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Nitrogen cycle

Definition: Nitrogen cycle is a process of circulation of nitrogen in nature (atmosphere,


terrestrial, and marine), which involves several processes (biological, geological, and
chemical) that help in the conversion of nitrogen into various chemical forms. The
processes that involve in this cycle are nitrogen fixation, ammonification, nitrification,
and denitrification.

All living organisms require nitrogen for survival. Although nitrogen gas (N 2) has the
highest composition in the air, which is 78 %, most of this nitrogen are not accessible
in their gas form, which makes them very limited and lead to a scarcity of usable
nitrogen in many ecosystem. The inaccessibility of nitrogen is mainly because of the
strong triple bond between the N atoms in N2 molecules that causes the molecules to
be unreactive and relatively inert.

Nitrogen exists in a wide variety of forms, which include both organic and inorganic
nitrogen. Examples of organic nitrogen are ammonium (NH4+), nitrite (NO2-), nitrate
(NO3-), nitrous oxide (N2O), and nitric oxide (NO). The inorganic nitrogen is in the
form gas which is nitrogen gas (N2). These inorganic nitrogen, which is more
acceptable for most living organisms, is obtained through a series of cycles, called
nitrogen cycle. In this cycle, plants secure their nitrogen in “fixed” form, such as, nitrate
ion, ammonium ion, and urea, whilst, animals secure their nitrogen from plants.
Microbes/microorganisms such as bacteria, archaea, and fungi play major roles in
most of the process during the conversion of nitrogen from one form into another form.

Figure 1: The nitrogen cycle. Yellow arrows indicate human sources of nitrogen to the environment. Red arrows
indicate processes in which microorganisms participate in the transformation of nitrogen. Blue arrows indicate
physical forces acting on nitrogen. And green arrows indicate natural processes affecting the form and fate of
nitrogen that do not involve microbe
(Reference: http://www.visionlearning.com/en/library/Earth-Science/6/The-Nitrogen-Cycle/98/reading)
Nitrogen Fixation

Living organisms require nitrogen because it is a part of amino acids that make up
protein, and nucleic acid that make up DNA (deoxyribonucleic acid) and RNA
(ribonucleic acid) Nitrogen fixation is a process that converts atmospheric nitrogen
gas (N2) into ammonia (NH3) that is useable by plants and other organisms. In this
process, the triple bond that binds the nitrogen molecule will break apart and frees
the nitrogen atoms. Nitrogen fixation in the biosphere can occur in three ways, which
are atmospheric fixation, industrial fixation, and biological fixation.

Atmospheric Fixation

Atmospheric fixation is a non-biological fixation which is triggered by lightning. In


atmospheric fixation, energy from lighting will breaks the nitrogen molecules to
enables the nitrogen atom to combine with oxygen in the air to form nitric oxide (NO).
This nitric oxide will be oxidised into nitrogen dioxide (NO2) in the presence of excess
oxygen. Nitrogen dioxide reacts with atmospheric oxygen and rain water to form nitric
acid (HNO3) and nitrous acid (HNO2). These acids will then be absorbed by the soil
and produces nitrates (NO3-) and nitrites (NO2-) ions when react with alkaline
radicals. The nitrate and nitrite ions formed are soluble in water and are directly
absorbed by the roots of the plants.

Figure 2: Lightning causing atmospheric fixation (Reference:


https://honchemistry.wikispaces.com/Nitrogen+Cycle)
Figure 3: Chemical reaction during atmospheric fixation

Industrial fixation

Nitrogen is fixed industrially by a process called, Haber process or Haber-Bosch


process. It is now a common method among many manufacturers to produce
nitrogenous fertilizers. It is an artificial nitrogen fixation by converting atmospheric
nitrogen (N2) into ammonia (NH3) through the reaction between hydrogen (H2) with
nitrogen (N2) using metal catalyst. This process happens under high temperature
(600 °C) and pressure (35-100 MPa). The equation below shows the chemical
reaction between nitrogen and hydrogen to produce ammonia.

N2 + 3 H2 → 2 NH3 (ΔH° = −91.8 kJ) => (ΔH° = −45.8 kJ·mol−1)

Some of this ammonia can be used directly as fertilizer, whereas some are further
processed into urea and ammonium nitrate (NH4NO3).

Figure 4: Industry contributing to nitrogen cycle (Reference: http://peakenergy.blogspot.my/2008/05/getting-


cheaper-nitrogen-fix.html)
Biological fixation

Biological nitrogen fixation (BNF) is a term that is used to describe the process in
which atmospheric nitrogen (N2) is incorporated into the plant tissues. This process
can only be carried out by certain type of prokaryotes by utilizing the enzyme
nitrogenase to convert atmospheric nitrogen (N2) into ammonia (NH3). Some
examples of nitrogen-fixing bacteria include Rhizobium sp., Anabaena sp.,
Azotobacter sp., and Clostridium sp.. In order to convert N2 into NH3, nitrogenase
requires a large amount of energy, which is supplied by the nitrogen-fixing bacteria.
For the bacteria to supply sufficient energy, it first has to obtain a substantial amount
of nutrients.

