BCH4236: ENVIRONMENTAL CHEMISTRY

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
method available to reduce environmental pollution and use of instruments 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 to use 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,
atmosphere, lithosphere and oceans.
 It is the sum total of the cos that influence life an individual or population
  It determines the quality of life of an organism and its in constant change
b) Environmental Chemistry
 Refers to the study of the sources, reactions, transport, effects and fates (end up)
of chemical specials in the water, soil and air environment.
 It is a multidisciplinary science.

c) Environmental pollution
 Refers to unfavourable alteration of our surrounding 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 un-favourable vs favourable effects or of benefits verses costs has been
difficult –subjective. Example

 Man -made alteration of the environment will probably have have un-favourable
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 god 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 particular 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, l2

Fluoride compounds

Solid pollutants

Metals: Hg, Pb, Fe, Zn, Ni, Sn, Cd

Complex organic pollutants – Benzen, benzpyrene, acetic acid, ether

Photochemical oxidants:

ozone, NOx, CH3C (O) OONO2, Peroxy acetyl nitrate (PAN), aldehyde, PBzNx.

Other pollutants are

 Deposited matter –sort, smoke, tar, dust

  Solid waste/domestic e.g dust, animal fur e.t.c
 Economic poisons- herbicides, fungicides, pesticides e.t.c
 Fertilizers/Agricultural e.g nitrates, phosphates
 Radioactive wastes
 Noise
 Heat

Industrial wastes eg. Cr3+ ions from tanneries (how is this treated to acceptable levels?)

1.3.2 Micotoxins and Microbial contamination

Examples of these are aflatoxins which can be carcinogenic

Can 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 cpds 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 eg. 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 health industrial
worker gets exposed during an eight hour day without getting any adverse effects. Eg. 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.

SAQ
Why is knowledge or sources important to an environmental chemist?

Receptor- Refers to anything which is affected by the pollutant eg. 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.

All illustrated example is limestone which is a sink for atmospheric H2SO4

H2SO4 + CaCO3 CaSO4 + CO2 +H2O

SAQ

Write the equations to show how water is a sink.

1.3.6 Pathway of a pollutant

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

Pb(C2H5)4 auto exhausts PbCl2 + PbBr2 released in the air

Or

To food chain PbCl2 + PbBr2

Released in the soil

NO2 auto exhausts acid rain/photochemical smog/global warming

CO

SAQ 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
organometallic compounds which are present in the environment (toxicology of any cpd
depents on its form) e.g. To determine Methylmercury 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/litre 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.

SAQ: 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.

SAQ:

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 sewerage 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 and deplete the oxygen supply (DO).

f) Synergism and Antagonism

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 o individual pollutants. This effect is called antagonism e.g cyaride is very poisonous but
in presence of Ni, Zn, Cd is less severe due to complex formation.

SAQ

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-
pollutants products (any example).
 Sectors of the economy must adhere to set rules and regulations on environmental
safety. (Public Health Safety Act).

UNIT 2 AIR POLLUTION

2.1 Composition of clean dry air

Component Volume (%)

Nitrogen (N2) 78.1
Oxygen O2 21.0
Argon (Ar) 0.9
Carbon dioxide (CO2) 0.003
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
Occurs when primary pollutants reacts in the atmosphere to produce other pollutants e.g
O3 + N2 high temp NO + O2 NO2
Pri. Pollutant sec. pollutant

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 tint 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 account for over 90% of air pollution
They include:-
Oxides if carbon (CO)
Nitrogen oxides
Sulphur oxides
Hydrocarbons
Particles
Oxides of carbon (Carbon Monoxide)
2.2.1 Carbon Monoxide
 Is a colourless oduorless, tasteless and non-irritating gas
 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 carboxyhemoglobin (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 desorb) 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).
Hb O2 O2Hb CO COHb
O2

Observations
It has been observed that:
 When COHb in blood is less than 7% the is 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:
Normal levels of CHb 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 jelly fish. It
therefore diffuses from ocean to the atmosphere.
Anthropogenic
Combustion-from combustion of coals, stoves, furnaces etc.
C + O2 CO

