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Textbook of Plant Nutrient Management

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Nitrogen Management
5
–Rajendra Prasad, H. Pathak, A.K. Patra and Yashbir Singh Shivay

INTRODUCTION
Nitrogen is essential for protein production in plants, which is the direct or indirect source of protein
for animal and human nutrition. Proteins not only make up the body tissue of animals and humans
but the enzymes that control all physiological processes in life are proteins. Protein malnutrition has
received considerable attention in the past (Prasad, 2003). To overcome protein malnutrition, more
and more protein-rich food, feed and fodder have to be produced. Global food production, already
under the credit crunch, must double by 2050 to level off hunger and in the next 40 years or so, the
world will need to produce annually as much food as in the last 8000 years (FAO, January 2009;
http://www.wfp.org/content/world-must-double-food-production-2050-fao-chief). This would be
possible only by an adequate use of fertilizer, specially the nitrogen. Further for full exploitation of
the higher yield potential of traditional, high-yielding varieties as well as genetically modified (GM)
crops, increased fertilizer nitrogen application is a must (Roberts, 2009). Nitrogen management of
crops is therefore of paramount importance in agriculture. It is estimated that by 2050 about 250
million tonnes of fertilizer nitrogen may be needed (Tilman et al., 2011) to meet global increased
food demands as against an estimated demand of about 109 million tonnes in 2013 (FAO, Rome,
2011).

NITROGEN CYCLE
Nitrogen constitutes 78% of the atmospheric gases and there is some 75,000 Mg (1 Mg = 1 tonne) of
N above each hectare of land; thus, virtually it is limitless. But this reservoir of N, which makes up
to 99% of total N in the atmosphere is inert (non-reactive). A part of this non-reactive N gets fixed
biologically or indusrially and forms reactive-N, which is less than 1% of the total N in the earth’s
atmosphere. Reactive N, which includes any form of N that is readily available to living organisms,
the N is usually bonded to hydrogen, oxygen or carbon. While moving through N cycle, N may
appear in many different chemical forms, each with its own properties, behaviours and consequences
for the ecosystem. Ammonium and NO3- are two critical forms of inorganic N in the cycle required
in large quantities for plant nutrition. Apart from possible losses, N in NH4+ is subject to immobilization
by micro-organism, removal by uptake, fixation in the interlayers of certain 2 : 1 clay minerals,
volatilization and oxidation to nitrate by nitrifying organisms (nitrification). Similarly, the N in NO3-
-N is subject to several possible fates, such as immobilization by micro-organism, removal by plant
uptake, loss to ground-water by leaching in drainage water and gaseous losses to the atmosphere as
several N containing gases formed by denitrification. Nitrogen cycle is a microbial driven process
(Fig. 5.1), which is affected by numerous biotic and abiotic factors prevailing in an ecosystem.
Understanding of each process at the ecosystem scale is of paramount importance for its better
management and environmental quality.

Nitrogen in soil
Nitrogen in soils occurs in organic or inorganic forms.
74 TEXTBOOK OF PLANT NUTRIENT MANAGEMENT

Fig. 5.1 Nitrogen cycle

Organic nitrogen
Most of the N in soil is in organic forms (95 to 99%), which is protected from various losses but
largely unavailable to higher plants. Depending on the soil and environmental conditions, the quantity
of total soil N to maximum rooting depth (1 m) has been estimated to range from 1 to 10 tonnes/ha,
much of which is in the top 15 cm or so. Soils in India except those in the hills are generally low in
organic matter and total N due to high temperatures. Reported values of total N in Indian soils vary
from 0.02 to 0.1% (Prasad, 2007a). The values of total N in hill soils vary from 0.01 to 0.319%
(Kanwar and Takkar, 1963; Manickam, 1965). In a process known as N mineralization, the organic
N contained in soil organic matter is converted into plant-useable inorganic forms (ammonium,
NH4+, and nitrate, NO3-) as a result of the activities of soil micro-organisms. Many studies have
shown that only about 1.5 to 3.5% of the organic N of soil mineralizes annually.

Inorganic nitrogen
Inorganic forms of N in soil include ammonium, nitrate, exchangeable ammonium and fixed
ammonium.
In well-aerated soils nitrate-N is the dominant form and its amounts (mg/kg) can vary from
11 to 36 in alluvial soils (Alfisols, Inceptisols), 3 to 28 in black cotton soils (Vertisols), 1 to 29
in red soils (Ultisols and Alfisols) and 12 to 14 in hill soils (Hapludalf) (Shukla and Singh,
1968).
Ammonium is the dominant form under anaerobic conditions and the general values would be
about 2–20 mg/kg. Values of exchangeable ammonium can vary from 10 to 50 mg/kg depending
upon soil texture and clay minerals (Sen et al., 1957).
 NITROGEN MANAGEMENT 75

It is well established that many soils and clays have the capacity to fix added NH4+ or NH4+
derived from mineralization. The contribution of clay-fixed NH4+ to nitrogen availability in soils
has been studied extensively since the 1950s. In soils with considerable 2 : 1 clay content interlayer-
fixed NH4+ typically accounts for 5–10% of the total N in the surface soils and up to 20–40% of the
N in the sub-soil. And 2 : 1 phyllosilicates are the minerals primarily responsible for NH4 fixation by
soils. Inorganic cations, e.g. NH4+ (radius of 0.143 nm) or K+ (radius of 0.133 nm), can be fixed in
the hexagonal cavity (radius of 0.140 nm) of silicate tetrahedral sheets of the tetrahedral-substituted
or octahedral-substituted layer charges. Understanding the nature and the extent of NH4+ fixation is
an important aspect of nitrogen fertilizer research. Ammonium fixation by soils are affected primarily
by temperature, concentrations of ammonium, and octahedral- or tetrahedral-substituted 2 : 1 layer
silicates. Native fixed ammonium in Indian soils may vary from 70 to 798 mg/kg soil and may
account up to one-fifth of the total soil N (Grewal and Kanwar, 1967).
NITROGEN FERTILIZERS
The first nitrogen fertilizer used was Chilean nitrate (NaNO3) containing 16% N. The largest
accumulations of naturally occurring sodium nitrate are found in Chile and Peru, where nitrate salts
are bound within mineral deposits called caliche. The first shipment of Chile saltpeter to Europe
arrived in England in 1820 or 1825, but did not find any buyers and was dumped at sea in order to
avoid customs toll (via internet, Wikipedia). With time, however, the mining of South American
saltpeter became a profitable business and in 1859, England alone consumed 47,000 tonnes. It was
later exported to the USA. In addition to supplying nitrogen sodium nitrate had also the advantage of
partly neutralizing soil acidity and this made the product quite favourable with the farmers.

