Nitrogen Oxides
- Since both nitrous and nitric oxide are ultimately converted to NO2. The determination of
NOx is basically analysis of NO2
- Contaminated air (NOx) is bubbled through a solution of sodium hydroxide over a period
of 24 hours.
- NO2 content in air is converted to sodium nitrate and sodium nitrate

- These contents are added to a mixture of hydrogen peroxide, sulfanilic acid, hydrochloric
acid and N (I-naphthyl) - ethylene diamine dihydrochloride. Sodium nitrate formed
diazotizes with sulfanilic acid.

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 The diazonium salt couples with N (2-naphthyl)-ethylenediamine dihydrochloride

-The coupled compound absorbs at 540nm. Its concentration is determined by Lambert’s Beer’s
law. (Write it down and define the terms)
- Mole ratio 1:1 Thus 1 mole of coupled compound corresponds to 1 mole of NO2
Self Assessment Question: Check for a relevant example and work it out
2.4 Effects of Nitrogen Oxides (NO2)
Very poisonous gas
1. Primary effects
(a) Humans
- Inflammation of lungs and edema after prolonged exposure resulting to death
- Threshold limit value (NO2) is 8ppm/8hrs
- Low levels cause acute bronchitis in children
- Cigarette and cigar smoke contains 100ppm nitrogen oxides which are inhaled/absorbed
by lungs. (Smokers are prone to effects of NOx)
(b) Vegetations
- Suppresses plant growth at 0.3ppm
- At high levels causes leaf injury and chlorosis
2. Secondary effects formation of
- Acid rain (?)
- Photochemical smog (peroxides aldelydes, ketones, acylnitrates)
- Aerosols
2.5 Control measures for Nitrogen oxides
a) Coal conversion technology
Involves an adjunct removal of sulphur from coal prior to combustion by treating it with sodium
hydroxide. To lower combustion temperature it is sprayed with steam so that N2 do not
combine with O2 hence NO are formed NO SO2 and NOx are formed during combustion.
NB: Coal used to produce electricity
b) Fluidized bed combustion
In fluidized bed combustion limestone is added at points of combustion to reduce amount of
sulfur dioxide emitted in flue gases

(NOx out technology)

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 Involves injecting aqueous solution of urea at points of combustion to react with NOx forming
carbon dioxide, nitrogen and water.

c) Selective catalytic reduction technology

- This technique involves addition of ammonia to the flue gases and passing the
mixture over the selective reduction catalyst.

- NO are reduced to N2
- Catalysts include Pt and vanadium pentoxide supported on TiO2 ( can withstand
600-700k)
d) Installing catalytic converters in the exhaust system of all automobiles
- Most important pollutants from exhaust CO, NOx and hydrocarbons
- Two way converter – this removes HC & CO

-
- Three way converter removes CO, HC & NOx

Three way catalysts consist of a mixture of Pt, Pd and Rh deposited on a high surface area
ceramic or alumina supports.
Sulphur Oxides
3.1 Sources (A) natural sources
- Eruption of volcanoes – SO2, SO3, H2S, S – SC
- Sea sprays – SOx in oceans exists as sulfate ions ( in oceans 2.5mg SO4/G H25. They are
sprayed out as aerosols and accumulate in lower atmosphere.
- Biogenic decomposition of sulfur containing matter e.g. H2S, dimethy/sulfide by marine
algae, anaerobic bacteria.
(B) Anthropogenic Sources/man-made)
- Burning of fossil fuels e.g. coal, petrol

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 - Petroleum refinery
- Smelting of sulfide ores especially Cu, Zn
- Manufacture of sulfuric acid
- Paper making
- Burning of domestic refuse
3.1 Fate of Sulfur oxides in the Environment
- H2S is oxidized to sulfur dioxide by atomic oxygen

- By molecular oxygen

- By ozone

- Sulfur dioxide persists the atmosphere is oxidized to SO3 photo chemically and non-
photo chemically.

(only excited SO2 reacts with O2) (Ground state does not)
Non-photo chemically

- Sulfur trioxide formed eventually reacts with water to form sulfuric acid

- Some H2SO4 may precipitate as rain or combine with ammonia or sodium chloride to
produce sulfates.

3.2 Analysis of Sulfur oxides

- Since SO2 is stable in atmosphere for 2-4 days. The concentration of SO2 can therefore be
determined.
- The sample of air is bubbled through a dilute aqueous solution of sodium
tetrachlomercurate, Na2 (HgCL4), containing sulfanic acid. The latter destroys any
nitrogen oxides that may be present in air.
- SO2, in the air sample, reacts with sodium tetrachloromercurate (II) and is quantitatively
converted to a stable nonvolatile complex, sodium dichlorosulfitomercurate (II), Na2
[HgCl2 (SO3)]

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 - A mixture of p-rosaniline dye, formaldehyde and phosphoric acid is the added to the
sodium dichlorosulfitomeraurate (II) complex. The p-rosaniline dye is converted to p-
rosaniline methylsufonic acid.

- H3PO4 serves to liberate sulfur dioxide from sodium dichlorosulfitomercurate (II)

complex, to maintain PH at 1 and tie up any heavy metals present in air e.g.

- P-rosanilinemethylsulfonic acid formed has a red violet color and at PH 1 it absorbs at

575nm. Its concentration can be determined calorimetrically by Lambert –Beer law. The
concentration of p-rosanilinemethylsulfonic acid is proportional to the concentration of
sulfur dioxide in the atmosphere.
3.3 Effects of Sulphur dioxide
(A) Human health
- TLV -0.03ppm
- Produces adverse effect at levels > 1.0ppm
- Higher levels can lead to bronchitis and cancer
(B) Vegetation
Destroys plant cells and interfere with chlorophyll synthesis leading to poor crop yield
(C) Non-Living material
- Corrosion metallic structures
- Discoloration of surfaces/paper/fabric
- Eating away of building stones, monuments

(D) Visibility – Sulfate aerosols can cause loss of visibility at 0.1ppm visibility is only on 5
miles/7km
(E) Acid rain Acid rain
● Rain water normally has a PH 5.6 below which is described as acidic.
● Acids that increase acidity include sulphuric and nitric. These come from fuels (all
sources of energy contain N and S) containing sulphur. Burning would also lead to NOx
and SO2. These are very soluble in water.

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 ● These react with water vapor to form the acid in the atmosphere and remain in the clouds
which later fall as rain
3.3.1 Consequences
On forest death/food crop
● Leaching of nutrients from soil (K, Mg, Ca, Na)-depend on the type of soil and bedrock
● Biological uptake of aluminum from soil by plant, resulting decline of forests/food crops
● Increased acid in the soil threatens human and aquatic life e.g. nervous system of human
is also affected making him easy prey to neurological diseases
On fisheries – a PH <5.5 the reproduction of fish is impaired resulting in poor fisheries
On drinking water supply – increased heavy metals and corrosion of water pipes
On monuments/buildings- constructed from marble are attacked by acid rain
How have the above been tackled?
● Liming has been done lakes to forest soil to reverse effects of acid rain.

● Liming also lowers the dissolved aluminum content by precipitating it out as aluminum
hydroxide.

● Corrosion of pipes prevented by coating with protective film of inert polymer.

