MINERALOGICAL CHARACTERISTICS

OF BARISAL SOIL SERIES

Debajyoti Roy
Examination Roll No. 021320
Session: 2004-05

Soil Science Discipline

Khulna University
Bangladesh

July, 2007

1
MINERALOGICAL CHARACTERISTICS OF BARISAL SOIL SERIES

COURSE TITLE: PROJECT THESIS

COURSE NO: SS-4106

This project paper has been prepared and submitted to Soil Science
Discipline, Khulna University, for the partial fulfillment of the four years
professional B. Sc. (Hon’s) degree in Soil Science.

Submitted by,
Debajyoti Roy
Examination Roll No. 021320
Session: 2004-05

Soil Science Discipline

Khulna University
Bangladesh

2
MINERALOGICAL CHARACTERISTICS OF BARISAL SOIL SERIES

Approved as to style and content by

Md. Sanaul Islam

Assistant professor and Chairman of
The Examination committee
Soil Science Discipline
Khulna University
Bangladesh

3
 Declaration

This project paper is entirely the candidate’s own investigation and no part of
this paper has been accepted for any degree, nor is it being concurrently
submitted for any degree.

Supervisor
Sheikh Mohammad Fazle Rabbi
Assistant professor
Soil Science Discipline
Khulna University
Bangladesh

Candidate

Debajyoti Roy
Examination Roll No. 021320

4
 ACKNOWLEDGEMENT
At first I wish to express all my devotion and reverence to almighty God, who has
enable me to complete the thesis paper for the fulfillment of the degree of Bachelor of
Science in Soil Science.

I would like to express my heartfelt gratitude, sincere appreciation and profound

regards to Sheikh Mohammad Fazle Rabbi, Assistant professor, Soil Science
Discipline, Khulna University, under whose careful supervision and scholastic
guidance this thesis has been conducted.

I am sincerely thankful to Md. Sanaul Islam, Assistant professor and Chairman of

the Examination Committee, Soil Science Discipline, University of Khulna for
providing all possible facilities during the course of this thesis paper and all other
teachers of Soil Science Discipline for their cordial co-operation at different stages for
accomplishing this study.

I convey my respect and gratefulness to Md. Sadiqul Amin, Lecturer, Soil Science
Discipline, University of Khulna for his cordial co-operation during this study.

I am also thankful to Md. Mainul Ahsan, principle scientific officer, Mr. Ifthekhar,
senior scientific officer and Abida Yesmin, scientific officer, SRDI, Dhaka, for their
cordial co-operation during my work.

Special appreciation goes to my friends Mukut, Shuvo, Prodeep and Manashi for their
excellent co-operation during this study.

Finally, I respectfully remember my parents and my younger sister for their support
for my higher education and without whose blessings this work would not have been
possible.

July, 2007. The Author

5
 To my parents

6
 CONTENTS

Titles Page No.

CONTENTS i
LIST OF TABLES iv
LIST OF FIGURES v
Chapter one: Introduction
1. Introduction 1
Chapter two: Literature review
2. Literature review 5
2.1. Primary soil minerals 5
2.2. Secondary soil minerals 6
2.3. Formation of clay minerals 7
2.3.1. Formation of Vermiculite 7
2.3.1.1. Release of Potassium 8
2.3.1.2.. Oxidation of Iron 8
2.3.1.3. Hydroxyl orientation 9
2.3.2. Formation of Smectite 9
2.3.2.1.Transformation from Mica 9
2.3.2.1.1. Environment that promote the 10
transformation of mica
2.3.2.2. Transformation from Chlorite 10
2.3.2.3. Formation from Solution 10
2.3.3. Formation of Kaolinite 11
2.3.3.1. Equilibrium environment and conditions for 11
Synthesis of Kaolinite
2.3.3.2. Kaolinite formation from Hydroxy-Al 13
Interlayered Montmorillonite
2.4. Structure of clays minerals 14
2.4.1. The 1:1 Type Minerals 17
2.4.1.1. Kaolinite 17
2.4.1.2. Halloysite 18
2.4.2. The 2:1 type Minerals 19
2.4.2.1. Smectite (montmorillonite) 19