Industrial fixation of nitrogen— Processes

Manufacture of nitrogen fertilizers or industrial nitrogen fixation began in 1898 with the
manufacture of calcium cyanamide. It was followed by the manufacture of nitric acid by arc process
and finally the manufacture of anhydrous ammonia by Haber-Bosche process. Anhydrous ammonia
is now the raw material for most N fertilizers. The global industrial production of ammonia for 2012
is anticipated to be 198 million tonnes.

Cyanamide process
Atmospheric N2 was first chemically fixed by passing it over calcium carbide by A. Frank, N
Caro and F.R. Roth in 1898 in Germany. The following reaction takes place:

CaC2 + N2  CaCN2 + C + 67 Kcal

Calcium Calcium
carbide cynamide

Calcium cyanamide was used as N fertilizer for sometimes in Germany. When applied to soil
CaCN2 hydrolyses to calcium carbonate and urea. CaCN2 when applied to standing crops can damage
the plants and therefore it has to be applied to soil 2 to 3 weeks before sowing. Due to its phytotoxic
properties it has also been used as herbicide.

Nitric acid or arc process

In this process, the N2 and O2 in air are reacted by passing through an electrical arc. The first
product is NO, which is further oxidized to NO2. The NO2 is then condensed in absorption towers to
form nitric acid. The reactions involved are:
76 TEXTBOOK OF PLANT NUTRIENT MANAGEMENT

N2 + O2  2NO
2NO + O2  2NO2
3NO2 + H 2 O  2HNO3 + NO

Ammonia synthesis (Haber-Bosch Process)

From the fertilizer N viewpoint this is the most important process. It was developed by German
Chemist Fritz Haber, who used osmium as a catalyst for reacting N2 and H2 gases. Haber received
Nobel prize for this discovery in 1918. However, ammonia synthesis by this process could still not
be industrialized because osmium was too costly a metal. Another German chemist Carl Bosch later
discovered iron oxide that could serve as a catalyst in this process. It is this discovery that placed
ammonia synthesis on a sound industrial basis. Bosch received Nobel prize in 1931 for the discovery.
This reaction is carried out at an atmospheric pressure of 200 to 100 atmospheres and at temperatures
1,000 to 1,200°C. The basic reaction is:

3H2 + N2  2NH3

Ammonia from destructive distillation of coal

When coal is heated at about 1,000°C temperature in closed chambers it gives out ammonia, tar
and coal gas. These materials being volatile come out of the chambers and are passed through coolers
maintained at 10°C and 6 atmosphere pressure. Both tar and ammonia are liquefied and accumulated
while coal gas escapes. Tar being heavier collects at the bottom, while liquid ammonia remains at the
surface and is separated from tar. The residue left in the chambers is known as coke, which is used as
fuel in the industry. The ammonia coming out is then reacted with sulphuric acid and ammonium
sulphate is obtained. Ammonia can also be reacted with gypsum to obtain ammonium sulphate. The
basic reactions are:

2 NH3+H2SO 4  (NH4) 2SO4

OR
2 NH3+CO2+H2O  (NH 4) 2CO3
(NH4) 2CO3+CaSO4.2H2O  (NH)2SO4 + CaCO3 + 2H 2O

Ramagundam (AP) and Talchar (Odisha) fertilizer plants in India are coal based.

Conventional nitrogen frtilizers

Anhydrous ammonia
Ammonia, as used commercially, is often called anhydrous ammonia. It contains 82% N and is
the low-priced fertilizer. This term ‘anhydrous’ emphasizes the absence of water in the material.
NH3 boils at –33.34°C (–28.012°F) at a pressure of 1 atmosphere, so the liquid must be stored under
high pressure or at low temperature From factory to farm, where it is injected in soil, marketing of
anhydrous ammonia requires stainless steel equipment, which is expensive. USA is major country
where anhydrous ammonia is widely used as a fertilizer; about 30% of fertilizer N consumed in the
USA is as anhydrous ammonia.

Aqua ammonia
A lot of anhydrous ammonia is marketed after its dissolution in water. The concentration of such
solutions is measured in units of the Baumé scale (density), with 26 degrees baumé (about 30% (by
 NITROGEN MANAGEMENT 77

weight) ammonia at 15.5°C) being the typical high-concentration commercial product.

Anhydrous ammonia forms the raw material for all the N fertilizers and some NP complex
fertilizers. These are listed below:

2NH3 + H2SO4  2(NH4)2SO4

Ammonia Sulphuric acid Ammonium sulphate
NH3 + HNO3  NH4NO3+ Lime  NH4NO3.CaCO3
Ammonia Nitric acid Ammonium nitrate Calcium ammonium nitrate or Nitrochalk)
2NH3 + CO2  NH2 . CO . NH2
Ammonia Carbon dioxide Urea
NH3 + HCl  NH4C1
Ammonia Hydrochloric acid Ammonium chloride
NH3 + H3PO4  NH4H2PO4
Ammonia Phosphoric acid Monoammonium phosphate (MAP)
2NH3 + H3PO4  (NH4)2HPO4
Ammonia Phosphoric acid Diammonium phosphate (DAP)

In India, urea is the main fertilizer and only small amounts of calcium ammonium nitrate and
ammonium sulphate are manufactured.