Self Assessment Question: Write chemical equations to show the formation of rain water where
SO2 and NO2 are the oxides involved individually
3.4 Control measures for Sulfur oxides
Fuel desulfurization techniques include
Physio-chemical method
For Fe ores (FeS2 pyrite) they are subjected to hydraulic washing. FeS2 being denser than S it
settles down and floating S is collected and removed.
-Organically bound S in coal is removed by passing H2 gas over fuel in presence of Co –MoO3
catalyst where it is converted to H2S. H2 S is absorbed in a solution of diethylanolamine where it
is regenerated as sulfur.
Microbial method
makes use of a bacterial strain.
3.4.1 Flue –gas desulfurization
Wet lime-limestone scrubbing
Here powdered limestone and powdered coal are injected into the boiler simultaneously.
Limestone decomposes to lime

Lime ties up any SO2 generated from coal combustion

Calcium sulfite and calcium sulfate are removed by scrubbing with a slurry of lime water

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(b) Catalytic reduction of sulfur dioxide. CO and SO2 are passed over a catalyst
(LaTiO3)/Cu-alumina

PARTICULATE MATTER
4.1 What is particulate matter?
● These include microscopic suspensions in air also called aerosols or suspended matter.
● They are finely divided solid particles or droplets of liquids in air.
● Their diameters lie in the range 0.001-100nm
● Despite their small size they are known to cause severe physical, chemical and
physiological adversities.
Major route into the body is through respiratory tract
Types of particulates
Primary and Secondary particulates
Primary particulates
These are ones directly injected into the air by physical or chemical means
Sources include: pollen, soil, dust, volcanic debris, sea spray, tornadoes, storms, meteorites etc.
Also cement, coal and milled flour, fires (by man), car exhaust, combustion etc.
Secondary particulates
These are particulates produced as a result of chemical reactions
They include: sulfate reactions
Nitrate particulates and Hydrocarbon particulates
4.1. 2 Harmful effects of particulate matter
Human health- the standard acceptable upper limit for the annual average of suspended particles
is 75ppm and 260ppm for 24h

● Silicosis of lungs- mainly affects miners particularly when duct levels go so high they
settle on the surface of alveoli. They suffers shortness of breath due to blockage of
alveoli.

● Asbestosis- breathing in fibers of asbestos is more dangerous because it is carcinogenic.

● These fibers lodges into the tissue of lungs causing irritation which triggers lung cancer.
4.1.3 PAH (Polycyclic Aromatic Hydrocarbon)
These are a class of organic compounds which carcinogenic and occur in –smoke of charcoal and
exhaust.
Two main sources- caused by incomplete burning
Major sources are domestic heating/firewood and car exhausts etc
Examples include:
Benz (a) anthracene , Benz (b) fluoranthere , Benz (c) pyrene
Self Assessment Question::Draw structures of the compounds listed above
● They are also commonly found in charcoal grilled meats, cigarette smoke, coffee, burnt
sugar
● Reactions or mechanism/explanations

19
 ● The epoxide is highly reactive molecule that can attach certain key proteins
● This type of reaction called potentiation converts a relatively harmless chemical into a
much more toxic one.
● Thus in the body benzpyrene is oxidized into an active carcinogen(epoxide) and this
binds to specific nucleotides in the gene sites(proteins)called hot spots where mutations
frequently occur (P53 gene).
● Many of these occur killing it and leading to growth which is cancer
There is a correlation suspended particles and altitude. In Murang’a County the level was
between 4000-5000 NgM-3 of respiratory suspended particles.
The sort of levels causes respiratory diseases e.g. persistent coughs, bronchitis. Lung problems.
The most common cancers in Kenya are that of the nose and throat because of use of wood for
cooking and heating.
Class activity
The average person takes 15 breaths per minute inhaling 0.50L of air with each breath. What
mass of particulate, in milligrams would the person breathe in a day if the particulate level in air
were 75µg/m3?. Would this affect the person?
4.1.4 Visibility
● Visibility or visible range refers to the distance at which an object can be just perceived
against the horizon sky.
● The airborne particulates scatter the sun and reduce the light flux.
● Urban areas have average particulate concentration of 100ppm, this reduces visibility 8-
10km.
● Rural areas average particulate concentration 20ppm visibility range in 50-60km.
4.1.5 Odors
● for volatile particulates they transmit unpleasant odors from one place to another e.g.
paints, sprays etc.
● Ozone depletion (covered in details later in stratosphere)
4.2 Control measures for particulate pollution
Use of electrostatic precipitators
These uses electric discharge to ionize the constituents of flue gases especially NOx, SOx. These
particulates are pulled out of flue gases and removed.
* Self Assessment Question:. Identify commonly used methods for removal of particulate
matter in addition to electrostatic precipitators and describe how any two of them work
4.3 HYDROCARBONS
● HC contain only C and H
● Divided into two
(i) Aliphatic HC – are alkanes (paraffins), alkenes (olefin), alkynes (acetylenes)
(ii) Aromatic HC e.g. benzene, Nephthalenes
Sources of HCs
Natural sources

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 ● Volcanoes, forest fires, vegetation, mousterpene r-pinene , natural gas seepage
(decomposition of organic compounds bybacteria)
Anthropogenic sources
● Automobile emissions-ships, vehicles, planes petroleum refineries Manufacture of
polymers, plastics, pharmaceuticals etc
Self Assessment Question: Students to identify more sources
4.3.1 Effects of HCs
(a) Human health
● aliphatic HCs are generally considered safe with no effects reported up to 500ppm
● aromatic HCs are toxic to human life (why?)
e.g. vapor are irritating
systemic injury at high levels leading to leukemia and lymphoma
● -polynuclea aromatic HCs are many times more toxic than benzene (carcinogenic) *[See
earlier mechanism on PAH]*
● Allowable concentration of HCs is 0.24ppm over a period of 3 hours.
(b) Plants
● Alkenes especially ethane is 50 times more phytotoxic than other HC contaminants.
(Why?)
Effects include:
Leaf damage, stunted growth, decreased size and yield of fruits, destruction of flowers
c) Photochemical smog formation (covered earlier)
HCs interact with NOx and Ozone resulting in formation of photochemical smog.
4.3.2 Fate of HC in the Environment [removal of HC in atm]
● The most abundant hydrocarbon in the atmosphere is methane since it is emitted not only
in large amounts but has also a long lifetime about eight months
.
● Other alkanes have short lifetimes in 2 months since they are easily oxidized by a set of
atmospheric reactions initiated by hydroxyl radicals as illustrated

4.4 Analysis of HCs

● The HC content of the air is analyzed by a gas-liquid chromatography fitted with a flame
ionization detector.

21
 ● The chromatographic column, into which air sample with HCs is injected contains a
liquid stationery phases. (Polydimethyl silixane and poly (trifluoroprophl)
dimethlsiloxane are used as stationery phases for HC analysis.
● HCs have a high rate of diffusion hence retained for lesser time. (NB rate of diffusion
depends on the molecular weight of the gaseous HC.
● At the detector HCs undergo pyrolysis at the temperature of hydrogen flame producing
ions and electrons. Ions are detected by MS and determined.
UNIT 5 ATMOSPHERIC PHOTOCHEMISTRY OF MAJOR GAS POLLUTANTS
5.1 Physical structure and nomenclature/regions of the atmosphere
● Atmospheric chemistry is concerned with chemical pathways that lead to removal of
gaseous pollutants, their magnitude and ways of analyzing them
● The chemistry of the atmosphere is controlled largely by atoms and free-radical species
present in very low concentrations in 107 cm-12 atmosphere. Their half-lives are very
short.
● It is important to understand the structure of the atmosphere, temperature profile and
variations of density with altitude. We shall focus on troposphere and stratosphere
● The presence of UV light is so important because it initiates some of the atmospheric
reactions.
● The x-rays and cosmic rays have a role to play especially in the upper atmosphere.
5.1.1 Deductions
● The troposphere is characterized by a positive lapse rate (i.e. the temperature decreases as
altitude increases).

● At low altitude it is hot and at a higher altitude it gets cooler. This encourages mixing of
air hence photochemical reactions.

● In the tropo pause the rate of vertical mixing falls sharply and the negative lapse rate
(temperature increases with altitude) inhibits vertical mixing.
● Moderate mixing occurs through turbulence and diffusion. Also transport of gases
between the troposphere and stratosphere is extremely slow.
● Pollution of troposphere and stratosphere is hard to clear due to limited conversion
processes.
● The smooth exponential fall in density with altitude results in general decrease in the rate
of third-order recombination reactions.
● The low temperatures in the upper atmosphere and lower stratosphere reduce the rate of
reaction having significant activation energies but favor combination reactions
characterized by negative activation energies.
5.1.2 Troposphere
-the most important free radicals are OH generated by photolysis

22
- O3 diffuses into the troposphere from stratosphere
- OH radicals are important in oxidation of pollutants e.g.