CO + O2 CO2

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

2CO + O2 fast 2CO

At high temperature
CO2 C(cpds) CO

Or

CO2 CO O

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

Sources of CO in the atmosphere

Hydroxyl radicals interact with methane to give methyl radicals

CH4 + OH H2O + CH3

Methyl radicals oxides by oxygen

CH3 + O2 CH3O2

Dissociates into ethanol

CH3O2 HCHO + OH

CH3O2 HCO + H2O

 Photochemical dissociation methanol

HCHO + hv H2 + CO

HCO + hv H + CO

2.2.2 Fate of Carbon monoxide in the atmosphere- CO sink (End up, or how its
removed)
 Residence of CO in atmosphere is in the order of 0.03 years (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 the methane are
similarly instrumental in removing CO from the atmosphere by oxidizing it to
CO2

CO + OH CO2 + H

ii) The CO may be transported from troposphere to stratosphere where it is rapidly

oxidized to carbon dioxide by oxygen free radicals.
iii) Soils act as an important sink for carbon monoxide e.g Methanosarcina barkerii of
methanobacteria formicum by oxidation to CO2 or Redn to
CO + 0.5O2 soil CO2
Bacteria

CO + 3H2 soil CH4 + H2O

The soil is able to remove about 5 times the discarded CO in the atmosphere. It is
a major sink since
Most CO remains in the atmosphere since the sink is 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:

CO has a dipole moment hence can absorb IR unlike other gases (IR in )

Control measures for CO

Mainly production if CO is through vehicular automobiles (space flights/submarines)

 Thus these have been fitted with catalytic burners/converters to oxide CO to

harmless CO2
 These catalytic converters not only reduce CO but also nitrogen oxides
 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 (N2O3), Dinitrogen
tetroxide (N2O4) 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
Oxide 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 plans 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 at high temperature

N2 + O2 2NO
In the atmosphere it is converted to nitrogen dioxide by aerial oxidation

2NO + O2 2NO2

Ozone can also oxide nitric oxide to NO2

NO + O3 NO2 + O2

2.3.2 Concentration and distribution of NOx in the atmosphere

(Use reactions above to explain)

 Before daylight, 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 evenings (5-8 pm), 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

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

SAQ

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 atmosphere NOx undergoes photolysis producing either nitric oxide (a) or free oxygen
atoms (b)

a) N2O + hv NO + N
b) N2O + hv N2 + O2

Free oxygen atoms interact with nitrous oxide producing intric oxide

N2O + O 2NO oxidized in O2 NO2

Nitrogen dioxide reacts with water vapors producing nitric acid

2NNO2+ H2O 2HNO3+ NO

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

NH3 + HNO3 NH4NO3

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).

SAQ

i) Write a summary equations to show formation of smog

ii) How are peroxy acetyl nitrates (PAN) formed

2.3.2 Analysis of Nitrogen

Since both nitrous 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

2NO2 + 2NaOH NaNO2 + NaNO3 + H2O

These contents are added to a mixture of hydrogen peroxide, sulfanilic acid, hydrochloric acid and

N (l-naphthy)- ethylene diamine dihydrochloride. Sodium nitrate formed diazotizes with sulfanilic acid.

Diagram

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

Diagram

The coupled compound absorbs at 540 nm. It concentration is determined by Lamberts Beers law (write
it down and define the terms

Mole ratio 1:1 thus 1 mole of coupled compound corresponds to 1 mole of NO2

SAQ

Check for a relevant example and work it out.

2.4 Effects of Nitrogen Oxides (NOx)

Very poisonous gas

1. Primary effects
a) Humans
 Inflammation of lungs and edma 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 100 ppm nitrogen oxides which are inhaled/absorbed by lungs
(smokers are prone to effects of NOx)
b) Vegetations
  Suppresses plant growth at 0.3 ppm
 At high levels causes leaf injury and chlororis

2. Secondary effects formation of

 Acid rain (?)
 Photochemical smog (peroxide aldelydes, ketones, acylnitrates)
 Aerosols

2.5 Control measures for Nitrogen ox ides

a) Coal conversion technology
Involves an adjunct removal of suphur from coal prior to combustion by treating it with sodium
hydroxide. To lower combustion temperature it is a sprayed with steam so that N2 do not
combine with O2 do not combine with O2 hence NO2 are formed NO SO2 and NOx are formed
during combustion.

