Documente Academic
Documente Profesional
Documente Cultură
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In the following sections the discussion will be made for a selected number of
elements usually found in soils not in order of merit for their importance to plant nutrition but
in order of merit for their abundance in most soils.
1.7.1. Silicon
The silicon content, expressed as percentage of SiO2, ranges from 50 to 70% of many
soils, which averages about the same as for the earths crust. In sandy soils, the SiO2 content
rises as in sandstone. The silicon percentage is decreased with the increases of organic matter
in organic soils and with the increase of CaCO3 as in marl.
Silicon is gradually lost from many soils especially in humid tropical soils which have
been subjected to intensive weathering and leaching. It can be clearly seen in the following
table.
Table 1.2. Comparisons between the chemical compositions of lateritic soil and black
cotton soil
Lateritic Soil Black cotton soil
(top layer) (Mandalay Soil)
%
SiO2 20.33 69.76
Al2O3 11.68 10.45
Fe2O3 41.60 4.48
CaO 0.59 1.38
MgO 0.88 1.0
K2O 0.90 0.71
Na2O 0.29 0.28
P2O5 0.21 0.05
SO3 0.24 0.20
Soil organic matter 5.00 0.75
1.7.2. Aluminum
After oxygen and silicon, aluminum is the most abundant element in the earths crust
and in the majority of rocks and soils. The aluminum content of soils, expressed on the basis
of Al2O3, frequently is in the range of 2 to 12%. The content ranges up to 20 to 60 percent in
the highly weathered soils and laterites. These examples are extreme and should not be taken
as a measure of the majority of the soils of the humid tropics. Aluminum occurs mainly in the
aluminosilicate minerals, feldspars, amphiboles, pyroxene, and layer silicates.
As silicon is depleted and aluminum is enriched, the molar ratio, SiO2/Al2O3 in soil
colloids falls from over 4 in colloids high in layer silicate to less than 1 in colloids high in
allophone.
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1.7.3. Iron
The iron content, expressed as percentages of Fe2O3, make up 1 to 6 percent of many
soils, which is comparable to the composition in the earths crust (about 7%) and the
composition in various rocks (1 to 7 percent). Iron is subject to increase in concentration
through soil development processes, as reflected by contents of 10 to 15 percent in many soil
colloids. In latosols and laterites, the Fe2O3content is frequently 20 to 80 percent. Soils
having the higher percentages are approaching the iron content of low-grade iron ore.
High stability of soil aggregates and high soil porosity are usually associated with
high iron oxide contents. Under poor drainage the iron becomes reduced and in the presence
of organic matter is frequently mobilized. It can be removed from the soil profile to a lower
position in the landscape, but frequently becomes concentrated as an iron-rich layer in the
lower portion of the soil profile.
The principle form of iron in soils is generally as hydrous oxides, but iron freely
enters the 2:1 and 2:2 layer silicate structures of soils, including biotite, vermiculite and
montmorillonite. Smaller percentages of iron occur in soils as pyroxene and amphiboles.
1.7.4. Titanium
The titanium content, expressed as TiO2, makes up 0.2 to 1 percent in many soils of
temperate regions. This value is similar to the range for sedimentary and igneous rocks.
The titanium of soils occurs primarily as fine grained crystals of free TiO2 (rutile and
anatase) and FeTiO3 (ilmonite). Since titanium oxide minerals are relatively resistant to
weathering the titanium content of soils tend to increase as other elements are leached away.
The TiO2 content of highly weathered soils tends to run 2 percent or more on a dry-soil basis.
That of laterites in various localities increases into the range of 5 to 20 percent or more,
approach the range of titanium ores. Not all latosols and laterites are extremely high in TiO2.
1.7.5. Calcium
The calcium content, expressed as CaO, is generally in the low ranges of about 1
percent in soils except when calcium occurs in carbonate or sulphate form. The content of
calcium in soils is thus low, compared to that in igneous and sedimentary rocks, the CaO
content of which averages about 5 percent. Limestone average 43 percent CaO. The decrease
reflects the fact that carbonates and sulphates of calcium leach readily from the upper
horizons of well drained soils except under arid climates.
Calcium carbonate occurs in many soils, in lower horizons. This form of calcium is
found in soil horizons at lesser depths as one transverse from more humid to more arid
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regions. The black earth soils of the world, including such broad groups as Chernozems and
Rendzinas in North and South Dakota, Texas, Alabama, South Africa, Central India, Russia
and Australia frequently contain 40 to 50 percent CaCO3 in the subsoil horizons. Younger
soils in the humid region may contain calcium carbonate, as calcite (CaCO3) or dolomite
(MgCO3CaCO3) inherited from the parent rock.
Pedogenic CaCO3 is mainly the mineral calcite, precipitated when leaching water
carries Ca(HCO3)2 downward to certain depth from which the water is removed by roots or is
evaporated. Crystalline gypsum (CaSO42H2O) also is accumulated in soils of semi-arid
regions. A few hundred parts of calcium phosphate per million of soil occur in nearly neutral
to calcareous soils.
1.7.6. Magnesium
In well-leached soils, magnesium is found chiefly in minerals, such as biotite, augite,
hornblende, and montmorillonite. The magnesium content of soils expressed as MgO
frequently is less than 1 percent in non-calcareous soils. Dolomite CaCO3MgCO3 and Mg
substituted calcite (Ca, Mg )CO3 occur in substantial quantities in some soils, inherited from
parent rocks. Soil contents of 2 percent or more of MgO in carbonate form occur in Brown,
Chestnut, and Chernozen soils of the semiarid parts of the world.
