Mineralization of Organic N in Soil

Mineralization of organic nitrogen can be defined as the process by which N in organic

compounds gets converted into the inorganic ammonium or nitrate ions. The organic N com-
pounds present in SOM, organic manures and crop residues are attacked by a heterogeneous
group of soil microorganisms, mineralizing it into inorganic form [Equation (3)]. Mineraliza-
tion covers the whole series of reactions brought forward by soil microbes till the formation
of NO, The mineralization is faster in the presence of fresh or easily decomposable organic
material. However, mineralization is very slow in the case of organic N forms that are less or
hardly oxidizable, including lignin and humus of complex nature and of high molecular
weights.

Under natural soil conditions, mineralization and immobilization processes (converting

mineral N to organic N) usually occur simultaneously. The process of mineralization includes
several steps like aminization, ammonification and nitrification, which are discussed below.

3.3.1. Aminization

It is a process of enzymatic digestion by non-specific heterotrophic bacteria, actino- mycetes

and fungi by which protein and proteinous compounds are decomposed into amino acids or
amines [Equation (4)]:

Amino acids or amines formed due to aminization are either utilized by microbes (im-
mobilized) or mineralized further to NH, by the process of ammonification.

3.3.2. Ammonification

It is defined as the process of transforma- tion of amines/amino acids to ammonia by mi-

crobial enzymes. These amino acids and amines are converted enzymetically by bacte- ria
(aerobes and non-aerobes), fungi and acti- nomycetes to ammonium form, as shown by
Equations (5) and (6):
Due to the production of OH and CO32- ions, the pH of the soil increases, especially in
flooded soil, Since many microbes are involved in the process of ammonification, it is
efficiently carried out in well-drained soil with abundance of basic cations. The ammonium
formed may nitrification, fixed by clay lattice (ammonium then be oxidized to nitrite and
nitrate through fixation). immobilized by heterotrophic organ- isms or released to the
atmosphere in gaseous form.

3.3. Nitrification

Nitrification is the process of enzymatic Oxidation of NH to NO, brought about by certain

nitrifying microorganisms. It is a two step oxidation process, the conversion of NH4+ to NO,
and NO, to NO3, as shown by Equa- tions (7) and (8):

The first step leading to the production of NO, is carried out by Nitrosomonas, Micro-
coccus, Nitrospira and Nitrogela bacteria and the second leading to NO, formation is carried
out by Nitrobacter and Nitrocystis. The population of nitrobacteria is usually between 1 × 10 5
and 1 × 107 per gram of soil. The process of nitrification results in the release of ionic
hydrogen which causes acidity Nitrification is affected by several factors such as supply of
ammonium ions, soil aeration, moisture, pH, temperature, and C:N ratio.

The presence of NH4+ is necessary for nitrification but excessive NH, is toxic to nitrobacteria
and inhibits the growth, especially of Nitrobacter and may result in the accumulation of high
levels of NO2, which is toxic to plants. (The nitrification rate in the soil where O, is not a
limiting factor (aerobic soils)) is quite high. Soil aeration is perhaps the most critical factor
affecting nitrification. The oxygen concentration of around 20% is most favourable.
Therefore, well-aerated soils are considered the best. The presence of adequate O2 is
necessitated because the nitrobacteria are obligate autotrophic aerobes and will not produce
NO, from NH, in the absence of molecular O,. In fact, nitrification is deter- mined by redox
potential (E) of the soil. In soils having Eh, more than +250 mV, nitrification takes place and
in soils with Eh less than +250 mV. NO, starts getting denitrified, which is common in
submerged soils.

The nitrification progresses well when the water content is one-third to one-half of the water-
holding capacity and would be less un- der dry to extremely dry conditions. Similarly. excess
of soil moisture has a negative effect on nitrification. Although nitrification can occur in soils
having pH 4.5 to 10.0, neutral to alkaline soils (pH 7-9) are more congenial, with the
optimum pH around 8.5. Soil temperature in the range of 25-40 °C is optimum for
nitrification. At freezing point and 50°C, the nitrification ceases. The temperature co-efficient
(Q10) between 5°C and 40°C is 2.0, i.e. the nitrification rate doubles for each 10 °C rise in
temperature between 5 and 40°C.

Several pesticides and other agrochemicals, including nitrification inhibitors have deleterious
effect on nitrification, as they may inhibit or retard it (discussed later in Section 4.3.2).