NB: Coal used to produce electricity.

b) Fluidized bed combustion

Influidized bed combustion limestone is added at points of combustion to reduce amount of
sulphur dioxide emitted in flue gases
CaCO3 heat CaO + CO2
2CaO + 2SO2 + O2 2CSO4

(Noxout technology)
Involves injecting aqueous solution of urea at points of combustion to react with NOx forming
carbon dioxide, nitrogen and water
NH2CONH2 + NO + NO2 2N2 + CO2 + H2O

c) Selective catalytic reduction technology

This technique involves addition of ammonia to the flue gases and passing the mixture over the
selective reduction catalyst
6NO + 4NH3 5N2 + 6H2O

6NO2 + 8NH3 7N2 + 12H2O

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 or all automobiles

Most important pollutants from exhaust CO, NOx and hydrocarbons

Two way convert – this removes HC & CO

2CO + O2 2CO2

HC + O2 CO2 + H2O

Three way converter removes CO, HC & NOx

2NO + 2CO N2 + 2CO2

2N2O cat 2N2 + O2

2CO + O2 cat 2CO2

NOx + HC cat N2 + CO2 + H2O

HC + O2 cat CO2 + H2O

Three way catalyst consist of a mixture of Pt, Pd and Rh deposited on a high surface area ceramic or
alumina supports.

UNIT 3: 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 2.5 mg SO4/G H2%. They are
sprayed out as aerosols and accumulate in lower atmosphere
 Biogenic decomposition of Sulphur containing matter e.g H2S, dimethyl/sulfide by
marine algae, anaerobic bacteria.

b) Anthropogenetic Sources/man-made

 Burning of fossil fuels e.g coal, petrol

 Petroleum refinery
 Smelting of sulfide are especially Cu, Zn
 Manufacture of sulfuric acid
 Paper making
 Burning of domestic refuse

3.1 Fate of Sulphur oxides in the environment

H2S oxidized to sulfur dioxide by atomic oxygen

H2S + O HS + OH

HS + OH + O2 SO2 + H2O

By molecular oxygen

H2S + 1.502 SO2 + H2O

By ozone

H2S + O3 SO2 + H2O

Sulphur dioxide persists the atmosphere is oxidized to SO3 photochemical and no-photochemical

SO2 + O3 hv SO3 + O2

SO2 + O2 hv SO3

(only excited SO2 reacts with O2) (Ground state does not)

Non- photochemically

SO2 + 0.5O2 particles SO3

Sulfur trioxide formed eventually reacts with water to form sulfuric acid

SO3 + H2O H2SO4

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

H2SO4 + 2NH3 (NH4)2SO4

H2SO4 + 2NaCL Na2SO4 + 2HCl

3.2 Analysis of Sulphur 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 Cu,
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 tetrachloremercurate (II) and is quantitatively
converted to a stable nonvolatile complex, sodium dichlorosulfitomercurate (II), Na2
[HgCl2(SO3] + 2HCl

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

Diagram

H3PO4 serves to liberate sulfur dioxide from sodium disclorosulfitomercurate (II) complex, to
maintain PH at 1 and tie up any heavy metals present in air e.g

Fe3+ 3PO43- [Fe(PO4)3]6-

P-rosaniline methylsulfonic acid formed has a red violet colour and PH it absorbs at 575nm. Its
concentration can be determined calorimetrically by Lambert-Ber law. The concentration of p-
ronilinemeth/sulfonic acid is proportion 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 > 1.0 ppm
 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
 Discolouration of surfaces/paper/fabric
 Eating away of building stones, monuments

CaCO3 + H2SO4 Ca2+ + SO42- + H2O + CO2

S aq aq aq l g

D. Visibility –Sulfate aerosols can cause loss of visibility at 0.1 ppm 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.
 These react with water vapour to form the acid in the atmosphere and remain in the
clouds which later fall as rain.

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 acquatic life e.g nervous system of human
is also affected making him easy prey to neurologica 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/building – 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.
CA(OH)2 + H2SO4 CaSO4 + 2H2O
(s) aq (s)

 Liming also lowers the dissolved aluminum content by precipitating it out as aluminium
hydroxide
2Al3+ + 3Ca(OH)3 + 3Ca2+aq
aq (s)

 Corrosion of pipes prevented by coating with protective film or inert polyn er.

SAQ
Write chemical equations to show the formation of rain water where SO2 and NO2 are the
oxides involved individually.

3.4 Control measures for Sulphur oxides

Fuel resulfurization 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 Sin coal is removed by passing H2 gas over fuel in presence of Co
 MoO3 catalyst where it is converted to H2S,.H2S is absorbed in a solution of
diethylanolamine where it is regenerated as sulfur.

