SOURCES, FORMS,

TRANSFORMATIONS AND
AVAILABILITY OF
NUTRIENTS
SOURCES, FORMS, TRANSFORMATIONS
AND AVAILABILITY OF NUTRIENTS
A.Nitrogen
1. Sources
 Air = 78% N2 = 3.8 x 1015 tons
 Lithosphere = 18 x 1015 (fixed in rocks and
sediments)
(atmosphere over 1 ha = 75,000 tons N2
 Mineral = saltpeter (KNO3), rainwater
(NO3, NO2-, Nitrous oxide, N2O, NH3)
 Irrigation water
2.Forms
 Organic
amino acids (30-50% N)
amino sugars (5-10% N)
soil OM – 5% N, if OM = 3%
1 HFS = 2 x 106 kg
.03 x 2 x 106 kg = 60,000 kg OM/HFS
.05 x 60,000 kg = 3,000 kg N/HFS

 Inorganic
NH4+
NO3- Available forms
NH3
mineralization rate: 2% /yr/ha
3,000 kg x .02 = 60 kg N
N must be combined with H or O to be reactive
N as NH4+ is easily fixed in clays.
NO3 – N moves more easily in the soil.

1.Nitrogen was discovered in 1772 by D.

Rutherford of Britain but was given the name
Azote (“without life”) by Antoin Laurent Lavoiser
(Azobacter is a N-fixing bacterium).
2. Oxidation is addition of O2 and also removal of
electrons. As an NH4 or amino (-NH2)
compound, N is highly reduced.
3. Sources of N
a. Atmosphere (ultimate source) – 78% N
b. Symbiotic and non-symbiotic BNF
c. Chilean nitrate
d. NO3- from electrical discharge
e. Industrial fixation (Haber-Bosch process)
f. Organic matter
4.BNF organisms
a. Azobacter
b. Azospirillum
c. Rhizobium
d. Actinomycetes, Frankia
e. Blue-green algae, Anabaena
5. 10 – 20% of NO3- in rainfall is due to
lightning. The rest from industrial waste
gases. Total N from rainfall 1 – 50 lb/A/yr.
6. Industrial fixation of N (Haber-Bosch
process)

catalyst
3 H2 + N2 2 NH3
1200ºC
500 atm
Chemistry of Nitrogen
N – non metal common in living organisms
N – has 5 outer electrons. Combines readily with
C compounds in living organisms. It is found as
two atom diatomic molecule, N2 like H2.

Ions electron pair

3 unpaired electrons available for bonding

In the simplest N compound, NH3 the 3 bonding
electrons are paired with one electron from a H
atom.

Tetrahedron arrangement
NH3 is dipolar
The 3 unpaired electrons can share electrons with
another N atom to produce the N Ξ N molecule.
This triple bond is strong making N2 an unreactive
molecule.

H
N + N
+ H
H H H
H H
PROTON

NH3 + H+ NH4+
7.Forms of soil N

Total N = 0.02 – 0.4%

organic N = 95% of total N in surface soil

inorganic N:

NH4+, NO3-, NO2 – most important

and 2 – 5% of total soil N.

The rest is N2O (nitrous oxide), NO

(nitric oxide) and N2.
Organic N:
Protein, amino acids, amino sugars,
nitrosamins, purines and pyrimidine derivatives
8.Forms of N absorbed by plants

NH4+ and NO3-

NO3- is more abundant in aerobic soils.
Most plants absorb both.
NH4+ abundant in reduced layer of paddy
soils.
Some plants, e.g., tobacco, potato, tomato
prefer high NO3-/NH4+ ratio. At low pH
NO3- uptake is high. Roots release HO3-
and maintain electroneutrality in the plant
and in the soil solution
NH4+ is the preferred source since NO3- reduction
for protein synthesis needs 2 NADH per NO3-
reduced. At low pH NH4+ uptake is low and high
at neutral pH.
NH4+ uptake reduces Ca, Mg, K uptake but
increases uptake of H2PO4-, SO4-, and Cl-. High
levels of NH4+ are toxic to plants but high NO3-
more tolerated by plants.
Uptake of NH4+ lowers rhizosphere pH because of
H+ exudation by roots.
 N Transformations

1. Mineralization

organic N NH4+

Aminization, ammonification by
heterotrophs (need organic C as source of
energy)
a. Aminization