3.3.4. Significance of C:N Ratio

The carbon nitrogen ratio of SOM, organic manures and crop residues assumes great
significance in MIT as relative degree of mineralization of organic N, its availability in soil,
and immobilization are governed by the C:N ratio. When an organic material of high C:N
ratio (for example, straw of cereals having C:N ratio 30:1 or wider) is added to the soil, the
microbes become active due to C substrate avail- ability and multiply rapidly to decompose
the material. As a result, their demand for N increases, which they meet from the mineral N
present in the soil, as also the N applied through fertilizer, leading to a sharp reduction in
mineral N (Figure 3). As the decomposition proceeds and the level of C substrate de- creases,
the demand for N by microbes also decreases, resulting in the mineralization of organic N. In
the case of organic material of narrow CN ratio (for example, leguminous green manure
containing 1.5-1.7% N and having CN ratio < 30.1) is added, due to less C substrate, the
multiplication of microbes is not so high and hence there is less demand for N, resulting in
mineralization of added organic N. Consequently, there is more availability of N in soil for
the crops. Therefore, the C:N ratio of the added residues is critical. Application of small
amounts of fertilizer N in soils receiving organic material with wide C:N ratio would
stimulate decomposition of nitrification.

With time after the addition of organic matter, the C:N ratio usually stabilizes almost to a
constant value in the soil under cultivation. The C:N ratio of Indian soils ranges from 8.5:1 to
12:1, being wider in forest soils and narrower in cultivated soils, with an average of
9.45±0.63 (Jenny and Raychaudhuri, 1960). The ratio becomes wider with increase in annual
precipitation, which enhances the leaching loss of mineral N from soils.

3.3.5. Calculation of Mineralization of Organic N in Soil

Studies have shown that only about (1.5- 3.5% of organic N of a soil mineralizes annually.
Even then this rate of mineralization of soil organic matter is able to take care of nor- mal
growth of plants, except under situations where soil is sandy, very poor in organic N or crop
demand for N is more than the mineralization.

Amount of nitrogen mineralized in a year can be computed if the organic matter content is
known. Using some hypothetical numbers, mineralization of organic N in soil can be
computed as
where, SOM is soil organic matter. A is the amount of SOM in soil (if suppose SOM is 2.0%,
then 'A' is 2 kg in 100 kg soil), 'B' is the weight of soil/ha in 15cm plough layer (this can be
calculated using soil bulk density of 15-cm depth, c.g. 2 x 10 kg soil/ha), 'C' is the amount of
N in soil (if suppose total N is 3% of SOM, then 'C is 3 kg N/ 100 kg SOM), and D is the
amount of SOM likely to be mineralized in one year in a given soil. This depends on soil
texture, climate and management practices. Assuming that 2.5% or 2.5 kg SOM is
mineralized per 100 kg soil, then the value of mineralized N will be:

3.4 Dynamics of Mineral N in Soil

Mineral N (also referred to as plant available N) includes NH 4+ NO3-, and NO2-, forms. Since
NO2- is highly unstable in soil, it is either immediately oxidized to NO 3-, form or reduced to
NOx forms. The dynamics of other two forms (NH 4+ NO3-) is influenced by the aeration status
or Eh of the soil. Upland soils are usually aerobic or oxic, whereas lowland or flooded nice
cultivation creates anaerobic or anoxic situations having low Eh value due to partial or total
absence of O, and oxidative compounds like NO 3-, Fe3+ and Mn4+. Soil mineral N is used by
plants, fixed in the clay lattice (ammonium fixation), immobilized by heterotrophic
organisms or released to the atmosphere in gaseous forms.

3.4.1. Transformations of Mineral N in Aerobic Soil

In aerobic soil, the mineralization of native SOM or added organic materials into soil
proceeds up to the nitrification stage, giving predominantly NO 3-, though some NH4+ is also
present. Similarly, any ammonium containing fertilizers like ammonium sulphate, ammonium
chloride, etc. when applied to soil, get dissociated into NH 4+ ions [Equation (10)].Ammo
nium ions so formed are either (a) readily oxidized to NO, through nitrification [Equations
(7) and (8)], (b) adsorbed on the clay complex [Equation (11)], thus entering into the
exchange complex, (c) remain in soil solution, (d) fixed by clay lattice, or, (e) immobilized
by soil microbes, but very little leach down. Hence, there is always accumulation of NO,
ions, which are either (a) taken up by the crop, (b) adsorbed onto the anion exchange sites of
soil colloid, (c) remain in the soil, (d) undergo leaching to the lower soil horizons as they are
readily soluble in water, or (e) immobilized by soil microbes during MIT. Nitrate ions, being
more mobile than NH, ions, are more prone to the leaching loss.

3.4.2. Transformation of Mineral N in Anaerobic Soils

Due to the presence of water layer on the soil surface of flooded rice fields, O 2 is displaced
from soil, besides its consumption by the soil microbes. In flooded soils, as the O 2 supply is
virtually cut off due to 10,000 times less diffusion of atmospheric O 2, through flood water
than in air, a two-layered soil profile is developed (Figure 4). Redox potential (Eh) drops
sharply, reaching even negative values because of reduction of the soil. The surface water and
upper soil layer of a few millimetre thickness remains oxidized due to diffusion of
atmospheric O2, and is characterized by the presence of oxidative compounds like NO 3-, Fe3+,
Mn4+, whereas the lower soil layer is a reduced one, which is anaerobic, grayish in colour,
containing reduced materials like NH4+, Fe2+, Mn2+, organic acids, H2S, etc. This two layered
soil profile influences the transformation of mineral N to a great extent in anaerobic soils.