Microbial method
Makes use 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.
CaCO3 heat CaO +CO2

Lime ties up any SO2 generated from coal combustion

CaO + SO2 CaSO3

CaO + SO2 + 0.502 CaSO4

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

CaO + H2O Ca(OH)2

Catalytic reduction of sulfur dioxide. CO andSO2 are passed over a catalyst (LaTiO3)/Cu-
alumina

2CO + SO2 cat 2CO2 + S

UNIT 4 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 parties or droplets of liquid 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 one directly injected into the air by physical or chemical means
Sources include: pollen, soil, dust, volcanic debri, 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 24 h.

 Silicosis of lungs- mainly affects miners particularly when duct levels go so high they
settle on the surface of alveoli. They suffer shortness of breath due to blockage of
alveoli.
 Asbestosis – breathing in fibres of asbestos is more dangerous because it is carcinogenic.
 The fibres 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
Draw structure

 They are also commonly found in charcoal grilled meats, cigarette smoke, coffee, burnt
sugar
 Reactioms or mechanism/explanations
Diagram
  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 nucleotide in the gene sites (protenins) called hot spots where mutations
frequently occur (P53 dene)
 Many of these occur killing it and leading to growth which is cancer.

There is a correlation suspended particles and altitude. In Muranga County the level was
between 4000-5000 Ngm3 or respiratory suspended particles.
The sort of levels causes respiratory diseases e.g. persistent coughs, brochilitis, lung problems.
The most common cancers in Kenya are that of the nose abd throat because of use of wood for
cooking and heating.

Class activity
The averages person takes 15 breaths per minute inhaling 0.50l of air with each breath. What
mass of particulate, in milligrams would be person breathe in a day if the particulate level in air
were 75ug/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 100 ppm, this reduces visibility 8-
10km.
 Rural areas average particulate concentration 20ppm visibility range in 50-60km.

4.1.5 Oduor
 For volatile particulates they transmit unpleasant oduors 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.

SAQ
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
 Volcanoes, forest fires, vegetation, mousterpene r-pinene, natural gas see page
(decomposition of organic compounds by bacteria).

Anthropogenic sources
 Automobiles emissions-ships, vehicles, planes petroleum refineries manufacture of
polymers, plastics, pharmaceuticals etc.

SAQ
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 vapour are irritating, systematic 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 phototoxic 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.

RCH3 + OH RCH2 + H2O

RCH2 + O2 + M RCH2OO + M another molecule ehN

to absorb E
RCHOO+ NO RCH2O + NO2
RCH2O+ O2 RCHO + HOO [aldehyde]

HOO+ NO NO2 + OH
Net reaction
RCH3 + O2 + 2NO RCHOH + 2NO2 + H2O

4.4. Analysis of HCs

 The HC content of the air is analyzed by a gas-liquid chromatography fitted with a flame
ionization detector.
 The chromatographic column, into which air sample with HCs is injected contains a
liquid stationery phases. (Polydimethyl silixane and poly (trifluoroprophy)
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 every 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 decrease as
altitude increases).
 At low altitude it is hot and at higher altitude it gets cooler. This encourages mixing of
air hence photochemical reactions.

Cold air

Convenction process

Hot air
 In the tropopause 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 tropopase and stratosphere is hard to clear due to limited conversion
processes.
 The smooth exponential fall in density with altitude results in general decease in the rate
of third order recombination reactions.
 The low temperatures in the upper and lower stratosphere reduce the rate or reaction
having significant activation energies but favour combination reactions characterized by
negative activation energies.

5.1.2 Troposphere

 The most important free radicals are OH generated by photolyis

O3 + hv O2 + O

O + H2O 2OH

 O3 diffuses into the troposphere from stratosphere

 OH radicals are important in oxidation of pollutants e.g

CO + OH M CO2 + H

NO2 + OH M HNO3

SO2 + OH M HSO3-3 + OH H2SO4

CH4 + OH M CH3 + H2O

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

CH4 OH CH3

 Reaction is essentially a low temperature combustion process with the end product
being CO2 and water
5.1.3 Removal of SO2 from Troposphere
 SO2 is 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

SO2 + O + M SO3 +M Slow

By photo oxidation of SO2 to SO3

SO2 + O3 SO3 + O2

SO2 + O2 hv SO3 (only inexcited state

Of SO2)

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

OH + SO2 + M HSO3 + M

5.1.4 Removal of NOx species from troposphere

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

NO2 light NO + O

 In dark low light level conditions

NO + O NO2

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

OH + NO2 + M HNO3 + M

 The nitric 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 oxidized 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 equation]
If R Benzene PBzN are formed instead of PAN
Diagram

5.2.1 Effects of photochemical smog

 Main constituents of photo chemical smog are aldlydes, ketones, PAN, Ozone, NOx.
 Ozone causes eye irritation, cough, chest discomfort and fatique, 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 discolouration.
 Organic derivatives of aldelydes/ketones cause eye irritation (peroxyacetylnitrate)
skin cancer etc.
 By controlling NOx, HCs in the atmosphere will suppress smog formation.

