Chemistry of N, P K Ca, Mg, S and Micronutrients

N- Transformation in soils

N- Availability in soil.

 Dynamics and transformation of nitrogen in soil is very important with respect to plant

nutrition. A bulk of total N is present in the organic form (98%) and only about 2% in

inorganic form. However there are continuous transformations between these two pools. The

crops utilize nitrogen in the inorganic forms only such as NO3-N and NH4-N. The inorganic

form of N is also liable to undergo different types of loses like runoff, ammonia volatilization,

leaching, denitrification and fixation by clay minerals.

Nitrogen Cycle in soil

 The cycling of N in the soil – plant – atmosphere system involves many transformations of N

between inorganic and organic forms.

N transformations in aerobic soils

 In aerobic soils, NO3-N is the dominant form of available N. The

mineralization/transformation of added or native organic matter in soil proceeds up to

nitrification stage and giving predominantly NO3-N and small amount of NH4-N. There is a

quick transformation of NH4+ to NO3-N in the aerobic soils occur which will be utilized by

plants.

 Any fertilizer containing ammonium nitrogen when added to soil gets dissociated to NH4+

which readily gets oxidized to NO3- ion which is either taken up by the crop or leaches down

to the lower horizon as it is readily soluble in water. Some amount of NO3-N is also

immobilized by soil microbes during the process of mineralization of organic matter.

 The organic form of N, particularly hydrolyzable form is slowly mineralized and is

transformed to mineral nitrogen through following process

a. Amminization

b. Ammonification.

c. Nitrification

d. Denitrification

Nitrogen mineralization

 Mineralization is the conversation of organic N to inorganic forms of N as a result of

microbial decomposition. Mineralization increases with a rise in temperature and is enhanced

by adequate, soil moisture and a good supply of O2. Mineralization of organic N involves in

two reactions.

Aminization

 Aminization is the decomposition of proteins and the release of amines, amino acids and urea.

A large number of soil microorganisms bring about this change.

 Under aerobic condition the major end products are CO2, (NH4)2 SO4 and H2O. Under

anaerobic conditions the end products are ammonia, amides, CO2 and H2S.

 The organic compounds and proteins are mainly decomposed by various species of

Pseudomonas, Bacilli, clostridium, serrotia, Micrococcus.

 Conversion of urea

 Urea is a product of aminization. The hydrolysis of urea by the action of urease enzyme is

effected by Bacilli micrococcus, Pseudomonas, clostridium, Acromobactor and coryne bactor.

Co (NH2) + H+ + 2H2O--------------> 2NH4+ + HCO3-

NH4+ ----------------->NH3 + H+

2NH3 + H2 CO3 ----------------------->(NH4)2 CO3 -------------------->NH4+ + CO3-

 The optimum water holding capacity for these reactions is 50 – 75% and optimum

temperature is 30 – 50°C.

Ammonification

“Amines and Amino acids produced during aminization of organic N are decomposed by

other heterotrophs with release of NH4+ is termed Ammonifcation

Nitrification
 Nitrification is the process of biological oxidation by which the ammonical (NH4+) form of N

converts to nitrate (NO3-) form of N. There are two steps.

(a) NH4 is converted first to NO2- and then to NO3-.

Nitrosomonas
2NH4 + 3O2 ------------------------->2 NO2- + 2 H2O + 4 H+

(b) In the second reaction NO2- is further oxidized to NO3- by nitrobactor

Nitrobactor
2 NO2- + O2 -------------------------->2 NO3-.

Nitrosomonas are obligate autotropic bacteria that obtain their energy from

the oxidations of N and their C from CO2.

Denitrification

 Denitrification is the biochemical reduction of NO 3-N or NO2-N to gaseous N forms, either as

molecular Nitrogen or an oxide of Nitrogen. The most probable bio chemical pathway is
NO3-----------------> NO2 ---------------------->NO---------------------
>N2O-----------------------------> N2

Nitrate Nitrite Nitrogen Nitrous monoxide Nitrous oxide Dinitrogen

This is loss mechanism of nitrogen happening in anaerobic soil conditions.