The above show pathways leading to removal of HC from troposphere

-Most HCs react with free radicals and undergo chain reactions in presence of quencher

- Reaction is essentially a low temperature combustion process with the end product being CO 2
and water.
5.1.3 Removal of SO2 from Troposphere
1) SO2 is a fairly soluble gas and is removed under wet conditions and can be removed as
sulphurous acid or by reactions in the liquid phase.
Dry removal of SO2 is possible by its oxidation to SO3 to sulphuric acid. The rate determining
step is oxidation to SO3

By photo oxidation of SO2 to SO3

Oxidation by OH0 radicals(most plausible for scheme for dry removal of SO2)

5.1.4 Removal of NOx Species from troposphere

● Nitric Oxide (NO) and Nitrogen Dioxide are the most important pollutants in the
troposphere

23
 ● N2O(Nitrous Oxide) is relatively inert in the troposphere but an important pollutant in the
stratosphere(main sink)
● NO and NO2 are rapidly interconverted during the day NO2 is photolysed to yield NO and
O

● In dark low light level conditions

● The main removal process for NOx species in atmosphere is by XXX involving OH
radicals.

● The nitric acid is then removed by rain.

● The reactions of NOx in the troposphere are well illustrated by their involvement in
photochemical smog formation [briefly covered earlier].
5.2 Photo chemical Smog
The four main requirements for photochemical smog formation are
i) Strong sunlight
ii) Stable meteorological conditions
iii)The presence of NOx
iv) The presence of unsaturated hydrocarbons
● The Cycle starts with HC and NOx emissions from automobile exhausts.
● The HCs are then attacked by hydroxyl radicals to yield perxyaklyl radicals (ROO0)
● ROO0 radicals oxidize NO to NO2
● NO2 is photolysed to yield NO2 and O
● O2 atoms combines with O2 to yield O3
● Once O3 is formed a rapid series of complex reactions follow which lead to formation of
aerosols and smog
Illustrated as follows [See earlier equations]
If R is Benzene PBzN are formed instead of PAN

5.2.1 Effects of photochemical smog

● Main constituents of photo chemical smog are aldeydes, ketones, PAN, Ozone, NOx.
● Ozone-causes eye irritation, cough, chest discomfort and fatigue, damages blood
capillaries
● Ozone is more harmful to plants e.g. reduction in plant growth, forest death, foliage death
● Ozone – damages materials especially dyes, rubbers and polymers through deterioration
of strength and discoloration.
● Organic derivatives of aldelydes/ketones-cause eye irritation(peroxyacetylnitrate);skin
cancer etc
● By controlling NOx ,HCs in the atmosphere will suppresses smog formation.
5.3 Stratosphere
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Stratosphere is the most vulnerable region of the atmosphere due to
a) Its low density
b) Its stability against vertical mixing
● main pollutants are supersonic aircrafts inject exhaust gases into lower stratosphere and
thereby possibly reduce the ozone concentration.
● The main effect of this would be to increase the levels of ultra-violet light reaching
ground level.
● This would cause undesirable biological effects e.g. skin cancer. But formation of ozone
absorbs these radiations

● Stratosphere is continually created and destroyed by suns radiation.

● An imbalance results when reactive atoms are released into the stratosphere
e.g,N2O ,Chlorofluorocarbons destroying. depletion of stratospheric ozone [covered
elsewhere]
5.3.1 Effects of NOx in Stratosphere
● The lack of sinks for N2O in the troposphere means that its main sink is by slow transport
into the atmosphere where it is photolysed or undergoes reaction with free oxygen atoms
to form nitric Oxide.
● The nitric Oxide enter directly into NOx cycle.
● This catalytic cycle has a strong influence on the ambient ozone concentration in the
lower stratosphere
Diagram

Explanations
● In the first step NO reacts with ozone to form [Link] NO2 is attacked by an oxygen
atom releasing NO which returns to the first cycle.

25
 ●
● The combined effect of these two steps is to consume oxygen atoms and ozone
converting them into molecular oxygen.
● The NOx Cycle accounts for 60% of ozone removal rate in the lower stratosphere
● The reaction between oxygen atoms and O3 is usually slow as it has activation energy of
19kg per mole.
● Thus the role of NOx is to catalyze the reaction increasing its rate
● The sink for NO2 generated is by its conversion to nitric acid by hydroxyl radical.

● After ammonium fixation, the ammonia and ammonium that is formed will be transferred
further, during the nitrification process. Aerobic bacteria use oxygen to convert these
compounds. Nitrosomonas bacteria first convert nitrogen gas to nitrite (NO2-) and
subsequently nitrobacter convert nitrite to nitrate (NO3-), a plant nutrient.

Nitrification is carried out according to the following reactions:

2 NH3 + 3O2 - > 2 NO2 + 2 H+ + 2 H2O
2 NO2- + O2 -> 2 NO3-

Increased use of Nitrate fertilizers will lead to increased rates of N2O release.
● Similarly supersonic aircraft inject NO2 into the lower stratosphere and thus
enhance the natural NOx cycle.

5.4 Ozone layer

● The bulk of ozone is in the lower stratosphere .concentration reaches a maximum of
8ppm(volume mixing ratio at 20-25Km)
● Doson units: convenient method of expressing O3 Conc. in terms of thickness of layer at
stp
● Of Dobson Unit(DU) =0.007 cm at stp or 0.07mm at stp.
● In normal condition the concentration of o3 varies between 300DU- 400DU.
5.4.1 How is Ozone formed
● Ozone is usually formed in the upper part of stratosphere by short wavelength radiation

.
● This Short wavelength is present in the upper part of the stratosphere

26
 ● The function of 3rd Body (Quenchet) is to remove the excess energy which could break up
the already formed ozone.
Most of the ozone is formed above the equator and then transported by winds to other parts of
the world.
5.5 Depletion of ozone layer
This is mainly by NOx and Chlorofluorocarbons (CFCs)
5. 5.1 Effect of NOx and Chlorofluorocarbons (CFCs)
● Mechanism of Ozone removal NOx(see earlier sections )
5.5.2 Depletion of ozone layer by Chlorofluorocarbons (CFCs)
● CFCs are a group of synthetic chemicals used in large quantities(in the yrs 1960s-70s) as
spray propellants, refrigerants, solvents and plastic forming agents and have accumulated
in the atmosphere mainly as CFCl3 and CF2Cl2
● These CFCs absorb the radiation even in low concentration and have long half lives.
These make these compounds very significant in ozone depletion
● They are generally inert in the troposphere but once they are transported into the
stratosphere they are photolysed or react with electronically excited oxygen atoms
producing chlorine atom and chlorine oxides(ClOx)
● These degradation products form the basis of a further catalytic cycle analogous to the
NOx cycle which leads to the net removal of ozone and oxygen atoms.

Note
● An important difference between pollution by CFCs and N2O is the time taken for the
stratosphere to recover for NO2 and NO injected directly by supersonic aircraft into the
stratosphere recovery occurs within approximately 3 years.

● However the release of CFCs and N2 O involves a much longer recovery times due to the
buffet effect of the large mass of the troposphere and the slow rate of transport from the
troposphere into stratosphere. For CFCs is 30 -50 years.

5.5.3 Effects of Ozone depletion (Ozone holes)

● Ozone depletion changes the special composition of solar electromagnetic radiation. the
increased solar UV-radiation activates the greenhouse effect affecting the global energy
and radiation balance. This would result in melting of ice caps hence rise in sea level.