7
Titles Page No.
2.4.2.2. Vermiculite 21
2.4.2.3. Mica 22
2.4.2.4.1. Illite 23
2.4.2.5. Chlorites 24
2.4.3.Interstratified clay minerals 25
2.4.3.1. Montmorillonite–vermiculite–chlorite intergrade 26
2.4.3.2. Swelling 2:1 to 2:2 intergrades 27
2.5. Soil mineral weathering sequences 27
2.6. X-ray diffraction analysis 34
2.6.1. Sources of X-Ray Radiation 34
2.6.2. Principles of X-Ray Diffraction 35
2.6.3. Pretreatment of soil samples 37
2.6.3.1. K-saturation 37
2.6.3.2.Mg-saturation and glycolation 38
2.6.3.3. Heating at 500°C 39
2.6.4. Preparation of slides 39
2.6.4.1. Random Powder Sample 39
2.6.4.2. Random-Oriented Samples 40
2.6.5. Diffractograms of Clay Minerals 40
2.7. Clay mineralogy of soils of Bangladesh 41
2.7.1. Clay Mineralogy of the Various Parent Materials 41
2.7.1. Tertiary sediments 41
2.7.2. Madhupur clay 42
2.7.3. Tista floodplain 43
2.7.4. Old Brahmaputra floodplain 43
2.7.5. Ganges river floodplain 43
2.7.6. Northern and eastern piedmont plains 44
2.7.7. Barind tract 44
2.8. Mineral Weathering of Soil of Bangladesh 44
2.9. Needs for Clay Mineralogy Study 46
Chapter three: Materials and Methods
3.1. Materials and methods 49

8
Titles Page No.
3.1.1. Methods of Analysis 47
3.1.2. Preparation of Sample for X-Ray Diffraction Analysis 48
3.2. Results and discussion 51
3.2.1. Morphological Characteristics 51
3.2.2. Chemical characteristics 54
3.2.3. Identification and Quantification of Clay Minerals 56
3.2.4. Weathering Stability of Clay Minerals 64
4. Summery and conclusion 66
5. References 67
6. Appendix 73

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 LIST OF TABLES
Title Page No.
Table 2.1 Common Primary Minerals in Soils 5
Table 2.2 Common Secondary Minerals in Soils 6
Table 2.3 Classification of phyllosilicates in soils 16
Table 2.4 Types of minerals as indicators for relative degree of 29
soil development
Table 2.5 Effect of parameters on the d-spacing of selected 38
Clay Minerals
Table 3.1 Morphological features of Barisal series 52
Table 3.2 Chemical characteristics of Barisal series 55
Table 3.3 Clay mineral percentages of various horizons of 63
Barisal series
Table 3.4 Pedological indices for different horizons of Barisal 64
series
Table 3.5 Pedological indices of different clay minerals under 64
equilibrium condition

10
 LIST OF FIGURES

Title Page No.

Fig. 2.1 General conditions for the formation of the various 7
layer silicate clays and oxides of iron and aluminum
Fig. 2.2 Composition of solutions equilibrated with 11
montmorillonites
Fig. 2.3 Classification of silicate minerals 15
Fig. 2.4 Schematic structure of Kaolinite 17
Fig. 2.5 Schematic structure of Halloysite 19
Fig. 2.6. Schematic structure of montmorillonite 20
Fig. 2.7 Schematic structure Vermiculite 21
Fig. 2.8 Schematic structure of Mica 23
Fig. 2.9 Schematic structure Chlorite 25
Fig. 2.10 Mineral stability sequence 28
Fig. 2.11 Relative solubility of a few clay minerals 31
Fig. 2.12 Relative solubility of selected primary and 33
secondary minerals
Fig. 2.13 The conditions for diffractions of x-rays from 36
crystal planes.
Fig. 3.1 Particle size and micro aggregate distribution of 53
Barisal series
Fig. 3.2 X-ray patterns for Barisal series 57

11
1. INTRODUCTION
The solid phase of soil is composed inorganic and organic materials. Of these the
inorganic materials, or minerals, predominate in virtually all soils except Histosols
(Essington 2004). A mineral is a naturally occurring, inorganic, solid element or
compound with a definite chemical composition and a regular internal crystal
structure (Montgomery 2000). Minerals are generally classified as primary minerals
and secondary minerals (Essington 2004). A primary mineral is one that has not been
altered chemically since its deposition and crystallization from molten lava or magma.
Quartz and feldspar are common primary minerals in the soil. A secondary mineral is
one resulting from the weathering of a primary mineral; either by an alteration in the
structure or from reprecipitation of the products of weathering (dissolution) of a
primary mineral. Common secondary minerals in soils are the aluminosilicate or
phyllosilicate minerals such as kaolinite and montmorillonite, oxides such as gibbsite,
goethite, amorphous materials such as imogolite and allophane (Sparks 1995). In soil,
a naturally occurring material composed primarily of fine-grained minerals (<2µm)
are defined as clay (Churchman 2000). The phyllosilicate are commonly associated
with clay fraction of soil and so they are called clay minerals. There are other
components that are also associated with clay minerals such as accessory minerals
(metal oxides, hydroxides, and oxyhydroxides) and soil organic matter (Essington
2004).

