Unit 5: Environmental Chemistry

Environmental chemistry is a branch of chemical science that deals with the production, transport,
reactions, effects and fates of chemical species in the water, air, terrestrial, and biological environments and
the effects of human activities thereon.
A common pollutant species is used to illustrate the definition of environmental chemistry.
S (in coal) + O2 → SO2
SO2 + O2 → SO3
SO2 + ½O2 + H2O → H2SO4
5.1.1. Components of the Environment
The environment consists of various compartments including: atmosphere, hydrosphere, lithosphere
and biosphere.
The atmosphere:
An atmosphere is the layers of gases surrounding a planet or other celestial body. Earth’s atmosphere
is composed of about 78% N2, 21% O2 and 1% other gases
The atmosphere provides many benefits to the Earth's living organism including human being. such
as a blanket of gas surrounding the earth (0-50 km), absorbs IR emitted by the sun and re-emitted from the
earth, controls temperature of the earth, allows transmission of significant amounts of radiation from near
UV (300nm) to near IR (2500 nm) & blocks transmission of damaging UV radiation.
EX. Important Reactions. occurred in the atmosphere
1. 2NO(g) + O2 (g) → 2NO2 (g) by the action of UV
SO2, SO3, and NO2 react with rain water & form H2SO3, H2SO4 & HNO3, respectively and cause acid rain.
2. Chlorofluorocarbons are used as refrigerants, solvents and plastic foam–blowing agents. When
entering the atmosphere, they penetrate into the upper layers & interact with ultra violet radiation as
follows:
CF2Cl2 + UV → CF2Cl• + Cl•
Cl• + O3 → ClO• + O2
chlorine monoxide
The Hydrosphere:
The hydrosphere is the combined mass of water found on, under & above the surface of the Earth. It
includes water that is on the surface of the planet, underground and in the air. And it is collective term for all
different forms of water, including oceans, seas, rivers, lakes, streams, reservoirs, glaciers and ground
waters. Only ~ 1% of global water supp is fresh water. The greatest source of water on the planet is the
ocean, which constitutes all salt water and at the same time in the greatest source of water vapor.
In the ocean, there are at least 77 important elements such as Na & Cl, Mg & Br…
Some EX. of chemical reactions in the Hydrosphere:
1. NH3 /NH4+ that are discharged from Agriculture, Aquaculture, Industry and Urban areas into large
water bodies, resulting in toxicity to fish or aquatic ecosystem.
EX. The biological oxidation of NH44 to NO2–
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NO3– /NO2– that are discharged from agriculture, Industry Aquaculture & Sewage into water bodies,
resulting in accelerating aquatic plant growth leading to eutrophication
EX. The organic form of N2, NH3 has been converted into an in Organic form of N2, NO3– that plants can
use.
2NH3 + 3O2 → 2NO2– +2H+ + 2H2O
The equation summarizes the entire Nitrification Process.
The Lithosphere:
The lithosphere consists of earth's crust & upper mantle in which the crust part is the Earth's outer
skin that is accessible to human beings.
This part of the earth, i.e. the crust consists of rocks & soil (most important part to humans and the
environment).
Some EX. of important reactions in the lithosphere are:
1. Different bacteria (mainly autotrophic, i.e. not dependent on organic materials for their Carbon
supply) can affect Oxidation or Reductions of minerals.
2FeCO3 + ½O2 + 3H2O → 2Fe(OH)3 + 2CO2 by the action of Ferrobacilia
2. Chemical weathering of rocks
Fe2O3 + 3H2O → Fe2O3•3H2O (Hydrogenation of rocks)
The Biosphere:
It refers to the realm of living organisms & their interactions with the environment (i.e. other
compartments).
The compartment divided into smaller units is called ecosystem.
Each ecosystem contains dynamic interrelationships between living forms & their physical
environment. These interrelations manifest as natural cycles such as hydrologic, oxygen, nitrogen, P & S.
EX. of some important reactions in the biosphere:
1. Photosynthesis
6CO2 + 6H2O → C6H12O6 + 6O2 by the action of SUNLIGHT
2. Respiration
C6H12O6 + 6O2 → 6CO2 + 6H2O + Heat energy
5.1.2. Natural cycles in the Environment
Among the common natural cycles:
i. The Hydrologic cycle
It is the most important natural cycle. In this cycle, there is the continuous exchange of water between
environmental compartments.
ii. The Oxygen cycle:
It is the important cycle in the environment. Important to atmospheric chemistry, geochemical
transformation & life processes.