Urea
Urea a diamide of carbonic acid is water-soluble white crystalline compound with a molecular
formula CO(NH 2)2. Urea is the major nitrogen fertilizer today; it contributes about 80% to the total
fertilizer consumption in India and about 55% of total fertilizer nitrogen consumed in the world.
The properties that make it a fertilizer of choice are:
1. Highest N content (46%) among the solid N fertilizers, which reduces per unit transportation
and application cost.
2. Its non-polar nature makes it ideal for foliar application and mixing with other fertilizer materials
to make different NPK complex fertilizers. It can be mixed and applied with pesticides including
herbicides.
3. Its ready solubility permits it to be used extensively in N, NP and NPK fertilizer solutions.
4. It is used as a substitute for protein in animal feed (Prasad, 1998).
As already given above urea is manufactured by reacting ammonia and carbondioxide at a
temperature of 175–210°C and under 170–400 atmospheric pressure. Urea slurry so formed is either
crystallized in a crystallizer or taken to the top of a prilling tower, from where it is dropped. Hot air
is blown from the bottom of the prilling tower and this converts the slurry into small prills of about
1 to 1.5 mm diameter. Almost all urea manufactured in India presently is prilled urea. Urea prills are
then bagged in 50 kg bags. There is currently considerable interest in granular urea and future plants
may produce granular urea. When the temperature in prilling tower goes above 150–170°C, two urea
molecules may combine together to form biuret.

H2N.CO.NH2 + H2N.CO.NH2  H2NCO.NH.CONH2 + NH3

Urea Urea Biuret Ammonia

Biuret is toxic to plants when urea is foliar applied. The permissible limit of biuret in urea is
1.5% as per Fertilizer Control Order of Government of India. There are 32 urea plants (by 1 October,
2000) in India manufacturing 20 million tonnes of urea per annum, contributing 80% of the fertilizer
N consumed in India.
78 TEXTBOOK OF PLANT NUTRIENT MANAGEMENT

Ammonium sulphate
Ammonium sulphate (20.5% N) is manufactured only at 11 plants in India; 6 plants of SAIL at
Bhilai, Bokaro, Durgapur, IISCO, Rourkela (2); and RIN, Visakhapatnam use coke oven gas as a raw
material, while C&C, Surat and GSFC, Vadodara use externally brought ammonia and FACT, Alwaye
uses Naphtha as a raw material. In addition at FACT, Alwaye and GSFC, Vadodara ammonium
sulphate is a by-product of Caprolactum (a synthetic fibre) process. The total licensed production in
India in 2000 AD was only 0.86 million tonnes of ammonium sulphate contributing only 1.5% fertilizer
N produced the country.

Calcium ammonium nitrate

There are only 3 plants manufacturing CAN (25% N) in India. These are GSFC, Vadodara;
NFL, Nangal and SAIL, Rourkela. The total licensed capacity of production in India in 2000 AD was
0.94 million tonnes, contributing 2% of fertilizer N produced the country.

Ammonium chloride
Ammonium chloride contains 25% N. There are only 2 plants manufacturing ammonium chloride,
namely GSFC, Nayanangal and TACF, Tuticorin. The total licensed capacity in India in 2000 AD was
0.17 million tonnes, contributing only 0.4% of fertilizer N.

NP/NP Complexes
In addition to above there are NP fertilizers such as diammonium phosphate (DAP), ammonium
phosphate sulphate (APS) and ammonium nitrophosphate (ANP) and several NPK complexes which
supply nitrogen but these are discussed along with P fertilizers.

New nitrogen fertilizers

Nitrification inhibitors-blended fertilizers

Nitrification inhibitors (NIs) are chemicals that inhibit or retard oxidation of ammonium to
nitrate N. Blending of nitrogen fertilizers with NIs increases their efficiency by reducing nitrification,
because nitrates formed on the oxidation of ammonium are easily lost by leaching under upland and
denitrification under submerged soil conditions. A large number of chemicals are known to have
nitrification-inhibiting properties. These include, N-Serve or nitrapyrin (2-chloro-6-(trichloromethyl)
pyridine), DCD (dicyndiamide), AM (2-amino-4-chloro-6-methyl pyrimidine), CMP (1-carbamoyle-
3-methylpyrazole), terrazole (etridiazole), CP (2-cyanimino-4-hydroxy-6-methyl pyrimidine), AT/
ATc (4 aminotriazole), ST (sulphatiazole or sodium thiosulphate), ATS (ammonium thiosulphate),
ZPTA (thiosulphoryl triamide) (Prasad and Power, 1995; Prasad 2005), neem extractives (containing
epinimbin, deacetylnimbin, azadirachtin (Prasad et al., 1993). Of this long list of NIs, only nitrapyrin,
AM and DCD have been widely tested.
Nitrapyrin was discovered in the USA, while AM was discovered in Japan and DCD in Germany.
Nitrapyrin is a volatile compound and is difficult to use with solid fertilizers. Its use is therefore
restricted with the use of anhydrous ammonia in the USA and is injected in soil. Yield increase in rice
with nitrapyrin and AM has been reported India (Thomas and Prasad, 1987). The DCD on the other
hand did not increase rice yield (Sudhakar and Prasad, 1986b) but increased wheat yield (Joseph and
Prasad, 1993a). The DCD is less effective above 20oC because of its rapid decomposition (Amberger
and Vilsmeier, 1979). This is why it did not perform well in rice (Oryza sativa L.) experiments in
India, where mean daily temperature during most rice growth is above 30oC.
 NITROGEN MANAGEMENT 79

Slow release N fertilizers

Since the major cause of low nitrogen-use efficiency (NUE) is the high solubility of N fertilizers,
attempts have been made to develop slow-release or controlled-release fertilizers. These are broadly
of two types: inherently low solubility N fertilizers and coated conventional fertilizers. Inherently
low solubility N fertilizers include oxamide, guanylurea, glycoluril and urea-aldehyde condensates
(Prasad et al., 1971; Trenkel, 1997). Of these urea-aldehyde condensates such as ureaform (urea-
formaldehyde), isobutylidene diurea (urea-butyraldehyde) popularly known as IBDU have received
considerable attention and have been tested for rice and other crops. Conventional N fertilizers can
be coated with pervious or semi-pervious substances such as sulphur, oilseed cakes or polymer to
control the release of N. The earliest coated slow release fertilizer tested for rice was sulphur-coated
urea (SCU), developed by the Tennessee Valley Authority, USA. A number of researchers reported
SCU to be better than urea (Bijay-Singh and Katyal,1987; Pandey et al., 1989).

