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SAC 503 SOIL CHEMISTRY (2+1)

Name : J. Lekhavarshinee
Id no: 2022520009
BIOLOGICAL PHOSPHORUS FIXATION

Importance of phosphorus in agriculture:

1. Phosphorus is particularly important in early growth stages.
2. It is mobile within the plant and promotes root development, tillering and
early flowering.
3. Addition of mineral P fertilizer is required when the rice plants root
system is not yet fully developed and the native soil P supply is
inadequate.
4. Phosphorus is remobilized within the plant during later growth stages if
sufficient P has been absorbed during early growth.
5. It also increases resistance to disease and strengthens the stems of cereal
plants, thus reducing their tendency to lodge. It offsets the harmful effects
of excess nitrogen in the plant.

Deficiency symptoms

1. Plants stunted with reduced tillering.

2. Leaves narrow, short, very erect ‘dirty’ dark green.
3. Older leaves turn brownish red and purple colors develop in leaves.
4. Stems thin and spindly.
5. Poor tillering/branching.
6. Poor root growth.
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FORMS OF PHOSPHORUS :

• AVAILABLE P
• ORGANIC P
• ADSORBED P
• PRIMARY MINERAL P

• ORGANIC FORM

 Inositol
 Nucleic acid
 Nucleotides
 Phospho lipids
 Sugar phosphates

INORGANIC FORMS

Ionic form

 H2P04-(primary ortho phosphate)

 HPO4-(secondary ortho phosphate)

Combined form

 Choloro apatite
 Fluro apatite
 Hydroxy apatite

TRANSFORMATIONS OF P IN SOIL:
• Solubilization ( conversion of insoluble to soluble form)
• Mineralization (conversion of organic to inorganic form)
• Immobilization(conversion of inorganic to organic form)
• Oxidation and reduction
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Solubilization
It is the process of converting the insoluble form of phosphorus into soluble
forms

Micro organisms associated with the solubilization are listed below

• Pseudomonas,
• Mycobacterium
• Micrococcus
• Bacillus
• Flavobacterium
• Aspergillus
• Fusarium

Mineralization
• It is the process of converting organic into inorganic form of phosphorus
• It can be utilized by plants
• Fungi , bacteria and actinomycetes play a vital role
• Phosphates enzyme involves in the mineralization reaction
• Phytic acid is also essential for the transformation
• It occurs when the C:P ratio is less than 200:1

Immobilization
• It is the process of converting inorganic form to organic form of P
• The utilizable form of P is converted to un utilizable form
• Phosphorus got converted into nucleic acid, phosphor lipids
• It occurs initially during decomposition
• It occurs when the C:P ratio is greater than 300:1
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Oxidation and Reduction

• Phosphite is converted to phosphate by the micro organism
• This reaction is stopped by the Toluene ( which is the biological
inhibitor)

FIXATION OF P IN SOILS
IN ACID , ALKALINE AND CALCAREOUS SOIL:

Calcium and magnesium phosphates

Calcium or magnesium phosphate compounds are not found in soils at low

soil pH but are stable, insoluble and dominant in neutral or alkaline soils
[13,37] They occur in soils in several forms and the most important forms
are

Ca (H2PO4)2.H2O, monocalcium phosphate, which is the water-soluble

component of superphosphate that is transformed to less soluble products.

b) CaHPO4.2H2O and CaHPO4, dicalcium phosphate, both hydrated and the

unhydrated forms that are slightly soluble in water.

c) Ca8H2 (PO4)6.5H2O, octa calcium phosphate.

d) Ca3 (PO4)2, tricalcium phosphate.

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e) Ca10 (PO4)6. (OH)2 (hydroxyapatite) and Ca10 (PO4)6F (fluorapatite),

and

f) MgNH4P04. 6H20 (struvite) which is alkaline and water-soluble

The conversion of monocalcium phosphate into di calcium phosphate and

octa calcium phosphate leads to the insolubility of phosphorus.

Iron and aluminium phosphates

The most common aluminum phosphates in soils are wavellite [Al3(PO4)

(OH)3.5H2O] and variscite (AlPO4.2H2O) The aluminium hydroxyl
phosphates so formed controls phosphorus concentration in solution in acid
soil by forming a surface complex on variscite. However, in pure systems,
where the pH of the equilibrium solution is less than 3.1, the solubility
product of variscite controls the phosphorus concentration in solution

Although variscite (AlPO4.2H2O) and strengite (FePO4.2H2O) are the least

soluble compounds at low soil pH (36,38], strengite is the most common iron
phosphate in soils. According to [47], strengite coexists with hydrated iron
oxide (Fe2O3.2H2O) at pH 3.8 to 6.7 in the tropics and in the pH range of
3.8 to 4.2 in temperate soils. Strengite also crystallizes rapidly when iron
phosphate is formed. Less crystalline aluminium phosphate has greater
surface area which is favorable for release of phosphorus into the soil
solution. Therefore, under very acid conditions minerals of the variscite and
strengite groups are precipitated from their soluble forms [13] according to
the reactions shown in equations (i and ii).