Physical and chemical activities of a soil are related to the kind and amount of clay
minerals. The clay minerals, that represent the weathering stage of a soil. In a general
sense, the occurrence of primary silicates in the clay fraction is indicative of a soil that
has not been subjected to the environmental forces that promote weathering. The
predominance of secondary phyllosilicate minerals in the clay fraction is a clear
indication that weathering has occurred, the degree of weathering depending on the
type of clay present (Essington 2004). Clay particles may have thousands of times
more surface area per gram than silt particles and nearly a million times more surface
area than very coarse sand particles. Thus, clay particles are the most chemically and
physically active part of mineral soil (Brady and Weil 2002). The nature, amount and
content of clay minerals in the soil determine the genesis of the soil as well as the
productivity, nature and maturity of the soil. Clay particles provide physical support

12
for plants, and create the water-and air-filled pores that make plant growth possible.
The kind and amount of clay influence plant growth by affecting available water
capacity, water intake rate, aeration, leaching, erodibility etc. By slightly slowing the
rate of water movement, it can reduce the rate of nutrient loss through leaching. It also
determines the swelling capacity of the soil (Brady and Weil 2002). Mineral
wreathing releases plant nutrients that are retained by other minerals through
adsorption, cation exchange, and precipitation. Clay content can be increase or
decrease in the soil. Up to a certain point, an increase in the amount of clay in the
subsoil is desirable. The amount of clay accumulation and its location in the profile
provide clues for the soil scientist about soil genesis. Irregular clay distribution as
related to depth may indicate lithologic discontinuities, especially if accompanied by
irregular sand distribution (Dixon and Weed 1989).

According to Jenny (1941) soil formation depends upon some factors. These are
isolated as the climatic factor, the biotic factor, the topographic factor, the parent
material and the time factor (Churchman 2000). The formation of clay minerals in
soils generally results from the combination and addition of ions and molecules from
the soil solution to the solid phase. Formerly, soil minerals were thought to form by
differential migration of ions into and out of existing silicate structures. The diffusion
of A13+ or Mg2+ out of the lattice was supposedly balanced by the inward diffusion of
other ions. Clay mineral formation occurs by ion substitution between soil solution
and an existing solid (Bhon et al. 1979). The synthesis of the clay minerals at elevated
temperatures and pressures from oxides and hydroxides and from various minerals,
particularly the feldspars, in the presence of acids and alkalies has been studied in
considerable detail. The environmental conditions favorable for the formation of the
clay minerals can be decided from the available data from synthesis experiments
(Grim 1986). At low temperatures and pressures, acid conditions apparently favor the
formation of the kaolinite type of mineral, whereas alkaline conditions favor the
formation of smectite or mica, if potassium is the alkali metal and if it is present in
concentration above a certain level. The presence of magnesium particularly favors
the formation of montmorillonite. At temperatures somewhat above about 350ºC and
with moderate pressures, pyrophyllite forms in place of kaolinite, with an excess
Al2O3 forming boehmite. At more elevated temperatures and pressures, other alumina
phases develop. Mica can form under acid conditions, and kaolinite or pyrophyllite

13
can develop in the presence of an excess of K2O, depending on the temperature, the
amount of K2O and the Al2O3:SiO2 ratio (Grim 1986).