Neem coated urea

Neem-coated urea (NCU) involving a neem oil micro-emulsion was developed for coating urea
(Prasad et al., 1999). Only 0.5 kg neem oil per tonne of urea is needed in the technique. Neem-coated
urea was superior to urea. This technique or its modifications are currently used in India by several
fertilizer manufacturers. The cost of coating urea with neem oil emulsion is only US$ 2-3/tonne
urea. In on-farm trials in Delhi, Uttar Pradesh and Haryana increase in rice yield with NCU varied
from 6 to 12% over urea (Prasad et al., 2002) Superiority of NCU over prilled urea has also been
reported from Punjab (Thind et al., 2010). This product using a technique similar to ours is being
manufactured in India and is generally known as neem-coated urea (NCU).

Polymer-coated urea
Polymer- or polyolefin-coated urea (PCU) is the latest addition. It requires in a smaller quanity
(3-6%) unlike sulphur or neem cake, which are needed in larger quantities. Salman (1998) reported
that the PCU has slower dissolution rate than urea and Blaise and Prasad (1995, 1997) reported that
PCU had reduced ammonia volatilization and leaching losses of N as compared to urea. In Japan,
substantial quantity of PCU is used and performs better than urea (Fashola et al., 2002).

Urease inhibitors
Urease inhibitors reduce the rate of hydrolysis of urea to ammonium and can reduce loss of N
due to ammonia volatilization when urea is surface applied. A number of urease inhibitors have been
reported which include PPD/PPDA (phenyl phosphorodiamide), NBTPT or NBPT (N-(n-butyl)
thiophosphoric triamide), TPT (thiophosphoryl triamide), CHTPT (cyclohexyl phosphoric triamide),
CNPT (cyclohexyl phosphoric triamide), PT (phosphoric triamide), HQ (hydrquinone), ATS (amino
thiosulphate), and HACTP (hexaamidocyclo triphosphazine) (Trenkle,1997; Kiss and Simihaian,
2002). The PPDA and NBTP have been tested for rice and the results did not show their advantage in
increasing grain yield (Buresh et al., 1988; Raju et al., 1989).

Urea supergranule (USG)

The urea supergranule (USG) was developed taking a lead from the mud-ball technique, of
application of fertilizer N. In this technique a small amount of fertilizer N is placed in the centre of
a mud ball and the balls are sealed with mud. Mud balls are then dried in the shade and are deep-
placed in rice field. The urea supergranules in rice on medium to heavy soils can increase the nitrogen-
use efficiency by 10–20%. (Tandon, 1989). During 2008, urea supergranules were used in 500,000
ha, which increased rice productivity by 268,000 Mt in Bangladesh and reduced country’s urea
80 TEXTBOOK OF PLANT NUTRIENT MANAGEMENT

import by 50,000 Mt saving US$ 22 million in fertilizer imports (IFA, 2009). The urea supergranules
has the built-in advantage of deep placement of N. In addition, ammonia concentration in the vicinity
of urea supergranules is high enough to inhibit nitrification for some time (Thomas and Prasad,1982).

Nitrogen-use efficiency

Defining nitrogen-use efficiency (NUE)

Nitrogen-use efficiency (NUE) means different things to different people. Some of the most
commonly used terms related to NUE are given below (Prasad, 2009).
Apparent recovery efficiency (AREn) = 100 (Uf–Uc)/N = U/N (% of applied N)
Agronomic efficiency (AEn) = (Yf–Yc)/N = Y/N (kg grain increase/kg N)
Physiological efficiency (PEn) = (Yf–Yc)/(Uf–Uc) = Y/U = AE/RE (kg grain/kg N absorbed)
Partial factor productivity (PFPn) = Y/N (kg grain/kg N applied)

In the above expressions, Yf and Yc are grain (or other economic produce) yield in kg/ha in
fertilized and control (check) plots, while Uf and Uc refer to the nitrogen uptake (kg/ha) in fertilized
and control plot, respectively, and N refers to the nitrogen applied (kg/ha). PFPn does not take into
account the control plot yield and is therefore a very useful term because it can be calculated for the
experiments on tillage, sowing dates, seed rates, weed control, water management etc, where a blanket
fertilizer application is made. PFPn can also be used for comparing NUE in different countries or in
different parts of a country. When tracers such as 15N are used the recovery is known as true recovery
efficiency (TREn). A lower case letter as suffix is generally provided to indicate the nutrient for
which the NUE refers to, e.g. AEn refers to the Agronomic efficiency of N

Response of crops to N and low nitrogen use efficiency

Response of crops to N (or any other nutrient) is expressed as kg grain or any other economic
produce per kg N applied as compared to control; the correct term for this is AEn. Agricultural
Statisticians refer to this as crop response ratio. The data from on-farm trials under the Project
Directorate of Cropping System Research, Modipuram, showed an average AEn value of 9.5 kg
grain/kg N for cereals (Sharma and Batra, 2011). Averaged over a number of experiments at the
Indian Agricultural Research Institute, New Delhi, Prasad et al. (2000) reported that AEn in rice
decreased from 22 to 13 kg grain/kg N and that in wheat (Triticum aestivum L. emend. Fiori & Paol.)
from 84 to 31 kg grain/kg N as the level of N was increased from 40–60 to 121–180 kg N/ha. The
PFPn values were same for rice and wheat and decreased from 84 kg grain/kg N at 40–60 kg N/ha to
32 kg grain/kg N at 121–180 kg N/ha. The PEn values in this study were 40–44 kg grain/kg N for rice
and 24–48 kg grain/kg N in wheat. In China, where N rates are generally 150 kg N/ha or more, AEn
values are reported to be 10.4, 8.0 and 9.8 kg grain/kg N for rice, maize (Zea mays L.) and wheat
respectively (Zhang et al., 2007).
Low NUE is a major concern the factors responsible for it are various N loss mechanisms,
namely ammonia volatilization, run-off, leaching and denitrificaion, which are discussed under the
section ‘Environmental Implications’. Globally the value of AREn is 55%, while TREn (True Recovery
Efficiency) is 44% (Ladha et al., 2005). TREn values are specially low in rice, for example, Katyal
et al. (1985) from Ludhiana reported a TREn value of 21–31%, while Goswami et al. (1988) from
Delhi reported a TREn value of 33%. TREn is higher (32–51%) for wheat. Some more data from 15N
on TREn in crops and cropping systems are in Table 5.1. One important point that these data bring
out is that inclusion of legumes reduces the unaccounted or lost N. This shows the importance of
legumes from the viewpoint of N conservation.
 NITROGEN MANAGEMENT 81