1.7.7. Potassium
The potassium content, expressed as K2O, ranges between 0.05 to 3.5 percent for
mineral soils. On a percentage basis, this is somewhat lower than the average content of
potassium in igneous rocks, but somewhat higher than that in some sedimentary rocks.
The proportion of the total potassium in soils held in soluble and exchangeable forms
is usually relatively small. The majority of it resides in potassium bearing feldspars and
micas. The high potassium primary silicate mineral are muscovite, biotite, orthoclase and
microcline; but other micas, feldspars, and other minerals may contain substantial amount of
potassium.
The chemical relationships between the various forms of soil potassium can be
expressed by the following equation.
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Because of equilibrium between primary mineral forms and exchangeable and water-
soluble potassium, plants can sometime survive on soils having primary minerals in fine
particle sizes as the sole source of potassium. Of the layer-silicate clays, only mica or illite
has a substantial potassium content. A very close correlation has been found between the
specific surface of mica in soils and potassium released for plant growth. In silt loam and
clay loam of the sub-humid region, the exchangeable potassium is kept at adequate levels by
weathering release of potassium. Intensive cropping and removal of potassium in the humid
region, on sandy soils generally, results in the development of stunted growth of plants
exhibiting potassium deficiency symptom. Application of water soluble forms of fertilizer
such as KCl and K2SO4 is necessary for intensive agriculture on such areas.
1.7.8. Sodium
The sodium content, expressed as Na2O, ranges from 0.1 to 1 percent of many soils.
This is much smaller than the average of 3.7 percent in the earth's crust. The Na2O content in
sedimentary rocks ranges from 1.3 percent in shale to 0.4 percent in sandstone and 0.05
percent in limestone. The decreases in Na2O content in soils and sedimentary rocks reflect
weathering away of sodium-bearing minerals. The high sodium content of ocean waters
reflects the leaching of sodium from soil minerals.
Sodium occurs as NaCl, Na2SO4 and sometimes as Na2CO3 and other soluble salts in
saline and alkaline-saline soils, soils in which, leaching has not been intensive enough to
remove the soluble salts. Sodic soils, containing exchangeable sodium on the order of
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15 percent or more of the cation-exchange capacity, tend to disperse and develop adverse
tillage properties.
1.7.9. Phosphorus
The phosphorus content of most mineral soils falls between 0.02 and 0.5 percent P, and
a general average of 0.05 percent (0.12 percent P2O5) frequently is representative of soils
compared to an average of 0.12 percent P in the earth's crust. About half the soil phosphorus
occurs in combination with organic matter of surface soils, and the remainder occurs in
mineral or inorganic combination.
Inorganic phosphorus occurs mainly as calcium phosphate in alkaline and calcareous
soils. The main calcium phosphate in soils is fluorapatite Ca10(PO4)6F2. As weathering
proceeds and the acidity develops in soils, the phosphate becomes increasingly bonded to
aluminum and iron ions released from silicate minerals by weathering.
Under reducing conditions, vivianite Fe3(PO4)28H2O forms in soils and being fairly
soluble, may be deposited in lower levels in the soil profile. Reduction of ferric ion renders
the oxides soluble and the phosphate becomes more available to plants, as to rice and paddy
culture. The phosphate which had been associated with iron may leach out of highly reduced
soils, while the relative amount of aluminum phosphate form increases in acid soils.
The solubility of phosphate from calcium aluminum and iron compounds are close to
each other in the soil pH range between pH 6 and 7. Below this pH range, the aluminum and
iron phosphate are more stable than calcium phosphate; above this range various calcium
phosphate are formed. The calcium formed include hydrooxy apatite [Ca10(PO4)6(OH)2],
dicalcium phosphate [CaHPO4] etc. Finely ground phosphate rock containing much
fluorapatite Ca10(PO4)6F2 is sometimes added to soils as an amendment. This phosphate in
acid soils is rapidly transformed into combination with aluminum and iron phosphate.
The rates of transformations of soil phosphates are very slow. Calcium phosphate is
highly unavailable at high soil pH values. Iron and aluminum phosphates of acid soils
become more available when the soil pH is raised by liming.
1.7.10. Molybdenum
The molybdenum content of soils generally ranges from 1 to 10 ppm but in certain soils
it may rise to 20 or 30 ppm or more. The element Mo occurs in soil mainly as MoO 4 ion and
undergoes fixation as basic iron and aluminum molybdates. The availability of soil
molybdenum rises with the rises in soil pH on liming. Plant deficiencies in Molybdenum
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occur in soils low in this element. Plant contents of Mo may become sufficiently high as to
become toxic to animals when level of available Mo in soil is high.
1.7.11. Nitrogen
The quantity of nitrogen in surface soils generally ranges from 0.02 to 0.25 percent. It is
closely related to the amount of soil organic matter which contains approximately 5 percent
nitrogen. The available forms of nitrogen for plant nutrition are nitrates, nitrites and
exchangeable ammonium and they make up less than 1 percent of total soil nitrogen content
of mineral soils.
An appreciable fraction of the nitrogen content of subsoil and rocks occur as NH4+ ions
substituting for K+ in micas. These NH4+ ions are released when mineral fractions are treated
with hydrofluoric acid.
1.7.12. Sulphur
Sulphur is present in soils in both inorganic and organic forms. In well-leached surface
soils, much of the sulphur is combined with organic matter. Soils of humid temperate region
have 50 to 500 ppm of water-soluble sulphates and 100 to 1500 ppm total sulphate. Soil high
in free iron oxides contains SO4 ions substituting for hydroxyl in basis sulphate complexes.