In the oxidized soil-water interface, mineralization of organic N continues up to the NO 3-

stage. When NH4+ -N containing fertilizers are added to such soil, then NH, ions in this upper
layer get oxidized to NH4+, which either (a) gets volatilized to the atmosphere because of
higher partial pressure of CO, and higher flood- water pH developed due to alkalinity, (b)
moves down to the reduced layer or (c) gets nitrified and NO 3-, thus formed moves down to
the reduced layer. On the other hand, mineralization of organic N in the reduced layer stops at
the NH4+ stage, since nitrification is inhibited due to lack of O 2. Therefore, there is either (a)
an accumulation of NH, ions in the reduced layer, (b) due to mass flow, NH 4+, ions move
towards the plant roots for absorption, or (c) as the root rhizosphere is oxidized, some of the
NH4+ ions get nitrified, and the resultant NO3-, is either absorbed by root or diffuse away from
the rhizosphere to the reduced soil. Nitrate in the reduced layer (both moved down from up-
per oxidized layer and from rhizosphere) is used as the terminal acceptor of electrons in the
respiration of facultative anaerobes and is reduced to NO, N 2O and finally to N2, via deni-
trification (discussed later in Section 5.3).

The dynamics of NH4+ in the reduced soil can be described by one of the reactions given
below [Equations (12) to (14)] (Mohanty and Patnaik, 1975):

(i) Y = a+bt+ct2...(12)
(For soils with high C and N, medium clay and CEC)
(ii) Y = a+b ln(t+1)+c [ln(t+1)]2...(13)

(For soils with low C and N, high clay and CEC)

(iii) In Y = a + bln(t+1) + c[ln(t+1)]2...(14)

(For soils with medium C and N, medium clay and CEC)
where, Y is the content of available NH4+-N (in ppm) at time 't' (in days) after submergence,
'a' is a constant and 'b' and 'c' are regression coefficients.

4. Crop Needs and Responses to Applied N

In a majority of mineral soils, the content of total N, organic N, mineral N as well as rate of
mineralization of organic N is generally low and therefore, response of crops to added N is
very common. Optimum supply of N from extraneous sources increases crop production
significantly.

In N-deficient plants, N being mobile in plant body, moves from older leaves to younger
leaves, and therefore, N deficiency symptoms (pale yellow or yellow) are first observed in
older leaves while young leaves are still green in colour. N-deficiency in plants leads to early
senescence, loss of yield and less protein content.

Before the advent of green revolution (pre- 1960s) mineralization of the SOM and low rates
of N application (20-40 kg N/ha), besides the organic material returned to soil in the form of
manure, crop residue, etc. were sufficient to get the low to medium yields of traditional (all)
varieties. In the era of green revolution during 1960s and thereafter, use of high-yielding,
short statured, nutrient responsive crop varieties assumed importance for boosting production
to feed the ever increasing population.

Then the extraneous supply of N (besides P and K) application became essential and the
optimum rate of application increased to about 120 kg N/ha or even more (Table 4). Major
cereal crops like wheat, rice and maize use 1 kg N to produce 44, 68 and 49 kg grain,
respectively (Ladha et al., 2005). Magnitude of response, however, depends on several
factors such as, inherent supply of soil N, SOM content, temperature, water management
practices, N management practices (time, method, and source), crop management and
magnitude of losses from the soil-plant environment.

An excessive use of N for crop production causes more succulent growth of crops, droop- ing
of leaves, low sugar accumulation, more soluble N, less vitamins and minerals (Brady and
Weil 2007). Further, the use of excessive N reduces fertilizer use efficiency, lowers crop
yields due to lodging from excessive vegetative growth, besides potential NO 3-, leaching
below the rooting zone and thereby causing NO, contamination of groundwater.

4.1. Sources of Nitrogen in Soil

Soil gains nitrogen from fertilizers, organic manures, crop residues, biofertilizers, green
manures, organic wastes, rain water and bacterial nitrogen fixation.