Table 5.1 15N balance sheet in some crops and cropping systems

Crop/cropping system Location TREn (%) Reference

Plant Soil Unaccounted
(lost)

Crop

Rice Ludhiana 21–31 24 46–50 Katyal et al. (1985)

Wheat Ludhiana 32–52 32–35 16–42 Katyal et al. (1985)

Cropping system
Rice–wheat New Delhi 35.8 25.6 38.6 Goswami et al. (1988)
Maize–wheat–mungbean New Delhi 23–27 55–65 0–13 Arora et al. (1980)
Wheat–mungbean–maize New Delhi 49 41–47 4–10 Arora et al. (1980)

TREn, True recovery efficiency of nitrogen

Note: Soil at Ludhiana was a Ustipsamment, while that at Delhi was a Ustochrept

Besides the low NUE in India more disturbing is its decline over time. Biswas and Sharma
(2006) reported that during 1970–2005 the AEn in irrigated areas declined from 13.4 to 3.4 kg grain/
kg nutrient. This is supported by the fact that the farmers in the rice–wheat cropping system belt
(Punjab, Haryana and Western Uttar Pradesh) are forced to apply more and more fertilizer to obtain
the same yields as in the preceding years.
The agricultural importance of enhancing NUE can be judged from the fact that a 10% increase
in NUE can save about 20 million ha of land at the present level of productivity in India. Another
way of looking at the importance of enhancing NUE in India is the fact that a 1% increase in use
efficiency of nitrogen, which is estimated to be 17 million tonnes in 2011–12, will amount to a
saving of 0.17 million tonnes of N or 0.4 million tonnes of urea, which is equal to the annual production
of four urea plants producing 1 lakh tonnes of urea per annum.

Nitrogen-loss mechanisms

Surface run-off
When heavy rains follow fertilizer N application on sloping lands, part of applied N may be lost
as surface run-off. Rice farmers in sloping lands in India are very familiar with this loss and it is
deters them from applying recommended doses. Van Drecht et al. (2003) using Integrated Model to
Assess the Global Environment (IMAGE) reported that in Western Europe and Japan 70–75 kg N/ha
was exported from the point of application, the suggested values for South Asia, East Asia, Canada
and USA were 30–40 kg N/ha. No Indian estimates on surface losses of N are available.

Ammonia volatilization
A major portion of N fertilizer applied to soil is lost through volatilization as gaseous NH3,
which acts as the precursor of several atmospheric pollutants (Aneja et al., 2012). Ammonia is the
most reduced form of reactive nitrogen and most abundant of alkaline constituent in the atmosphere.
Agriculture sector contributes more than 80% of total anthropogenic NH3 emission to the atmosphere.
Application of N fertilizer in soil contributes more than 25% of the total NH3 emission from agriculture.
The emission from soil varies from 1 to 26 kg/ha depending upon soil type, crop and fertilizer
material (Adhya et al., 2007). Some other studies have shown that ammonia volatilization loss is
about 20–30% of N applied through fertilizer and manure (Pathak et al., 2006).
82 TEXTBOOK OF PLANT NUTRIENT MANAGEMENT

Leaching
Leaching of N in the form of NO3 beyond soil profile is one of the major loss mechanisms that
can be as high as 80% depending upon the soil properties and water and nutrient-management practices.
It is particularly a major sink for surplus N in agro-ecosystems on well-drained porous soils. A lot of
attention has already been paid world over particularly in the developed countries on this phenomenon.
In developing countries like India its importance is being felt recently because of sporadic reports of
NO3 enrichment in groundwater in a few agriculturally intensive areas in Punjab, Haryana, Delhi,
Maharashtra, and Andhra Pradesh. They have attributed the high NO3-N in groundwater to high
nitrogenous fertilizer use. But there were several exceptions, for example, in West Bengal, the average
NO3 level was low in spite of high dosage of N fertilizer use (Kundu et al., 2008). Sporadic reports
of high NO3-N contamination in groundwater from different parts of India may be related more to a
sewage-sewerage and dumping of organic wastes rather than agricultural N fertilization barring a
few sites where the soil is highly coarse textured and hence permeable. Using crop-simulation model
Pathak et al. (2006) calculated that N losses due to leaching from rice–wheat cropping systems of the
Indo-Gangetic plains could account for 10% of applied N.

Denitrification
Denitrification, a sequential reduction of NO3- to N2 driven by denitrifying bacteria under
anaerobic conditions, is controlled by soil moisture, redox potential (Eh), temperature, pH and substrate
(NO3, NO2, NO and N2O) concentrations. Denitrification is usually not explicitly accounted for in N
budgets on the national level, but estimated indirectly from N balances. Yet it is generally accepted
that denitrification is a major sink for the surplus N in agro-ecosystems. On an average, denitrification
losses reported in India ranged from 10 to 30 and 5 to 10 kg N/ha in rice and wheat respectively
(Aulakh et al., 2001). The N loses due to denitrification are likely to be most under alternate flooding
and drying (Prasad and Rajale, 1972) as obtained under aerobic rice systems (Prasad, 2011).