AlPO4.2H2O ↔ HPO4 -2 + Al3+ + OH- + H2O (i)

Fe2PO4.2H2O ↔ HPO4 -2 + Fe3+ + OH- + H2O (ii)

FACTORS AFFECTING P AVAILABILITY:

Phosphorus adsorption occurs at very low and very high soil Ph

The dominant P ion species present in acid soils are H2PO4 - and PO4 3- in
alkaline soils

Adsorption of phosphorus by iron and aluminium oxides also declines with

increasing pH due to reduced solubility of Fe and Al ions
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At lower pH, adsorption results from the reaction with iron and aluminium and
their hydrous oxides while above pH 7.0, ions of calcium, and magnesium and
their carbonates cause P precipitation

Gibbsite (Al (OH)3) adsorbs high amount of phosphate between pH 4 and 5

while adsorption by goethite (an-FeOOH) decreases steadily between pH 3 and
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This is because Al3+ is more dominant and soluble between pH 4 and 5 while
Fe3+ is dominant and soluble at pH levels below 3. Therefore, maximum P
availability is attainable in most soils at the pH range 6.0 to 6.5

Ionic strength and composition of the soil solution:

Both organic and inorganic anions in the soil solution compete with phosphate
for adsorption sites to varying extents. This results in either adsorption of added
phosphate or desorption of retained phosphate in conformity to the anion
exchange mechanisms. Weakly held inorganic anions such as nitrate and
chloride are of little significance, whereas specifically adsorbed anions like
hydroxyl, sulphate and molybdate are competitive. The strength of bonding of
the anions with the adsorption surface determines the competitive ability of that
anion. For example, sulphate, even though considered to be a specifically
adsorbed anion, is unable to desorb much phosphate because of the affinity for
colloidal surfaces. Additionally, divalent cations enhance P sorption more than
monovalent cations . For example, clays saturated with Ca2+ retain greater
amounts of P than those saturated with monovalent cations like Na+

Organic matter
There are two principal mechanisms by which organic matter may affect the
adsorption and hence availability of phosphorus in soils: (a) negatively charged
organic matter adsorbs or complexes cations such as Al and Fe in acid soils and
Ca in calcareous soils and hence reduces their activities in solution and their
role in P sorption and/or precipitation or (b) presence of organic acids such as
humic acid, fulvic acid and citric acid on the surface of (hydroxides could
inhibit phosphate adsorption through site competition, electrostatic effects, and
steric hindrance . The existing correlation between phosphate and organic
matter. This increase is attributed to the ability of humic molecules to adhere to
sorbing surfaces and masking of fixation sites hence preventing them from
interacting with phosphate ions in solution. Organic acids produced by plant
roots and microbial decay can also serve as organic anions which compete with
P for positively charged sites. Other organic compounds can also entrap reactive
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Al and Fe in stable organic complexes called chelates hence their unavailability

for reaction with phosphorus

Clay mineralogy
Generally, clay minerals possessing high anion exchange capacity have a high
affinity for phosphate ions. The clay content of a soil also has great impact on
phosphate adsorption. Soils containing large quantities of clay would adsorb
more phosphate than those with less clay content. Generally, the layer silicate
clay minerals of the 1:1-type minerals (kaolinites) are made up of one
tetrahedral (silica) sheet and one octahedral (alumina) sheet, while 2:1 type
minerals (montmorillonite) are characterised by an octahedral sheet sandwiched
between two tetrahedral sheets. The 1.1 clays with low SiO2/R2O3
(sesquioxide) ratios have therefore higher phosphate adsorption capacity than
2.1 clays (montmorillonite) with high SiO2/R2O3 (sesquioxide) ratios. The high
amount of P fixed by 1:1 clays is probably due to the higher amounts of
hydrated oxides of iron and aluminium associated with kaolinitic clays.
Kaolinite has large number of exposed hydroxyl groups in the gibbsite layer that
can be exchanged for P [36,110]. In addition, kaolinite develops pH dependent
charges on its edges which can enter into adsorption reactions with P .

Free iron and aluminium

Oxides and hydroxides of Al and Fe play a significant role on P availability and
sorption properties. According to oxides of Fe and Al positively correlate with P
adsorption maxima. The high value of P adsorption maxima in cases of soil
containing high contents of oxides of Fe and Al might be due to formation of
their respective metal phosphates . The sorption of inorganic phosphate of soils
with pH less than 7.0 is closely related to the amount of reactive Fe and Al
compounds The amorphous hydrous metal oxides of Fe and Al have, however,
been reported to sorb relatively greater amounts of P than their crystalline
counter part .This is because the amorphous hydrous metal oxides have more
exposed sites for reaction as compared to the crystalline metal oxides

Effect of temperature
Temperature affects the equilibrium between phosphate solution and adsorbed P
and the rate of transfer from adsorbed, to firmly adsorbed phosphate [120]. High
temperatures slightly increase the molar solubility of compounds such as
apatite, hydroxyapatite, octa calcium phosphate, variscite and strengite. It may
also stimulate biological activity which enables phosphate to be released from
organic residues. This can be attributed to increased mobility and rate of
chemical reactions
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BIOLOGICAL P FIXATION:

Mycorrhiza is a symbiotic relationship between a fungus and a green plant.

