SOIL SCIENCE AND TECHNOLOGY

Dr. SOMSUBHRA CHAKRABORTY

AGRICULTURAL AND FOOD ENGINEERING
IIT KHARAGPUR

Topic
Essential Plant Nutrients
Concepts Covered:

 What is essential plant nutrient

 Criteria for essentiality

 Classification of the essential elements

 Deficiency symptoms
What is Essential Nutrient

• An element without which a plant cannot survive or complete its life cycle is
termed as the essential nutrient.
• 17 elements are considered as the essential nutrients for the plant growth and
development.
• The elements are – C,H,O,N,P,K,Ca,Mg,S,Fe,Mn,Zn,Cu,B,Mo,Cl and Ni
 Criteria of essentiality
• A total of only 17 elements are essential for the growth and full development of
higher green plants according to the criteria laid down by D.I. Arnon and P.R.
Stout (1939). These criteria are:
1. A deficiency of an essential nutrient makes it impossible for the plant to
complete the vegetative or reproductive stage of its life cycle.
2. Such deficiency is specific to the element in question and can be prevented or
corrected only by supplying this element.
3. The element is involved directly in the nutrition of the plant quite apart from
its possible effects in correcting some unfavourable microbiological or
chemical condition of the soil or other culture medium.
Criteria of essentiality

• The essentiality of most micronutrients for higher plants was established

between 1922 and 1954.
• The essentiality of nickel (Ni) was established in 1987 by Brown et al., although
there is no unanimity among the scientists as to whether Ni is essential or
beneficial.
• However, this list may not be considered as final and it is probable that more
elements may prove to be essential in future.
Chronology of discoveries of essential
nutrient elements
Element Discoverer of Essentiality Year
Oxygen (O) Since time immemorial
Hydrogen (H) Since time immemorial
Carbon (C) Priestley et al. 1800
Nitrogen (N) Theodore de Saussure 1804
Phosphorus (P) C. Sprengel 1839
Potassium (K) C. Sprengel 1839
Magnesium (Mg) C. Sprengel 1839
Calcium (Ca) C. Sprengel 1839
Sulphur(S) Sachs and Knop 1860
Chronology of discoveries of essential
nutrient elements
Element Discoverer of Essentiality Year
Cl T.C. Broyer, A,B. Carlton, 1954
C.M. Johnson and P.R. Stout
Fe E. Gris 1843
B K. Warington 1923
Mn J.S. McHargue 1922
Zn A.L. Somme and C.P. Lipman 1926
Cu A.L. Somme and C.P. Lipman 1931
and G. McKinney
Mo D.I. Arnon and P.R. Stout 1939
Ni P.H. Brown, R.M. Welch and 1987
E.E. Cary
Classification of essential plant nutrients
 Beneficial plant nutrients
• Beneficial elements have been reported to enhance resistance to biotic stresses
such as pathogens and herbivory, and to abiotic stresses such as drought,
salinity, and nutrient toxicity or deficiency. They are not required by all plants
but appear to benefit certain plants.
• Cobalt (Co), sodium (Na), vanadium (V) and silicon (Si) are sometimes called as
beneficial plant nutrients.
• Cobalt is required for nitrogen fixation in legumes. Silicon is found in plant cell
walls and appears to produce tougher cells. This increases the resistance of
these plants to piercing and sucking insects and decreases the spread of fungal
diseases.
 Frame-work nutrient elements
• Carbon (C) and oxygen (O) are obtained from the gas CO2, and hydrogen (H) is
obtained from water (H2O).
• These three elements are required in large quantities for the production of
plant constituents such as cellulose or starch.
• Hence, many times referred as frame-work elements.
• Oxygen, carbon and hydrogen make up 95 percent of plant biomass, and the
remaining 5 percent is made up by all other elements.
 Mineral nutrient elements
• 14 elements are called mineral nutrients because they are taken up in mineral
(inorganic) forms. They are traditionally divided into two groups,
macronutrients and micronutrients, according to the relative amounts required.
• The 14 mineral elements are taken up by plants in specific chemical forms
regardless of their source.
• The difference in plant concentration between macronutrients and
micronutrients is enormous. The relative contents of N and molybdenum (Mo)
in plants is in the ratio of 10,000:1. Plants need about 40 times more
magnesium (Mg) than Fe.
 Macronutrients
• Macronutrients are nitrogen (N), phosphorus (P), potassium (K), calcium (Ca),
magnesium (Mg), and sulphur (S).
• N, P, and K are often referred to as primary nutrients and are the most common
elements found in commercial fertilizers. They are required in a large amount
and they produce wide-spread deficiency symptoms.
• Ca, Mg, and S are referred to as secondary nutrients and are also found in
fertilizers and soil amendments. They are moderately required by the plant.
They produce deficiency symptoms in patches. They are applied through
fertilizers containing primary nutrients like SSP.
Micronutrients