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 The following reactions show the importance of the Oxygen Cycle in the environment. For:

• Energy production
CH4 + 2O2 → CO2 + 2H2O + Heat energy
• Degradation of organic material (ex. glucose)
C6H12O6 + 6O2 → 6CO2 + 6H2O
• Weathering of minerals
4FeO + O2 → 2Fe2O3
• Photosynthesis
6CO2 + 6H2O → C6H12O6 + 6O2 by the action of SUNLIGHT
• Sun Screen (O3)
‘O’ + O2 → О3
iii. The Nitrogen Cycle
It is the second most important cycle after the C-cycle for living organisms. N is essential for plant
growth, therefore, is a significant contributor to the human food chain.
Important reaction of N-cycle in the environment are:

• Fixation by bacteria & algae

2N2 + 3CH2O + 3H2O + 4H+ → 3CO2 + 4NH4+
• Nitrification By Nitro somas & nitrobacteria
2O2 +3NH4+ → NO3– + 2H+ + H2O
• Nitrate reduction by microbial action
2NO3– + CH2O → 2NO2 + H2O + CO2
2NO2– + 3(CH2O) + 4H+ → 2NH4+ + H2O + 3CO2
• Denitrification returns N to the atmosphere
2NO3– + 5(CH2O) + 4H+ → 2N2 + 7H2O + 5CO2
• Perturbed by anthropogenic activity
• N2 + O2 + … → (combustion) NOx + …
iv. The Phosphorous Cycle
It is responsible for increasing the availability of P in the soil for plant growth and soil fertility and helps
to understand the physiology of different microorganisms involved in the process.

1. Central to many processes, including

a. Cell division involving production of DNA & RNA
b. Growth maintenance of animal bones and teeth
2. Sources include
a. in organic P such as soluble H2PO4– ; HPO42– & insoluble Ca5 (OH) (PO4)3 &
Fe3(PO4)2•8H2O
b. Terrestrial plants convert inorganic P salts to organic phosphate.
3. Animals obtain phosphate by eating plants.
4. Upon death, P is returned to soil
5. Soil microorganisms convert returned phosphate into soluble in organic phosphate (mineralization)
6. In water, P solubility is controlled by availability of Fe & Al (under acidic conditions) & Ca (under
basic conditions).
v. The Sulphur Cycle
It is essential as it balances the concentration of S in different reservoirs so as to make the Earth a
hospitable place for life.

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 S occurs in all living matter as a compound of certain amino acids. It is abundant in the soil, in proteins
& through a series of microbial transformations, ends up as sulfates usable by plants. The following are
importance of S cycle in the environment.

• Atmospheric oxidation produces higher charge states

• In hydrosphere & soil, S is present in many in Organic & organic forms with Oxidation states from –2 to
+6.
• Most common forms of S include
a. SO42– produced via a variety of pathways (EX. bacterial)
2H2S + 4O2 → 4H+ + 2SO42–
b. S2– produced by reduction of SO42– in organic rich reducing aqueous environments.
SO42– + 2CH2O + H+ → H2S + 2H2O + 2CO2
vi. The Carbon Cycle
The Earth’s atmosphere contains 0.035% CO2 & the biological environment depends upon plants to
convert CO2 into sugars, proteins and fats. Green plants convert atmospheric CO2 & water into glucose &
O2 in a process called PHOTOSYNTHESIS.
6CO2 + 6H2O → C6H12O6 + 6O2 by the action of SUNLIGHT; ΔH = +2803 KJ/mol
Photosynthesis is an endothermic reaction.
Both plants & animals respire & they release CO2 during respiration.
C6H12O6 + 6O2 → 6CO2 + 6H2O + Heat energy; ΔH = –2803 KJ/mol
Respiration is an exothermic reaction.
The process of decomposition of Organic matter also releases CO2 back into the atmosphere.
Dead organisms under high pressure & in the absence of air can be converted into fossil fuels such as
coal, oil & gas. Humans combust these fuels as energy sources which releases CO2 back into the atmosphere.
C(s) + O2 (g) → CO2(g)
Combustion of fossil fuels is Exothermic.
CO2 is a greenhouse gas & is a major contributor to global warming.
5.1.3. Concepts related to Environmental Chemistry
Pollutant: A substance whose concentration has increased due to human activity, ultimately having
detrimental effects on the environment.
EX. Include SO2, CO2, O3, Pb, Hg, excess heat light & sound.
Contaminant: A substance that doesn't occur in nature, but it is introduced into the environment through
human activity.
A contaminant is called a pollutant when it exerts detrimental effects on human health receptor.
Sink: The medium that interacts & retains pollutants or converts them chemically
Dissolved oxygen (DO): Oxygen dissolved in water. It is vital for aquatic life. The optimum levels of DO in
good quality water are 4 - 8 mg/L. Water with levels <4 mg/L is considered polluted & unfit for human or
animal consumption.