5.3 Stratosphere
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.

O2 + hv 2O (very reactive atoms)

O2+ O O3 (absorbs very harmful radiations

O3 + hv O2 + O

 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, and depletion of stratospheric ozone. [covered
elsewhere]

5.3.1 Effects of NOx in stratosphere

 The lack of skin for NO2 in the troposphere means that its main sink is by slow
transport into the atmosphere where it is photolyed 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 reactions with ozone to form NO2. The NO2 is attacked by an
oxygen atom releasing NO which returns to the first cycle.
 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
o 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.
 In the soil NO3, NO2 by nitrogen fixing bacteria which are recirculated rapidly into
the troposphere.
 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 ration at 20-25km)
  Doson units: convenient method of expressing O3 Cnc in terms of thickness or layer
at stp
 Of Dobson unit (DU) = 0.007 cm at stp or o.07 mm at stp.
 In normal condition the concentration of O3 varies between 3000DU-400DU.

5.4.1 How is ozone formed

 Ozone is usually formed in the upper part of stratosphere by short wave length ration

O2 hv O* + O

 This short wave length is present in the upper part of the stratosphere

O + O2 + M O3 + M*

 The function of 3rd Body (Quennchet) is to remove the excel energy which could
break up the already formed ozone.
 Most of the ozone is formed above the equator and then transported by wins 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 Chlorofluorcarbons (CFCs)

 CFCs are a group of synthetic chemicals used in large quantities (in the years 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 live.
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 oxide (ClOx).
 These degradation products form the basis of a further catalytic cycle analogous to
the NOx cycle which leads to the removal of ozone and oxygen atoms.

CFCl3 hv CFCl2 + OCl

Cl + O3 ClO + O2

Net reaction
O + O3 2O2
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 air craft into the
stratosphere recovery occurs within approximately 3 years.
 However, the release of CFCs and N2O 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.
 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, breast cancers since UV-b is known to
damage cell DNA.
 Poor crop yield (tea, soybean) due to reduction in leaf size, poor seed quality, plant
proteins are excellent absorbers of UV-rays hence susceptible to chrolophyl injuring
(reduction and mutation)

5.5.4 Control of ozone depletion

 Reduction and stoppage of CFCs and instead use of carbon flouro carbons (Ch2FCH ) 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).
 The glass roof of a greenhouse is permeable to radiation 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 the 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: plant use large quantities of CO2 as a result of deforestation, an important
sink of CO2 is being eliminated
 Livestock-breath 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, refrigerants 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.
 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
 Carbondioxide fertilizers –plant biomass may increase to 25-30% by CO2 fertilization
 Nitrogen content plants growth 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.

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
Diagram

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

Diagram

 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 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 of. This pre-ignition causes 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 rating (knock- rating of a fuel). This is measured by research octane number (RON).
If the fuel is too involatile, engine warm up is delayed to inefficient combustion which can cause
pollution.
In Kenya Bureuau of standards:- 90% of fuel should boil below 1800c
General motors (Europe) 90% of fuel boil below 1600c.
Even in modern cars, warm-up stage (30 sec) 33% of total HC and 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 questions 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 o) e.g for n-heptane
 Very resistant to knocking when octane number is high (e.g 100) eg for isooctane

6.1.4 Factors that increase octane number (cf SCH102)

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 buten (97)
iv) Aromatization e.g n-heptane (o) 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 cane be
increased to 85-100.

Note
  The more refining we do, the less petrol you get and therefore the more expensive it
become 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’s 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:

Diagram

Alternatives
Diagram

 The alternatives can be used as substitutes because they are stable and secondly they are
liquids
 Carbonyls are toxic. E.g have high vapour 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.
Diagram

 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 inhibits enzyme activity at concentrations of 10Ng/100ml. The enzyme inhibited

will that be involved in haemoglobin production. The enzyme is Delta-aminolaevulinic
acid dehydrate (DEAT-ALAD)
 Pb therefore, interferes with metabolism of blood, reduces the red blood cell formation
and hence leads to anaemia.
 Pb also replaces calcium in the bones.

ii) Chemical
Below 60-80 Ng/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) Deficiencies
This occurs over a 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.