• Micronutrients include iron (Fe), manganese (Mn), zinc (Zn), boron (B), copper
(Cu), chloride (Cl), molybdenum (Mo), and nickel (Ni).
• Micronutrients are required in relatively minute quantities
 Typical concentrations of macronutrient
elements sufficient for plant growth
Relative number
Element Symbol mg/kg percent
of atoms
Nitrogen N 15,000 1.5 1,000,000
Potassium K 10,000 1.0 400,000
Calcium Ca 5,000 0.5 200,000
Magnesium Mg 2,000 0.2 100,000
Phosphorus P 2,000 0.2 30,000
Sulphur S 1,000 0.1 30,000
Relative concentration of essential
elements in plants
• Some microelements can be toxic for plants at levels only somewhat higher
than normal. In the majority of the cases this happens when the pH is low to
very low.
• Aluminium and manganese toxicity are the most frequent ones, in direct
relation with acid soils.
Typical concentrations of micronutrient
elements sufficient for plant growth
Relative number
Element Symbol mg/kg percent
of atoms
Chlorine Cl 100 -- 3,000
Iron Fe 100 -- 2,000
Boron B 20 -- 2,000
Manganese Mn 20 -- 2,000
Zinc Zn 20 -- 300
Copper Cu 6 -- 100
Molybdenum Mo 0.1 -- 1
Nickel Ni 0.1 -- -
 Classification based on biochemical
behaviour and physiological functions
• Mengel and Kirkby (1987) have divided essential plant nutrients into four
groups
 Group I includes C, H, O, N and S, which are major constituents of the organic
plant materials (carbohydrates, proteins, fats, etc.).
 Group II includes P and B, which are involved in biochemical reactions such as
esterification.
 Group III includes K, Ca, Mg, Mn and Cl. These elements are present in the free
ionic state or are adsorbed to indiffusible organic anions (e.g. absorption of Ca2+
by the carboxylic group of pectins).
 Group IV includes Fe, Cu, Zn and Mo. These elements are predominantly
presented as chelates in the plant.
Classification on the basis of biochemical
and physiological functions in plants
Group Nutrients Form in which taken up by Biochemical/physiological
plants functions
I C CO2, HCO3- Major constituents of
H H2O organic material, essential
O O2 elements of atomic groups
N NH4+, NO3-, N2 (in fixation) which are involved in
S SO4-2, SO2 (gaseous enzymatic process, etc.
absorption in leaves
II P H2PO4-1, HPO4-2 Esterification with native
plant alcohol. Phosphate
B B(OH)3 esters are involved in
energy transfer.
Classification on the basis of biochemical
and physiological functions in plants
Group Nutrients Form in which taken up by Biochemical/physiological
plants functions
III K K+ Nonspecific functions,
Mg Mg+2 involved in establishing
osmotic potential. Ca is a
Ca Ca+2
component of plant
Mn Mn+2 structural parts.
Cl Cl-1
IV Fe Fe+2 Present predominantly in
Cu Cu+2 a chelated form in
prosthetic group, enable
electron transport by
valency change
Deficiency symptoms of the nutrient
elements
 SOIL SCIENCE AND TECHNOLOGY
Dr. SOMSUBHRA CHAKRABORTY
AGRICULTURAL AND FOOD ENGINEERING
IIT KHARAGPUR

Topic
Soil Nitrogen
Concepts Covered:

 Importance of nitrogen

 Forms of nitrogen

 Nitrogen cycle

 Fate of nitrogen in soil

Why is nitrogen management important?

Nitrogen is an integral part of amino acids, chloroplasts and nucleic acids

Hugely impacts the world ecosystems
Imbalance of nitrogen cycle leads to global warming and ozone depletion (due
to emission of nitrous oxide, N2O)
 Influence of nitrogen on plant growth
 Chlorosis(more in  Deep green leaves  Excessive vegetative
older leaves)  Increased vegetative growth
 Stunted growth growth  Weak plants
 Less protein, more sugar  More protein content  Delayed maturity than
 Mature quickly than  More grain yield healthy plants
healthy plants  Harmful buildup of
 Premature senescence excess N in tissues

N deficiency Optimal N Excess N

 Influence of nitrogen on plant growth

Excess
Nitrogen
nitrogen
deficiency

Ray R. Weil

Chlorosis of older leaves in corn Lodging of paddy due to excessive

vegetative growth
Forms of nitrogen

Two major forms – ammonium (NH4+) and nitrate (NO3-) (inorganic/mineral

form)
NH4+ uptake lowers the rhizosphere pH whereas NO3- raises it
Dissolved organic compounds also supply nitrogen (organic form)
Among these various forms, uptake depends on their availability and the crop
 Organic Nitrogen pool
Soluble Organic Nitrogen (SON)
 Portion of organic nitrogen easily extracted
using salt solutions (eg. KCl) or water

Dissolved Organic Nitrogen (DON)

 Portion of soluble organic nitrogen present
in soil solution and drainage waters
Reason for inherent fertility of some forests
Ray R. Weil
Easily leached – hence a potential
environmental problem in downstream
Movement of nitrogen
Anthropogenic causes