Most of the bacteria get their nutrients from other sources through symbiotic
relationship or symbiosis. Symbiosis is a relationship in which two organisms form a
mutual beneficial relationship. Some example can be seen through the relationship
between bacteria Rhizobium and the root of legume plants. The Rhizobium colonize
the host plant’s root system and cause the roots to form nodules to house the bacteria.
The bacteria then begin to fix the nitrogen required by the plant and the plant can
produce leaves fortified with nitrogen, which in turn allow the plant to increase its
photosynthetic capacity and eventually yields seeds rich in nitrogen. Usually, plants
without nodules will have low nitrogen content, more chlorotic (iron-deficiency) and
yield very little seed.

Apart from the symbiotic relationship between Rhizobium and legumes, plants will
also supply carbohydrates, proteins and oxygen to the bacteria. However, the oxygen
concentration inside the nodules must be closely regulated because oxygen may
inhibits the enzyme nitrogenase. This regulation is aided by the presence of
leghemoglobin, an oxygen-binding protein similar to hemoglobin. The heme (oxygen-
binding) portion is produced by the bacterium, while the globin (protein) portion is
produced by the host plant, again illustrating the closeness of the symbiotic
relationship.
Figure 5: Nodules on the roots of legume plant (Reference:
http://edtech2.boisestate.edu/nixonr/edtech_573/activities/uses_plants.htm)

The following equation shows the reaction that take place during biological fixation.

N2 + 8H2+ 16ATP ------> 2 NH3 + 2H2+ 16ATP + 16 e-

The equation above indicates that one molecule of nitrogen gas (N2) combines with
eight hydrogen ions (also known as protons) (8H+) to form two molecules of ammonia
(2NH3) and two molecules of hydrogen gas (2H2). The 16 molecules of ATP (ATP =
Adenosine Triphosphate, an energy storing compound) represent the energy required
for the BNF reaction to take place. In biochemical terms 16 ATP represents a relatively
large amount of plant energy. Thus, the process of BNF is 'expensive' to the plant in
terms of energy usage. Therefore, the sun has been the ultimate source of this energy
via a process called photosynthesis. As ammonia (NH3) is formed, it is converted to
amino acid such as glutamine. The nitrogen in amino acids can be used by the plant
to synthesize proteins for its growth and development.
Nitification
Nitrification is the process of converting ammonia into nitrite (NO2-) and then into
nitrate (NO3-) through oxidation. The chemical reaction is shown by the following
equations.

2 NH3 + 3 O2 → 2 NO2 + 2 H+ + 2 H2O

2 NO2- + O2 → 2 NO3-

There are two distinct steps of nitrification. The first step is the oxidation of ammonia
into nitrite (NO2-). This is carried out aerobically by ammonia-oxidizers microbes or
nitrifying bacteria such as Nitrosomonas and Nitrobacter. Nitrosomanas will convert
nitrogen into nitrite (NO2-) first, then nitrobacter will further convert nitrite into nitrate
(NO3-). Plants utilize nitrate as nutrients, whereby animals, especially omnivores
and herbivores obtain nitrogen by eating the plants. This process generates small
amount of energy relative to many other types of metabolism.

Ammonification

Amminofication is a process where all plants and animals are recycled after their
death. This is done by the bacteria/microorganisms found in soil and water. These
bacterias convert nitrogen nutrients back into ammonia by breaking down proteins
and amino acids in dead plants and animal matter and feces. Ammonia that is
released usually retained in the soil and water in the form of ammonium ion which is
available for the growth of plants and other microorganisms. In agriculture or
horticulture, the addition of compost and manure to soil provide extra sources of
nitrogen for ammonification.

At the same time, other microorganisms will convert some of the ammonia into nitrate,
which can be absorbed by plants, and thus maintaining the nitrogen cycle.

Denitrification.

Denitrification is a process in which ammonia is converted back into nitrogen gas by


facultative heterotrophic bacteria, such as Psedomonads. The term “heterotrophic” is
referring to organisms that could not manufacture their own food and instead they
obtain their food and energy by taking in organic substance from plant and animal
matter. “Facultative” means that bacteria is able to obtain their oxygen by taking
dissolved oxygen out of the water or by taking it off from nitrate molecules.
Denitrification allows for the production of nitrous oxide (N2O), which is a greenhouse
gas that can have a considerable influence on global warming.

NO3- + CH2O + H+ → ½ N2O + CO2 + 1½ H2O

Denitrification takes place under special conditions in both terrestrial and marine
ecosystems. It occurs when oxygen level become limited and nitrate becomes the
primary source of oxygen for microorganisms. In general, it occurs where oxygen, a
more energetically favourable electron acceptor, is depleted, and bacteria respire
nitrate as a substitute terminal electron acceptor. Denitrification only takes place in
anoxic environments where oxygen consumption exceeds the oxygen supply and
where sufficient quantities of nitrate are present. These environments may include
certain soils and groundwater, wetlands, oil reservoirs, poorly ventilated corners of
the ocean, and in seafloor sediments.

Denitrification generally proceeds through some combination of the following


intermediate forms:

NO3− → NO2− → NO + N2O → N2 (g)

The complete denitrification process can be expressed as a redox reaction:

2 NO3− + 10 e− + 12 H+ → N2 + 6 H2O

Nitrogen that is formed will then returned to the atmosphere and the cycle is now
complete.
Figure 6: Reaction route of nitrification and denitrification
(http://www.shein.com/?ici=www_navbar03menu01&aff_id=5092&icn=exclusives)

Figure 7: Overall reaction of nitrogen cycle


(https://simple.wikipedia.org/wiki/File:Nitrogen_Cycle.jpg)
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