1.

Introduction:

Soils are made up of a complex mixture of solids, liquids and gases.

The solid fraction of soils are made up of organic and inorganic
components. The inorganic component of the soil makes up more than 90%
of the soil solids.
Inorganic components occur mainly in limited number of compounds
with definite crystalline structure called minerals. The inorganic component
includes both primary and secondary minerals.
The secondary minerals normally are found in the clay fraction of the
soil which is the fraction of the soil solids which is less the 2 micron or 0.002
mm. Clay minerals are minerals which mainly occur in the clay sized fraction
of the soil.

2.

Importance of Clay Minerals:

The clay minerals and soil organic matter are colloids.

The most important property of colloids is their small size and large
surface area. The total colloidal area of soil colloids may range from 10m2/g
to more than 800 m2/g depending the external and internal surfaces of the
colloid.
Soil colloids also carry negative or positive charges on their external
and internal surfaces. The presence of charge influences their ability to
attract or repulse charge ions to or from surfaces.
Soils colloids play a very important role in the chemical reaction which
take play in soil and influence the movement and retention of contaminants,
metals, and nutrients in the soil.

3.

Origin of Clay Minerals.

Clay minerals are formed weathering a variety of minerals.

The two main processes may involve slight physical and chemical
alteration or decomposition and recrystallization.
Clay mineral types are normally determined by the types of minerals
and acidity of the leaching water.
Based on their origins clays may classified as Inherited, Modified,
Transformed or Neoformed (see pages 147 and 148 of text for definitions).

4.

Charge Development on Clays.

Two main sources of charge in clay minerals are isomorphous

substitution and pH-dependent charges.
Charge development of on silicate clays is mainly due to isomorphous
substitution. This is the substitution of one element for another in ionic
crystals with out change of the structure. It takes place during crystallization
and is not subject to change afterwards. It takes places only between ions
differing by less than about 10% to 15% in crystal radii.. In tetrahedral
coordination, Al3+ for Si4+ and in octahedral coordination Mg2+, Fe2+, Fe3+
for Al3+. Charges developed as a result of isomorphous substitution are
permanent and not pH-dependent.
In allophanes, some silicate clays e.g. kaolinite, and the metal oxides
the main source of charge are termed pH -dependent charges because these
charges depend on the pH of the soil. pH depend charges are variable and
may either be positive or negative depending on the pH of the soil. In the
metal oxides acid soils tend to develop positive charges because of the
protonation of the oh ggoud on the oxide surfaces.

5.

Type of Clay Minerals.

There are four major types of Clay minerals ( see Table 5-1).
These include the layer silicates, the metal oxides and hydroxides and

oxy-oxides, amorphous and allophanes, and crystalline chain silicates.

6.

Silicate Clays.

The silicate clays are layers of tetrahedral and octahedral sheets.

The basic building blocks of tetetrahedral and octahedral sheets are
the silica tetrahedron and the aluminum octahedra.
The Si+4 cation occurs in fourfold and tetrahedral coordination with
oxygen whilst the Al3+ is generally found in sixfold or octahedral
coordination.
Layer silicate minerals are sometimes defined on the basis of the
number of certain positions occupied by cations. When two-thirds of the
octahedral positions are occupied , the mineral is called dioctahedral; when
all 3 positions are occupied it is called trioctahedral.
When one octahedral sheet is bonded to one tetrahedral sheet a 1:1
clay mineral results. Presence of surface and broken - edge OH groups gives
the kaolinite clay particles their electronegativity and their capacity to absorb
cations.
In 2:1 clay mineral an octhehedral sheet is bonded to two tetrahedral
sheets. The octahedral sheet is generally sandwiched between the two
tetrahedral sheets. The 2:1 clays can be classified into expanding (smectites)
and non-expanding clays (Illite and micas) on the basis of the sheet where
isomorphous susbstitution is taking predominantly taking place (Refer to
Figure 5-3).
In the 2:1:1 lattice clays, a positively charge brucite sheet sandwiched
between layers restricts swelling, decreases effective surface area, and
decreases the effective CEC of mineral. The Idealized formular of half cell is Al
Mg2(OH)6)K (Mg3(Si4-x Alx)O10(OH)2. Substitution occurs is in the
tetrahedral layer and the layer change is variable but similar to mica. It
occurs commonly in sedimentary rocks.

Table 12.1 Silicate Clay Mineral Groups:

Group

Layer Type

Layer Charge (x)

Type of Chemical Formula

Kaolinite

1:1

<0.01

[Si4]Al4O10(OH)8.nH2O (n= 0 or 4)
Illite

2:1

1.4-2.0

Mx[Si6.8Al1.2]Al3Fe.025Mg0.75O20(OH)4
Vermiculite

2:1

1.2-1.8

Mx[Si7Al]AlFe.05Mg0.5O20(OH)4
Smectite

2:1

0.5-1.2

Mx[Si8]Al3.2Fe0.2Mg0.6O20(OH)4
Chlorite

2:1:1

Variable

(Al(OH)2.55)4[Si6.8Al01.2}Al3.4Mg0.6)20(OH)4
Adapted from Sposito1989. The Chemistry of Soils. Oxford University Press.

7.

Sesquioxide Clays (Metal Oxides and Hydrous Oxides)

Also found in finer component. These tend to form in soils as Si is

depleted by leaching.
Gibbsite is the most common Al oxide mineral and is often found in
highly weatherd sois such as oxisoils in tropical areas and ultisols found
predominatly in the southeastern U.S.

The most commn iron oxides are Goetihte (FeO(OH) and Hematiite
(Fe2O3) Thess are also found in highly weathered soils and gives many red
soils their color.
The metal oxides gibbsite and goethite tend to persist in the
environment because Si is readily leached than Al, or Fe and significant
amount of soluble organic matter is present.
Manganese oxides are also quite common in soils. Apart from being an
essential plant nutrient, they are an nutrural oxidant to certain metals such
as As3+ and Cr3+. Birnessite(MnO2) is the most comon Mn oxide found in
soils.
Most of the charges developed on the metal oxides are pH-dependent.

8.

Allophanes and Imogolite

These are structurally disordered aluminosilicates.

They are normally derived from volcanic ash materials and constitute a
major component of volacnic soils.
Allophane is is often associated with clay minerals of the kaolinite
group.
Imogolite has the empirical formula SiAl4O10.5H2O.

9.

Carbonate and Sulfate Minerals

The carboate and sulfate minerals are highly soluble compared to the
alumino-silicates and are more prevalent in arid and semi arid regions.
The major carbonate minerals are calcite (CaCO3) and Dolomite
(CaMg(CO3)2.
The major sulfate mineral is gypsum.

10.

Use of Clay Minerals.

Clay minerals have many industrial uses in the chemical and oil
industries.
Organoclays, which have the metals in the clay replaced by large
surfactant cations, such as long chain alkyl amine cations can be been used
as liners in landfills to reduce transport of contaminants. Organoclays also
could be used in wastewater treatment and spill control situations.