Through photosynthesis, the plant produces organic molecules like sugars and
supplies them to the fungus, and the fungus supplies the plant with water and
mineral nutrients, such as phosphorus which is taken up from the soil

The fungus sends out a large network of hyphae across the soil after
colonisation of the root to shape a greatly improved absorptive surface area.
This leads to improved acquisition and absorption of nutrients by plant roots,
especially elemental phosphorus (P), zinc (Zn), manganese (Mn) and copper
(Cu) and water. The plant supplies nutrients for the fungus in exchange

Classification of Mycorrhizae
The mycorrhizal classification is mainly based on the interrelationship between
plant root cells and fungal hyphae. They are classified into two common groups,
which is endo mycorrhizae and ecto mycorrhizae

On the outer surface of the plant roots, ectomycorrhiza forms a compact mantel
of hyphae, but do not penetrate the plant root cells. They form structures with
the cortical cells, growing intercellular at the same time which enables the
fungus to be in direct contact with the plant .Even though there are many types
of endomycorrhizae, the most commonly known endomycorrhizae is Vesicular-
arbuscular mycorrhiza (VAM), ericoid and orchid mycorrhiza. VAM fungi
being the most abundant are at present classified as a separate phylum,
Glomeromycota. They belong mainly to four genera, Acaulospora, Gigaspora,
Glomus and Sclerocystis

The VAM is characterized by the formation of (i) intracellular structures within

the cortex cells, (ii) intercellular hyphae in the cortex, and (iii) a mycelium that
extends well into the surrounding soil. They are obligate symbionts with limited
saprophytic ability. They depend on plants for their carbon nutrition . VAM
fungi are capable of symbiotic association with most terrestrial plants and play
an important role in supplying the plant with P, S, N, and various other
micronutrients from the soil. VAM fungi mobilize N and P from organic
polymers, release mineral nutrients from insoluble particulate matter, and
mediate plant responses to stress factors and resistance to plant pathogens. The
hyphae of these fungi can access soil pores that are inaccessible to plant roots.
They also have positive interactions with various microorganisms promoting
two-way transfer of resources. Endomycorrhizae helps plants by improving the
absorption of plant nutrients and water, minimizing environmental stresses, and
improving overall plant growth .Numerous studies have shown advantages for
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land reclamation plants, landscape installations, home planting, fruit and

vegetable crop producers, and greenhouse/nursery crop growers. These benefits
can improve plant production efficiencies and decrease the cost of plant
production for growers.

Endo mycorrhizae penetration into the roots

Importance in Agriculture

 Mycorrhiza apart from providing nutrients to the plants also contributes

to soil health and other benefits which include  The threads of
mycorrhizal fungi, or filaments, facilitate drought tolerance in the partner
plant by improving the soil's water-holding ability.
 The fungi specifically exclude the passive absorption of toxic
components that restrict the sensitivity of the partner plant to heavy
metals, such as lead & cadmium.
 Mycorrhizal fungi degrade and absorb nutrients from primary rock
surfaces at high latitudes, high altitudes and other rocky conditions. 
 Mycorrhizal fungi can also protect plants both directly and by fostering
plant vigour against pests, such as nematodes, and diseases.
 The fungi may shield their partner plants against high salt concentrations
in saline soil.
 The filaments' outer walls produce gluey compounds that cause fine earth
particles to clump together, forming soil structure and make the soil less
susceptible to erosion In addition to plant growth promotion, by fixing
more carbon in the vegetation, mycorrhizal fungi may also contribute
directly or indirectly to the stabilisation of soil carbon.
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 First, the filaments of fungi have a portion rich in carbon that can remain
for decades in the soil. Second, it provides the first step in transforming
plant waste into stable soil carbon for other soil fungi.

Advantages of Mycorrhizal Application

 A single treatment can last for the whole lifetime of the plant
 Minimizes the fertiliser use, watering costs and plantation management
costs.
 It is compatible with herbicides and insecticides that are commonly used.
 Mycorrhizal plants exploit nutrient sources in the soil at maximum
making it a sustainable approach of cultivation and production systems
while using the minimum of agrochemicals.
 Artificial inoculation with mycorrhizal fungi brings mycorrhiza to new
planted plants and trees helping them in their establishment, growth and
survival rate

QUESTIONS:

0.5 MARKS
1. The substance produced by the mycorrhizae is called as GLOMALIN
2. The insoluble form of phosphorus in calcareous soil is octa calcium
phosphate
3. Mineralization occurs when the C:P ratio is less than 300:1
4. Immobilization occurs during intial stage of decomposition
5.VAM is the example of endo mycorrhiza
1 marks
1. Define mycorrhiza
2. How the mycorrhiza improves the soil stability?
3. List out the types of mycorrhiza with examples
4. List out the transformations of P in soil
5. List out the forms of P with examples

3 marks

1. Write briefly on the transformation of P in soil

2. How the mycorrhiza helps the farmer to increase the yield?
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3. Among different micro organisms mycorrhiza gets more advantages

over others. Justify it with the explanation