CHEM115 Environmental Chemistry

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TOPIC 8

NATURAL CYCLES
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General Introduction
The total amount of matter on earth is fixed.

The chemicals essential for life continuously
cycle in the earth.

Natural cycles can also be called as
biogeochemical cycles.
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Energy originates from the Sun.

All cycles are interdependent.

Chemicals needed by organisms to sustain their
lives are nutrients.

Chemical element essential for life are essential
elements or bioelements.
General Introduction (contd)
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Biogeochemical Cycles
1. Iron cycle
2. Carbon cycle
3. Nitrogen cycle
4. Oxygen cycle
5. Phosphorus cycle
6. Sulfur cycle
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Iron Cycle
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Iron
Iron is a hard, silver-grey metallic element.

It is stable in dry environment but it rusts
rapidly in moist air.

The earths core is mainly composed of
liquid iron while concentration of irons in
the crust is relatively much lower.
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Dissolved iron (Fe
2+
) is found in trace
amount in water while insoluble (Fe
3+
) iron
compounds suspend in water.

Iron is also found in suspended particles in
the atmosphere.
Iron (contd)
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Iron cycle
Land
Ocean
Atmosphere
Lake
Groundwater
Rock
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Importance
Biological system
Works as oxygen carrier in red blood cells

An important component of the catalyst
involved in chlorophyll formation.

Essential micro-nutrient for animals and
plants.


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Iron deficiency in animals can happen due
to poor diet and excessive bleeding.

When soil is iron-deficient or high on pH,
iron availability decreases.

It can be solved by using organic compounds
to form chelate with iron. It can hold iron
tightly but releases it at plant roots, making
it bioavailable.
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Carbon Cycle
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Carbon
FOUR main reservoirs of carbon
1. CO
2
in the atmosphere
2. Dissolved CO
2
in oceans and other water bodies
3. Organic compounds (living or dead)
4. Calcium carbonate in limestone and carbon
buried in organic matter

Carbon reservoirs store most of the carbon.

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Carbon cycle is largely based on conversion
of CO
2
into organic carbon compounds in
living organisms via photosynthesis, the
release of CO
2
during aerobic respiration,
the decomposition of plants, oceanic
absorption and release of CO
2
and the uplift
of minerals from sediments.







Carbon and CO
2

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Involves the exchange of carbon between
the biosphere, lithosphere, hydrosphere and
atmosphere.

Usually exists in 3 pure forms in lithosphere
diamond, graphite, buckminsterfullerene.








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Exists as CO
2
gas (0.04%) and other carbon
containing gases such as methane and
Chlorofluorocarbon (CFC) in atmosphere.

Carbon is passed along the food chain in
biosphere.

Exists as calcium carbonate (limestone) or
dissolved as carbonic acid in hydrosphere
(ocean).
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Source: http://www.globe.gov/
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Removal from atmosphere
Plants remove carbon dioxide from the atmosphere
for photosynthesis

6CO
2
+ 6H
2
O C
6
H
12
O
6
(s) + 6O
2





Interaction within the cycle
Energy from sunlight
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Return of carbon to the atmosphere

Respiration process

Decomposition of plant and animal
(methane or carbon dioxide is produced)

Fossil fuel combustion

Burning of plants and forest fire

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Importance
An essential element to support living
organisms.

Trapping heat to keep the earth warm
greenhouse effect

Used for carbon dating.
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Anthropogenic effects
1. Increase of CO
2
emission due to
industrial activity increases the CO
2
concentration
2. Deforestation increases CO
2
concentration.
3. Increase of CO
2
level causes global
warming.
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Nitrogen Cycle
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Nitrogen
Nitrogen is a non-metal that readily combines with
itself to form colorless, odorless and tasteless gas.

It occurs as nitrogen or oxidized gases in the
atmosphere.

It appears in organic and inorganic forms in
hydrosphere. -- ammonium, NH
3
, nitrate, NO
3
-

and nitrite, NO
2
-
ions.
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It is incorporated in all plant and animal
tissues as amino acids and proteins.