41.1. Fertilizer N

Nitrogen is added to soil through inorganic and organic sources, which undergo several
processes in the soil, as discussed above. The chemical fertilizers contain concentrated N and
are widely used to meet the demand of high- yielding crop varieties. In these fertilizers, N is
present as either NH4+, NO3-, or both or as amide (NH2-). Some of the NH4+-N-containing
fertilizers are ammonium sulphate (20.6% N). Yield of wheat ammonium chloride (25% N)
and diammonium phosphate (18% N)) While (potassium nitrate (16% N) is a NO, -N-
containing fertilizer, others like calcium ammonium nitrate (25% N)) ammonium nitrate
(35% N)) and (ammonium sulphate nitrate (26% N) are the examples of fertilizers containing
N in both NH, and NO, forms. Urea, the amide form of nitrogenous fertilizer, containing 46%
N. is the most commonly used fertilizer in India.

Ammonium-containing fertilizers get solublized in the water present in soil and are
dissociated into acid and basic radicals, and the fate of NH 4+, ions formed [Equation (10)] in
aerobic and anaerobic soils is discussed in Section 3.4. Nitrate-containing fertilizers dis
sociate in soil to give NO3-, ions, and the fate of which is also discussed in Section 3.4.(A
nitrate containing fertilizer should not be used in the anaerobic soils as it will be lost from the
soil due to denitrification.

4.1.1.1. Hydrolysis of Urea

As urea contains N in NH 2 (amide) form. it is converted into ammonium carbonate in soil by

the enzyme (úrease) (Equation (15)]. Urea is readily soluble in water and also being non-
poplar in nature, it is liable to be subjected to leaching losses before its conversion to ammo
nium carbonate. Therefore, soil-fertilizer management should endeavour efforts to complete
the process of hydrolysis in the shortest possible time. The hydrolysis of urea takes about 3-7
days in soil. Since the process is essentially a microbial enzymatic one, a soil having higher
C-substrates will take less time for completion of hydrolysis. Urea hydrolysis is usually faster
in high-pH soils.

Under acrobic soil conditions, ammonium carbonate, being an unstable compound, is fur-
then hydrolyzed to ammonium hydroxide and carbonic acid as per Equation (16). Carbonic
acid subsequently decomposes to yield water and CO, [Equation (17)]. Ammonium ion is
oxidized to nitrate through nitrification [Equations (7) and (8)]. The fate of nitrate thus
formed is discussed in Section 3.4.1.

In the anaerobic soil, the ammonium car- bonate gets dissociated into NH, and CO2 ions.
Ammonium ions either enter into the ex- change site of soil colloids or remain in soil
solution, as discussed above in Section 3.4.2.

4.1.2. Organic Sources

The organic manures, besides containing N have other macro and micro-nutrients, mostly in
complex organic molecules with little amounts of NH 4+ and NO3-, forms. The mineralization
of organic N up to NH 4+, or NO3-, level has been discussed above in Section 3.3.

As these sources contain much less N as compared to chemical fertilizers, they are required to
be applied in large amounts to meet the N requirement of high-yielding crop varieties, which
may not be easily available, besides handling and transportation difficulties. How- ever,
organic sources are useful in maintaining the soil health and are eco-friendly also. There-
fore, integrated use of chemical and organic sources of N is the best option for sustaining
high levels of crop production and maintaining soil health. The benefits of integrated nutrient
management (INM) are discussed later in Section 4.3.7.

4.1.2.1. Farmyard Manure, Compost and Other Organic Wastes

The commonly used organic sources are farmyard manure (0.5-1.5% N) and compost (0.5-
2% N). Organic refuses of urban areas are composted without or with the introduction of
earthworms (vermicompost). Water storage tank silt, sewage sludge, and press mud from
sugar mill are the other sources of N. However, the addition of N through these materials is
not large. With upcoming of poultry and piggery farming, large quantities of poultry and
piggery manures are also becoming available for use. As these manures contain more N (1-
3%) than other manures, they release substan- mineralization, and their applications have
shown increase in yield of horticultural crops, cereals and other crops.

4.1.2.2. Green Manures

Green manuring is a traditional practice being followed for a long time, particularly in rice. It
has several advantages like faster mineralization, eco-friendliness, and multiple nutrient
supply capability. It also helps in of chemical fertilizers when applied along with
sustainability and in improving the efficiency it. Twenty tonnes of fresh green manure can
supply as much as 40-90 kg N/ha. Among the aculeaae and Sesbania rostrata) and green
manure crops, dhaincha (Sesbania used. (Glyricidia maculata is also used as a sunnhemp
(Crotolaria juncea) are commonly green leaf manure These green manure crops belong to the
leguminous group and are capable of fixing atmospheric N2 by root nodules (discussed later
in Section 4.1.3), which be- comes available to the crop on their incorporation into the soil.
For a better and quicker de- composition, 45-60 day-old succulent green manure crop should
be incorporated into the soil.