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Biological Oxygen Demand (BOD): Indicates the capacity of the DOM (dissolved organic matter) in a
sample of water to consume Oxygen. Determined experimentally by measuring DO at beginning and end of
a 5-day period in a sealed sample, it also gives the measure of Oxygen utilized as a result of Oxidation of
DOM Present in the water sample.
Threshold Limit Value (TLV): Indicates the permissible level of a toxic pollutant in the atmosphere to
which a healthy individual can be exposed during an 8-hour day without adverse effects.
TLV is found by experimentation on animal, medical knowledge and environmental studies.
5.2. Environmental Pollution
Pollution is any discharge of a solid, liquid or gaseous substance or radiation (energy) into an
environment that causes unwanted changes.
A Pollutant is any substance that changes air, water or any other natural resource in a way that
impairs the use of the resource.
Pollutants are discharged into the environment as a result of natural events (like a Volcanic eruption)
& as a result of human activities.
Pollutants can be classified as air, water & land pollutants.
5.2.1. Air Pollution
Atmosphere is considered as solution.
N2 is a solvent in our atmospheric solution. The solute present in largest amount is O2.
Some common pollutants are: SO2, Oxides of N, CO, O3, hydro-carbons, particulates, CFC and Pb comps.
SO2:
enters the atmosphere air from the combustion of coal, È petroleum e during extraction of metals
from their S2– ores. It causes coughing, chest pain & shortness of breath. It is thought to be a cause for
bronchitis & lung diseases. It slowly oxidizes to SO3 by reacting with the Oxygen in the air.
Oxides of Nitrogen:
Formed in the atmosphere by

• natural processes like thunderstorms

• combustion of fossil fuel containing N- comps as impurities & exhaust gases from furnaces &
engines increase the amount of NO & NO2 in the atmosphere.
NO catalyzes the decomposition of O3 in the upper layer of the atmosphere to O2; thus, decreasing the O3
layer.
2O3 (g) → 3O2(g) by the action of NO
2NO (g) + O2 (g) → 2NO2 (g) by the action of UV
SO2, SO3 & NO2 react with rain water & form H2SO3 , H2SO4 & HNO3, respectively and cause acid rain.
Acid rain accelerates corrosion & the deterioration of metals, building status & causes tree defoliation,
release of heavy metal ions from soil into water courses & drops the pH of water in rivers and lakes.
Hydrocarbons & Ozone:
are responsible for photochemical smog.

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 characterized by a reddish-brown haze containing substance irritating to the eye, nose & lungs &
causes extensive damage to vegetation.
Hydrocarbons are released into the atmosphere by the evaporation of gasoline as unburnt
hydrocarbons into auto exhaust.
CO:
escapes into the atmosphere due to the incomplete combustion of fuel.
prolonged exposure to CO impairs vision, produces headaches & exerts strain on the heart.
reduces the Oxygen carrying capacity of the blood by reacting with hemoglobin.
Particulates:
Dust storms, forest fires, volcanic eruptions & human activities such as mining & burning coal & oil
increase the amount of solid particles in the air.
Industrial areas contain particles of limestone, fertilizers coal, stones, cement & silica. These
particulates irritate the lungs & deleteriously affect breathing.
Chlorofluorocarbons (CFCs):
CFCs are used as refrigerants, solvents & plastic foam - blowing. agents. When entering the
atmosphere, they penetrate into the upper layers and interact with UV radiation as follows
CF2Cl → CF2Cl• + Cl• by the action of UV
Cl• + O3 → ClO• + O2
These reactions contribute to the depletion of the Ozone layer and allow dangerous UV radiation to
reach the Earth's surface.
This radiation causes skin cancer in human beings.
Volatile Organic Comps. (VOCs):
are compounds that can easily become gas or vapor.
They are mostly released from the burning of gasoline, wood, natural gas, & coal.
Other sources of VOCs include thinners & paints, cigarettes, solvents, wood preservatives, air
fresheners, furnishings, copy machines and printers, cleaners, pesticides, and disinfectants.
PEBs (Poly chlorinated biphenyls):
are organic Cl comps. that were at one point extensively used as coolant fluids & dielectric in
electrical gadgets, in heat transfer fluids & in carbonless copy papers.
Excess CO2:
Combustion of coal & petroleum to generate electricity, move our vehicles, heat our homes & supply
power to our industrial machinery causes a significant increase in the concentration of CO2 in the
atmosphere.
Combustion of these fuels releases about 20 billion tons of CO2 annually. The increase in the conc.
of CO2 in the atmosphere has resulted in a rise in the average global temp. owing to the greenhouse effect.
CO2 & H2O vapor absorb infrared radiation, re-radiated from the earth, behaving like the glass in a
greenhouse. Since CO2 & water vapor absorb heat, they are called greenhouse gases.