This form of sulphate is gradually extractable in NaOH solutions and forms a sulphur
reservoir of slowly available sulphate.
Crops remove 10 to 30 pounds of sulphur per acre per year, and 40 to 60 pounds of
sulphur per acre appear in the leachate of soils. Only a few area shows sulphur deficiency.
Sulphur is added to soils in rain and snowfall, amounting to as much as 30 pounds of sulphur
per acre in industrial and urban areas where coal, oil and gas are burned, and as little as 5
pounds in thinly populated areas. Sulphur is added to soils in many commercial fertilizers and
in irrigation waters.
1.7.13. Selenium
Selenium is found in trace amounts in most soils. But crops grown on soils which are
exceptionally high in selenium have an excessive selenium content. Under conditions of
limited rainfall, enough Se can be present in the crops grown on these soils to produce
vegetation toxic to livestock. Certain native plants are ''accumulators'' of Se. Analysis of then
may be used as a guide to soil areas of excess selenium supply.
The element Se behaves much like Se, oxidizing to selenite on weathering, being
subject to leaching, and combining with free iron oxides to form basic selenates.
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1.7.14. Boron
The total boron content of soils generally ranges from 4 to 98 ppm and may average
about 30 ppm. This is comparable to 10 ppm in igneous rocks and 4.5 ppm in sea water.
Sandy soils may contain as low as 2 to 6 ppm. The boron, soluble in 85 percent H3PO4 at
100C (The average is about 17 ppm) consists of that present in organic matter and associated
with layer silicates. Acid-soluble boron is associated with the mica fraction of sediments and
mica-derived clays of soils.
Plant availability of soil boron is most closely correlated with boiling water-soluble
boron which ranges from 0.2 to 1.5 ppm in soils of humid temperate regions. Soils of arid and
semiarid areas may contain 10 to 40 ppm. Extensive leaching of fine-textured desert soils
may be required to decrease the boron toxic levels before crop production under irrigation
can be carried out.
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CHAPTER 2
CHEMISTRY OF SOIL COLLOIDS
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formed by the resilication of aluminum oxide when silica rich water is present. Although
kaolinite is very stable, it can weather to form gibbsite, Al(OH)3.
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In addition to the fineness of the particle and their shape (i.e. plate-like structure), the
internal surface in some clay particle also play an important role in determining the reactive
surface area. The internal surface occurs between the plate-like crystal units that make up
each particle. It is illustrated in the following diagram.
Diagram 2.1. Silicate clay crystal with its sheet-like structure, its in-numerable negative
charges and its swarm of adsorbed cations and an enlarged schematic
view of the edge of the crystal illustrates the negatively charged internal
surface of this particular particle to which cations and water are attracted
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Diagram 2.5. Six silica tetrahedrons joined together to form a hexagonal ring by
sharing basal oxygen with each other.
Single Chain
All basal oxygen atoms of the silica tetrahedral layer are shared. The apical oxygens
of the layer are unshared and all point in the same direction. The layer has a net negative
charge and the formula is n(Si2O5).
Alumina octahedron
The alumina octahedron is an eight sided building block. It consists of a core
aluminum atom surrounded by six hydroxyls or oxygen (See Diagram 2.7.).
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NOTE:
x That the aluminum atom is larger than the silicon.
x That the interstice formed by an octahedron is larger than the interstice formed by a
tetrahedron.
x That the size of the interstice governs the kind of atoms that can exist in these structures.
(This will be further discussed in the origin of the negative charge of clay minerals.)
Adjacent aluminum octahedra share common hydroxyls to form an octahedral layer in
a manner comparable to the sharing of oxygen in the silica tetrahedral layer.
All of the hydroxyls are shared, giving the layer a neutral charge and the formula
Al(OH)3. This is the structure of the mineral gibbsite.
These two basic layers (i.e. Silica tetrahedron and alumina octahedron), in different
stacking arrangements and combinations, provide the fundamental structural units of silicate
clays. The layers are bound to each other within the clay crystals by shared oxygen atoms.
Isomorphous substitution
The silicon in the tetrahedral layer and the aluminum in the octahedral layer can be
replaced or substituted by other ions of comparable size. The atomic radii of a number of ions
common in clays are listed in Table 2.1 to illustrate this point.
Table 2.1. Ionic Radii of Elements Common in Silicate Clays and an Indication of
which are found in the Tetrahedral and Octahedral Layers.
Ion Radius (A) Found in
Si4+ 0.41
Silica Tetrahedra
Al3+ 0.50
Fe3+ 0.64
2+
Mg 0.65
Alumina Octahedra
Zn2+ 0.70
Fe2+ 0.75
Ca2+ 0.94
Na+ 0.98 Exchange sites
K+ 1.33
O 1.45 Both layers
An angstrom unit (A) is 10-8 centimetre.
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Note that aluminum is only slightly larger than silicon. Therefore aluminum can fit
into the centre of the tetrahedron in the place of the silicon atom. When some silicates form,
part of the silicon atoms in the layer are replaced by aluminum by a process called
isomorphous substitution. This substitution of a three-valent ion (Al3+) for one with four
valences (Si4+) results in one negative charge in a previously neutral silicate layer. The extent
of such substitution helps determine the net negative charge.
The Table 2.1 also shows that ions such as iron, zinc, and magnesium are not too
greatly different in size from aluminum. As a result these ions can fit in the place of
aluminum as the central ion in the units making up the octahedral layer. The isomorphous
substitution of the two-valent ion such as Mg2+ for three-valent Al3+ leaves unsatisfied
negative charges from the oxygen atoms in the layer. This type of substitution helps account
for the overall negative charge associated with several silicate clays.