Identification of clay mineral is a part of clay mineralogy. By various processes and

techniques clay minerals can be identified. Such as Thermogravimetric analysis
(TGA), Differential scanning calorimetry (DSC), Differential thermal analysis (DTA)
and X-ray diffraction (XRD) (Tan et al. 1986). The X-ray diffraction analysis is a
useful method to identify and to make semiquantitative estimates of the crystalline
mineral components of soil. Angles of diffraction, as affected by differentiating
sample treatments, are distinctive for a particular mineral and help to identify that
mineral. Intensities of diffraction maxima are related to the number of corresponding
diffraction planes in a sample and provide a basis for the estimation of concentrations
of the mineral species present (Whittig and Allardice 1986). Diffraction can occur
whenever Bragg's Law is satisfied. However, in X-ray analysis of soils or clay
samples, there are difficulties in evaluation and compensation for variations in
chemical composition, crystal perfection, amorphous substances, and particle-size
(Whittig and Allardice 1986). A more reliable and accurate estimation of mineral
percentages is provided when X-ray diffraction analysis is used in conjunction with
other methods, e.g., differential-thermal, surface-area, elemental analysis, and other
species-specific chemical methods (Alexiades and Jackson 1966).

Clay mineralogy of Bangladesh soil varies with physiography. The soils on the Tista
and Old Brahmaputra River floodplains are of silty-texture and the clay fraction is
composed predominantly of mica and chlorite. In addition the soils of the Old
Brahmaputra contain relatively large amounts of vermiculite. Two kinds of soil are
found in the Ganges river floodplain. One is calcareous and fine-textured in
mechanical composition and contained considerable amounts of smectite in addition
to mica. The other is a noncalcareous soil of silty-texture, dominated by mica and
chlorite and lack smectite. In these soils kaolinite present in a small amount and less
important compared with mica, chlorite, smectite, and vermiculite. Clay mineralogical
composition of the soils from the piedmont alluvial plains is common in principle to
that of the river floodplain soils, but the piedmont soils indicates the features of more
or less intensive weathering of minerals (Egashira and Yasmin 1990).

14
The study of clay mineralogy of soils of Bangladesh has been carried out by Soil
Resource Development Institute (SRDI), Dhaka University, Bangladesh Agricultural
University and other national and international research organization for several
decades. However, the generated informations are not conclusive and much research
is necessary to identify and quantify the clay minerals present in soils of Bangladesh.

The objectives of the present research work were

1. to identify and quantify clay minerals in Barisal soil series and
2. to describe the weathering stability of clay minerals.

15
2. LITERATURE REVIEW
2.1. PRIMARY SOIL MINERALS
A primary mineral is one that has not been altered chemically since its deposition and
crystallization from molten lava. Examples of common primary minerals in soils
include quartz and feldspar. Other primary minerals that are found in soils in smaller
quantities include pyroxenes, micas, amphiboles and olivines. Primary minerals occur
primarily in the sand and silt fractions of soils but may be found in slightly weathered
clay-sized fractions (Sparks 1995). The most common primary minerals found in soil
are presented in Table 2.1

TABLE 2.1
Common Primary Minerals in Soils (Sparks 1995)
Name Chemical formula
Quartz SiO2
Muscovite KAl2 (AlSi3 O10) (OH)2
Biotite K(Mg, Fe)3(AlSi3 O10) (OH)2
Feldspar
Orthoclase KAlSi3O8
Microcline KAISi3O8
Albite NaAlSi3O8
Amphiboles
Tremolite Ca2Mg5Si8O22(OH)2
Pyroxenes
Enstatite MgSiO3
Diopside CaMg(Si2O6)
Rhodonite MnSiO3
Olivine (Mg, Fe)2SiO4
Epidote Ca2(Al, Fe)3Si3 O12(OH)
Tourmaline (Na, Ca) (Al, Fe3+, Li, Mg)3 Al6 (BO3)3 (Si6O18) (OH)4
Zircon ZrSiO4
Rutile TiO2

16
2.2. SECONDARY SOIL MINERALS
The secondary mineral is one resulting from the weathering of a primary mineral
(Table 2.2) either by an alteration in the structure or from reprecipitation of the
products of weathering (dissolution) of a primary mineral. Common secondary
minerals in soils are the aluminosilicate minerals such as kaolinite and
montmorillonite, oxides such as gibbsite, goethite, and birnessite, amorphous
materials such as imogolite and allophane, and sulfur and carbonate minerals. The
secondary minerals are primarily found in the clay fraction of the soil but can also be
found in the silt fraction (Sparks 1995).