4.1.2.3. Crop Residues

Nearly half of the dry matter produced annually in cereals, legumes, root and tuber crops is
the inedible phytomass (aboveground plant parts). Agricultural crop residues are also good
sources of N and other nutrients. After harvesting of crops like rice, wheat, pearl millet,
sorghum, sugarcane, jute, etc., large amounts of straw and dried leaves remain on the soil
surface. On decomposition, they supply some amount of N. The extent of addition of N
through these materials is highly variable and may vary from 5 to 20 kg N/ha. Residues of
leguminous crops, including roots are better sources of N than cereals. Numerous field
studies conducted in different regions of India have illustrated considerable yield benefits due
to incorporation of legume residues after maturity in different cropping systems. The benefits
of legume residues are mainly due to their high N-contents sequestered through biological N.
fixation

4.1.3. Biological Nitrogen Fixation and Biofertilizers

Biological N, fixation (BNF) is an important biochemical process associated with plants

kingdom. The BNF is carried out by certain bacteria, actinomycetes, blue green algae, fungi
and yeast. The most important of these are the bacteria, which have the ability to fix the
atmospheric N, in symbiosis with the plants or Symbiotic N fixation is of more importance
and as free-living organisms (non-symbiotically). The amount of N fixed is quite appreciable.

Biofertilizers are microorganisms, which can bring about soil nutrient enrichment. Among
these, (symbiotic (Rhizobia species) and non-symbiotic fixers of N (Azotobacter and
Azospirillum)) are commonly used in agriculture. Free living blue-green algae in rice fields
can provide 10-20 kg N/ha, while azolla, a fern, in association with blue-green algae, can
supply 30-40 kg N/ha. However, these biofertilizers alone cannot meet the N requirement of
crops and their use has to be integrated with fertilizer N to get a good yield. Biofertilizers are
discussed later in Section in 4.1.3.2.

4.1.3.1. Symbiotic Nitrogen Fixation

Rhizobia species are bacteria and are capable of having symbiotic relationship with
leguminous crops of vital agricultural importance. These Rhizobia have the ability to infect
the plant roots and form nodules in them. It is in these nodules that atmospheric N 2 is reduced
to NH3, in the presence of the enzyme nitrogenase. A energy required to break the triple bond
between nitrogen atoms in the N molecule is supplied by the host plant from photo- synthesis.
The ammonia is further converted to L-ketoglutamic acid and finally to glutamic acid. It is
pertinent to note that there is a specific association between the Rhizobia species and the
legume species, and there are 20 species of Rhizobia. The biochemical pathway of nitrogen
fixation is illustrated by Equations (18) and (19):
Most of the N fixed in nodule is utilized by the plants themselves. However, during the
process, some N is released in the form of amines and amino acids into the soil. Upon the
death of the microorganisms and incorporation of the roots, the N remaining in the nodules is
added to the soil. The symbiotic relationship requires that the plants, in turn, should provide
carbohydrates needed by the microbes. Infec- tion takes place when the C:N ratio in the soil
is wide, whereas less infection occurs when the C:N ratio is narrow. During the initial stages,
the nodules absorb some N from the soil. Therefore, a small starter dose of 15-20 kg N/ha is
beneficial to stimulate the growth of young seedlings. Seed inoculation with Rhizobium
proves effective. Excessive N application could cause considerable inhibition in the activity
of glutamine synthetase and nitrogenase.

The amount of N fixed ranges from 40 kg/ ha to more than 200 kg N/ha/year. Some
representative figures are given in Table 5. The fixation depends on the type of legume;
effectiveness of bacterial strain; inorganic or mineralizable N-content of soil; fertilizer N
applied; adequate supply of phosphorus, potassium and secondary nutrients and favourable
soil environmental conditions (mainly temperature, moisture and pH) In soils where a
particular legume crop is introduced, the native populaton of specific Rhizobium sp. may be
absent or insufficient and inoculation of the right type may be very beneficial After the native
population builds up over a number of years, inoculation may be omitted.

The mere presence of nodules on legume roots does not necessarily mean that they would fix
nitrogen. The occurrence of red colour leghaemoglobin in the nodules indicates the presence
of effective N, fixers. Also, all legumes do not have nodules.
4.1.3.2. Non-Symbiotic Nitrogen Fixation

Blue-green Algae and Azolla Autotrophic blue-green algae play an important role in N2
fixation in waterlogged rice culture. More than 125 species accomplish this task under certain
conditions. Some well known species are: Nostoc. Calothrix, Anabaena, Aulosira,
Tolypothrix, Scytonema, Chlorogea, Cylinderospermum and Mastigocladus. They are aerobic
and photosynthetic. They thrive best in waterlogged rice soils on the surface of water under
neutral to alkaline pH conditions. The amount of BNF varies from 14 to 50 kg N/ha/year.