H2O NH2 NH2

PROTEINS R – C – COOH + R – NH2 + C = O + CO2 + ENERGY
Bacteria
fungi H NH2
AMINO ACID AMINES

b. Ammonification

R – NH2 + H2O NH3 + R – OH + ENERGY

+ H2O

NH4+ + OH-
Fate of NH4+
1. Nitrified
2. Absorbed by plants
3. Used by organisms for further decomposition
of OM
4. Fixed by clays
5. Released to atmosphere as N2
Amount of N mineralized
if OM = 4%; % N in OM = 5%
mineralization rate = 2% per season
(2 x 106 kg) (0.04) = 80,000 kg OM/ha
(80,000) (0.05) = 4,000 kg N/ha
(4,000) (0.02) = 80 kg N/ha mineralized
 2. Nitrification
2 NH4+ + 3 O2 2 NO2- + 2 H2O + 4 H+
nitrosomonas

2 NO2- + O2 2 NO3-
nitrobacter

Nitrosomonas are obligate Autotrophs and get

energy from oxidation of N and C from CO2. NO2-
is toxic to plant roots but do no accumulate
because NO2- NO3- is faster than NH4+ NO2-.
1 mole of NH4+ produces 2 moles H+ thus causing
acidification.
3. NH4+ fixation
Vermiculite and illite can fix NH4+. Fixed
NH4+ can be replaced (and released) by Ca, Mg,
Na & H but not by K.
Presence of K+ restricts NH4+ fixation due to
competition for fixation sites.
4. Gaseous loss of N
a. Denitrification
+ 4H + 2H + 2H
2 HNO3 2 HNO2 2 NO N2O
-2 H2O -2 H2O - H2O

+2H
N2O N2
-H2O
Denitrification
5.Total worldwide BNF:
17.2 x 107 tons/year
Crops:
food legumes
cowpea: 90 kg N/ha
soybean: 100 kg N/ha
peanut: 42 kg N/ha

trees
ipil-ipil
acacia
kakawate (Glyricidia sepium)
pasture
stylosanthes
sesbania
crotolaria

azolla
450 – 600 kg N/ha/year
doubling time: 5 – 7 days
6. Factors affecting BNF by rhizobia
a. Soil pH
b. Concentration of NO3, NH4, NO2, urea
c. Ca, P, K, Co, Mo (enhance fixation)
Schematic diagram of the nitrogen cycle
Phosphorus
Sources, transformations and availability
1.Composition of earth’s crust:
% P = 0.11
2.Total soil P (organic and inorganic)
0.02 – 0.15%
3. Forms of organic P (20-25% of total P)
a.Phytin and phytin derivatives
Phytin occurs as hexaphosphoric ester of
inositol and is formed mainly in seeds.
P

OH

P – O – HC CH – O – P

P – O – HC CH – O – P

OH
O

P
b.N or oleic acids – complex N-P carbohydrate
compounds found in association with cell
nucleus (e.g., RNA, DNA)
c. Phospholipids – combination of phosphoric acid
and glycerol (e.g., lecithin)
Availability
Organic P becomes available through
decomposition by microorganisms and like N can
also become immobilized by utilization of
microorganisms.
immobilization
Organic P H2PO4, HPO4
mineralization

Phytin is rendered insoluble in acid soils by

formation of Fe and Al phytates.
Nucleic acids can be fixed by clay, especially
montmorillonite.
4.Forms of inorganic P
a. Hyroxyapatite – Ca10(PO4)6OH2
b. Fluorapatite – CA10(PO4)6F3
c. Monocalcium phosphate – Ca(H2PO4)2
d. Dicalcium phosphate – CaHPO4
e. Tricalcium phosphate – Ca3(PO4)2
 f. Variscite – AlPO4 · 2H2O
g. Strengite – FePO4 · 2H2O

5. Conditions of occurrence:

acid soils: Fe and Al-phosphates

alkaline soils: Ca-phosphates

6. P fractions in the soil
P in the soil may be grouped into 3 fractions:
solution P, labile P, non-labile P
Non-occluded P – easily to slowly available P
Occluded P – difficulty available P
Solution P is in rapid equilibrium with labile
P. As solution P is absorbed by plants or
leached out, it is quickly replenished by the
labile P.