Canfield et al. (2010))

Nitrogen cycle

University of Minnesota Extension

Fate of nitrogen in soil
Ammonium (NH4+) Nitrate (NO3-)

• immobilization • immobilization
• plant uptake • plant uptake
• anammox • anammox
• volatilization • denitrification
• nitrification • dissimilatory reduction
• fixation • leaching
 Immobilization and mineralization
 Mineralization and immobilization – conversion of organic N form to inorganic forms
and vice versa
 Caused mainly by microorganisms
 Net nitrogen depends on carbon-nitrogen ratio

low C:N ratio

high C:N ratio

Importance of carbon nitrogen ratio

Directly impacts the residue decomposition and nitrogen cycling

Optimal C:N ratio = 20:1
Higher the ratio, longer the time for decomposition and vice versa
Hence, higher C:N ratio results in immobilization
 Ammonium fixation within clay minerals
NH4+ being a positive ion is attracted to clay surface
However, due to its size, it is trapped in non-exchangeable sites
Happens mainly in 2:1 clays as their ionic radii allows them to fit exactly in the space
A slow-release reservoir is created with release rates slower than the rate of fixation
Affects the indigenous nitrogen supplying capacity of soils

Fixed NH4+ in
illite

vaxteko.nu, modified after Wiklander, 1958, and Schachtschabel, 1961

Ammonia volatilization

NH4+ + OH- ⇌ H2O + NH3↑

Dissolved ions Gas

High pH level drives the reaction to right, producing ammonia gas

Volatilization results in loss of valuable nitrogen
High temperature and less clay content speeds up the volatilization
Prevention of volatilization
Applying fertilizers at certain depth rather than at the surface
Irrigating the field when fertilizer is applied at the surface
Ammonia volatilization
Effect of irrigation on NH3 volatilization Effect of pH and temperature on NH3 volatilization

Redrawn from Glibert et al. (2006) using data in Franzen Redrawn from Holcomb et al. (2011)
(2004)
Nitrification

Biological oxidation of ammonium to form nitrites and then nitrates

Step 1 causes acidity
Nitrosomonas
NH4+ + 1 ½ O2 NO2- + 2H+ + H2O + 275 kJ energy
Ammonium bacteria Nitrite

Step 2
Nitrobacter
NO2- + ½ O2 NO3- + 76 kJ energy
Nitrite bacteria Nitrate
Factors affecting nitrification
1. Substrate availability (NH4+)
2. Temperature
Lower the temperature, slower the nitrification (20-30° C optimal)
3. Aeration
Aerobic environment enhances nitrification
4. Moisture content
well drained soils enhance nitrification (60% water filled pores optimal)
5. Type of clay
6. pH
 Denitrification
Loss of soil nitrogen by sequential reduction of nitrate in soil
-2O -2O -O -O
2NO3- → 2NO2- → 2NO↑ → N2O↑ → N2↑
nitrate ions nitrite ions nitric oxide gas nitrous oxide gas Dinitrogen gas
(+5) (+3) (+2) (+1) (0) Valence state of nitrogen

Microbes utilize the oxygen in nitrate for respiration thereby reducing them
End product of denitrification depends on the bacteria involved and soil conditions
Low lying, organic rich, oxygen depleted zones are more prone to denitrification
Denitrification results in loss of valuable N in nutrient management
However, it is useful in removing the N from waste water
Denitrification
Deep
application of
fertilizers
helps in
reducing
loss of N in
flooded
systems

Ray R. Weil

Denitrification in a temporarily Modified from Patrick (1982

waterlogged, warm lowland
Denitrification in flooded systems
Denitrification

Denitrification in a moist soil in the

absence of oxygen

From Leffelaar and Wessel (1988)]

 Anammox

Anaerobic oxidation of ammonium yielding N2 gas

Caused by the unusual bacteria of phylum “planctomycetes”
Occurs in redox transition zones e.g. upper layer of saturated soils, rhizosphere etc.

NH4+ + 1 ½ O2 → NO2- + 2H+ + H2O (aerobic)

NH4+ + NO2- → N2 + 2H2O (anaerobic)

2NH4+ + 1 ½ O2 → N2 + 2H+ + 3H2O (combined net

anammox reaction)
Nitrogen loss and environment

N loss by denitrification and anammox is detrimental to plant growth in soils

whereas it is beneficial in waste water management
N2O and NO are greenhouse gases and cause acid rain, ozone depletion, etc.
Slow release nitrogen fertilizers and deep placement of fertilizer can reduce the loss
of N
Reference:
 The Nature and Properties of Soils by Nyle C. Brady
and Ray R. Weil
 SOIL SCIENCE AND TECHNOLOGY
Dr. SOMSUBHRA CHAKRABORTY
AGRICULTURAL AND FOOD ENGINEERING
IIT KHARAGPUR

Topic
Biological Nitrogen Fixation
Concepts Covered:

 What is biological nitrogen fixation

 Importance

 The mechanism of nitrogen fixation

 Different fixation systems

 Factors affecting nitrogen fixation

 What is biological nitrogen fixation
• Next to plant photosynthesis, biological nitrogen fixation is the most important
biochemical reaction for life.
• This process converts the inert dinitrogen gas of the atmosphere (N2) to
reactive nitrogen that becomes available to all forms of life through the
nitrogen cycle.
• The process is carried out by a limited number of bacteria, including several
species of Rhizobium, actinomycetes, and cyanobacteria (formerly termed blue-
green algae).
Importance of biological nitrogen fixation

• Increased crop yield

• Reducing the need to manufacture nitrogen fertilizer (and therefore lowering
the amount of reactive nitrogen circulating in the environment)
• Reductions in N2O emissions.
The mechanism of nitrogen fixation

• Regardless of the organisms involved, the key to biological nitrogen fixation

is the enzyme nitrogenase, which catalyzes the reduction of dinitrogen gas
to ammonia

• The ammonia, in turn, is combined with organic acids to form amino acids
and, ultimately, proteins

• The site of N2 reduction is the enzyme nitrogenase, a complex consisting of 2

proteins, the smaller of which contains iron while the larger contains
molybdenum, sulfur, and iron.
The mechanism of nitrogen fixation
The mechanism of nitrogen fixation
• The nitrogenase complex consists of two proteins.
• The larger protein converts atmospheric N2 to NH3 using
electrons provided by the smaller protein (left). Energy-
rich hydrogen gas (H2) may also be produced.
• Energy from ATP conversion to ADP along with
electrons from Ferredoxin reduce the Fe(III) in the
smaller Fe–protein.
• Meanwhile, the Mo–Fe–S clusters in the large protein
capture nitrogen (N2) from the air, while the Fe in the
clusters receives the electrons (e−) provided by the
small protein so that N2 can be reduced to NH3.
• Nitrogen fixation in nature may be limited by
insufficient supplies of S, Fe, Mo or P.
 Facts about nitrogen fixation
• Breaking the strong N N triple bond in N2 gas requires a great deal

III
of energy. This microbial process is greatly enhanced when it is
carried out in association with plants, which can supply energy from
photosynthesis.
• Nitrogenase is destroyed by free O2, so organisms that fix nitrogen
must protect the enzyme from exposure to oxygen. The fixation takes
place in the root-nodules which has Leghaemoglobin. It binds O2 to
protect the nitrogenase.
• The reduction reaction is end-product inhibited—for example, an
accumulation of NH3 will inhibit nitrogen fixation. Also, too much
nitrate in the soil will inhibit the formation of nodules.
• Nitrogen-fixing organisms have a relatively high requirement for Mo,
Fe, P, and S.
Fixation systems

1. Symbiotic fixation with legumes

2. Symbiotic fixation with non-legumes
3. Non-symbiotic fixation
Symbiotic fixation with legumes
• Plants of the legume family (Leguminosae) are famous for their
distinctive ability to provide the major biological source of fixed
nitrogen in agricultural soils.
• They do so in association with several genera of bacteria (in the
subclass Alpha-Proteobacteria) collectively termed rhizobial bacteria.
These bacteria include species in the genera Rhizobium,
Mesorhizobium, Bradyrhizobium, and Ensifer.
• The legume plants and rhizobial bacteria form a symbiosis (a mutually
beneficial relationship) in which the host plant supplies the bacteria
with carbohydrates for energy, and the bacteria reciprocate by
supplying the plant with reactive nitrogen with which to make
essential plant compounds such as proteins and chlorophyll.
• In the “conversation” involving many specific signaling compounds, the
rhizobial bacteria find and infect the legume plant root hairs and
colonize the cortical cells and form root nodules that serve as the site
of nitrogen fixation.
Symbiotic fixation with legumes
(a) (b) (c)

(a)Root nodules of sunhemp used as a cover crop to add N

in soil
(b)Cross section of the nodule in soybean plant. It shows
the red colour of oxygenated leghemoglobin.
(c) A single plant cell within soybean nodule shows that it
is stuffed with the Bradyrhizobium japonicum bacteria.
 Pea Plant

R. leguminosarum
nodules

Pink color is leghaemoglobin a protein that carries

oxygen to the bacteroids
Rhizobia and their classification
Symbiotic fixation with non-legumes
Nodule forming non-legumes
 Some 220 species from eight plant families are known to develop
nodules and to accommodate symbiotic nitrogen fixation when their
root hairs are invaded by soil actinomycetes of the genus Frankia.
 On a worldwide basis, the total nitrogen fixed in this way may even
exceed that fixed by agricultural legumes. Because of their nitrogen-
fixing ability, certain of the tree–actinomycete associations are able to
colonize infertile soils and newly forming soils on disturbed lands,
which may have extremely low fertility as well as other conditions that
limit plant growth.
 Certain cyanobacteria are known to develop nitrogen-fixing symbiotic
relations with green plants. One involves nodule formation on the
stems of Gunnera, an angiosperm common in marshy areas of the
southern hemisphere. In this association, cyanobacteria of the genus
Nostoc fix 10–20 kg N/ha/yr.
• Nodule forming non-legumes
Symbiotic fixation with non-legumes