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 The over au effect is global warming. This causes melting of Polar Ice & thus additional water
flowing into the oceans.
Heavy Metals:
Pb contamination in the atmosphere is a result of vehicle engines that use fuels containing tetraethyl
lead which is added to the fuel to reduce Engine Knocking.
The use of Pb paints also contributes towards Pb contaminant ions. High levels of Pb cause damage
to the brain, kidneys and liver.
Method of Reducing Air Pollution

• Using public transport

• Turn of the lights when not in use
• Recycle and reuse
• Not use plastic bags
• Reduction of forest fires & smoking
• Use of fans instead of air conditioners
• Use of filters for chimneys
• Implement afforestation
• Avoid using of products with chemicals
• Avoid usage of Crackers
5.2.2. Water Pollution
is the degradation of the quality of water brought by the discharge of untreated sewage, industrial &
agricultural waste and oil spillage.
Water is said to be polluted if it contains matter that affects the health of living things or causes
damage to property.
The major water pollutants are NO3– & PO43– fertilizers washed out of the soil, phosphate detergents,
untreated sewage, insecticides, herbicides & heavy metal ions, acidic and /or basic residues released by
industrial processes.
The dissolved minerals are valuable nutrients for plants & their discharge into the water systems
accelerates the growth of surface-water plants such as algae. As a result, less light reaches the bottom-living
plants which reduces the photosynthesis they need to live & they die. The amount of O2 in water decreases
This depletion of O2 kills aquatic animals like fish. This sequence of events is called EUTROPHICATION.
Some EX. of water pollutants
Domestic sewage:
is also a major source of plant nutrients, mainly NO3– & PO43–
Excess NO3– & PO43– in water promote the growth of algae, sometimes causing unusually dense &
rapid growths known as ALGAL BLOOMS.
When the algae die, O2 dissolved in the water declines because microorganisms use O2 to digest
algae during the process of decomposition.
Solid Waste:
includes garbage, rubbish, electronic waste, trash & construction and demolition waste
Fertilizers:

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 causes water pollution from excessive amounts of NO3– & PO43– washed out from food & animal
waste as well as in Organic fertilizers.
Insecticides (Pesticides) & Herbicides:
are applied in agriculture may also be washed into lakes, rivers, streams and seas.
Lead:
is a dangerous toxin found across the world.
Methods of Reducing Water Pollution

• Treatment of water before discharge into rivers & lakes

• Industries should not discharge heat ladened water into them.
• Recycling industrial & agricultural wastes
• Using moderate amounts of agricultural chemicals
5.2.3. Land Pollution
is caused by things we put into it.
Causes of Land pollution

• Spillages of oil from leaking pipelines

• Harmful heavy metal ions from buried waste leaching into water systems
• Leaching of harmful chemicals from corroded metal drums which have been buried underground
• Dumping of non-biodegradable wastes like plastics
• Excessive use of synthetic fertilizers.
Some EX. of the pollutants that cause land pollution:
❖ Garbage
❖ Plastic
❖ Mercury
Method of Reducing Land pollution
Reducing non- biodegradable wastes
Non-biodegradable wastes are major sources of soil, air & water pollution.
EX. of non- biodegradable waste: glass, medical waste, plastic, man-made synthetic materials, electronic
components, cans, nuclear waste, man-made polymers and artificial rubber
5.3. Global Warming & Climate Change
The emission of certain substances to the atmosphere produces a green-house effect contributing to
the global warming.
Many of these emitted gases resulted from:

• certain types of chem. reaction mainly combustion of fuel

CxHy + O2 → CO2 + heat energy

• some of them may be manufactured products like ClFCs, solvents & volatile organic comps
• some of them have a natural origin
5.3.2. Chemistry of Green-house & their Effects on Climate Change