In water bodies, a close associationship has been observed between the blue green algae,
Anabaena and an aquatic fern, Azolla pinnata. The algae live in cavities in the leaves of the
fern. Azolla has been used for centuries in the South East Asia as a green manure under ideal
conditions (humid and optimum 20-30 °C) as this association can meet 30 kg N ha1 to 50%
of the N requirements of rice. In India, however, this is not very prominent; due to the
prevalence of hot and dry climate in most of the rice growing areas, except eastern India and
to some extent in south India.

Free Living Bacteria and other Organisms Certain bacteria, fungi, yeasts (heterotrophs) and
actinomycetes (autotrophs) living in the soil system could fix N 2. The bacteria groups include
both aerobes Azospirillum, Beijerinckia, Enterobacter and (Azotobacter, Derxia) and the
anaerobes (Clostrodium, Aerobacter, Methanobacterium, Rhodospirillum Chromatum,
Chlorobium and Rhodomicrobium). These organisms live in rhizosphere or even at surface of
plant roots and in the intercellular spaces of epidermal root cells. However, the amount N
fixed is low and is only 5-10 kg N/ha/year, though there are reports of N-fixation as high as
60-90 kg N/ha/year (Brady and Weil, 2007). The C 4 plants (maize, sorghum and tropical
forages) are the specific host plants for Azospirillum lipoferum, while the C, plants (wheat,
barley, oats, rye and rice) are specific hosts for Azospirillum brasilense.
Besides carbon energy sources, microorganisms need low levels of available soil N, adequate
supply of other mineral nutrients, near neutral pH and suitable moisture for proper growth.
After their death, the organic N present in their bodies mineralizes and becomes available to
plants.

Fixation by Trees and Shrubs- In agroforestry systems, both leguminous and non-
leguminous trees and shrubs fix considerable N2. Mimosa and Acacia species are examples
of such leguminous plants. Some non-legumes, belonging to genus Alnus (Betulaceae),
Myrica and Umptonia (Myricaceae), Casuarina (Casuarinaceae), etc. have root nodules and
fix N2 in the same way as do legumes. Phyllospheric fixation of N 2 carried out by Frankia, an
actinomycetes, has also been reported in these plants.

4.1.4. Nitrogen from Rain Water

The nitrogenous compounds present in the atmosphere are brought down with rain and snow
to the earth's surface. The origin of many of these compounds is the earth's surface. Ammonia
is lost to the atmosphere due to volatilization from soil and possibly from plant foliage;
industrial activities (combustion of fossil fuel) and natural fires. The N 2O is from
denitrification losses. The NO3-, and NO2-, ions result from the electrical discharges in the
atmosphere due to oxidation of N2 by O2 (acid rain). The organic N is swept from the soil
surface to the upper layers in the atmosphere by wind erosion. On an average, 7-9 kg N/ha/
year is brought down by rain water and added to soil. Tropical areas receive 10-30% more N
than temperature zones through this route.

5. Nitrogen Losses from Soil-Plant System

Mineral-N is gained by soil through inorganic fertilizers, mineralization of SOM and organic
manures, BNF or other sources, as discussed above in Section 4.1. It is partially utilized by
the crops, and the remaining N rarely accumulates in the soil because of its susceptibility to
several avenues of losses during crop growth or fallow period, thus reducing NUE. The
various ways of N losses from soil-plant system are leaching to deeper soil layers be- yond
the active root zone, gaseous losses of N to atmosphere via NH 3 volatilization and as NO,
N2O and N2, through denitrification, thereby causing environmental pollution. Losses ranging
from 4 to 21% of 15N-fertilizer applied to wheat crop from the soil-plant system have been
seen by Aulakh et al. (1984), depending on the treatments of crop residue (0 and 3 t ha) and
tillage (conventional and zero-till). A substantial portion of applied N is lost from the soil
during the year of application.

5.1. Leaching of Nitrogen

The magnitude of leaching loss of N, mostly as NO 3-, ion, depends upon soil texture, hydro-
logical conditions, water holding capacity, permeability and hydraulic conductivity of soil,
water table depth, rainfall, crop canopy and dose of applied N, and it may vary from 2% to
50% of applied N. Among these factors, the major ones controlling leaching losses of NO 3-
are concentration of NO3-, in the soil profile and quantity of water passing through the soil
profile. Under irrigated systems, application of high fertilizer rates on porous soils could lead
to substantial leaching losses of NO3-.

Leaching loss of nitrogen has been found to vary from 5% to 7% at Cuttack to as high as 60%
in the laterite soil of Kharagpur under rice cultivation (Table 8). Vegetation retards NO 3--N
leaching from the root zone by absorbing nitrate and water. Leaching losses of N can also be
reduced by increasing water- holding capacity of soil through addition of organic materials,
split application, controlled irrigation (light irrigation with higher frequency instead of heavy
irrigation), using nitrification inhibitors, using slow-releasing fertilizers, following crop
rotations that include shallow and deep-rooted crops, and integrated use of organic and
inorganic nitrogen fertilizers.