• Fixation without nodules

• Among the most significant non-nodule nitrogen-fixing
systems are those involving cyanobacteria.
• One system of considerable practical importance is the Azolla–
Anabaena complex, which flourishes in certain rice paddies of
tropical and semitropical areas.
• The Anabaena cyanobacteria inhabit cavities in the leaves of
the floating fern Azolla and fix quantities of nitrogen
comparable to those of the more efficient Rhizobium–legume
complexes.
 https://upload.wikimedia.org/

Azolla–Anabaena complex used in rice cultivation

Non-symbiotic nitrogen fixation

 Certain free-living microorganisms present in soils and water are able to fix
nitrogen. Because these organisms are not directly associated with higher
plants, the transformation is referred to as non-symbiotic or free-living.
 There are two types of non-symbiotic nitrogen fixation-
1. Fixation by heterotrophs
2. Fixation by autotrophs
Fixation by heterotrophs
• Several different groups of bacteria and cyanobacteria are able
to fix nitrogen nonsymbiotically. In upland mineral soils, the
major fixation is brought about by species of several genera of
heterotrophic aerobic bacteria, Azotobacter and Azospirillum (in
temperate zones) and Beijerinckia (in tropical soils).
• Certain anaerobic bacteria of the genus Clostridium are also
active in fixing nitrogen. Because pockets of low oxygen supply
exist within aggregates even in well-drained soils aerobic and
anaerobic bacteria probably work side by side in many well-
drained soils.
• These organisms obtain their carbon either from root exudates
in the rhizosphere or by saprophytic decomposition of SOM,
and they operate best where soil nitrogen is limited.
 Fixation by autotrophs
• In the presence of light, certain photosynthetic bacteria and
cyanobacteria are able to fix carbon dioxide and nitrogen
simultaneously.
• The contribution of the photosynthetic bacteria is uncertain, but that of
cyanobacteria is thought to be of some significance, especially in
wetlands (including in rice paddies). In some cases, cyanobacteria
contribute a major part of the nitrogen needs of rice, but nonsymbiotic
species rarely fix more than 20–30 kg N/ha/yr.
Levels of nitrogen fixation from different
systems
Rhizobacteria

• Bacteria adapted to life in the rhizosphere are called rhizobacteria.

Rhizobacteria that benefit plant growth and development are
referred to as plant growth–promoting rhizobacteria (PGPR). Many
PGPR bacteria belong in the genera Spirillum, Rhizobium, and
Azotobacter. These microorganisms obtain their energy supply for
their nitrogen-fixation from the exudates of plant roots.
Factors affecting nitrogen fixation

• The natural population of the rhizobium in soil is too low to fix N2.
In this condition, special mixtures of the appropriate rhizobial
bacteria may be applied as an inoculant, either by coating the
legume seeds or by applying the inoculant directly to the soil.
• The legume–Rhizobium associations generally function best on
soils that are not too acid (although Bradyrhizobium associations
generally can tolerate considerable acidity)
• The soils should be well supplied with essential nutrients and have
sufficient amount of organic matter.
• High amount of nitrogen in soil inhibits the nitrogen fixation.
 Factors affecting nitrogen fixation
• Nitrogen fixation requires energy.
• The inorganic nitrogen merely
replaces biologically fixed N, saving
the plant some energy that would
have been allocated to the nodule
bacteria.
• However, some legume species fix
nitrogen so inefficiently (e.g.,
Phaseolus bean) that they are more
likely to respond positively to the
use of nitrogen fertilizer.
 SOIL SCIENCE AND TECHNOLOGY
Dr. SOMSUBHRA CHAKRABORTY
AGRICULTURAL AND FOOD ENGINEERING
IIT KHARAGPUR

Topic
SOIL PHOSPHORUS AND POTASSIUM
Concepts Covered:

Phosphorus and its available forms

Fixation of phosphorus

Potassium and its available forms

Fixation of potassium

P and K fertility management

 Phosphorus in plant growth

An essential component of ATP, DNA,RNA and phospholipids

Phosphorus is found in very limited amounts in soil
Majority of them is also held in non-available forms, hence P presents a major
problem
Deficiency of P causes stunted growth, bluish-green leaves and delayed
maturity
Highly weathered warm, humid regions have major P deficiency
 Phosphorus cycle
P is very low in soil Loss of P occurs through
solution and very erosion, leaching, plant uptake
immobile
For efficient P uptake of crops,
Very slow diffusion to satisfying the fixed P capacity
root surfaces of soil should be considered
while fertilizer management
Symbiotic mycorrhizal
fungi extract P from Unlike N, not usually lost from
areas normally soil in gaseous form
inaccessible to plant
roots, thereby
supplying P
Forms of Phosphorus
P content of various soil orders