Losses from plants

During plant senescence, a part of N taken up by crop plants is lost as ammonia from the plant
canopy. From the USA, Francis et al. (1993) reported that post-anthesis losses from corn ranged from
49 to 81 kg N/ha, which was about 10–25% of applied fertilizer N. Post-anthesis losses from wheat
are reported to range from 6 to 80 kg N/ha (Harper et al., 1987; Papakosta and Gagianas, 1991).
METHODS AND TIMING OF NITROGEN APPLICATION
Methods of application

Soil application
Basal nitrogen in widely spaced crops such as maize, sorghum [Sorghum bicolor (L.) Moench],
pearl millet [Pennisetum glaucum (L.) R. Br. emend.], cotton (Gossypium hirsutum L.), sugarcane,
kharif pulses etc and the winter season crops such as wheat which are sown with a ferti-seed drill is
deep placed, while in rice and most other crops it is broadcast. Bulk of the top-dressed fertilizer N is
also broadcast Surface broadcasting N fertilizer leads to ammonia volatilization, which can be reduced
by deep placement of fertilizer N (Mohanty et al., 1999). Humphreys et al. (1992) reported that the
recovery efficiency (REn) increased from 37% for broadcasting to 46% for banding in direct-seeded
rice in Australia. Devasenapathy and Palaniappan (1995) from India reported that band placement of
urea solution at 50 kg N/ha resulted in higher rice yield and improved agronomic and recovery
efficiency than the conventional three split applications of urea. Schnier et al. (1993) reported that
band placement of urea solution into the reduced soil layer was as effective as deep placement of
 NITROGEN MANAGEMENT 83

urea supergrnules in reducing N losses and improving rice grain yield. In rice fields,where water can
be drained, fertilizer N is best applied after draining the soil and incorporating it into the soil with a
rotary weeder and then flooding the soil after 2–3 days. This practice is reported to give a yield
advantage of about 1 tonne/ha (Ponnamperuma and Detruck, 1993).
In wheat the common practice in India is to deep place basal N dose (about 50% of the total)
along with P, K and Zn (if needed) at seeding. The rest 50% is banded or broadcast at first irrigation
21–25 days after sowing. The second dose of N is to be applied before irrigation on light sandy soils
(Katyal et al., 1987) and after irrigation on medium to heavy soils (Verma and Srivastava, 1995).

Foliar application
Foliar application of N is reported to have high recovery efficiency (De,1971; Nova and Loomis,
1981) In rice, Balasubramanian et al. (2004) reported higher efficiency of foliar applied N.
Thanunathan et al. (2004) recommended foliar application of N in flooded rice fields where soil
application is not possible. The major disadvantage with the foliar application is that about 10 kg N/
ha can be applied in a single spray with high volume (500–600 litres/ha) sprayers; generally available
with the farmers, since the highest permissible concentration of urea in the spray solution is 3%,
beyond which the leaves get scorched.

Time of application
In dryland agriculture specially for post-rainy season crops all nitrogen (as matter of fact all
fertilizer) is applied at seeding, and farmers generally deep place it. If additional nitrogen is needed,
it can be applied only through foliage.
In irrigated agriculture split application of N is a well-established practice adopted in most
crops; the number of splits and the proportions in different doses vary with the crop and soil (Tandon,
1989b). Smaller the doses of N in each application and more the splits, the better it is. In a China–
Japan joint study (Katsura et al., 2008) when N was applied in 4 splits (22% one week after
transplanting, 28% at panicle initiation, 28% before heading and 22% at heading), the ARn was 47%
at Yunnan (China) and 37% at Kyoto (Japan) at 140 kg N/ha.

Ways to increase nitrogen-use efficiency

Since the crop yield (or any other economic produce) is the nominator for all the terms used for
expressing NUE, adoption of Best Crop Management Practices (BMP’s) is the best way for increasing
NUE. Components of BMP’s are:
● Growing of high-yielding crop varieties recommended for the area.

● Use of recommended rate of quality seed.

● Timely sowing/transplanting.

● Use of organic manure

● Site-specific nutrient management including application of balanced NPK and adequate amount

of deficient secondary and micronutrient(s).

● Application of economic optimum dose of N.

● Placement of basal N, split application as per recommendation, foliar application if

recommended.
● Use of neem-coated urea/urea supergranules

● Efficient water management.

● Efficient weed management.

● Adequate pest management.

84 TEXTBOOK OF PLANT NUTRIENT MANAGEMENT

Nitrogen uptake and needs of crops

Nitrogen is taken up by crop plants as nitrate (NO3-) or ammonium (NH4+) ions. Most crop
plants will equally well take nitrate or ammonium, although rice is reported to prefer ammonium
(Prasad et al., 1983). Nevertheless it is true that rice grow under anaerobic conditions, where
ammonium ions dominate the soil solution. As regards crops grown under well-drained conditions,
Joseph and Prasad (1993b) reported that wheat preferred more ammonium at early growth stages
and nitrate at later growth stages. Higher ammonium concentrations in soil solution could be toxic to
plants for crops grown under well-drained conditions (Prasad, 2007b). Cereals remove 20-27 kg N,
8-18 kg P2O5 and 20-40 kg K2O per tonne of grain harvested; amounts being larger for coarse grains.
Chickpea, rapeseed-mustard and cotton remove 39-50 kg N, 6-9 kg P2O5 and 30-50 kg K2O per
tonne of grain or seed cotton (Prasad et al., 2004).

Interaction with other nutrients

Nitrogen interacts positively with all plant nutrients and therefore fits in well with balanced
NPK fertilization programme or site specific nutrient management (SSNM). A large number of data
are available on positive interaction between N and other plant nutrients. For example Dwivedi et al.
(2003) reported a positive N × P interaction in rice–wheat cropping system, while Gupta et al. (2007)
reported a positive N × K interaction in potato (Solanum tuberosum L.). Similarly, Aulakh et al.
(1980) reported a positive N × S interaction in mustard [Brassica juncea (L.) Czernj & Cosson].
Positive interaction of N with micronutrients is also well known (Takkar et al., 1989).