The leaching of unhydrolyzed urea could also occur in flooded rice grown on porous soils,
particularly when applied as USG. If the soil is porous, a large amount of NH 2--N from
applied urea fertilizer may get leached during the process of hydrolysis.
5.2. Ammonia Volatilization

Losses of nitrogen through NH3, can taken place from soil from both the mineralized organic
N and added fertilizer N sources. Volatilization of NH 3, occurs whenever there is free NH, in
soil near the surface, and the losses can range from 5% to 35%, depending on the soil,
environment and fertilizer management practices. However, NH 3 loss is less in flooded soil
due to dilution of NH4+ ion in floodwater The rate of loss of NH, from the soil surface is
related to the partial pressure difference between aqueous ammonia in soil-water system
[NH3(aq)] and ammonia in the atmosphere (pNH 3) immediately above the soil-water surface,
as shown by Equation (23), where, KH is Henry's constant:...(23)

[NH3 (aq)]= KH pNH3

Increase in the [NH3 (aq)] concentration or an increase in pH results in a shift in the

equilibrium between [NH3,(aq)] and [pNH3,], resulting in loss of NH3, to the atmosphere (At
pH 9.5, the NH4+, and NH3 (aq) are almost in equal proportions (50% each). At pH 5.0, 7.0
and 9.0, NH3 (aq) is 0.00316%, 0.316% and 31.6%, respectively, which shows that for each
unit increase in pH up to 9.5, there is a 10-fold increase in [NH 3(aq)] concentration of the
total ammoniacal N in the system. Therefore (at low pH values, NH 3, volatilization losses are
less but increase with increasing pH.

Volatilization losses also depend on the type of fertilizer used Ammonium containing
fertilizers, when applied to neutral or acid soils, result in negligible volatilization losses. But,
when urea is added to the acid soils, the losses could be more because of the consumption of
H+ during hydrolysis of urea causing, increase in the pH around the granules of urea
[Equation (24)]. In alkaline soils, the prevailing high pH triggers more volatilization losses
[Equations (25) to (27)]. Calcium sulphate so produced is sparingly soluble and so the
reaction favours NH3 losses. Conversely, NH3 volatilization losses would be less when soluble
Ca salts are produced during the reaction.

In soils under upland conditions, losses of applied ammoniacal fertilizers through NH 3

volatilization could be substantial. The timing of fertilization and irrigation influence the
losses through NH3 volatilization. If applied on the wet soil surface following irrigation, as
much as 40% of the top-dressed urea could be lost, but its application before irrigation
reduces losses due to the movement of urea to subsurface layers NH 3 volatilization (Table 8)
could be minimized through light irrigation after urea application, and incorporation or
placement of the fertilizers in the lower layers, use of coated fertilizers and addition of
organic matter) Sandy soils or soils with low CEC favour more NH 3 losses because such soils
hold only small amounts of NH4+ on the soil exchange complex besides having low pH
buffering capacity.

In the flooded rice soils, high NH3 concentration, especially in the overlying floodwater, high
temperature, and carbonate and bicarbonate contents of floodwater also influence the NH 3
volatilization from soil-water system. Ammonia produced in the aquatic systems from
fertilizer additions or mineralization of SOM may be involved in reactions, as shown by
Equations (28) to (30):

Liming and high velocity wind also increase NH, volatilization losses, while crop canopy and
higher floodwater depth often reduce such losses.

5.3. Denitrification Loss

Denitrification is a process limited to an oxic soils in which bacterial reduction of NO 3- and

NO2-, takes place leading to the release of NO, N 2O and N2 gases. A most commonly.
accepted reductive pathway for denitrification is illustrated in Equation (31). However the
relative proportions of the resultant gases could vary considerably and depend upon the
prevailing soil and climatic factors.

Some of the organisms involved in the denitrification, Thiobacillus denitrificans, Thiobacillus

thioparus (autotrophic). Pseudomonas, Micrococcus, Achromobacter and Bacillus,
Denitrification is influenced by several factors, such as supply of nitrate substrate, organic C
supply, aeration and water status (Eh of soil), soil texture, pH, temperature, etc. Denitrifying
organisms use organic C compounds as source of energy and for synthesis of cellular
constituents. Therefore, denitrification is strongly dependent on the availability of organic C
supply through SOM, crop residues, root exudates, and green and farmyard manures.

Soil water can directly and indirectly influence denitrification through (a) provision of
suitable conditions for microbial growth and activity, (b) restricting supply of O 2 to
microsites by filling soil pores, (c) release of available C and N substrates through wetting
and drying cycles, and (d) providing a diffusion medium through which substrates and
products are moved to and away from soil microorganisms. When there is a shortage of O 2,
the Eh of flooded soil falls below +250 mV in soil, some of the microbes utilize the
combined oxygen present in inorganic compounds. Soil texture influences the denitrification
process in several ways such as physical variations in soil structure, pore size, aggregation
and water infiltration rates that affect aeration, water-holding/ absorption capacity, and
microenvironment. Denitrification is often more during day time than night due to higher
temperature.