Organic Phosphorus
Present as
mono-esters (inositol phosphates) eg. Phytic
acid. They are most common forms
Phosphate di-esters eg. Nucleic acids
Phospholipids
Type of phosphate present depends on
soil type
N. Brady and Ray R. Weil
Forms of Phosphorus
Organic Phosphorus undergoes mineralization and immobilization

Organic P is a major supplier of Phosphorus in highly weathered soils

Forms of Phosphorus
Inorganic fixation of added phosphates at various pH
Inorganic phosphorus
Very immobile
Calcium phosphates are the dominant
P supplying in highly alkaline soils
Iron and aluminium phosphates are
dominant in acid soils
P gets fixed in the soil, the longer it
stays in it N. Brady and Ray R. Weil
Influence of pH on different forms of P
Mechanism of P fixation
Fixation occurs especially in1:1 clays
First, dissolved ions are precipitated

Then they are adsorbed as outer sphere complex

This P is exchangeable

Further, the P replaces a structural hydroxyl

ion and forms an inner-sphere complex
This P is very tightly bound and
availability is very low

Finally the phosphate becomes

an integral part of oxide mineral
This P is relatively unavailable
Factors affecting P fixation

1. Amount of clay present

More the clay content, more the P fixation, less release of P for plants
2. Type of clay present
(less fixation) 2:1 clays << 1:1 clays < carbonate crystals < crystalline Al, Fe, Mn
oxides < amorphous Al, Fe and Mn oxides, allophane (more fixation)
3. pH
Greatest fixation occurs at pH extremes. Lowest fixation at pH 6-7
4. Amount of organic matter
Organic matter reduces P fixation
Mycorrhizae [fungus – root]

1. Symbiosis with fungi

2. Mutual benefit
• Carbohydrates for the fungus
• P, Zn, Cu, water, N for plant
3. Different types
1. Vesicular-arbuscular mycorrhiza – VA-mycorrhiza
2. Ectomycorrhiza
Other types: ericoid, orchid endomycorrhiza
 Vesicular Arbuscular Mycorrhiza (VAM)
Inside root
• Intercellular mycelium
• Intracellular arbuscule
• tree-like haustorium
• Vesicle with reserves

Outside root
• Spores (multinucleate)
• Hyphae
•thick runners
•filamentous hyphae

Form extensive network of hyphae

even connecting different plants
Vesicular Arbuscular Mycorrhiza (VAM)

Arbuscule of Glomus mosseae Outside of root network of

– branching provides large hyphae and spores
surface area
Ectomycorrhiza (EM)
Inside root
• Intercellular hyphae
• Does not enter cells

Outside root
• Thick layer of hyphae around root
• Fungal sheath
• Lateral roots become stunted
• Hyphae
•Mass about equal to root mass

Forms extensive network of hyphae

even connecting different plants
Why mycorrhiza?
• Roots and root hairs
cannot enter the smallest
pores

• Hyphae is 1/10th diameter

of root hair

• Increased surface area

Enhancing P availability

Enhancing mycorrhizal symbiosis by crop rotation and minimum tillage

Growing P-efficient plants
P application to overcome the P-fixation capacity of soil
Localized placement of P
Using organic matter from P-efficient crops as mulch
Use of P-efficient cover crops
www.dtnpf.com

Maintaining pH 6-7 by liming or acidification

Importance of Potassium

Unlike N and P, K remains in cell solution rather than as component

It is an enzyme activator and responsible for maintaining osmotic potential
within cells
Potassium increases the hardiness of the plant and makes it more resistant to
insects, pests, diseases and environmental stress
A balance should be maintained between K and other nutrients
Deficiency of potassium

Can be easily identified by chlorosis of leaf edges

White necrotic spots may also appear

Ray R. Weil

Necrotic margins White necrotic spots Chlorotic margins

in brinjal in alfalfa in soybean
Potassium cycle

Ray R. Weil
Problems in potassium management

Though potassium is found in Liming helps in fixation of

relatively large amounts in soil, potassium because Ca ions
are easily exchanged with
plant available K at a moment is K instead of Al ions in
low otherwise acid soils
Readily lost by leaching
Liming helps in reducing
leaching of potassium

Ray R. Weil
Luxury consumption of potassium

When K is present in excess in soil,

plants consume more potassium than
needed
“Luxury consumption of K”
Results in wasting of K
Also, depresses the consumption of
Ca and Mg

Ray R. Weil
 Forms of potassium

Four major forms of potassium can be found in soil

1. K in primary minerals unavailable to very slowly available
2. Nonexchangeable K in secondary minerals slowly available
3. Exchangeable K on soil colloids
readily available
4. K soluble in water
The two readily available forms are in equilibrium with each other
Factors affecting potassium fixation in soils
1. Type of clay and moisture
2:1 clays have more K fixing capacity than 1:1 clays
2. pH
liming increases the K fixation
2. Alternate wetting/drying and freezing/thawing
both enhance K fixation and also release of fixed K in solution

Modified from McLean (1978

Managing K fertility

Frequent light applications may

reduce the luxury consumption of input
K
Liming helps in overcoming the
leaching losses of K
Well weathered soils provide a
good native K availability
loss
While harvesting forage crops,
residues should be returned back
to the field
Reference:
 The Nature and Properties of Soils by Nyle C. Brady
and Ray R. Weil
 SOIL SCIENCE AND TECHNOLOGY
Dr. SOMSUBHRA CHAKRABORTY
AGRICULTURAL AND FOOD ENGINEERING
IIT KHARAGPUR

Topic
Fertilizers
Concepts Covered:

 What is fertilizer

 Classification of fertilizer

 Different straight fertilizers

 Liquid nitrogenous fertilizer

 Customized fertilizer
What is fertilizer?