1:1-type mineral
The crystal units of the 1:1-type minerals are made up of one silica (tetrahedral) layer
alternating with one alumina (octahedral) layer, hence, the terminology 1:1-type crystal
lattice (see Diagram 2.9).
In soils, kaolinite is the most prominent member of this group which includes
halloysite, anauxite, and dickite.
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Isomorphous substitution of magnesium for some of the aluminum in the octahedral
sheet and also the substitution of aluminum for silicon in the tetrahedral sheet provides
montmorillionite crystals with a high net negative charge. This charge is satisfied by a swarm
of cations (H+, Al3+, Ca2+, K+, etc.) which are attracted to both the external and internal
surfaces. Montmorillonite possesses a high cation adsorption capacity perhaps 10 15 times
of kaolinite.
Montmorillonite has high plasticity and cohesion. It also has a marked shrinkage on
drying. Wide cracks are formed when soils containing a high percentage of montmorillonite
are dried out. The dry aggregates or clods are very hard, making such soils difficult to till.
2:2-type mineral
The most important member of this silicate group is chlorites which are common in
some soils. Chlorites are basically silicates of magnesium with some iron and aluminum
present.
A typical chlorite crystal unit is composed of alternate tale (similar to a
montmorillonite crystal unit) and brucite Mg(OH)2 layers. Magnesium dominates the
octahedral position in the tale layer thus the crystal unit contains two silica tetrahedral sheets
and the two magnesium octahedral sheets, giving rise to the term "2:2" type lattice structure.
Chlorites have about the same cation exchange capacity as illite but they have less
CEC than montmorillonite and vermiculite.
Particle size and specific surface area for chlorite are about the same as for illite.
There is relatively little water adsorption between the chlorite crystal units, with a
result of relatively non-expansive nature of this mineral.
Si Si
Diagram 2.11. A broken edge of a kaolinite crystal, showing oxygen as the source of
negative charge. At high pH values the hydrogen ions tend to be hold
loosely and can be exchanged for other cations.
The presence of thousands of such groups gives the kaolinite clay particles a definite
electronegativity.
In acid soils, the hydrogen is tightly hold and not readily replaced by other cations.
Therefore this type of electronegativity is known as pH-dependent charge.
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In most cases, the properties of the amorphous mineral do not differ greatly from
those of crystalline materials. The amorphous mineral has a high cation exchange capacity,
which is pH dependent.
Diagram 2.13. Colloidal organization of a humus colloid. Note the phenolic hydroxyl
groups are attached to the aromatic rings ( OH); and carboxyl
groups (COOH) are bonded to other carbon atoms in the central unit.
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Some important properties of organic colloids should be noted in composition with
the inorganic colloids.
1. The humus micelle is composed basically of carbon, hydrogen, and oxygen. (Silicate
clays are composed basically of aluminum silicon, and oxygen.)
2. The cation exchange capacity of humus per unit weight is very high (It is higher than
that of monmorillonite.)
3. The humus micelle is not crystalline. (Most of silicate clays are crystalline.)
4. The humus is dynamic, i.e., it is being formed and destroyed rapidly. (Silicate clays
are more stable, i.e., they are being formed and destroyed more slowly.)
5. The charge on humus colloids is pH dependent. (The charge for part of the silicate
clays is pH dependent.)
6. The major sources of negative charge are thought to be carboxylic (COOH) and
phenolic ( OH) groups. (The major sources of negative charge on clay colloids
are exposed crystal edges and isomorphous substitution.) (See Diagram 2.13)
7. Because of their complexity, specific structure of humus colloids is not clearly
understood yet. (Specific structure of clay colloids are more or less understood.)
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CHAPTER 3
CATION AND ANION EXCHANGE PHENOMENA
Ion exchange is the reversible process by which cations and anions are exchanged
between solid and liquid phases. This exchange also occurs between solid phases which are
in close contact with each other. Ion exchange is generally considered as the most important
of all the processes occurring in a soil.
The ion-exchange property of a soil is due almost entirely to the clay and silt fractions
(<20 P) and the organic matter. The colloidal material of the soil is considered most
important for this exchange process.
2+ + 2+
Ca Micelle + 2H H+ Micelle + Ca
H+
The reaction takes place fairly rapidly. The interexchange of calcium and hydrogen is
chemically equivalent. If the hydrogen ion concentration were decreased for any reason or the
calcium ions are increased by adding a calcium-containing limestone, the adjustment would
be to the left in response to mass action.
If the hydrogen ions are increased or if the calcium ions are removed by leaching, the
adjustment would be to the right.
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3.1.2. Important Factors Governing the Cation Exchange Process in Soil
The efficiency of cation exchange process is determined by a number of factors such
as:
(1) Relative concentration or numbers of the ions,
(2) The number of charges on the ion, and
(3) The speed of movement of the different ions.
The first factor is an application of the well-known chemical law of mass action
(sometimes known as the law of chemical equilibrium). Guldberg and Waage in 1867 stated
the law of mass action as the velocity of chemical reaction is proportional to the product of
the active masses (concentrations) of the reacting substances.
The second factor, the greater the number of charges carried by the ion the greater is
its efficiency, other factors being the same.
For the third factor, the speed or activity of an ion is primarily a function of its size.
However, the degree of hydration should also be considered. When an ion associates itself
with water molecules, its size becomes larger due to the shell of water. Consequently the
speed of its activity is much reduced.
Micelle Micelle
NOTE:
For the salt of simplicity, it is assumed that the number of calcium (Ca), aluminum (Al),
hydrogen (H), and other metallic cations (M) are in the ratio 40, 20, 20 and 20 per micelle,
respectively. The metallic cations are considered monovalent.