Nitrogen immobilization

 “Immobilisation is the process of conversion of inorganic N (NH4+ or NO3-) to organic N

and it is basically the reverse of N mineralization”. By this process plant available N forms are

converted to unavailable organic forms. The Microorganisms accumulate NH4- N and NO3-
 N in the form of protein, nucleic acid and other complexes. If C:N ratio is wider than 30, it

favors immobilization and lesser C:N ratio encourage mineralization.

Losses of Nitrogen

 The major losses of N from the soil are due to (1) crop removal and leaching, however under

certain conditions inorganic N ions can be converted to gases and lost to the atmosphere. The

primary pathway of gaseous N losses are

1.Denitrification

2. NH3 volatilization.

Nitrogen fixation

 The conversation of atmospheric nitrogen to plant available forms readily usable by biological

process mediated by microorganisms. .

Nitrogen Transformation in anaerobic soils

 The N-transformations from added or native sources stops at NH 4+ stage, since nitrification is

not possible due to lack of oxygen. When NH 4+-N containing fertilizers are added to soil, then

NH4+ is oxidized to NO3- in the top layer (aerobic) of flood water or oxidized layer and later

which moves down to reduced layer. On the reduced layer NH 4+-N remains as NH4-N only for

plant uptake. If NO3-N exists, then it moves down to the reduced layer, where it undergoes

denitrification by bacteria (NO3-NO2-N2). The denitrified NO3- is lost from the soil to the

atmosphere in the form of N2O or N2.

 If NH4+ ions present in the flood water it is subjected to volatilization to atmosphere as

NH3 (ammonia gas) because of higher partial presence of CO 2 and high pH value developed
 due to alkalinity. Therefore, there is an accumulation of NH 4+ ions in the reduced layer, which

is either absorbed by root or gets oxidized in the rhizosphere to NO 3- ions and are lost due to

dentrification. Some of the NH 4+ and NO3- ions also get immobilized by the soil microbes &

some NH4+ may get fixed by the clay lattice.

Phosphorus

P cycle-

 In P cycle the phosphorus is not involved in any exchange process with the atmosphere. The

amount of dissolved or solution P mostly H 2PO4- and HPO42- ions in the soil is very small and

crops will utilize P from this source. The soil solution P can come from mineralization of

organic matter, added fertilizers, adsorbed phosphate ions and solid P compounds (primary &

secondary minerals).

 Any P present in solution P form and it is available to plants is called Labile P, where as any P

which is bounded in solid P compounds such as primary and secondary minerals is called Non

Labile P which is not available to plants.

P- Transformation in aerobic soils:

 P transformation depends on their solubility, interaction with other soil components. When a

water soluble phosphate fertilizer, such as super phosphate is applied to a soil, P dissolves

immediately and enters the soil solution and readily forms new compounds with Ca as Ca-

PO4 and carbonates of hydroxyapatite in calcareous and alkaline soils respectively. While in

acid soils rich in Al, Mn and Fe, applied P is converted as Al-PO 4 , Mn –PO4 and Fe-
 PO4 which are are precipitated as newly formed insoluble compounds and thus reduce the

availability of P to crops.

P Transformation in Anaerobic soils:

 Submerged or flooded conditions/soils create reduced conditions (anaerobic soil) which lead

to reduction of Ferric-PO4 to ferrous PO4 resulting in greater availability of P in the reduced

soil. Organic acids formed under submerged conditions also solubilize PO4 there by P is

available to plants.

K- Availability in soil

 Potassum is present in soil solution as K+ ion which is readily available to plants. But

this form is in dynamic equilibrium with exchangeable K which intern with fixed K.

Fixed K is in equilibrium with mineral K. The available K is the solution-K and

Exchangeable K which can be easily absorbed by plants.