• Fertilizer is a material which contains one or more of essential plant nutrients

required for the plant growth and development.
• It may be solid, liquid or gaseous substance of definite chemical composition
and high analytical value.
Classification of fertilizers

Fertilizers

Straight Complex Mixed

fertilizers fertilizers fertilizers
Straight fertilizers Complex fertilizers Mixed fertilizers

Straight fertilizers are Complex fertilizers Physical mixture of

those which supply only contain two or three straight fertilizers. They
one primary plant primary nutrients of contain two or three
nutrient, namely nitrogen which two primary primary plant nutrients.
or phosphorus or nutrients are in a Mixed fertilizers are made
potassium. E.g. Urea, chemical combination. by thoroughly mixing the
ammonium sulphate, These fertilizers are ingredients either
potassium chloride and usually produced in mechanically or manually.
potassium sulphate. granular form e.g.
Diammonium phosphate,
nitrophosphates etc.
Fertilizers can also be classified based on physical form

Solid fertilizers Liquid fertilizers

1.Powder (single superphosphate),

2.Crystals (ammonium sulphate),
3.Prills (urea, diammonium phosphate, superphosphate),
4.Granules (Holland granules),
5.Supergranules (urea supergranules) and
6.Briquettes (urea briquettes).
Fertilizer

Ammonium Sulphate SSP

DAP MOP
Urea

DAP MOP
Nitrogenous fertilizers

• The straight nitrogenous fertilizers are those that contain N either in the form of
ammonium(NH4+), nitrate (NO3-), or both NH4+ and NO3-, and amide (-NH2) and
cyanamide (-CN2). Out of these, the ammonium and nitrate forms are inorganic,
whereas amide and cyanamide forms are organic in nature.
Nitrogenous fertilizers
• Urea
a. 46% N
b. Synthesized first from urine in 1773
c. Lab synthesized first in 1928 by Wohler
d. NH3+HCNO= C0(NH2)2
e. First organic compound from inorganic material
f. Now: 2 NH3+ CO2<-> NH2CO2NH4
NH2CO2NH4 <-> C0(NH2)2+H2O
Nitrogenous fertilizers

• Urea
a. 0.3%-0.4% formaldehyde mix: Improve physical strength and resistance to
caking
b. Therefore , formaldehyde is termed as a conditioner
c. Other conditioners ; china clay, talc
d. Biuret :
1. NH2-CO-NH-CO-NH2
2. >2% biuret can damage foliage
3. Biuret sensitive : citrus
Synthesis of nitrogenous fertilizer

• The process of industrial production of N, developed in the 20th Century, are:

i. Cyanamide process (End product is calcium cyanamide [CaCN2]. It is not
produced in India)
ii. Electric Arc process (End product is nitric acid)
iii. Serpek’s process (End product is ammonia)
iv. Haber-Bosch process (End product is ammonia. It is a popular method for the
production of direct ammonia from the atmospheric air. The power
requirement is also less compared to cyanamide and arc process)
Haber Process for Fixing Nitrogen from the
Atmosphere