It is important to note that where sufficient rainfall is available to leach the calcium,
the reaction tends to go toward the right that is, hydrogen ions are entering and calcium and
other bases (M) are being forced out of the exchange complex into the soil solution. As long
as bases are removed and the hydrogen ion concentration is not correspondingly reduced, the
adjustment will continue to the right.
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In regions of low rainfall, the calcium and other salts are not easily leached from the
soil. Thus the removal of bases from the exchange sites is prevented, and the pH of the soil is
kept neutral or alkaline.
It is important to note that the interaction of climate, biological processes, and cation
exchange helps determine the properties of soil.
Micelle Micelle
Some of the added K pushed its way into the colloidal complex and forces out
equivalent quantities of calcium, hydrogen, and other elements which appear in the soil
solution.
The adsorption of the added potassium is considered to be advantageous because a
nutrient so held remains largely in an available condition but is less subject to leaching.
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place of two H ions. Therefore, their atomic weight must be divided by 2 to obtain the
equivalent weight.
The milliequivalent weight of a substance is one thousandth of its atomic weight.
Since the equivalent weight of hydrogen is about 1 gram, the term milliequivalent (meq) may
be defined as 1 milligram of hydrogen or the amount of any other ion that will combine with
or displace it.
Thus, if a clay has a cation exchange capacity of 1 milliequivalent (i.e.1 meq per 100
gram), it is capable of exchanging 1 mg of H+ to 100,000 mg of clay, or 10 parts per million
(10 ppm) of H+. Therefore, an acre-furrow slice of such a clay weighing 2 million pounds
could adsorb 20 pounds of exchangeable hydrogen or its equivalent.
The milliequavalent method of expression is so convenient and so commonly used
that it is important to be familiar with it.
It is well to note this term "equivalent". It indicates that other ions also may be
expressed in terms of milliequivalent. For example, consider calcium. This element has an
atomic weight of 40 compared to 1 for hydrogen. Each Ca2+ ion has two charges and is thus
equivalent to 2 H+ ions. Therefore, the amount of Ca required to displace 1 mg of hydrogen
is 40/2 or 20 mg. This is the weight of 1 meq of calcium.
If 100 grams of certain clay is capable of exchanging a total of 250 mg of calcium, the
cation exchange capacity is 250/20, or 12.5 meq per 100 grams.
The milliequivalent method of expression can be converted easily to practical field
terms. For instance, 1 meq of hydrogen can be replaced on the colloids by 1 meq of CaCO3
contained in ordinary limestone. The molecular weight of CaCO3 (100) contains 2 equivalent
weights. Since the amount of CaCO3 needed is only 1 meq weight, 100/2 = 50 mg will be
needed to replace 1 mg of hydrogen.
Since 1 meq of H+ per 100 grams is the same as 20 pounds of H+ per acre-furrow slice
(as explained earlier) , 1 meq of CaCO3 per 100 grams is the same as 20 50 = 1000 pounds
of CaCO3 per acre-furrow slice. Thus, 1/2 ton of CaCO3 per acre-furrow slice has the
potential of 1 meq of H+ per 100 grams of soil.
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As the pH is raised, the hydrogen held by the inorganic and organic colloids becomes
ionized and is replaceable. The result is an increase in the cation exchange capacity.
In most cases the cation exchange capacity is determined at a pH of 7.0 or above. This
means that it includes most of those charges dependent on pH as well as the more or less
permanent ones.
Micelle Micelle
The Mg left in the solution is back titrated using standard EDTA (Ethylene diamine
tetra acetic acid) solution.
The difference between the added Mg and the left over Mg in the solution will give
the amount of Mg which replaces the Ba cations adsorbed on soil colloids.
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A1 ml of std. EDTA = 5 ml of supernatant liquid.
B ml of std. EDTA = 5 ml of original MgSO4 solution.
The volume A1 ml of the EDTA solution used to titrate the soil extract must be
corrected for the effect of the volume of liquid retained by the centrifuged soil after washing
with water.
Corrected volume A2 ml = A1 (100 + W2 W1)/ 100 ml
The CEC of soil is calculated using the following equation.
CEC = 8 (B A2) meq/ 100 g soil.
3.2. Anion Exchange
Under certain conditions hydrous oxides of iron and aluminum, allophane and even
kaolinite show evidence of having positive charges on their crystal surfaces. These charges
are thought to have two sources:
(a) the protonation of adding of hydrogen ions to hydroxyl groups on the edge of
these minerals; and
(b) the exchange of the hydroxyl group for other anions, such as phosphate. These
mechanisms can be illustrated by the appropriate equations. First the protonation
reaction can be shown as follows.
At high pH values (left) the hydrogen ion tends to dissociate from the oxygen, leaving
a negative charge on the surface. As the pH is lowered, an additional hydrogen ion associates
with the hydroxyl, leaving a net positive charge. This charge will attract anions such as
H2PO4, SO42, NO3, Cl. Those ions can exchange with each other, giving rise to the term
anion exchange.
The second mechanism that shows a positive charge on certain colloids is that in
which phosphates and similar ions exchange for hydroxyl:
This reaction also occurs primarily at low pH values, the negative hydroxyl ion being
replaced from positively charged aluminum ion in the crystal.
By one of the two of these mechanisms of anion exchange, SO42, Cl, and NO3 ions
as well as phosphates become adsorbed by allophane, the hydrous oxides, and to a degree by
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the kaolinite group. The reactions are most significant for phosphates since these ions tend to
be quite tightly adsorbed. These reactions emphasize once again the importance of the type of
clay in determining the basic reactions in soils.