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 AGRICULTURAL 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
tends 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 ie nitrates

ii) Phosphonous based fertilizers 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 unfavourable 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 higly
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

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 responsibility 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 wellbeing (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 ar
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

Included 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 economica; e.g
parathion and diazinon.

SAQ: Draw structure of parathion

iii) Carbamates

They are intermediate between organochloride hydrocarbons and organophosphates i.e less toxic
and less persistent e.g carbonyl and…..

Diagram

 Methiocarbs
 Neurotoxic
iv) Pyrethroids

 Are analogs of pyrethrum (naturally occurring insect repellant) present in chrysanthemum

 They are neither persistent nor toxic e.g pyrethrum and deltamethrin.

Diagram

7.3 ENVIRONMENTAL EFFECTS OF INSECTICIDES

7.3.0 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 insecticides lower in the tropics
level in the food chair.

Insects/planktons Fish Birds of prey (high levels of DDT)

Mosquitoes (DDT) spray

ii) Broad spectrum characteristics

Since 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 insecticides with its gradual use.

iv) Birds
Birds of prey at high position in food chain concentrate enormous quantities of insecticides in
their tissue especially orgabochlorine 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 insecticides 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.
Draw back they are expensive

ii) Viral insecticides

Highly specific

iii) Hormonal insecticides

 Kill insects by upsetting its normal metabolic processes e.g Juvenile hormone
Drawback –target 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 a are treated with sterilizing
chemical or exterminating device. [An important area of research]

vi) Genetically engineered crops

 Resistant to attack by pest/insects (transgenic crops).

7.4 FUNGICIDES AND HERBICIDES

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 as mould inhibitors
v) In paints an vanishes- fungicides are used as mildew prevention
vi) In wood industries they are used as preservatives

White herbicide/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 part, rapidly distributes itself in the plant tissue.
Examples thiabendazole and [thiaphanate]
Diagram

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
Diagram

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 bromail.

Effects on plants
Rapid darkening of green leaf followed by necrosis hence death
Infective for weeds whose roots produce new shoots e.g
Diagram

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).
Diagram

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 phenylmercury acetate.
3. Competitive inhibition where a fungicide resembles a metabolic (antimetabolite) e.g
thiobendazoloe.
4. Fungicides may interfere with utilization of essential metal ions by complexing them
making unavailable for fungi e.g carboxin.

7.4.5 Mechanism 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. Photocynthesis 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-trichlo-2,2-bis (p-chlorophenyl) ethane also called dichlorodipheny/trichloromethane
hence the name DDT is obtained by the reaction of chloral with chlorobenzene.
Diagram

Methoxychlor synthesis
Diagram

 Methoxychlor is biodegradable but less effective as an insecticide

 More costly to prepare because anisole is more expensive than chlorobenzene

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.
Diagram.

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

 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
Diagram

SAQ: Explain the food chain (how can one aspect of food chain affect the other?).

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)
 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 Sulphates
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.
They 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 low 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 leads to increase in the quantity of plant and animal life in
the water.
 Over many years the amount of living matter increases. This die of 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 is overrun by vegetation.
 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 of 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 phosphorus added to the surface water are from
man-made sources
 Run off 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 aklylbenzene sulfonates which are 90-95%
biodegradable.
Diagram

The most commonly used builders are sodium tripophyphosphate, 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 P3O10-5 is slowly
dehydrolysed to produce non-toxic orthophosphates.

P3O10-5 + 2H2O 2HPO42- + H2PO4

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

eutrophication.
 For this reason, some formulations incorporate non-phosphate builders’ e.g trisodium
nitrolotricetate, sodium citrate, EDTA, etc
Diagram
8.3 Environmental impact of Detergents

1) Eutrophication- detergents containing polyphosphate builders and phosphate

based fertilizer shave 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 e.t.c
 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
 Colour e.g Fe3+ (Fe(OH)3 impart a yellow colour/orange
 Turbidity due to presence of colloidal matter imparting cloudiness to water
 Suspended matter
 Froth
 Radioactivity- natural radioactive elements
 Taste and oduor

c) Thermal pollution
d) Inorganic pollutants
 Acids- H2SO4, H3PO4, HCL e.g acid mine drainage
 Alkalis- caustic soda, lime
 Cations (Heavy metals)- Hg, Pb, Ar, etc.
 Anions –sulfides/cyanides.