27
 ● Increased incidence of cataracts and photokeratis as Uv-rays are easily absorbed by the
lens and the cornea of eye.
● It is estimated that for every 10% loss of ozone leads to 20% increase in diseases in
humans-Melanoma/skin cancers; leukemia, breastcancers since UV-B is known to
damage cell DNA.
● Poor crop yield(tea, Soybean)due to reduction in leafsize,poor seed quality, plant proteins
are excellent absorbers of UV-rays hence susceptible to chlorophyll injuring(reduction
and mutation)
5.5.4 Control of Ozone depletion
● Reduction and stoppage of CFCs and instead use of carbon flouro carbons (CH2FCH3) or
hydrochloroflourocarbons (CH3CCl2F).
● These break down more readily in the troposphere and hence fewer ozone depleting
molecules reach stratosphere
● Use of environmentally safe/friendly methods to kill insects(biological)
5.6 The Greenhouse effect
● The glass roof of a greenhouse is permeable to radiations from the sun. Once inside
greenhouse, the radiations strike the surface and are transformed into heat.
● The glass roof of the greenhouse impedes the heat to pass out. Since much heat is trapped
inside of a greenhouse is warmer than the outside.
● Atmospheric carbon dioxide and a host of other gases CO2,CH4,N2O tropospheric ozone
and chlorofluorocarbons(CFCs)transmit short wavelength radiations escape into space.
The result is warming up the atmosphere-Global warming or Greenhouse effect.
Relative contribution of radioactively active gases to greenhouse effect
CO2 50%
H2O 2%
N2O 4%
CFCs 17%
O3 8%
CH4 19%
5.6.1 Sources of Greenhouse gases
● Burning of fossil fuels from automobile factories, coal.
● Deforestation: plants use large quantities of CO2 as a result of deforestation, an important
sink of CO2 is being eliminated.
● Livestock-breathe out CO2
● Volcanoes emit large quantities of CO2 to the atmosphere
● Methane-by actions of anaerobic bacteria on rice and wetlands
-Vegetation
● N2O –see NOx
● Ozone-see NOx and HCs
● CFCs –solvents,refridgerants etc
5.6.2 Consequences of Greenhouse effect
Effects on global climate.
-Rise in sea level-it is estimated that sea level may rise 0.5 to 1.5m in the next 50 to 100 years.
This would lead to increase the frequency and severity of floods, damage of coastal areas etc.
- Evaporation of water from aquatic systems and changing patterns of rainfall

28
- It is estimated that if earth’s temperature increases from 2 to 4.5 it would lead to melting of
glaciers and disappearance of rivers, lakes etc.
Effects on Plants
-Carbon dioxide fertilizers-plant biomass may increase to 25-30% by CO2 fertilization
-nitrogen content-plants grown in high CO2 concentrates have less nitrogen and more carbon
content.
-increased rate of decomposition leading to more CO2 release
-increased threat of pests
- evaporation of water from soil.
Effects on Humans
Increase in global temperature is likely to increase the incidence of infectious diseases e.g.
malaria, yellow fever etc.
Effect on wildlife
-increase in temp would result in extinction of plant and animals
5.6.3 Abatement of greenhouse effect
-Develop renewable alternatives to fossil fuels e.g. wind power, biogas
-reducing deforestation and enhancing forestation
-halting CFCs production
-Stabilizing world’s population
-restricting emission of greenhouse gases (see NOx)
- reducing consumption of Fossil fuels e.g. coal and petroleum.
UNIT 6 PARTICULATE AND GASEOUS EMISSIONS FROM COMBUSTION OF
PETROLEUM BASED FUELS
6.1 Combustion engine and how it can pollute the environment
Smooth and efficient combustion in automobiles results when the engine is able to convert
hydrocarbons to water and CO2 and energy.

When there is incomplete combustion part of the HC will be emitted as pollutant some of the HC
are Deposited as Carbon in the engine and air, CO is also obtained as a pollutant.
6.1.1 Factors involved in achieving smooth combustion
Volatility of fuel
● with a fixed volume of fuel in both cylinders.
● The more powerful stroke is that with a less volatile fuel its expansion volume will have
been taken by the fuel in the gaseous form

-prior to ignition we want a minimum amount (%0 of fuel in gaseous form.

-if the fuel is too in volatile then the efficient of the engine drops because it takes much more
time to vaporize the fuel thus causing the combustion to be inefficient
Octane rating and pre-ignition
-for smooth combustion, the flame front should spread smoothly throughout the cylinder.
-pre-ignition is when a separate flame front is started off. This pre-ignition cause’s engine
knocking “pinking”. The pre-ignition transmits itself to the piston at the proper (main)ignition.
6.1.2 How do we select the right type of fuel for engines?
Octane ratings(knock-rating of a fuel)This is measured by research octane number(RON).

29
 -If the fuel is too involatile, engine warm up is delayed to inefficient combustion which can
cause pollution
-In Kenya Bureau of standards:-90% of fuel should boil below 1800c.
-general motors’(Europe )90% of fuel boil below 160oc
-even in modern cars, warm-up stage(30Sec)33% of total HC ad 53% of total CO are produced
during the warm-up stage of car engine
NB: Don’t start car and drive-give time to warm up. [modern ones require less time for
warming]
6.1.3 What is Octane number of fuel?
Refers to the %of iso-octane in the blend with n-heptane that gives the same knocking
characteristics as the fuels in question e.g.
● A mixture of 80% iso-octane and 20% n-heptane gives the octane number is 80

● In Kenya super and regular petrol has alcohol.

For Super -octane number 90
Regular -octane number 85
Note
● Very prone to knocking when octane number is low (e.g. 0) e.g. for n-heptane
● Very resistant to knocking when octane number is high (e.g. 100) e.g. for isooctane
6.1.4 Factors that increase octane number
(i) Chain length reduction e.g. pentane to butane(94) +methane(110)
(ii) Chain branching formation e.g. Butane to isooctane(90)
(iii) Increased double bond character e.g. Butane to butene (97)
(iv) Aromatization e.g. n-heptane(0) to toluene (104)
6.2 Improving octane numbers of Straight Run Gasoline (SRGs)
Feedstock/petroleum primary SRG (one of the fraction)
distillation
Octane number of SRG are between 50-70 SRGs octane number is improved by:
(i) Extra refining- cracking, reforming, chain level reaction
(ii) Use of addictives e.g. Pb
(iii) Both (use of addictives and extra-refining).
● For instance-reforming of SRG by increasing the aromatic character of the SRG increase
the SRG octane number to 80-85
● When put through extra-refining to increase double bonds, the octane number can be
increased to 85-100.
Note
● The more refining we do, the less petrol you get and therefore the more expensive it
becomes since more complicated equipment are required.
6.2.1 Additives of fuels ( or antiknock additives) use of lead alkyls:
● With lead (Pb) additives we can reach 85-100 octane number very easily and it is a
cheaper route since little petrol is lost and less equipment is required.
● Lead addictives were first used in 1923. By adding a small amount of lead (Pb) you
increase the octane number dramatically but rather cheaply.
● Concentration of lead (Pb) in the Kenyan fuels is around 0.85g/L
The lead addictives are:

30
Alternatives

- The alternatives can be used as substitutes because they are stable and secondly they are
liquids.
- Carbonyls are toxic, e.g. have high vapor pressure and they decompose to give CO which
is a pollutant.
- When these carbonyls are absorbed in the skin, they have quite severe effects on the
biochemistry of the body.
- Manganese is also toxic, when released in the atmosphere can cause environmental health
problems similar lead.
- Fe carbonyl has severe corrosion problems.
- Pb is a softer metal and therefore does not cause corrosion problems. Pb powder acts as a
lubricant in the engine especially in the fast moving components. The main problem of
Pb is a health hazard.
6.2.2 How do lead addictives work?
During the combustion process O. are produced. The O. is so reactive and this causes pre-ignition in the
engine.

31
 - There is a problem in that PbO formed will accumulate in the engine. Halogen-alkanes
are added to get rid of the accumulated PbO.
e.g. 1,2 – dibromoethane
1, 2-dichlotoethane
1-bromo-2-chloroethane
- These compounds combine with lead oxides to give very volatile Pb Br Cl
6.2.3 Absorption of lead into our bodies
- Sources of Pb that get into human by
Average daily intake
(i) Ingestion in food- 200-300ng
Drink -20ng
(ii) Inhation - 20ng
- 90% of the Pb inhaled comes from petroleum
6.3 Environmental Health impacts of Pb
(i) Biochemical
- Lead inhibit enzyme activity at concentrations of 10Ng/100ml. the enzyme inhibited will
that involved in haemoglobin production. The enzyme is Delta-aminolaevulinic acid
dehydrate (DETA-ALAD).
- Pb therefore interferes with metabolism of blood, reduces the red blood cell formation
and hence lead to anaemia.
- Pb also replaces calcium in the bones
(ii) Chemical- below 60-80Ng/l no symptoms above which Pb affects the brain with the following
symptoms due to lead poisoning: irritable, excitable, excessively depressed; peripheral
neuroparthi e.g. (shaking). Pb is a neurotoxin.
(iii) Mental deficiencies – this occur offer after prolonged exposure 3-6 years especially in kids.
Other sources of Pb
Petrol, Paint flakes, Lead accumulators , Cable sheathing, Alloys
Glazed pottery/solder
6.4 Control of exhaust emissions from internal combustion engines
(i) Engine design
Improved carburetor and combustion chamber can improve the mixing of the gases prior to
combustion and ensure greater homogeneity of the reaction mixture.