K Cycle

K- Transformations in soil:

 When potassic fertilizers are added to the soil, K may either remain in soil solution or

in exchangeable form on the clay surface or in non-exchangeable form held by illitic

clay minerals as fixed K which is not available to plants directly. Plants get K mainly

from solution-K and exchangeable-K form. As and when the exchangeable K fraction

is depleted form the soil substantially or exhausted by crop uptake, the non
 exchangeable form of K replenishes the exchangeable K and supply of K to plants is

maintained and equilibrium is attained. The reserve source of K is mineral lattice K

which undergoes weathering and releases K to soil. In all these transformations some

sort of equilibrium is maintained always in soil among different forms of K thereby

plants get continuous supply of K.

Ca &Mg availability in soils:

 Ca and Mg are the most abundant cations occupying the exchange sites of the soil

colloids of both inorganic (clay) and organic (humus). Soil Ca and Mg mainly come

from the weathering of rocks and minerals (Calcite and Apatite (Ca 5PO4)). Thus most

soils contain enough Ca and Mg except highly weathered leached acid soils and alkali

soils. Deficiencies of Ca and Mg most commonly occur in coarse textured soils, acidic

soils of high rainfall area due to leaching losses. In soil solution occurs as cations and

also adsorbed cation on the clay and humus surfaces and involved in exchange

process. The critical limits of exchangeable Ca and Mg vary widely among soils.

However average value of <2.0 m.eq/100g for exchangeable Ca and < 0.5 m.eq/ 100g

for exchangeable Mg are considered critical limits for availability.

 Ca & Mg Transformations:

 Ca and Mg occupying the exchange sites of the soil colloids (clay & humus) are

subjected to cation exchange reactions with other monovalent and divalent cations

then released into soil solution for plants absorption or adsorbed on the clay and

organic matter surfaces. Soils usually contain less Mg than Ca because Mg 2+ ions are

not adsorbed as strongly by clay and organic matter as Ca 2+ ions and further Mg2+ ions

are more susceptible to leaching than Ca2+ions. The solution Ca and Mg is subjected to

leaching/erosion losses and crop uptake, thus it may deplete the Ca and Mg content

soil.
S-Transformations In aerobic soil
 The sulphur in soil is being cycled continuously between inorganic and organic forms

just like Nitrogen. The nature of compounds formed and their transformations are

influenced by the biologically mediated process. Organic matter is the major of source

of S, it undergoes oxidation to SO42- . This is brought about by autotrophic bacteria

belonging to the genus Thiobacillus under aerobic conditions of soil.

Aeration (O2)
Organic S ---------------------------> SO42- + H+

(Proteins, Amino acids).

 The released SO42- ion is taken up by plants and microorganisms. The rate of

mineralization is affected by factors such as moisture (60% field capacity), aeration,

temperature (35-40oC) and Soil pH.

In anaerobic soil

 Under anaerobic conditions or flooded soils, the soil aeration is completely cut off.

The SO42- ion is reduced to sulphides (S2-) by the autotrophic bacteria such as

Desulpho vibrio and Desulpho maculans which use SO42- for their O2 requirements.

 SO42- + 8 H+ + 8e- = S2- + 4H2O.

 Micro or trace elements in soil are derived from the parent materials and
natural deposition from the atmosphere, organic manures and fertilizers. Trace
elements are largely bound in mineral lattices, to be released by weathering.
Iron, Cu, Mn, Zn, Co, Mo, Ni and Cr occur in ferromagnesian minerals
common in ultrabasic and basic igneous rock.

 The total content of Fe, Mn, Zn, Cu, Co, Cl & B varies considerably in

different soils. Except Zn, Cu and B, all other micronutrients (Fe, Mn, Cl, Mo)

are present in Indian soils in sufficient amounts to sustain agricultural

productivity. Zn and Boron deficiency is found in all the soils of agro

ecological regions of the country. The availability of micronutrient cations in

soil is highly affected by inorganic ions in soil solution, soil solid constituents

like free oxides of Fe & Al, soil organic matter, fertilizers and amendments

applied to soil