https://www.need.org/Files/presentations/Fertilizers.ppt
 Dehydration
Anhydrous NH3 (82.2% N)
HCL
NH4CL (25% N)
H2SO4
(NH4)2SO4 (20.6% N)
HNO3
NH4NO3 CaCO3
(34% N) CAN (25% N)
6:4 (NH4NO3:CaCO3)
CO2
CO(NH2)2 (46% N)
NH3
1:1 ratio
H3PO4 MAP (11:52:0) NH4H2PO4
2:1 ration
DAP (18:46:0) (NH4)2HPO4
SSP Ammonium Urea ammonium phosphate (UAP) or
Urea
superphosphate Gromor (20:20:0) and (28:28:0)
Odda process
Nitrophosphate or Suphala (15:15:15)
H2SO4+ H3PO4
Ammonium phosphate sulphate (16:20:0) and (28:28:0)
H2SO4+ HNO3
Ammonium sulphate nitrate (26% N) (75% NH4-N and
Ostwald Process 25% NO3-N)
HNO3
Phosphatic fertilizers
• The original source of phosphate in the early
manufacturer of P-fertilizer was bones, but the supply of
bones was soon exhausted. Today, worldwide demand of
P-fertilizer is met essentially from the rock phosphate, a
finite, non-renewable mineral resources.
• Rock phosphate occurs in the nature as mineral phosphate
in deposits (may be igneous, sedimentary or
metamorphic), which contain apatite (P-bearing mineral)
along with the other accessory minerals such as quartz,
silicates, carbonates, sulphates, sesquioxides etc.
• Commercial grade rock phosphates contain about 32%
P2O5(w/w) and they are apatites
 Phosphatic fertilizers: classification
1. Water soluble: monocalcium phosphate . eg- Single superphosphate (16% P2O5 or
6.88% P), DSP (32% P2O5), TSP (46% P2O5). DSP also called enriched
superphosphate ( mixture of SSP and TSP).
2. Citric acid soluble: Dicalcium phosphate [CaHPO4], eg- Dicalcium phosphate (34%
P2O5)
3. Insoluble (both water and citric acid): Tricalcium phosphate [Ca3(PO4)3], eg- Rock
phosphate (20-40% P2O5), only soluble in strongly acid soils and organic peat soils.
 Direct application
Direct application
H2SO4
Single superphosphate (SSP) NH3
Monoammonium
H3PO4 phosphate (MAP)
Triple superphosphate 2NH3
(TSP)
Diammonium
Rock Thermal or Elemental phosphate (DAP)
Phosphate process Phosphoric acid
NH3+H2SO4
Acid treatment (H3PO4) Ammonium sulphate
(Acidulation Rout) phosphate (ASP)

NH3 Ammonium
Super phosphoric acid
polyphosphate
HNO3
Nitrophosphate
HCl
Dicalcium phosphate
(DCP) (CaHPO4)
 SSP
• Single Super phosphate [Ca (H2PO4)2]
• This is the most important phosphatic fertilizer in use.
• It contains 16 Per cent P2O5 in available form.
• It is a grey ash like powder with good keeping or storage qualities.
• Phosphatic fertilizer hardly moves in the soil and hence they are placed in the, root zone.
 Potash fertilizer
• Potash fertilizers are commercially prepared from K-bearing minerals namely,
sylvite (KCl, 63.1% K2O), langbeinite (K2SO4.2MgSO4, 22.6% K2O), Kainite
(KCl.MgSO4.3H2O, 18.9% K2O) and carnallite (KCl.MgCl2.6H2O, 17% K2O). The
most important K-fertilizers are muriate of potash (MOP) and sulphate of
potash (SOP).
• MOP (60% K2O) is manufactured from sylvinite, a mixture of sylvite (KCl) and
halite (NaCl), after benefication (a process of removing impurities).
• SOP (48% K2O + 18.3% S) is manufactured by treating sylvite with sulphuric acid.
KCl + H2SO4 K2SO4
 MOP
• Potassium chloride or muriate of potash is a white or red, crystal
containing 60.0 per cent K2O.
• It is completely soluble in water and therefore readily available to the
crops.
• It is not lost from the soil, as it is absorbed on the colloidal surfaces.
• It can be applied at sowing or before or after sowing.
• The Cl content is about 47.0 per cent.
• Its Cl content is objectionable to some crops like tobacco, potato, etc
where quality is the consideration. For those crops SOP is used.
Secondary nutrient fertilizers

• Magnesium Sulphate (MgSO4)

• Calcium Chloride (CaCl2, 6H2O)
• Sulphate Fertilizers
Micronutrient Fertilizers

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Liquid nitrogenous fertilizer

• Liquid nitrogenous fertilizers are the principle forms of mixed fertilizers.

• The main advantages are the low cost per unit N and easy to handle and apply
if suitable equipment is available. However, these are corrosive and require
special applicator and storage containers.
• The important nitrogenous solution is the mixture of urea, ammonium nitrate
and water, often referred to as UAN-solution containing 35% N.
• Liquid nitrogenous fertilizers can be applied either as foliar spray or through
irrigation known as fertigation.
Fertilizer grade
• Fertiliser grade refers to the guaranteed minimum percentage of nitrogen (N),
phosphorus (P) and potash (K) contained in fertiliser material.
• The numbers representing the grade are separated by hyphens and are always stated
in the sequence of N, P, and
• For example, label on the fertilizer bag with a grade 28-28-0 indicates that 100 kg of
fertiliser material contains 28 kg of N, 28 kg of P and no potash.
• Different grades of fertilisers are available in India.
• Some of them are:
28-28-0
20-20-0
14-35-14
17-17-17
14-28-14 etc.
Fertilizer: other important terms
• FERTILIZERRATIO: it refers to the ratio of the percentage of
N, P2O5 and K2O in the fertilizer mixture e.g., the fertilizer grade
12-6-6 has a fertilizer ratio of 2:1:1.
• CONDITIONERS: these are low grade organic materials like peat
soil, paddy husk, groundnut hulls etc., which are added to fertilizer
mixtures during their preparation for reducing hygroscopicity and
to improve their physical condition.
• FILLER: A filler is a weight make material like sand, soil, coal
powder etc, added to the fertilizer ingredients so as to produce a
mixture of the desired grade.
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Methods of fertilizer application