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CHAPTER 4
SOIL REACTIONS
Soils may be acid, neutral or alkaline in reaction. Each set of chemical conditions in
soil produces corresponding degree of soil reaction. Each degree of soil reaction affects plant
growth in certain way due to either depressed solubility of some elements or to an increased
solubility of others. The chemical condition which produces different degrees of soil reaction
may be favorable to the growth of some crops and affects the growth of other crops to a great
extant. Therefore, soil reaction is considered important in crop-production and soil-
management practices.
Soil reaction may be considered as symptom of the particular chemical conditions
which caused it. Therefore, it may be used to indicate the possible effect of these conditions
on plant growth.
It is also useful in diagnosing the fertility of soils.
Micelle Micelle
Water molecules H2O dissociate into positively charged H+ ions and negatively
charged OH ions. H+ ions are held close to the micelle and OH ions go into soil solution.
When the number of H+ ions and the number of OH ions in the solution around the
micelle are equal a neutral reaction exists. When the number of H+ ions exceeds the number
of OH ions, the reaction of the soil is acid.
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Other factors also contribute to soil acidity to some extent.
Traces of inorganic acids such as HNO3, HNO2, H2SO4, H3PO4, etc. may be present in
soil as a result of some chemical and biological reactions.
Soils containing mineral like FeS2 may produce H2SO4 to a considerable extent.
CO2 is present in most soils and with H2O it produces H2CO3.
Other organic acids such as acetic, citric, and oxalic are liberated during the decay of
fresh plant tissue.
Although these organic and inorganic acids contribute to the acidity of the soil to
some extent the reaction is due primarily to the relative proportion of H+ ions and other
cations on the colloidal complex.
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If the concentration of H+ ions in a solution were 0.000001 gram per liter (106), the
pH would be 6. As the concentration of H+ ions in the solution is 10 times that in water, it is
clear that a solution with a pH 6 is 10 times as acid as a solution with pH 7. It should never be
forgotten that the pH values are logarithms.
As the product of the concentration of the H+ and OH ions is always equal to 1014,
the concentration of the OH can be calculated if the pH value of the solution is known.
Thus pH 7 indicates a concentration of H+ ion, [H+] = 107g/liter and a concentration
of OH ion, [OH] = 107g/liter
Kw = [H+] [OH] = 107g/liter 107 g/liter = 1014
A pH of 6 indicates a concentration of H+ ion, [H+] = 106g/liter and a concentration of OH
ion, [OH] = 108 g/liter
Kw = [H+] [OH] = 106g/liter 108 g/liter = 1014
On the other hand a pH of 8 would indicate a concentration of H+ ion [H+] =108g/lit and a
concentration of OH ion, [OH]= 106g/liter
Kw = [H+] [OH] = 108g/liter 106 g/liter = 1014
Therefore, OH ion concentration, [OH]= 106g/liter at pH 8 is 10 times higher than
the OH ion concentration, [OH]= 107g/liter at pH 7 or neutral. This solution therefore is
alkaline. Any pH value above 7 indicates alkaline condition.
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4.1.3. Range of Reaction in Soils
Range of soil reaction or soil pH can be roughly divided into the following groups:
Extremely acidic less than pH 4.5
Very strongly acidic from pH 4.5 to 5.1
Strongly acidic from pH 5.1 to 5.5
Moderately acidic from pH 5.6 to 6.0
Slightly acidic from pH 6.1 to 6.5
Neutral from 6.6 to 7.4
Mildly alkaline from 7.5 to 8.0
Strongly alkaline from pH 8.1 to 9.0
Very strongly alkaline higher than pH 9.0
The pH 4.0 is usually the lower limit for soils of humid region. It is unusual to find a
soil with a pH of more than 7.5 or 8.0 in humid regions.
However, in arid regions, where soluble salts of sodium (Na2CO3) may accumulate, a
pH of 9.5 to 11.0 is sometimes attained.
The usual pH of agricultural soils in the humid region ranges approximately from 5.0
to 6.8.
All soils do not have the same pH for a given percentage base saturation, because the
exchangeable hydrogen does not ionize with equal case from the different clay minerals and
organic colloids.
The bonding strengths for hydrogen-
(1) of a site originating from isomorphous substitution
(2) of a site originating from the broken bonds at the edges of particles
(3) of a site originating from an exposed hydroxyl
(4) of a site originating from a carboxyl group are different from one another.
This is the basic explanation of why soils containing high percentage of kalonite clays
have a higher pH than those with 2:1 clays at a given percentage base saturation.
Calcareous soils contain free carbonates of calcium and magnesium. These salts give
alkaline reaction when hydrolyzed and produce a maximum pH of 8.3.
A pH of higher than 8.3 indicates the presence of exchangeable sodium that
hydrolyses to form NaOH, a very strong base. Such soils are termed alkali. Soils containing
high percentage of soluble salts, tend to have a neutral reaction and such soils are termed
saline.
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4.1.4. Source of Hydrogen Ions
Adsorbed aluminum ions
Under acid conditions, much aluminum becomes soluble. They are present in the form
of aluminum or aluminum hydroxy cations. They are adsorbed by the permanent charges of
clay minerals.
The adsorbed aluminum is in equilibrium with aluminum ions in the soil solution.
Micelle
The aluminum ions in the soil solution are then hydrolyzed in a manner such as the
following;
The H+ ions thus released give a very low pH value in the soil solution.
Micelle
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Some of positively charged aluminum hydroxy ions adsorbed and act as exchangeable
cations. They are in equilibrium with those in soil solution.