Predicting N availability from soil and recommendations

Determining available N in soils

Soil nutrient availability indices are values that presumably correlate with the amount of nutrient
available to a crop during a growing season. Available N methods could be biological or chemical.
The most popular biological method [Iowa (a state in the USA) method] is one which estimates N
released on incubation of a moist soil sample for 2 to 16 weeks (Stanford and Smith, 1972). However,
due to a long period required for biological tests, chemical tests are preferred, which include alkaline
permanganate oxidizable N (Subbiah and Asija, 1956), calcium hydroxide hydrolysable N (Prasad,
1965) and 6 N hydrolysable N (Gallagher and Bartholomew, 1964). Also in use is the estimation of
nitrate-N in 60–120 cm soil profile, known as pre-plant nitrogen test (PPNT) (Fox and Piekielek,
1983 or nitrate-N present in 30 cm top soil at the time of top-dressing, known as pre-side dress
nitrate test (PSNT) (Fox et al., 1992).One of the methods for available N currently popular in the
USA is Illinois (a state in USA) method in which amino sugar in soil is estimated by heating 1 g soil
with 10 ml of 0.2 M NaOH at 48-50°C (Kahn et al., 2001). In India, alkaline permanganate-oxidizable
N (Subbiah and Asija, 1956) is the most widely used method for available N. Limits for low, medium
and high KMnO4- oxidizable N (kg/ha) for Indian soils are below 280, 280–560 and above 560,
respectively.

Environmental Implications of fertilizer N use

Humans have substantially altered the global N cycle, increasing both the availability and the
mobility over large regions of the earth. This N burden has also disturbed the ecological N equilibrium.
In order to revert back to original equilibrium, ammonium (NH4+) tends to be oxidized to nitrate
(NO3-) by aerobic chemo-autotrophic bacteria (NH4+NO2-NO3-). Again in anaerobic conditions
(water or anoxic sediments), facultative anaerobic bacteria can utilize nitrite (NO2-) and nitrate
(NO3-) resulting in formation of nitrous oxide (N2O) and nitrogen (N2) gases. All the above forms except
 NITROGEN MANAGEMENT 85

gaseous N have individual potentials for adversely affecting the environment. In addition to natural
sources, inorganic N can enter through point or non-point sources, mostly anthropogenic in origin. Major
point sources could be livestock farming, aquaculture practices, sewage effluents, industrial waste water,
waste disposal, ore mining and overflow of sewer. On the other hand, most common non-point sources
are agriculture (cultivation, fertilizer application), forest run-off, septic leachates, emissions and biomass
burning. Generally non-point sources have greater relevance than point sources, since these are large
and difficult to control. The anthropogenic inputs of reactive N are increasing around the world causing
significant degradation of freshwater and river ecosystems. Again N inputs to river systems have a
consequent impact on groundwater and the aquatic environment, often along downstream; thus affecting
the ecosystem health of estuarine and marine areas, which are often N limited.

Nitrogen budget for Indian and world agriculture

During 2010, 16.6 million tonnes of N fertilizer was used in Indian agriculture, while animal
manure and wastes, crop nitrogen fixation and deposition (including rain, irrigation water and grazing
of animal) contributed 1.4, 1.4 and 2.7 million tonnes, respectively (Fig 5.2). Removal of N by
agricultural crops in the country during 2010 was 9.8 million tonnes. Besides, the losses of N included
leaching and run-off (3.1 million tonnes), ammonia volatilization (4.1 million tonnes), and
denitrification (3.1 million tonnes). This resulted in an accumulation of 1.9 million tonnes N in
agricultural soil-water system.
In comparison to the annual N budget for Indian agriculture, about 120 million tonnes of fertilizer
N was used for global food production during 2000–10 (Fig. 5.2.). The other sources, namely, animal
manure and wastes, crop nitrogen fixation and deposition (including rain, irrigation water and grazing
of animal) contributed 57, 60 and 70 million tonnes, respectively. Approximately equal amount of
fertilizer N was removed by the harvested crop (122 million tonnes). The losses of N through leaching
and run-off, ammonia volatilization and denitrification were 37, 95 and 25 million tonnes, respectively,
resulting in a positive balance (soil accumulation) of 28 million tonnes of N annually.

NH3 volatilization
Deposition
2.7 (70)
Fertilizer Crop removal 4.1 (37)
Denitrification
Manure, wastes 9.8 (122)

16.6 (120) 3.1 (25)

Crop
1.4 (57) fixation Leaching/run-off
1.4 (33)

3.1 (95)

Agricultural Soil
Input = 22.0 (307), Output = 20.1 (279), Balance = 1.9 (28)

Fig. 5.2 Annual budget of N (million tonnes) in agricultural soils of India and World (in parentheses).
Source: Pathak (2013, unpublished)
86 TEXTBOOK OF PLANT NUTRIENT MANAGEMENT

During 1970-2010, Indian agriculture increased its fertilizer N consumption by about 11 times,
whereas the uptake by crop increased by 3 times and loss of N increased by 4 times (Fig. 5.3). India’s
share in N loss mechanisms may increase as more fertilizer N will be applied in future to produce
more food for the fast soaring population. On the other hand USA and European countries are gradually
reducing their N accumulation in soil. Therefore, in India research on the ways to increase the efficiency
of applied fertilizer N such as use of nitrification inhibitor and slow release fertilizer, deep placement
of N, conjunctive use of organic manure, and use of better agronomic practices needs to be intensified.
Attempts also need to be made for including more and more legumes in cropping systems to reduce
chemical fertilizer N application in soil.