TABLE 2.2
Common Secondary Minerals in Soils (Sparks 1995)
Name Chemical formula
Clay minerals
Kaolinite Si4Al4O10( OH)8
Montmorillonite MX (Al, Fe2+, Mg)4Si8O20 (OH)4 [M = interlayer metal
cation]
Vermiculite (Al, Mg, Fe3+)4 (Si, Al)8O20(OH)4
Chlorite [M Al (OH)6](Al, Mg)4(Si, Al)8 O20(OH, F)4

Allophane Si3Al4O12 . nH2O

Imogolite Si2Al4O10 . 5H2O
Goethite FeOOH
Hematite α-Fe2O3
Maghemite γ-Fe2O3
Ferrihydrite Fe10O15 . 9H2O
Bohemite γ-AlOOH
Gibbsite Al (OH)3
Pyrolusite β-MnO2
Birnessite δ-MnO2
Dolomite Ca Mg(CO3)2
Calcite CaCO3
Gypsum CaSO4 . 2H2O

17
 2.3. FORMATION OF CLAY MINERALS
The silicate clays are developed from the weathering of a wide variety of minerals by
at least two distinct processes: (1) a slight physical and chemical alteration of certain
primary minerals, and (2) a decomposition of primary minerals with the subsequent
recrystallization of certain of their products into the silicate clays (Brady and Weil
2002). The simplified framework of mineral weathering is presented in fig. 2.1

Microline Hot wet climate (-Si)

Rapid removal of bases
Orthoclase
Much Mg in weathering zone
Others
High in K

-K
-K Fine-grained
Muscovite +K
+H2O micas (illite)
Primary aluminosilicates

-K
Mica +H2O
-K
-Mg Smectite - Si Kaolinite - Si Oxides of
Vermiculite Montmori-
Biotite Fe and Al
-Mg llonite
-Mg
Primary -K Clay -Mg
chlorite
High in Mg, Ca, Na, Fe

chlorite

Soda lime Slow removal of bases

Feldspars Rapid removal of bases
Auguite Hot wet climate (-Si)
Hornblen-
de
Others

Fig. 2.1 - General conditions for the formation of the various layer silicate clays and
oxides of iron and aluminum (Brady and Weil 2002)

2.3.1. Formation of Vermiculite

Vermiculites will not form from solidification of a magma, and it is most universally
assumed that the mineral can be formed only by alteration of a micaceous mineral.
Borchardt et al. (1966) showed that trioctahedral vermiculite pseudomorphs after
mica are common in many soils. Trioctahedral vermiculite in soils may be formed by
alteration of biotite, phlogopite, or chlorite either in the soil or in the parent material
(Johnson 1964).

18
The alteration of micas to vermiculites may be subdivided into separate steps, or
factors affecting alteration: (i) release of K, (ii) oxidation of Fe2+and (iii) OH
orientation. These reactions may be mitigated by the presence of organic acids
(Robert et al. 1979).

2.3.1.1. Release of Potassium

The rate of release of K from interlayer positions in mica and replacement by other
ions may be considered a diffusion process, with diffusion of K+ out and diffusion of
the counter ion to the vacated spot (Chute and Quirk 1967). A biotite disk, when
placed in an appropriate salt solution, will alter so that in a short time a vermiculite
halo will appear to encircle the biotite core. Alteration proceeds parallel to the X and
Y directions, with little apparent alteration parallel to the Z direction in the crystal.
Potassium may diffuse from all interlayers, with mica going directly to vermiculite. In
other cases K may diffuse along a specific (001) plans but not from adjacent (001)
planes. The latter causes a wedge-shaped K+ depleted zone in the mica (Rich 1964).
This process results in the widely reported (Jackson 1963, Bassett 1959, Roux et al.
1963) mica-vermiculite interstratified minerals. Very small amounts of K in solution
will prevent the replacement of K+ by such cations as Mg2+. The reaction biotite to
vermiculite will proceed only when leaching is effective removes K (Bassett 1959).

2.3.1.2. Oxidation of Iron

Most of the iron in biotite is in the reduced state, and most of the iron trioctahedral
vermiculite is in the oxidized state (Weaver and Pollard 1973). Some of the octahedral
position are lost during the alteration process (Hwang 1970) and some Al migrates
from tetrahedral sites to octahedral sites (Vicente et al. 1977), resulting in a larger
proportion of more stable dioctahedrel sites in the weathering product. This increase
in number of dioctahedrel sites also causes an increase in the rotation of tetrahedra
and thus decreases the length of the b axis (Farmer et al. 1971). Divalent iron may be
dissolved and lost via the soil solution or oxidation and precipitation. The
simultaneous oxidation and expulsion of iron from a mica may result in the formation
of either hydroxy-Fe vermiculite (Vicente et al.1983) or a crystalline external phase of
β-FeOOH. Under acidic conditions the oxidation of Fe is enhanced by a need by a
decrease in total charge of the octahedral sheet through loss of octahedral Fe and Mg;

19
the decrease in surface charge is minimal and vermiculite is formed (Farmer et al.
1971).