In the soil solution they are able to produce hydrogen ions by the following hydrolysis
reactions:
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phosphate of iron and aluminum may be formed. These complex iron and aluminum
phosphates have a very low solubility and do not supply sufficient phosphorus for plants.
Under strongly acid conditions when soluble phosphate fertilizers are applied to the
soil, they are converted into the insoluble forms. Therefore, on these soils, the efficiency of
applied phosphates is greatly reduced.
Calcium supply in acid soils
Soil reaction becomes acidic only when the supply of basic ions, such as Ca, on the
soil colloids is depleted. It has been generally accepted that a nutrient deficiency of calcium is
a factor in the poor growth of plants on many acid soils.
Activity of microorganisms
The microorganisms which convert ammonia into nitrite and nitrite into nitrate are
sensitive to acidity.
One group of bacteria (Azotobactor) which utilizes atmospheric nitrogen without
association with a legume does not function properly below a pH of 6.0. Symbiotic bacteria
which grow in conjunction with several legumes, such as alfalfa, clover, soybeans, etc. are
badly affected by acidity.
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Dye or indicator methods
The dye methods are very simple and easy, but the results may not be very accurate.
The method consists of using certain indicators. Many dyes change colors with an increase or
decrease of pH. It therefore becomes possible (within the range of the indicator) to estimate
the approximate hydrogen ion concentration of a solution. By using a number of dyes either
separately or mixed, a range of pH from 3 to 8 is easily covered.
To carry out such a pH determination on soil, the sample is first saturated with the
dye. After standing for a few minutes, a drop of the liquid is taken and observed in thin layer.
By the use of a suitable color chart, the approximate pH value may be ascertained. The
indicator or dye method is accurate within about 0.2 pH unit, when the determination is
carefully and correctly done.
Electrometric method
The most accurate method of determining soil pH is by a pH meter. In this
electrometric method, the hydrogen concentration of the soil solution is balanced against a
standard hydrogen electrode. The potential may be measured by using a potentiometer. The
potential established is proportional to the concentration of H+ ions.
Although the instrument gives very accurate results, its use requires a skilled operator
having the knowledge of complicated mechanism how a pH meter works.
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Saline soils
These soils contain a sufficient concentration of neutral soluble salts to interfere with
the growth of most plants. The electrical conductivity of a saturated extract (ECe) is greater
than 4 mmhos/ cm.
Less than 15 percent of the cation exchange capacity of those soils is occupied by
sodium ions and the pH usually is below 8.5. This is because the soluble salts present are
mostly neutral and because only a small amount of exchangeable sodium is present.
Such soils are sometimes called white alkali soils because the surface crust is usually
light in color.
The excess soluble salts are mostly chlorides and sulphates of sodium, calcium, and
magnesium. These salts can be easily leached out of these soils, with no appreciable rise in
soil pH. However, care must be taken to be certain that the leaching water is low in sodium.
Saline-alkali soils
These soils are sometimes known as saline-sodic soils. These soils contain
appreciable quantities of neutral soluble salts and enough adsorbed sodium ions to seriously
affect most plants.
Although more than 15 percent of the total exchange capacity of these soils is
occupied by sodium, their pH is likely to be below 8.5. This is because of the repressive
influence of the neutral soluble salts, as in the saline soils previously described.
The electrical conductivity of a saturated extract is more than 4 mmhos/ cm.
But unlike the saline soils, leaching will markedly raise the pH of saline-alkaline
soils, unless calcium or magnesium salt concentrations are high in the soil or in irrigation
water. This is because the exchangeable sodium, once the neutral soluble salts are removed,
readily hydrolyses and thereby sharply increases the hydroxyl ion concentration of the soil
solution.
It is important to note that these sodium ions destroy the soil structure and at the same
time, sodium toxicity to plants is increased.
Alkaline soils
These soils do not contain a large amount of neutral soluble salts. The bad effects are
mainly due to the toxicity of the sodium as well as of the hydroxyl ions. The high pH is
largely due to the hydrolysis of sodium carbonate, which occurs as follows:
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The resulting hydroxyl ions give pH values of 10 and above.
Also, the sodium complex undergoes hydrolysis as follows:
Micelle Micelle
The exchangeable sodium occupies more than 15 percent of the total exchangeable
capacity of these soils. These exchangeable sodium ions are free to hydrolyze because the
concentration of neutral soluble salts is low.
The electrical conductivity of a saturated extract is less than 4 mmhos/cm.
Consequently, the pH is above 8.5, often rising as high as 10.0.
Due to the deflocculating influence of the sodium, such soils usually are in poor
physical condition.
Because of the extreme alkalinity resulting from the Na2CO3 present, the surface of
alkali soils is usually discolored by the dispersed humus carried upward by the capillary
water. Therefore, these alkaline or sodic soils are sometimes known as black alkali soils.
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Eradication methods
The methods used to free the soil of excess salts are (a) under drainage and (b)
leaching or flushing.
Heavy and repeated application of water is made in irrigated regions. The salts which
become soluble are then leached and drained off. The irrigation water should be relatively
free of sodium salts.
This leaching method is very good for treating saline soils, which contain mostly
neutral salts.
Leaching of saline-alkali and alkali soils may intensify the alkalinity, because of the
removed of neutral soluble salts. This allows an increase in the percent sodium saturation
thereby increasing the concentration of hxdroxyl ions in the soil solution.
This may be avoided by converting the toxic sodium carbonate and bicarbonate to
sodium sulphate by treating the soil with heavy application of gypsum or sulphur. Then
leaching of soil can be done more satisfactorily.