Fig. 5.3 Trends of N inputs and outputs in Indian agriculture during 1970–2010
Source: Pathak (2013, unpublished)

Nitrogen and global warming

Nitrogen has direct, indirect and also short- as well as long-term effects towards global warming
and cooling and thereby climate change (Fig. 5.4).
The warming effects of N include:
1. N2O emissions, which is a greenhouse gas with long atmospheric lifetime;
2. NOx emission, which contributes to formation of tropospheric O3, a short-lived GHG lasting
several weeks, and
3. detrimental effects of ozone on plant C sequestration (Pathak, 2013).
The cooling effects include:
1. C sequestration due to application of N, which increases plant CO2 fixation;
2. losses of N to water-bodies, where freshwater and marine eutrophication can increase CO2
removal from the atmosphere;
3. increasing oxidation potential of the atmosphere by O3, which decreases the atmospheric lifetime
of CH4 and increases rates of aerosol formation; and
4. NOx and NH3 emissions, which contribute to formation of ammonium and nitrate aerosols.
In addition, tropospheric O3 and NH3 both accelerate the oxidation of sulphur dioxide (SO2) to
 NITROGEN MANAGEMENT 87

Fig. 5.4 Role of N in climate change and its mitigation and adaptation
Source: Pathak (2013)

sulphate aerosols. The Nr supply also affects CH4 production and consumption in soils and albedo of
the land surface by affecting vegetative cover and increasing chlorophyll content of vegetation. The
quantitative importance of these effects is, however, uncertain. The net effect of these multiple Nr
interactions indicates net global cooling of –16 (–47 to +15) mW/m2 for European emissions and –
240 (–500 to + 200) mW/m2 for the global release of Nr (Erisman et al., 2011). This global cooling
effect is about 15% of the overall net radiation effect of different anthropogenic contributions of
+1,600 mW/m2.

SUMMARY
Nitrogen is essential for protein production in plants and is the key primary plant nutrient
responsible for rapid growth of green vegetation in plants. Nitrogen constitutes about 78% of the
atmospheric gases and more than 99% of it is present in non-reactive N2 form. The reactive N
(ammonia, ammonium, nitrogen oxides) is estimated to be less than 1% in the atmosphere.Rhizobia
associated with legumes and few other organisms, such as, Azotobacter sp can fix non-reactive N2
and make it available to growing plants. Global estimates of biological nitrogen fixation (BNF) are
at 175 million tonnes per year. Industrial N fixation (fertilizer nitrogen) by Haber-Bosch process is
estimated at about 150 million tonnes per year by 2015. Both BNF and fertilizer N form the part of
soil–plant–animal–atmosphere nitrogen cycle.
Nitrogen in soil is present in organic (95–99%) and inorganic (1–5%) forms. Most Indian soils with
the exception of hill soils and peat soils are poor in organic matter and hence in total N. Inorganic forms
88 TEXTBOOK OF PLANT NUTRIENT MANAGEMENT

of N include ammonium (exchangeable and fixed), nitrite (present in very small amounts) and nitrate.
There are a number of nitrogen fertilizers, but in India only urea (about 80%), calcium ammonium
nitrate (CAN), ammonium sulphate and ammonium chloride are used.
The recovery efficiency of fertilizer N in crop production is about 30–60%, it is the lowest in
rice. This is due to various N loss mechanisms, which include ammonia volatilization, denitrification
and leaching. These losses of N have a bearing on climate change. In India the estimates of ammonia
volatilization losses are at about 4 million tonnes, while those for denitrification and leaching are at
3 million tonnes per year. To reduce loss of fertilizer N, slow release fertilizers have been developed
and nitrification inhibitors are used. From the Indian point of view neem coated urea is the most
important.
QUESTIONS
A. Answer whether the following statements are ‘Right (R)’ or ‘Wrong (W)’.
1. Plant leaves turn yellow due to N deficiency, because N is an important component of
chlorophyll.
2. Nitrogen deficiency first shows up in upper leaves.
3. Cereal crops remove 5–6 kg N/ha/day from the field.
4. Enzymes are proteinaceous substances.
5. Nitrogen content in rice grains is lesser than in wheat grains.
6. Losses due to denitrification occur only in rice fields.
7. About 80% of fertilizer N is consumed as urea.
8. Nitrate pollution of groundwaters is of no relevance to India, because rates of N application
are generally low.
9. For winter crops grown under dryland agriculture, split application of N is the best method.
10. Deep placement of fertilizer N increases its use efficiency.
B. Find out the correct answer from the choices given.
11. For producing each tonne (1,000 kg) of wheat, the crop removes .... kg N/ha.
(a) 5 (b) 1 (c) 25 (d) 40
12. Apparent recovery of fertilizer N applied to rice in India is ...%.
(a) 60–70 (b) 60–65 (c) 50–60 (d) 30–40
13. Nitrogen content in urea supergranules (USG) is .... %.
(a) 30 (b) 40 (c) 46 (d) 82
14. If urea is applied @ 200 kg/ha, how much of urea will be needed for an experimental plot of 20
m2 .
(a) 0.4 kg (b) 1 kg (c) 2 kg (c) 4 kg
15. If 500 litres of 0.2% solution of urea is sprayed on one hectare of land, the amount of urea
required
For a 5 hectare farm will be:
(a) 2.5 kg (b) 5 kg (c) 10 kg (d) 15 kg
C. General questions
16. Enumerate five mechanisms of N loss from a crop field.
17. In which three ways fertilizer N can contribute to global warming.
18. Current crop removal of N in India is estimated at .... million tonnes.
19. Loss of N due to ammonia volatilization from agricultural field in India is estimated at ....
million tonnes.
20. Loss of N due to denitrification from agricultural field in India is estimated at .... million
tonnes.
 NITROGEN MANAGEMENT 89

ANSWERS
1. R 2. W 3. W 4. R 5. R 6. W 7. R 8. W 9. W 10. R
11. C. 2.5 kg N/ha 12. d. 30–40% 13. 46% 14. a. 0.4 kg 15. b. 5 kg
16. 1. Ammonia volatilization, 2. Surface run-off, 3. Leaching, 4. Denitrification, 5. Post-anthesis
ammonia loss from plants.
17. 1. Production of N2O, 2. Production of NOx gases, 3. Detrimental effects of Ozone on C
sequestration by plants.
18. 9.8 million tonnes 19. 4.1 million tonnes 20. 3.1 million tonnes

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