2.3.1.3. Hydroxyl Orientation

In trioctahedral micas OH- ions sit in a hole above three divalent (Fe2+ or Mg2+) ions.
This causes a uniform charge distribution below the OH and repels the H portion of
the OH. In trioctahedral micas the H end of the OH is pointed directly toward the K.
In dioctahedral micas the cations in the octahedral sheet are primarily trivalent (Al3+),
with only two-thirds of the available octahedral positions occupied; each OH sits
above two cations and a structure vacancy. The octahedral cations orient the OH- ion
so that the H- ion points in the general direction of the interlayer K+, but is tilted
toward the vacant octahedral site. Thus, in trioctahedral micas the K+ sits in a volume
strongly affected by the repulsive forces (polarity) of the H portion of the OH (Dixon
and Weed 1989). Dioctahedral micas slowly alter to dioctahedral vermiculite, and
trioctehedral micas alter to trioctahedral vermiculite rather rapidly. Absolute times for
the alteration of micas or chlorites to vermiculites varying from three to several
thousand years (Novak et al. 1971).

2.3.2. Formation of Smectite

In the environment smectite can form by the transformation of mica, chlorite and
solution. They are discussed bellow.

2.3.2.1. Transformation from Mica

Similarities in their sheet structures have long led to the conclusion that smectites
could be derived from micas by depotassication (Crawford et al. 1983). Smectites
weathered from micas are likely to be tetrahedrally substituted, approaching the
beidellite end member in chemical composition (Ozkan and Ross 1979). Trioctahedral
micas are likely to produce unstable trioctahedral smectites that tend to lose Mg and
Fe from the octahedral sheet during further weathering. The term transformation
smectite has been proposed for smectites derived from micaceous minerals (Robert
1973). The following equation describes the weathering of phlogopite mica to
saponite, a trioctahedral smectite: (Robert 1973)
(Si3Al)(Mg3)O10(OH)2K + O.5Si4+ + 0.25Ca2+
(Si3.5Al0.5)(Mg3)O10(OH)2Ca 0.25 + 0.5Al3++ K+

20
The equation illustrates the essential changes necessary for smectite transformation
from a mica. They are (Komarneni et al. 1985)
1. Depotassication as in vermiculite formation
2. Dealumination of the tetrahedral sheet followed by
3. Silication of the tetrahedral sheet
Without these extensive changes, micas do not have the low-charge characteristics
necessary for them to exhibit the properties of smectites.

2.3.2.1.1. Environment that promote the transformation of mica

First, temperatures and pressures must be low enough to destabilize the tetrahedral Al
that distinguishes weatherable micas (Jackson 1963). Second, the concentration of K
must be low, such as in rainwater and in soil solutions of heavily cropped soils. Third,
Si(OH)4 concentrations must be high as provided by mafic minerals with Si potentials
higher than that of smectite (Huang 1966). Fourth, Al concentrations must be low, as
they are in soils with pH’s above 6 or 7. Thus, soils with low K+ and Al3+ and high
Si(OH)4 and Ca2+ or Mg2+ activities and pH above 6.5 are likely to contain
transformation smectites. At a soil pH < 6, mica weathers to vermiculite, which
subsequently tends to form kaolinite (Ismail 1970).

2.3.2.2. Transformation from Chlorite

Mafic chlorite is highly unstable in most soils. It would he expected to lose its
hydroxide interlayer at pH levels < 6 and under severe leaching and oxidizing
conditions, thus forming a smectite that is, in turn, relatively unstable due to its
trioctahedral nature. These are not conditions that would be expected to preserve
smectite indefinitely. The laboratory weathering of trioctahedral, Fe-rich chlorite can
be accomplished in a saturated Br2 solution at 100°C (Senkayi et al. 1981). The
reaction proceeds with the production of regularly interstratified chlorite-vermiculite
and chlorite-smectite intermediates occurring in the first 2d. Within 2 weeks, the
chlorite disappears entirely (Adams et al. 1971).