32
 (ii) Exhaust reactors
- Here products of partial combustion (HC, NOx, CO) oxidized to CO2, water, N2 and O.
- See catalytic reactors

UNIT 7 IMPACT OF AGRICULTUAL CHEMICALS ON TERRESTRIAL AND

AQUATIC ENVIRONMENTS
- Broadly classified into 3
(a) Fertilizers
(b) Insecticides
(c) Fungicides and herbicides
7.1 FERTILIZERS
- Population explosion has compelled the to procure more food. Continuous agricultural
activity tender to decrease soil fertility. As a result chemical fertilizers are used to boost
food production. The continued use of fertilizers has also threatened the human
environment and ecology with deleterious consequences.
- Fertilizers are defined as materials if added to the soil, result in a better growth of crops.
Those needed in large amounts primary nutrients (macronutrients) and secondary
nutrients (micro-nutrients) required in extremely small/trace amounts.
- Fertilizers are classified into three broad types:
(i) Nitrogen-based fertilizers i.e. Nitrates
(ii) Phosphorous based fertilizer i.e. phosphates
(iii) Potassium based fertilizers
7.1.2 Environmental implication of fertilizers
(i) Soil
Continued use of N-based fertilizers tend to increase soil acidity, this in turn inhibit microbial
activity in the soil. The change of physical, chemical and biotic characteristics of the soil lowers
its productivity.
(ii) Vegetation
High soil acidity provide unfavorable chemical and biological conditions to plants e.g. high
acidity leads to leaching of essential nutrients at PH 5.5 Al, Ca, Mg ARE LEACHED AWAY.
(iii) Pest problem
Increase in leaf nitrogen makes plants more susceptible to attack by grazers, beetles etc.
(iv) Herbs problems
Fertilizers encourages growth of weeds that compete with main crops.
(v) Human activity
Consumption of excessive nitrates is harmful to humans. Microbes in the stomach convert
nitrates to nitrate which is toxic. Nitrate reacts with haemoglobin curtailing oxygen carrying
capacity of the blood. Blue baby syndrome or methaemoglobinaemia.
Since nitrates are highly soluble, these manage to seep into drinking water.
Stomach cancer - associated with concentration of in portable water.
(vi) Eutrophication-
The greatest problem associated with use of fertilizers is Eutrophication of lakes. This occurs
when plant nutrients ends up in ponds, lakes and slow moving rivers usually results in
shallowing of lakes through natural aging processes. Ultimately the lake dies and becomes part
of the solid crust. details later)
7.1.3 Abatement procedures for fertilizers pollution

33
 (i) Crop rotation and intercropping- mix plants that consume a lot of nitrates with those
that consume less (e.g. grass and beans).
(ii) Use of modern scientific farming methods
(iii) Providing for a period for soil to regenerate during which no fertilizers are applied.
(iv) Use nitrogen fertilizers responsibly under professional advice.
7.2 PESTICIDES
Insecticides
Pesticides are chemicals which are used for eliminating pests.
Why use insecticides?
(i) To control pests which would otherwise reduce yield of agricultural crops
(ii) To stop spillage of food during storage
(iii) To kill disease carrying organisms
(iv) To promote aesthetic well being. (kill housefly, cockroaches, mosquitoes)
How do they reach the environment (soil)?
● Large portion of the sprays do not reach the target or remain on the target (residues)
● May reach the soil when leaves that have been sprayed fall or bodies that have been
sprayed are buried
● Reach the atmosphere as dust (Hg), acid rain falling
● Some are volatile so escape to the environment
7.2.1 Classification of Insecticides
(i) Organochloride hydrocarbons
- Include P.P-dichlorodipheny/trichloroethane (DDT), aldrin, dieldrin, methoxychlor
- structurally they are very stable hence persistent in the environment. As a result they tend to
accumulate in the environment and affect many non-target organisms.
E.g. DDT
SAQ: Draw the structure and give the full name of DDT
(ii) Organophosphates
- Have very low persistence in the environment
- They rapidly breakdown hence do not cause long term effects
- Their compounds however are toxic in nature. Apart from killing insects they harm
humans and wildlife.
- Due to their rapid breakdown they are applied at frequent intervals not economical; e.g.
parathion and diazinon.
Self Assessment Question:: Draw structure of parathion
(iii) Carbamates
- They are intermediate between organochloride hydrocarbons and organophosphates i.e.
less toxic and less persistent e.g. carbanyl and

- methiocarbs
- Neurotoxin
(iv) Pyrethroids

34
 - Are analogs of pyrethrum (naturally occurring insect repellant) present in
chrysanthemum.
- They are neither persistent nor toxic e.g. pyrethrum and deltamethrin

7.3 ENVIRONMENTAL EFFECTS OF INSECTICIDES

7.3.1 These are infested in the following among others
(i) Bioamplification
- Animals which occupy higher trophic level in the food chain tend to accumulate traces of
insecticides (DDT) in their fatty tissues as a result of feeding on insects lower in the
tropics level in the food chair.
Insects/planktons Fish Birds of prey (High
Mosquitoes (DDT) spay levels of DDT)
(ii) Broad spectrum characteristics
Sine insecticides kill large variety of insect their predators they interfere with normal food
chain/web.
(iii) Resistance
Target insects tent to develop resistance against an insecticide with its gradual use.
(iv) Birds
- Birds of prey at high position in food chain concentrate enormous quantities of
insecticide in their tissue especially organochlorine HCs (DDT)
- Among effects – decline in their population since eggs laid do not hatch. (soft shell).
(v) Fish
Insecticides find their way into water systems with lethal consequences to fish
(vi) Human health
Organochloride HCs and carbonate insecticide are highly toxic. They are consumed through
food and insecticide poisoning while spraying.
7.3.2 Abatement of procedures for insecticide pollution
(i) Bacterial insecticides
- These are specific and do not harm human, livestock etc.
- Do not damage plants
- Insects do not become resistant in the long run
Drawback- they are expensive
(ii) Viral insecticides
Highly specific
(iii) Hormonal insecticides
- Kill insects by upsetting its normal metabolic processes e.g. Juvenile hormone
- Drawback: targets only certain stages of insects’ development.
(iv) Chitin inhibitors
Stop chitin (glucosamine polysaccharide) grow hence the shell becomes fragile, raptures killing
the insect
(v) Sex attractants
Insects are attracted to traps using pheromones where they are treated with s sterilizing chemical
or exterminating device .[An important area of research]
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 (vi)Genetically engineered crops
Resistant to attack by pest/insects (transgenic crops).
7.4 FUNGICIDES AND HERBICIDES
7.4.1 Definitions
Fungicides
Are chemicals applied to plants or their seeds to inhibit or prevent fungal diseases e.g. rots,
molds, mildew etc.
Herbicides
Class of compounds that kill unwanted weeds or interfere with their growth
Fungi- are plants without chlorophyll therefore cannot use solar system to convert CO2 and water
into energy-rich carbohydrates.
They live as saprophytes on decaying organic matter or as parasites.
-fungicides counter growth of fungi
- main uses include:
(i) Protect commercial crop from disease e.g. potato blight, cassava mosaic
(ii) For seed treatment
(iii) Protect forest trees e.g. pine blister rust
iv) In building fungicides are used ad mould inhibitors
(v) In paints and vanishes – fungicides are used mildew prevention.
(vi) In wood industries they are used as preservatives
White herbicides/acaricides
- Remove weeds from agricultural land
- Remove unwanted growth from lawn, pasture
7.4.2 Classification of fungicides
(i) Systemic fungicides
- Are ones when applied to the plant, rapidly distributes itself in the plant tissue. Examples
thiabendazole and [ thiaphanate]

(ii) Non- systemic fungicides

- These do not move from one part of the plant to the other i.e. when applied to the stem,
non-systemic fungicide only protects the stem.
- Drawback: they must be applied in larger doses therefore systemic fungicides are being
emphasized.
Examples

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7.4.3 Herbicides are classified into two broad categories
(i) Contact herbicides- are quick-acting substances that kill the weeds by direct contact
with their leaves. e.g. Diquat and bromacil
Effects on plants:
- rapid darkening of green leaf followed by necrosis hence death
- ineffective for weeds whose roots produce new shoots
- e.g.