In upland conditions, heavy irrigation, intensive rainfall events and incorporation of fresh
organic material could lead the development of congenial anaerobic conditions for
denitrification in short spells only and therefore, N losses through denitrification are usually
very small. However, anaerobic situations often develop and prevail for longer periods in
flooded and lowland rice soils where denitrification is a major pathway of loss of N. The
losses due to denitrification may range from 10 to 40% of the applied N.

Denitrification can be reduced to certain level by the use of non-nitrate fertilizers and their
split applications, deep placement of NH 4+-N proper management of water and organics.
Magnitude of N losses through different path ways from Indian rice soils are indicated in
Table 8.

5.4. Chemodenitrification

Denitrification is mostly biologically catalyzed and closely linked to bacterial respiratory

mechanism. Some N-oxides are, however, produced by non-microbial processes known as
chemodenitrification (Brady and Weil, 2007), which is catalyzed by abiotic agents. This pro-
cess is of minor importance in acidic and frozen soils. Acidic soil conditions favour NO 2-
accumulation, and chemodenitrification occurs when NO 2-, comes in contact with ammonium
salts, amino compounds such as urea, and with lignins, phenols and carbohydrates [Equations
(32) to (34)]. Chemo denitrification is not a very important process of gaseous N loss from
the soil system.
5.5. Immobilization of nitrogen

The conversion of (inorganic N (NH4-, and NO3-,) to organic forms by soil microorganisms is
called immobilization). It is the reverse process of mineralization. Immobilization of N can
take place by both biological (through microorganisms) and non-biological (abiotic)
processes, with the latter being more important in forest soils. Soil microorganisms have a
C:N ratio of about 8:1. To build up body tissues, the added or native inorganic N is utilized
by these microorganisms. When any organic material of wide CN ratio is added to soil,
microorganisms initiate its decomposition (Equation (35) The availability of large C substrate
results in an elevated N demand because of increased microbial activity and this N has to be
supplied by soil, and added fertilizer N, or organic material, as discussed in Section 3.3.4.
The immobilized NH4+ or NO3- ion enters into the microbial cell where it is converted into
protein. This process results in temporary immobilization of N. Also, a significant
immobilization of fertilizer N could occur in the surface oxidized layer of rice soils due to
excessive algal growth.

C6H1206+602 - 6CO2+6H2O ...(35)

(Glucose)

As the two opposite processes - continuous mineralization of organic N, and conversion of

mineral N into organic products occur concurrently in soil under natural conditions (Figure
3). "net mineralization" would take place if mineralization exceeds immobilization.
Conversely, net immobilization would occur if immobilization exceeds mineralization.
However, the immobilized N, though not available to plants for a certain period, is not a
permanent loss to the soil system.

5.6. Ammonium Fixation by Clay Minerals

When an ammonium-containing or ammonium-forming fertilizer (urea) is added to a soil,

most of ammonium gets adsorbed on the cat- ion exchange sites, but a part of it is susceptible
to strong adsorption in the interlayer spaces of some 2:1 laver silicate clay minerals. The clay
minerals with this property are: fine-grained micas > smectites. (vermiculite The ammonium
ion has an ionic diameter of 96 A 0 which is close to the 2.8 A 0 diameter of interlattice spaces
in the 2:1 layer silicate minerals. This ammonium fixation is similar to the fixation of K + ions
(ionic diameter 2.68 A0) and therefore NH4+ and K+ ions compete for fixation of these
minerals by clay. Fixed ammonium is normally not easily available for plants and microbes,
though, recently fixed NH4+-N has been found in dynamic equilibrium with other forms of
soil mineral N and a portion of which could move out of clay and become available to the
nitrifying microorganisms/Ammonium fixation is often higher in subsoil than surface soil

5.7. Soil Erosion and Runoff

Water and wind erosion could take away not only fertile surface soil but also the productivity
of the soil as well. The surface soil has more organic matter than the lower layers, and
therefore, the loss of the surface soil layer results in N loss. This loss depends on the severity
of the erosion. In case of water erosion, the duration and intensity of rainfall, slope of the land
and vegetation cover are the main factors influencing the losses (Erosion losses are more
under fallow conditions than under vegetation cover Runoff losses may be as high as 70% if
heavy rainfall occurs on the day of fertilizer application The magnitude of loss sharply
decreases with the delay in rainfall. The average loss of N through erosion is considerably
reduced when proper soil conservation and conservation tillage methods are adopted.
Therefore, proper soil conservation measures go a long way in conserving the pre- cious soil
resources.