7.Phosphorus adsorption and fixation

These are mechanisms/processes that
render P less available or insoluble.
a.Precipitation by Fe, Al and Mn ions
In acid soils high amounts of Fe, Al and Mn
may be present in soil solution or in
exchangeable forms. They can react with
H2PO4 and form insoluble compounds as
follows:

Al 3+ + H2PO4 Al(H2O)3(OH)2H2PO4
Exchangeable Al Complex dihydroxy Al phosphate
b.Flooding
Available soil P increases upon flooding (as in
paddy soils) due to conversion of Fe3+
phosphate to the more soluble Fe2+ phosphate
and hydrolysis of Al phosphate.
Other mechnisms are:

1.Dissolution of occluded P
2.Hydrolysis of Fe phosphate
3.Increased mineralization of organic P in acid
soils.
4.Increased solubility of Ca phosphate in
calcareous soils.
Soil Potassium
1.Availability
 K in most soils is large, 1.9%.
 Generally low in sandy soils.
 Availability of K in minerals:
biotite > muscovite > K-feldspars
2.Available amount from different forms:
• Mineral K: 5,000 – 25,000 ppm
• Non-exchangeable (fixed or difficulty
available): 50 – 750 ppm
• Exchangeable: 40 – 600 ppm
• Solution K: 1 – 10 ppm

3.Equilibria and cycling of K in soils

• Fixed K is mainly in clay minerals like illite,
vermiculite and chlorite.
• Felspars and micas are very resistant to
weathering.
 Unavailable K – 90 – 98% of total soil K
Slowly available K – 1 – 10%
Readily available K – 0.1 – 2%
4. Estimate of K availability

(aK)
ARK =
aCa + Mg

Where:
AR+ = activity ratio of K
aK = activity of K
aCa + Mg = activity of Ca and Mg
5.Absorption mechanism
Diffusion accounts for 88 – 96% of K
absorption by roots.

6.Fixation of K
2:1 clays like illite has high K fixing capacity.
Kaolinite, 1:1 type does not fix K. NH4+ has
about the same ionic size as K and thus fixed in
similar manner.
CALCIUM: Sources and Tranformation
1.Ca content of earth’s crust = 3.64%
2. Inorganic sources:
a. Calcite – CaCO3
b. Dolomite – CaCO3·MgCO3
c. Apatites and Ca-phosphate (Hydroxyapatite,
fluorapatite)
d. Feldspars (e.g. anorthite, CaAl3Si2O8)
e. Pyroxenes and amphiboles
Hornblende – H2Ca2Na(Mg, Fe)4·(Al, Fe, Ti)3
Augite – Ca(Mg,Fe,Al)(Al,SiO2O6)
f. Gypsum – CaSo4·2H2O
3. Ca content of soils
Very low in excessively leached soils but may
range from 10-20% in limestone derived soils.
Soils of humid regions are low in Ca. Soils of
arid regions have high Ca due to low rainfall and
less leaching.
4.Fate of Ca in soils
1. leached through drainage
2. absorbed by microorganisms
3. adsorbed by clay particles and organic colloids
4. reprecipitated as secondary Ca compound
MAGNESIUM: Sources and Transformations
1.Content of earth’s crust, 2.07%
2.Content in soils
0.05% - sandy soils
5% - clay soils
Podzols and laterites (highly leached) – low
in Mg
3.Inorganic sources
a. Ferromagnesian minerals
biotite – H2 K(Mg,Fe)3Al(SiO4)3
 serpentine - Mg6 Si4 O/O (OH)8
hornblende – H2Ca2Na(Fe,Mg)4·(Al,Fe,Ti)3
Olivine – (Mg,Fe)2 SiO4
b.Secondary clay minerals
montmorillonite
vermiculite
illite
chlorite
c. Dolomite – CaCO3·MgCO3
MgSO4
Transformations of Sulfur
• 0.06% of earth’s crust
Sources
a. Original sources sulfides in metals
contained in plutonic rocks
b. Organic matter (S-containing amino acids)
c. Ca, Mg, Na, K, NH4 sulfates (in arid areas)
d. Atmosphere, as sulfur dioxide (SO2)
especially as pollutants of industrial
processes e.g., ore smelting, petroleum
refining.
 e. Sulfides in small amounts (in waterlogged
soils) – H2S
f. Pyrites – FeS2
g. Gypsum

1. Organic sulfur
C:N:S of Scottish calcareous soils = 113:10:1.3
N:S of Australian soils = 10:1.21 to 10:1.52
 S is immobilized in soil if N:S is too wide.
Hence, if straw with wide N:S ratio is to be
incorporated into the soil, S must be added
(possibly by using (NH4)2SO4) as source of N and
S.