(ii) Systemic herbicides

These are translocated within the plants body. Diffuse from one tissue to another eventually
killing the weed e.g. 2,4-dichlorophenoxyacetic acid. (2,4-1) 2, 4, 5-trichlorophenoxy acetic
acid (2,4,5-7)

Are effective at low doses therefore more economical.

7.4.4 Mechanisms of Action of Fungicides
1. They act as growth inhibitors for fungus i.e. mitosis inhibitors/poisons. Mitosis involves
duplicating of chromosomes and transferring them to new cells-dinitro-o
2. Non-competitive inhibition- whereby fungicide interacts with essential metabolite of
fungi making it unavailable e.g. phenyl mercury acetate.
3. Competitive inhibition where a fungicide resembles a metabolic (antimetabolite) e.g.
thiobendazole.
4. Fungicides may interfere with utilization of essential metal ions by complexing them
making unavailable for fungi e.g. carboxin.

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7.4.5 Mechanisms of Herbicides
1. Growth inhibition e.g. pentachlorophenol
2. Growth stimulators –enhance metabolic processes hence aging the weeds at faster rate
e.g. 2,4-D and 2,4,5-T
3. Photosynthesis inhibitors e.g. Diuron
4. Respiratory inhibitors e.g. picloram
Reduces uptake of water.
7.4.6 Environmental implications of Fungicides and Herbicides
- Similar to those of insecticides
- Control/abatement – similar strategies as to insecticides
7.5 EFFECT OF PESTICIDE RESIDUES ON FOOD CHAINS
7.5.1 Preparations
DDT – Synthesis
1, 1g 1-trichloro-2,2-bis (p-chlorophenyl) ethane also called dichlorodipheny/trichloromethane
hence the name DDT is obtained by the reaction of chloral with chlorobenzene.

Methoxychlor synthesis

- methoxychlor is biodegradable but less effective as an insecticide

- more costly to prepare because anisole is more expensive than chlorobenzane.
7.5.2 Environmental degradation
- DDT undergoes a relatively rapid elimination of HCL to yield DDE (1,1-dichloro-2,2-bis
(p-chlorophenyl) ethylene when heated in water.
- The subsequent hydrolysis of DDE is extremely slow because there are only unreactive
vinyl and aryl chlorides in DDE. As a consequent DDE is the principal DDT degradation
product found in the environment.

- Methocychlor are less persistent in the environment due to their metabolism by soil
microorganism to phenols which are further degraded to acetate

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 ● The toxic action of most of the organochlorine compounds is believed to be due to
interference with the transmission of impulses in the nervous systems, hence cause death
by tremors and convulsions. (In insects)
● In low dosages in man it is known to increase excitability and tension.
● Use DDT has been burnt around the world because of its persistence in the environment
resulting in its bioaccumulation in food chains.
● Insects are more susceptible to DDT because it is readily absorbed through the insect
auticle.
Typical food chain concentration of DDT

Birds of prey

10.0ppm

Fresh water fish Marine fish

2.0ppm 0.5ppm

Aquatic plants Aquatic invertebrates Planktons

0.01ppm 0.001ppm 0.0003ppm

Fresh water Sea water

0.00001ppm 0.000001ppm

8.0 WATER POLLUTION

- The pollution of water is defined as the addition of undesirable foreign matter that
impairs the beneficial uses of water.
- Water pollutants are broadly classified into two:
(i) Those which are poisonous/harmful to animal or plant life e.g. microorganisms,
heavy metals, chemicals e.g.
(ii) Those which either directly or indirectly reduce the dissolved oxygen content of
natural water e.g. raw sewage, plant nutrients, (phosphates nitrates, sulphates),
organic pollutants.
8.1.1 BOD and its determination
The amount of oxygen required to oxidize a given quantity of an organic material is
called BOD (Biochemical Oxygen Demand)

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 Biochemical oxygen demand is experimentally determined by incubating a sample of
water for 5 days at 293k followed by measuring dissolved oxygen before and after 5
days. The difference is BOD.
For pure water 1ppm 3ppm
Examples
Untreated sewage waste – 100-400ppm
Food processing wastes – 100-10,000ppm
8.1.2 Aerobic and Anaerobic Bacterial processes
How do they contribute to water pollution?
If water contains low level of organic pollutants, aerobic bacteria(thrive in the presence of
oxygen) are able to breakdown the organic matter completely resulting in self-purification of
water BOD is said to be low
C CO2 Carbonates + Bicarbonates
H H2O,
N NH3
S Sulfates
P Phosphates
Under high BOD of the contaminants, the dissolved oxygen is rapidly exhausted. Under these
conditions, putrefaction results. The aquatic life perishes. The aerobic bacteria die. The
components of organic matters decompose into entirely different sets of compounds.
C Organic acids
N Organic amines
S H2S + Organic sulfur compounds
P PH3 + Organic phosphorous compounds

Under high BOD conditions anaerobic bacteria (thrive in absence of oxygen) takes over. There
are able to extract oxygen from oxygen-containing compounds e.g. sulfates, nitrates, oxides and
oxidize the organic matter to harmless end products. (Similar to those of aerobic bacteria) until
normalcy returns i.e. (low BOD).
SAQ: Explain how oxygen demanding wastes contribute to water pollution. Use
8.2 Effects of organic pollutants: plants nutrients
- Ponds, lakes and slow flowing rivers and streams are subject to natural aging processes
by the gradual enrichment of the waters with plants nutrients known as eutrophication.
- The various stages take place very slowly, perhaps over several thousand years for a large
lake.
- Initially, streams from the drainage basin gradually deposit soil and nutrients increasing
the fertility of the lake. This lead to increase in the quantity of plant and animal life in the
water.
- Over many years the amount of living matter increase. This die off accumulating dead
organic matter at the bottom. This has three effects on the lake:
(i) The lake slowly becomes shallower
(ii) Plants roots in the fertile soil at the bottom of the lake and their remains add to the
accumulating dead organic matter.
(iii) The increasing quantities of dead organic matter raises the BOD level of the lake.
The high BOD levels favors anaerobic bacteria resulting in formation of a swamp.
This eventually become forest or field as it overrun by vegetation.

40
 - Most of the essential elements and nutrients required by plants are freely available in
lakes and rivers, however a few nutrients and essential elements are in relatively short
supply and this limits the rate of plant growth and hence the rapidity of the overall aging
process.
- It could appear that man’s main role in accelerating the natural aging process of water
bodies is by increasing the supply growth limiting nutrients and elements.
- It is believed that in most cases nitrogen and phosphorous are the growth limiting
nutrients/elements although conditions vary widely.
- Both nitrogen and phosphorous are present in small amounts in natural waters but as
much as 80% of nitrogen and 75% of the phosphorous added to the surface water are
from man-made sources.
- Runoff water from agricultural areas in which nitrate and phosphate fertilizers are
intensively used plays a major part in the addition of these plant nutrients into the lakes.
SAQ: Outline the main effects of eutrophication to a lake or a pond
8.2.1 Detergents
- Another major source is from phosphates is modern detergents.
- In general, detergents consist of synthetic surfactant which acts as a wetting agent and
can solubilize dirt and grease.
A sequestering “builder” which ties up calcium (II) and magnesium (II) ions. Builders also
extend or cleansing performance of detergents by assisting in grease emulsification.
- The most commonly used surfactants are the alkylbenzene sulfonates which are 50-60%
biodegradable and unbranched analogs, linear alkylbenzene sulfonates which are 90-95%
biodegradable

The most commonly used builders are sodium tripohyphosphate, sodium trimetaphosphate
- Although the cleansing mechanism of soaps and detergents is similar, their biochemical
and chemical characteristics are not. Soaps are considered environmentally-friendly
products (100% biodegradable) soaps are acted upon by micro-organisms and completely
broken down into harmless products- CO2, H2O, carbonates and bicarbonates.
- Phosphates-based builders presents no biodegradability problems since
is slowly dehydrolysed to produced non-toxic orthophosphates

- These hydrolysed cause extensive colonies of algae to bloom in lakes, resulting in

entrophication.