It is excreted in urea of human.
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Nitrogen Cycle
Nitrogen fixation --Nitrogen gas is converted
in soils and waters to ammonia (NH
3
),
ammonium (NH
4
) or many other nitrogen
compounds.

Nitrogen-fixing bacteria and algae mediate
biological nitrogen fixation.
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In land, nitrogen-fixing bacteria lives on
nodules on the roots of legumes. (Rhizobium,
Actinomycetes, Azozpirillum, Azobacter)

In water, cyanobacteria (blue-green algae) fix
nitrogen.

3CH
2
O + 3H
2
O + 2N
2
+ 4H
+
-> 3CO
2
+ 4NH
4
+



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Nitrogen can be oxidized in microbial
nitrification or assimilated by an organism
into its biomass in ammonia assimilation.

4NH
+
+ 6O
2
->4NO
2
-
+ 8H
+
+ 4H
2
O

4NO
2
-
+ 2O
2
-> 4NO
3
-




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When plants and animals die, complex
organic molecules are broken down into
simpler molecules through ammonification.
Ammonia is produced.

(NH
2
)
2
CO + H
2
O -> 2NH
3
+ CO
2


Denitrification is done by denitrifying
bacteria that use nitrate as source of
respiratory energy. Nitrogen gas is the end
product.
5CH
2
O + 4NO
3
-
+4H
+
-> 2N
2
+5CO
2
+7H
2
O


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Source: forages.oregonstate.edu
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Source: http://www.biotechnolog.pl/foto_mat/rhiz02.jpg
Source:
http://www.earthlife.net/prokaryotes/images/cy
anobacteria.jpg
Blue-green algae
nodules
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Anthropogenic effects
Combustion of fossil fuels by vehicles
produce much NO
x
which disrupts the
natural nitrogen cycle.

Nitrogen oxides in the atmosphere cause
health and environmental effects. Example?
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Sewage effluent and agricultural run-off
into freshwater also disrupt nitrogen cycle.

High nitrate content in freshwater causes
eutrophication and methaemoglobinaemia
and formation of carcinogenic nitrosamines
in human digestive system.

Anthropogenic effects (contd)
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Oxygen Cycle
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Oxygen
Non-metallic element that readily combines
with itself to form a colorless, odorless and
tasteless gas.

It is reactive. And strong oxidizing agent.

Slightly soluble in water.

Most abundant element in lithosphere.
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Source: http://www.fossweb.com/resources/pictures/488256817.gif
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Photosynthesis is a process in which the
green plants use light energy and CO
2
to
form carbohydrates.

6CO
2
+6H
2
O -> C
6
H
12
O
6
+ 6O
2


Oxygen cycle
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Respiration which is a biochemical process
in which organic compounds are broken
down to release energy in adenosine
triphosphate (ATP) using Oxygen.

C
6
H
12
O
6
+ 6O
2
-> 6CO
2
+6H
2
O + energy
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Combustion refers to the combination of a
substance with oxygen, accompanied by
heat.

Example: Hydrogen sulfide and oxygen
2H
2
S + 3O
2
-> 2SO
2
+ 2H
2
O

Incomplete combustion occurs when there is
not enough oxygen. CO

is usually released.

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Ozone formation
Created by ultraviolet light striking
oxygenmolecules (O
2
) splitting them into
individual oxygen atoms

These O atoms combine with unbroken oxygen
(O
2
) and create O
3
which is known as ozone.

O
3
is unstable and can split back to oxygen
molecule and oxygen atom.

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At Troposphe
Tropospheric ozone is formed by reaction of
nitrogen dioxide with sunlight, producing
oxygen atoms that react subsequently with
oxygen molecules in the presence of a third
body.