-Drying of soil enhances mineralization of S

-SO4 = is easily lost by leaching due to its organic
nature. Experiments showed that 77-78% of
applied sulfur (as gypsum) is leached.
Fe Sources and Transformations/Availability
1.Earth’s crust – 5% Fe
2.Total content of soils – 200 ppm – 100,000 ppm
3.Toxic level of available Fe – 300 ppm
4.Sources
a. Ferromagnesian minerals
• Olivine – (Mg,Fe)2SiO4
• Augite – Ca(Mg,Fe,Al)(Al,Si)2O6
• Hornblende – NaCa2(Mg,Fe,Mn)5(Al,Si)8
O22(OH)2
• Biotite – K(Mg,Fe)3AlSi3O10(OH,Fe)2
 b. Haematite – Fe2O3
c. Ilmenite – FeTiO3
d. Magnetite – FeCO3
e. Siderite – FeCO3
f. Goethite (limonite) – FeO(OH)
5.Solubility/availability
a. Soluble forms:
Fe2+, Fe3+, Fe(OH)2+, FeOH2+
 b. Precipitation reaction:
Fe3+ + OH Fe(OH)3
ppt
low pH acid soils High pH calcareous soil

c. Fe in paddy soils (anaerobic condition)

Fe3+ Fe2+

oxidized state anaerobic condition

-When high S is present FeS2 precipitate is formed

-Fe reduction is hastened by the presence of OM and
time of submergence
d. Effect of bicarbonate, P and Ca, Cu and Mn
HCO3-, P and Ca, Cu and Mn causes
precipitation or on/in the plant and causes iron
chlorosis in soybeans. In paddy soils where Fe is
present in toxic amounts MnO2 addition can
correct toxicity.
BORON: Sources, Transformations/Availability

1.Content in soils: 7-80 ppm (H3BO3 as borate or

boric acid)
2.Content in rocks
shale – 100 ppm granite – 15 ppm
3. Sources
a. Tourmaline
(Li,Na,Mg,Fe)7Al6B3-Si6O27(OH)4

A flourine borosilicate mineral which is

very resistant to weathering.

b. Kernite – Na2B4O7·4H2O
 MOLYBDENUM – Sources and
Transformations/Availability
1.Content in soils
Total: 0.6 – 3.5 ppm
Soil solution: 2 x 10-8 – 8 x 10-8 M
2.Sources
a. Minerals
b. MoS2 – molybdenite (under reduced conditions)
c. Ca – molybdate
d. Hydrated Mo oxides
e. Mo in association with Fe oxide minerals in
adsorbed occulded or semi-cystalline forms.
Zn – Sources and Transformation/Availability
1.Soil content: 10-300 ppm (total)
3 x 10-8 – 3 x 10-6 M (soil solution)
2.Sources
a. Ferromagnesian minerals

augite, hornblende, biotite (Zn

substitutes for Fe and Mn which have about
the same ionic radius as Zn, by isomorphous
replacement.
b. Salts
1. ZnS
2. Sphalerite – (ZnFe)S
3. Zincite – ZnO
4. Smithsonite – ZnCO3

c. Zn silicates
1. ZnSiO3
2. Willemite – Zn2SiO4
3. Factors affecting availability
a. Soil pH
Increasing pH (6-8) reduce availability
(but Zn deficency does not occur in all
alkaline soils).
b. Soil P level
High P presumably causes Zn-P
precipitation but this is still not very clear.
Nevertheless at pH 6.5-8.5, high P level
caused decrease in Zn uptake.
c. Organic matter
Zn forms organic complexes with OM
forming both soluble and insoluble
complexes. Soluble complexes are
associated with amino acids and fulvic
acids while insoluble complexes are
associated with humic acids.
d. Clay minerals
The longer the zinc remains adsorbed
on the clay surface the less available it
becomes. This happens when adsorbed
Zn enters the crystal lattice of octahedral
layers and substitutes for Al3+
e. Carbonates of Ca and Mg
Zn is strongly adsorbed by magnesite
(MgCO3) to a lesser degree by dolomite
(Ca,Mg)(CO3)2 and least degree by calcite
(CaCO3). Zn presumably substitute for Mg
in the crystal lattice.
Cu – Sources and Transformations/Availability
1.Content in soils
Total: 5 – 50 ppm
Soil solution:
1 x 10-8 – 60 x 10-8 M
2. Sources
a. In crystal lattices of primary and
secondary minerals
Chalcopyrite – CuFeS2
Malachite – Cu2CO3(OH)2
b. Organic compounds
Mn – Sources and Transformation/Availability
1.Sources
a. Pyrolusite – MnO2
b. Manganite – MnO(OH)
2.Content in soils
200 – 300 ppm (total)
10-6 – 10-4 M (in soil solution)
3. Forms and availability

Thus, the availability of Mn is governed chiefly

by oxidation-reduction reactions/processes.
THE END