- For this reason, some formulations incorporate non-phosphate builders e.g. trisodium
nitrolotricetate, sodium citrate, EDTA, etc

41
 CH3 COO Na

N CH2 COO Na
CH2 COO Na
8.3 Environmental impact of Detergents
1) Eutrophication- detergents containing polyphosphate builders and phosphate based
fertilizers have been under indictment for causing eutrophication. Phosphates are
believed to contribute to the unwanted growth of algae that of choke bodies of water
and that, in their decay can exhaust the oxygen supply, so that the lake becomes
uninhabitable for fish.
2) Foam- most widely surfactants produce forms that blanket rivers/lakes and can be
blown to distant places. Foam limits the rate at which oxygen is absorbed by water
(exchange coefficient). Aquatic life of every soft is suffocated.
3) Toxicity to aquatic organisms and plants. Some plants are unable to grow at 2.5ppm
while fish die at 3ppm of detergents.
4) Objectionable taste of portable water
5) Reduce efficiency of water purification
Detergents kill aerobic bacteria reducing BOD activity.
8.3.1 Pollutants which are harmful to animal or plant life
(a) Pathogenic micro-organisms
-include bacterias, viruses, protozoa, worms, weeds etc
- have been responsible for-typhoid, fever, cholera, amoebic dysentery, hepatitis and all water
borne diseases.
(b) Physical and physiological pollutants
Originates as a consequence of chemical pollution. Affects the
o Color e.g. Fe3+ (Fe(OH)3 impart a yellow color/orange
o Turbidity due to presence of colloidal matter imparting cloudiness to water
o Suspended matter
o Froth
o Radioactivity – natural radioactive elements
o Taste and odor
(c) Thermal pollution
(d) Inorganic pollutants
o Acids, - H2SO4, H3PO4, HCL e.g. acid mine drainage
o Alkalis – caustic soda, lime
o Cations (Heavy metals) – Hg, Pb, Ar, etc
o Anions – sulfides /cyanides
HEAVY MEATALS
- These include mercury, lead, arsenic and cadmium
- They enter living organisms as inorganic salts or as organometallic derivatives
- These metals are present in all components of the environment (land, atmosphere and
aquatic systems). They are considered as water pollutants since considerable amount of
these metals present in the soil are ultimately leached into water bodies, while those in
atmosphere are rained down into natural water courses.
Hg (Mercury)

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 - Mercury is known to be toxic at such low levels that it leaves but small margin of safety
to humans.
- Mercury and mercury based compounds have a wide variety of users in industry
- Among the sources include:
-chlor-alkali industry – it serves as the cathode in hydrolysis of brine for manufacture of
chlorine and sodium hydroxide.
- Hg thermometers (replaced with alcohol ones)
- fungicides/insecticides (mercurials)
Examples of fungicides
CH3 Hg C
Biomethylation of mercury
- In elemental form or inorganic salts Hg is less toxic. However, in the environment its
converted into highly toxic methylmercury ion CH3 Hg+
- The methylation of Hg in water bodies is brought about by methanogenic bacteria hence
the name biomethlation.
- Methyl mercury ion (CH3 Hg+) tends to accumulate/concentrate among the food chains.
Being more soluble in the tissues of simple organisms it becomes a concentrated
component of the more complex species which feed on simpler ones. This process is called
bioamplification. Since humans are usually at the top of the food chain, high concentrations
of mercury may occur in diets, with tragic consequences e.g. minamata disease. In Japan
where 50 people died with 700 paralyzed due methyl mercury poisoning caused by eating
contaminated fish.
Mercury poisoning
The highly toxicity of methymercury is due to:
(i) Amphilitic nature
(ii) It can penetrate the membrane separating the blood stream from the brain and those in
placenta through which the nutrients must pass to unborn fetus.
(iii) In methyl mercury, the metal ion is firmly bound to the carbon so that the molecule is
not easily broken down and maintains its destructive action for weeks or months.
Symptoms of mercury poisoning
(a) Enzyme inhibition
Most enzymes have sulfhydryl (-SH) groups. Hg has a high affinity for SH group leading to
enzymatic inhibition.
CH3Hg + enzyme –SH CH3Hg -S
(b) Cellular disfunction
Methyl mercury may bind to proteins altering distribution of ions, change in electrode potentials
and therefore interfere with movement of fluids across membranes
(c) Neurological disorders
Brain is the main target of methyl mercury poisoning where it causes irreversible damage to the
nervous system e.g. Ataxia, loss of sensation, coma, death
(d) Erethism
For mild doses of Hg, neurological disorders manifest themselves as behavioural problems e.g.
anxiety, indecision, lack of concentration, depression.
(e) Teratogenic effects
CH3Hg+ - go through placenta
Damage to brain of foetus – mental retardant

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Celebral palsy and convulsions
Assignment
Read on how Hg can be estimated/analysis from the environment (Rocks and tissues) and
control/abatement procedures against Hg pollution
Examples of antidotes to mercury poisoning
N-acetyl –D, L-penicillamine
Dimercaptosuccinic acid British antilewisite (BAL)
- Common therapeutic agents of mercury poisoning. These agents tie up mercury in form
of complexes which are rapidly excreted from the body.
- BAL is not used, although very effective in treatment, because the complex formed with
methyl mercury crosses the blood-brain barrier very rapidly and becomes concentrated in
rather than being excreted.
Read: Pb, As and Cadmium
o Sources
o Poisoning
o Analytical; procedures
o Antidotes
o Abatement procedures against their poisoning
WASTE MANAGEMENT
Solid Waste
Refers to discarded material that is not a liquid or gas. Comprise of a complex mixture of
diverse materials include:
- Agriculture waste-fertilizer residues etc
- Food processing waste-slaughter house
- Industrial waste-metal scraps, plastics
- Mining waste-e.g. slag
- Municipal waste e.g. sewerage, paper
Ways of solid waste management
Four broad methods of disposal
i) Sanitary landfill dumping
ii) incineration
iii) recycling
iv) Source reduction
1. Sanitary landfill dumping
-here waste is spread out in thin layers in a large garbage pit compacted and covered with
a layer of soil
Advantages
● Low operating cost
● Landfills can be put into operation within a short period of time
● Can handle huge amounts of wastes
● After being filled up, the damp may be converted into a park or
recreational area
Draw backs
- with increasing pressure on land resources it is becoming difficult to
choose appropriate sites for new landfills
- since decomposition occurs under anaerobic conditions it takes a long time

44
 - Noise pollution as a result of transporting wastes to dump sites.
- landfills encourage waste production rather than waste reduction(No
Recycling)
2. Incineration
Is a process of burning waste materials under oxidizing conditions and at high
temperatures. The efficiency of incineration depends on:-
● Sufficient supply of free oxygen in combustion chamber
● Thorough turbulence to mix waste and oxygen
● High temperatures 1200 -1400 K
● Residue time
Advantages
● Drastically reduces waste up to 80% by volume and 75% by volume
● It kills pathogenic micro-organisms
● It serves as an energy resource
Drawbacks
- Costly to build, operate and maintain
- Release toxic air pollutants
3. Recycling
Waste are reclaimed into valuable resources
Advantages
- Reduces volume of solid waste
- Reduces volume [Link],paper,cars
- Ensures net energy required to manufacture a commercial item.
- Ensures economic savings to consumers who use recycled articles
- Reduction of costs associated with pollution control and waste management
Drawbacks
- Technical problems
- All materials cannot be recycled hence needs sorting ,sometimes there are no
cost-effective techniques to separate recyclables
- Economic problems. Recycling benefits the community as a whole and not an
individual
4. Source Reduction
Land filling, inceration and recycling methods of waste disposal suffer from one common
drawback. They address the waste after it has been produced. Source reduction on
the other hand, emphasizes on efficient (green) production-process where less
waste is produced.