Conversion methods
Gypsum is often used for treating alkali soils. The gypsum reacts with Na2CO3 salt
and also with the adsorbed Na on the soil colloids as follows:
Micelle Micelle
Several tons of gypsum per acre are usually necessary. The soil must be kept moist to
improve the reaction. This treatment is followed by leaching with sodium free irrigation
water.
Sulphur can also be used to change harmful sodium carbonate to less harmful sulphate
form. When applied to soil, sulphur is oxidized to form sulphuric acid. The reactions of
sulphuric acid with sodium carbonate or adsorbed sodium take place as follows:
Micelle Micelle
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Sulphuric acid not only transform sodium carbonate in to less harmful sodium
sulphate (because it is a mild neutral salt), but also reduce the intense alkalinity to a
considerable extent.
Control methods
The retardation of evaporation from the surface of the soil not only saves moisture,
but also prevents the translocation upward of soluble and harmful salts into the root zone.
This method can be very expensive when dealing with large acreages.
The method of irrigation is also important. Frequent and light irrigations is more
advantageous than heavy application of water at less frequent intervals.
The timing of irrigation is extremely important on salty soils. Since young seedlings
are especially sensitive to salts, irrigation often proceeds or follows planting to move the salts
downward.
The use of salt-resistant crops is another way of managing saline and alkali soils.
Sugar beets, cotton, sorghum, barley, rye, sweet clover, and alfalfa are found to be salt
resistant and should be chosen to grow on salty soils.
The use of farm manures also alleviates the alkalinity of soil temporarily. This
situation will help the less resistant crops such as alfalfa before the root system is well
established. Once the plant is growing vigorously, it may maintain itself in spite of salt
concentration that may develop later.
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CHAPTER 5
SOIL ORGANIC MATTER
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5.3. General Composition of Compounds
The composition of the green plant materials usually added to the soils can be
summarized as in the following flow charts.
The types of the compounds which are usually found in the dry matter of green plant
materials can be briefly summarized as follows:
Carbohydrates range in complexity from simple sugars to celluloses. Fats and oils are
glycerides of fatty acids such as butyric, stearic and oleic. Lignins are complex compounds
which are very resistant to decomposition. Of the various groups, the crude proteins are the
most complicated compounds which carry not only C, H and O but also N, S, Fe and P. They
are compounds of high molecular weight.
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1. Sugars, starches, and simple proteins Rapidly Decomposed
2. Crude proteins
3. Hemicelluloses
4. Celluloses
5. Lignin, fats, waxes, etc. Very slowly decomposed
The rate of the decomposition decreases from the top to the bottom of the list. Thus,
sugars and water soluble proteins are examples of readily available energy sources for soil
organisms. Lignins are very resistant source of food, although they eventually supply much
total energy.
When organic tissue is added to soil, three general reactions takes place.
1. The material undergoes enzymatic oxidation with carbon dioxide, water and heat
as the major products.
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Of this large amount of energy carried by the soil organic matter, only a part is used
by soil organisms. The remainder is left in the residues or is dissipated as heat. This heat loss
represents a large and continual removal of the energy from the soil.
The autotrophic bacteria obtain energy by these reactions, which produce nitrates that
are assimilated by plants. The hydrogen ions that are produced by this reaction show that
nitrification tents to result in an increase in soil acidity. This effect is of even greater
important when dealing with commercial fertilizers containing ammonium salts such as
(NH4)2SO4. Extra increments of lime are often added to counteract this acidifying effect.
Under certain conditions, the reduction of nitrates and nitrites takes place in soils, and free
nitrogen or oxides of nitrogen may be evolved. This reduction reaction is serious since these
nitrogen gases ordinarily are relatively inert and are not recombined into compounds useful to
higher plants. The cultivated soils lose considerable amount of nitrogen in this way.
The organisms involved obtain energy by the transfer and the sulphur is left as
sulphate.
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5.11. Mineralization of Organic Phosphorus
A large portion of the soil phosphorus is in organic form. Organic phosphorus
compounds are mineralized by soil microorganisms, that is, they are changed to inorganic
combinations. The particular forms depend to a considerable degree upon soil pH. As the pH
goes up from 5.5 to 7.5, the available phosphorus changes from H2PO4 to HPO42. Both of
these forms are available to higher plants. Since the small amount of phosphorus held in
complex mineral combinations in soils usually is very slowly available, the organic sources
mentioned above become especially important.
It is important to note that the maintenance of soil organic matter at normal or even at
high levels will not solve the soil phosphorus problems. Most field soils need liberal
application of phosphate fertilizers. Since soil microorganisms utilize phosphorus quickly
becomes part of the soil organic matter. Thus, this phosphorus is held in an organic condition
and is later mineralized by microbial activity.
5.12. Humus
As organic tissue is incorporated into a moist warm soil, it is immediately attacked by
a host of different soil organisms, and first intermediate substances and finally the simple and
soluble products are formed.
5.19.5. Cropping
Cropped land contains much lower nitrogen and organic matter than comparable
virgin soils. This is because much of the plant materials are removed for human or animal
food and relatively little portion is returned to the soil in cultivated areas.
Soil tillage breaks up the organic residues and brings them into easy contact with soil
organisms, thereby increasing the rate of decomposition.
Considerable loss of soil organic matter and nitrogen is usually observed with
cropping.
Crop rotation, especially if legumes are included, helps to maintain soil organic
matter.
Soils that are kept highly productive by supplemental application of fertilizers, lime,
and manures are found to contain a higher organic matter content than a comparable less
productive soil. The amount of root and top residues to be returned to the soil are dependent
upon the level of soil productivity. However, even the most productive tilled field soil will
contain considerably lower organic matter than a virgin soil.
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