NO + O
3
->NO
2
+ O
2
NO
2
+ h
v
-> NO + O
O+O
2
+M -> O
3
+ M


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Effects of tropospheric ozone:
- cause the stomata of plants to shut and
prevent uptake of CO
2
from atmosphere.
Therefore, vegetation would take up less
carbon dioxide and this leads global
warming

- Ozone is the second most important
greenhouse gas after CO
2



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At Stratosphere
Stratospheric ozone
Formation,
O
2
+ h
v
-> 2O ( = 242nm)
O
2
+O+M -> O
3
+M

Destruction,
O
3
+ h
v
-> O
2
+ O
O
3
+ O -> 2O
2


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Importance of Stratospheric Ozone:
- Absorb harmful UV-C radiation before it
reaches the Earths surface.
- It absorbs part of UV-B and no ability to
absorb UV-A.
- If the Ozone concentration in the
stratosphere is reduced, lethal UV-B can
penetrate the troposphere and the
radiation can cause the development of
skin cancer
- Affect aquatic system.

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What destruct ozone?
Free radicals formed by methane gas,
nitrogen-containing species and chlorine-
containing species

Chlorofluorocarbons (CFC)



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Importance of Oxygen


What are they?
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Phosphorus Cycle
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Phosphorus
Phosphorus (P) is highly reactive, non-
metallic.

Most common forms are white and red
phosphorus.

It appears as phosphate rocks in lithosphere,
suspended solids in water bodies and dust
particles in atmosphere.
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Source:http://bioh.wikispaces.com/file/view/36-17-PhosphorusCycle-L.gif
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Phosphorus cycle
There is relatively small circulation of
phosphorus between atmosphere and other
parts.

The cycle mainly involves transfer of
suspended solids from rocks and sediments
to living organisms and back again.
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Phosphate is present in a simple, inorganic
form before plants can take it up. Main
phosphates species present in soil are
- orthophosphate (PO
4
3-
),
- hydrogenphosphate (HPO
4
2-
)
- dihydrogenphosphate (H
2
PO
4
-
).
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Importance
Essential element in living organisms and
main constituent of bone, nerve, brain
tissue, teeth.

It is macro nutrient/ biolimiting element

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It is an important component to form ATP
which supplies energy to cells in biological
system.

ATP + H
2
O ADP + H
3
PO
4
+34kJ mol
-1

It is also an essential component for
deoxyribonucleic acid (DNA).
ATPase
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Anthropogenic effects
Human activities below will add to
phosphorus in the environment disrupting
phosphorus cycle balance.
Sewage treatment plant effluent
Soil erosion
Farming activities (surface run-off)
Organophosphate pesticides.

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Stinging
Nettles
Source: http://www.natural-pregnancy-mentor.com/images/z-net.jpg
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Sulfur Cycle
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Sulfur
It is non-metallic and brittle.

Appears in oxidized forms in atmosphere,
soil and surface water. Example: sulfur
dioxide (SO
2
), gypsum (CaSO
4
.2H
2
O) and
sulfuric acid (H
2
SO
4
)

Appears in reduced forms in rocks,
sediments and deep sea. Example: hydrogen
sulfide (H
2
S)
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Source:http://www.omafra.gov.on.ca/english/crops/field/news/croptalk/2006/ct_0606a2f1.gif
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Sulfur Cycle
Sulfur cycle involves lithosphere,
hydrosphere, atmosphere and biosphere.

Naturally, sulfate tends to be reduced to
sulfides. However, sulfate is usually oxidized
to sulfites and sulfates in anthropogenic
processes.
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Microbes are important in the cycle.

The most important biogenically produced
sulfur compound in the oceans is
dimethylsulfide, generated by
decomposition of
dimethylsulfonopropionate (DMSP).
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Importance
Important in industries.

Sulfur dioxide is used to produce sulfuric
acid as bleach for flour and textiles.
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Anthropogenic effects
Particulate-associated SO
2
aggravate
existing respiratory diseases.

SO
2
can damage plants
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Source:http://www.ohiocitizen.org/campaigns/coal/acid_rain_woods1.jpg
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Thank you