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160 L. Philippot and J.C. Germon<br />

2<br />

Nitrogen Transformations in the Soil<br />

With 79% of gaseous N2 and a total mass of 3.8 × 10 21 g of nitrogen atoms,<br />

the atmosphere is the largest reservoir of nitrogen. However, this N2 is<br />

metabolically unavailable to the higher plants which do not have the ability<br />

to break the triple covalent bond of N2. Nitrogen from the air enters the<br />

nitrogen cycle through the action of several unique types of microorganisms<br />

that can convert N2 gas to inorganic forms available to plants. This<br />

conversion of molecular nitrogen into the available form is known as nitrogen<br />

fixation. Nitrogen is the nutrient element most frequently found<br />

to be limited to plants because of its continual loss by denitrification, soil<br />

erosion, leaching, chemical volatilization, etc. Therefore, biological nitrogen<br />

fixation (BNF) is important in agriculture because it provides a source<br />

of fixed nitrogen for the growth of plants that does not require fossil fuels<br />

for production. Biological nitrogen fixation is mainly performed by<br />

microorganisms called diazotrophs and can be represented by the following<br />

equation, in which 2 moles of ammonia are produced from 1 mole of<br />

nitrogen gas:<br />

N2 +8H + +8e − +16ATP → 2NH3 + H2 +16ADP +16Pi .<br />

The product of nitrogen fixation is generally used directly by free nitrogenfixing<br />

bacteria or exported to the plants by symbiotic nitrogen-fixing bacteria.<br />

Exported nitrogen is used by plants to synthesize organic nitrogen<br />

compounds. These organic nitrogen compounds are used by animals as<br />

a nitrogen source. After the death of an organism (plant, animal, fungi,<br />

bacteria etc.) organic nitrogen, i.e., proteins, amino acids and nucleic acids,<br />

is degraded by microorganisms into ammonia. This decomposition of dead<br />

organic matter by saprophytic microorganisms is termed ammonification<br />

or mineralization. Urea and uric acid excreted by living animals are also<br />

mineralized by microorganisms in the soil. Once ammonia is produced, it<br />

can be (1) fixed by clays or by soil organic matter, (2) volatilized as NH3,<br />

(3) assimilated by plants and microorganisms or finally (4) converted to<br />

nitrate by highly specialized bacteria during a two-step process: nitrification.<br />

In the first step of nitrification, ammonia is oxidized into nitrite via<br />

NH2OH:<br />

NH3 + O2 +2H + +2e − → NH2OH + H2O → NO − 2 +5H+ +4e − .<br />

Inthesecondstep,nitriteisoxidizedintonitratewithoutdetectableintermediates:<br />

NO − 2 + H2O → NO − 3 +2H+ +2e − .

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