Source reduction shifts focus from pollution control and waste management to pollution
prevention and waste reduction examples
a) Modern cars-made to consume less material
b) All plastic have replaced steel parts fiber optics are replacing copper wires. products
may be designed to last longer
c) products may be packaged into light weight materials
Hazardous waste

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Refers to waste if improperly managed can cause irreparable damage to human health
and environment. a waste is classified as hazardous if it posses any of the
following four characteristics:-
I. Ignitability-pose a fire hazard
- Low boiling liquids e.g. alcohol
- Substances that catch fire on reaction with water e.g. K
- Pyropholic-catch fire in air spontaneously
- Substances that supply oxygen for combustion of normally non-flammable
material e.g. Lithium peroxide
II. Corrosiveness-cause to denature or corrode
- Strong acids
- Strong alkalis
- Strong oxidants e.g. oxygen difluoride
- Strong dehydrating reagents e.g.BrF3
- Protein denaturing agents e.g. HNO3
III. Reactivity-these undergo transformation with an extremely low value of
activation energy
- Substances which spontaneously react with water e.g. phosphorous
pentoxide
- Substances that spontaneously or vigorously react with air e.g.
trimethlaluminium
- Substances that generate toxic fumes e.g ammonium nitrate under
influence of heat.
- Explosive substances e.g. dynamite
IV. Toxicity
Are substances which above certain level of exposure or dose have detrimental effects on
living beings
- Substances which elicit acute toxicity effects immediate
[Link]
- Substances which alict chronic toxicity .slow in poisoning and manifests
symptoms after prolonged exposure e.g. lead salts
Hazardous Waste management
1. Waste burial technologies
a)Deep-well disposal
- This meant for dealing with liquid hazardous wastes e.g. brine [Link]
metal ions and organic liquids
- The waste is pumped under pressure through a pipeline into dry porous
formation that is for beneath aquifers that hold portable water
Self Assessment Question: Draw a relevant diagram
b) Surface impoundment
- This caters for both liquid and solid wastes e.g. sludge and [Link]
waste is placed in excavated pits, ponds or lagoons. The floor and walls of
the vault are lined with a rubber or plastic coating to control seepage out
of and infiltration into the landfill. In addition to being impermeable the
lining material should be resistant to chemical attack, biodegradation and
tearing.

46
 - For surface impoundment to be effective, since liquid wastes evaporate\
become airborne, it has to be covered just like a sanitary landfill.
2. Waste destruction technologies
a) Thermal treatment
The waste is combusted in a flame- powered incinerator. This ensures that
carbonaceous matter is completely burnt, toxic material era destroyed and
pathogens are exterminated. Residue left out after incineration is non-
hazardous and can be disposed off in sanitary landfills.
b) Neutralization
Acidic wastes may be destroyed by neutralizing them with a paste
c) Oxidation
The organic matter wastes may be destroyed using strong oxidizing agents like ozone
or hydrogen peroxide or chloride e.g.
Equations

d) Hydrolysis
Reaction with water under controlled conditions

Equations

3. Waste Recycling Technologies

a) Recycling waste oil
b) Recycling solvents
[Link] separation Technologies
Mainly entail either segregation of one hazardous waste from another or isolation
of a hazardous component from a non-hazardous dump include:-
a)stripping
- Used to remove low boiling liquids such as ethanol, dissolved gases (NH3
Cl2) from an aqueous solution or suspension of a waste. Mainly steam/air is
bubbled through waste to remove volatile components which are condensed.
b)Sorption
Activated carbon is commonly used absorbent for treating waste e.g.
xylene,naphthalene,cyclohexane and chlorinated [Link] carbon is then
buried in landfills.
c)Precipitation
- Used to separate toxic metal ions from the waste
- A precipitating reagent which precipitates out metal ion followed by
separation via sedimentation or by filtration
d)Electrolysis
Toxic metal ions are reduced and deposited at the cathode when current is passed
through aqueous waste solution.
e) Solvent Extraction
This removes a toxic solute from aqueous solution of a waste into an organic solvent in
which it has a higher solubility. E.g. Iodine can be extracted out of aqeous state into
carbontetrachlride

47
 [Link] immobilization Techniques
-involves the conversion of the hazardous waste into an inert solid so that it does
not seep into the environment. Include
a)Solidification
Is by embedding solid waste into the matrix of Portland cement. Good for
hydrocarbon waste

b) Fixation
Here the waste is not physically trapped but chemically reacts with the matrix
e.g.Al3+ or Ba2+ can interact with cement and be converted into highly insoluble
inert carbonates and hydroxides.
c) Encapsulation
here the waste is covered with an impervious material mainly water soluble
salts that can be leaded into ground water materials used in encapsulating-Asphalt
and polythene.
d) Vitirification
-similar to solidification
6. Green chemistry approach
-This blends the applications of chemistry with economic growth and
environmental preservation.
- It aims to develop strategies for sustainable chemical industries so as to
achieve cost effectiveness and pollution prevention at the same time.
- It helps design products and processes that reduce or eliminate use and
generation of hazardous waste
7. Waste Bioremediation technologies
Here Micro-organisms consume waste products as nutrients through biodegradation.
Used to get rid of oils,gasoline,polynuclear aromatic hydrocarbons, chlorinated
hydrocarbons and phenols-e.g.
- Bact:Pseudomonas Sp –consume phenols
- Fungi:Phanerochate Sp – used in biodegradation of PAHcs and DDT
ENVIRONMENTAL REGULATIONS GUIDING KENYAN INDUSTRIES OF
ENVIRONMENTAL POLLUTION
Case study:- NEMA-National Environmental management Authority est 2002(parastal)
-is the principal instrument of the government in the implementation of all policies
relating to the environment.(sustainable environmental management)
Mission
Safeguard and enhance the quality of the environment through coordination, research,
facilitation and enforcement while encouraging responsible individual corporate and
collective participation towards sustainable development.
Functions
-coordinate the various environmental management activities being undertaken by lead
agencies
-promote the integration of environmental considerations into Development of
policies,plans,programs and projects with a view to ensuring the proper management and
rational utilization of environmental resources.
-to take stock of the natural resources in Kenya and their utilization and conservation

48
-to establish and review land use guideline
-carry out surveys, which will assist in proper management and conservation of
environment.
- initiate and evolve procedures and safeguards for prevention of accidents, which may
cause environmental degradation and evolve remedial measures where accidents occur
e.g. floods, landslides,oilspills.
-monitor and assess activities in order to ensure that the environment is not degraded.
- publish and disseminate manual codes or guidelines relating to environmental
management and prevention of abatement of environmental degradation.
Examples of Legislations/Laws by NEMA
a) Environmental Act
What is an act of parliament?

b) Environmental impact Assessment and Audit

-critical examination of the effects of a project on the environment
c) Water Quality Regulations
-Applies to water used for domestic, industry, agricultural and recreational
purposes. These regulations provide for the protection of lakes, rivers, streams,
springs etc.
d) Waste Management Regulations
-Meant to streamline the handling, transportation and disposal of various types of
wastes
e) Controlled Substances Regulations
-Provides guidance on how to handle them by importers and exporters (licensed By
NEMA)
f) CBD and Biodiversity Regulations
-protect ecological zones and habitats e.g. forests, aquatic, coastal and marine ecosystem,
wildlife are all under protection/conservation.
g) Air pollution Regulation
Provide for the prevention control and abatement of air pollution to ensure clean and
healthy ambient air.
h) Noise Regulations
i) Designated Labs for Testing
Audit labs to determine their capacity and competence to perform designated analysis.

49