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Green-house effect
happens when certain gases which are known as green-house gases, accumulate in Earth's
atmosphere.
Green-house gases include: CO2, CH4, N2O, O3, H2O, & fluorinated gases
These gases warm our planet by absorbing in light radiation that would otherwise escape into space.
Without this warming effect (called the green-house effect, the average temp. on Earth would be -18°C.
Because these green-house gases in our atmosphere absorb IR light, Earth's average temp. is 15°C. CO2(g) &
H2O(g) do absorb IR light and gain energy which is transferred to the rest of the Earth. CO2 & H2O are the
main contributors to the green-house effect
N2 & O2 do not absorb IR light & do not contribute to the green-house effect.
Contribution of Green-houses Gases for Global warming
There are 5 gases of human origin that contribute to increase in global warming.
CO2 52.92%, CH4 14.88%, CFCs 10.78%, O3 10.72%, N2O 10.70%
5.4. Green Chemistry & Cleaner Production
5.4.1. Principle of Green Chemistry
Green chemistry is a movement to make industries that involve chemicals more environmentally
friendly & sustainable.
The 12 principles of green chemistry:

1. Prevention: prevent waste than to treat or clean up waste after it has been generated.
2. Atom economy: to improve chemical processes by avoiding the waste of atoms from reactants &
products.
is the ratio of mass of the desired product by the total mass of the products
EX.
A+B→C+D
Atom economy = (mass of C) * 100
(mass of C + D)
For optimal process, the atom economy should be near or equal to 100%.

3. Less Hazardous Chemical Synthesis: synthetic methods should be designed to use or generate
toxicity to the environment.
The goal should be to avoid reactions that give hazardous biproducts.
4. Design of Safer Chemicals
5. Safer Solvent & Auxiliaries: replace toxic; non-recyclable solvents with safer solvents.
6. Design for Energy Efficiency
7. Use of Renewable Feedstock
8. Reduce Derivatives
9. Catalysis: Catalytic processes are achieving the goals of environmental protection & economic
benefit.
10. Design for Degradation:
"Chemical products should be designed so that at the end of their function they break down into innocuous
degradation products and do not persist in the environment.”

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 11. Real-time Analysis for pollution prevention: Real-time monitoring & control during synthesis to
minimize or eliminate the formation of by products
12. Inherently safer chemistry for accident prevention: It involves choosing a safe or safer chemical
to mitigate the chances of occurrence of an accident.
5.4.2. Cleaner Production in Chemistry
An ideal chemical reaction should have a number of attributes such as safety, simplicity, selectively, high
yield, energy efficiency, use of renewable or recyclable raw materials and reagents, & absence of hazardous
byproducts or at least minimizing or containing them.
Goals Of Green Chemistry from The Perspective of Cleaner Production

1. to reduce adverse environmental impacts by appropriate and innovative choice of materials & their
chemical transformation.
2. To develop processes based on renewable (plan-based) rather than non - renewable (fossil carbon-
derived) raw materials
3. To develop products that are less toxic or which require less toxic raw materials/feed stocks
4. To develop products that degrade more readily/rapidly in the environment than the current products.
5. To reduce the requirement for hazardous or environmentally persistent solvents and extraction in
chemical processes.
6. To improve energy efficiency by developing low temperature & low-pressure processes by using
new /improved catalysts.
7. To minimize by products in chemical transformation through redesign of reactions and reaction
sequences. In other words, to achieve better "atom economy".
% of atom economy = Formula weight of the product * 100
Sum of formula weights of all reactants
Atom economy: (a measure of atom utilization or efficiency) is a measure of the amount of starting materials
that end up as useful products.
Atom economy = mass of desired or useful product * 100
total mass of all reactants or products
The reactions that only give one product have the maximum atom economy of 100% and these are the most
economy reactions.
EX. N2 + 3H2 → 2NH3 and CH2= CH2 + H2O → CH3–CH2–OH
EX. Fe2O3 (s) + 3CO (g) → 2Fe (l) + 3CO2 (g)
(2*56)+(3*16) 3(12+16) 2*56
112+48 3*28 112g
160g 84g
244g
Atom economy = (112*100) / 244 = 45.9%
Good atom economy means most of the atoms of the reactants are incorporated in the desired products and
only small amounts of unwanted byproducts are formed. Hence, lesser problems of waste disposal or waste
treatment.

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