2.3.2.3. Formation from Solution

Smectites that precipitate directly from soil or matrix solutions may be called
neogenetic smectites. Vast regions of the world have simectitic soils formed primarily

21
in young glacial and alluvial materials, a fact suggesting that smectite neogenesis
occurs rapidly if it occurs at all. (Dixon and Weed 1989).

2.3.3. Formation of Kaolinite

Formation of kaolinite depends upon the Equilibrium environment and conditions. There
are also possibilities to form kaolinite from Hydroxy-Al Interlayered Montmorillonite

2.3.3.1. Equilibrium environment and conditions for synthesis of Kaolinite

Formation of kaolinite in the presence of smectite at 25°C provides an example of
mineral precipitation under conditions much like those in field soils. Several samples
of three reference smectites were acidified with HCl and adjusted with solutions of Si
and Al to provide a range of conditions prior to incubation (Kittrick 1970). Analyses
were made periodically to determine solution compositions. After 3 to 4 year, the
formation of kaolinitic was shown in some samples. A stability line for kaolinite
derived from data obtained at equilibrium and an equation for the precipitation of
kaolinite are shown in fig 2.2.

8
Gibbsite
7

6
log Al3+ + 3pH

4
Amorphous Silica

3
-4 -3 -2
log H4SiO4
Fig. 2.2 - Composition of solutions equilibrated with montmorillonites from Belle
Fourche, South Dakota (□); Otay, California (○); and Aberdeen, Mississippi (∆)
after 3 to 4 year of equilibration. Solid symbols indicate kaolinite formation, and
open symbols indicate no detectable kaolinite. Size of the symbols indicates analysis

22
precision. Arrows indicate the direction of sample equilibration as shown by
previous analyses. Dashed solubility lines indicate metastable area (Kittrick 1970).

A stability line for kaolinite is drawn from Eq. [2.1] for the precipitation of kaolinite
from Al3+ and H4SiO4:

2 Al3+ + 2 H4SiO4 + H2O 6H+ + Si2Al2O5(OH)4(kaolinite) … … [2.1]

The equilibrium constant, K, for the reaction is

(H+)6
K =
(A13+)2(H4SiO4)2
An activity of unity is assumed for kaolinite and H2O. Taking log on both sides. [eq.
2.2] 3
log K = - 6pH - 2log Al - 2log H4SiO4 … … [2.2]

Dividing by 2 and rearranging gives [eq.2.3]

log Al3+ + 3pH = - log H4SiO4 - 1/2 log K … …[2.3]

The slope of the kaolinite stability line in fig. 2.2 is -1, and the intercept is -1/2 log K
from Eq. [2.3]. The intercept is based on the sample with the lowest log H4SiO4-the
point (□) at the far left in fig. 2.2 The last analysis of this sample had a pH of 3.47, log
H4SiO4 of -3.53 (assuming all dissolved Si as H4SiO4) and log Al3+ of -3.78 (corrected
from a molar concentration of log Al = -3.59 for Al equilibria and influence of ionic
strength). Thus, employing Eq. [2.2] gives

log K = - 6(3.47) - 2(- 3.78) - 2(- 3.53)

log K = - 6.20.

From Eq. [2.3] the intercept of the kaolinite stability line in fig. 2.2 is
- 1/2 log K, or 3.10.
The stability line in fig. 2.2 represents the boundary between the areas of
supersaturation (above) and undersaturation (below) for kaolinite. Kaolinite was
detected by X-ray diffraction analysis only in solutions saturated or supersaturated
with respect to kaolinite (solid data points). None of the data points indicated
supersaturation with respect to gibbsite. All of the undersaturated solutions and all of
the supersaturated solutions, except for one unexplained example, appear to be
progressing toward the kaolinite stability line (Dixon and Weed 1989).

23
By calculating the free energy of formation, ∆G, equivalent to the stability line for the
kaolinite derived above, comparison can be made with the stability of other kaolinite
subgroup minerals from Eq. [2.1]
3+
∆Gr = ∆G (kaolinite) - 2∆G Al - 2∆G H4SiO4 - ∆GH2O … ...[2.4]

where ∆Gr is the standard free energy of reaction. And = ∆Gr = - RT In K = 1.364 pK,
or 35.4 kJ mol-1 at 25°C. Hence
∆G (kaolinite) = -3.783 MJ mol-1

The ∆G of -3.783 MJ mol-1 suggests a slightly greater stability for the synthetic
kaolinite than does the ∆G of -3.78 1 MJ mol-1 for a kaolinitic of reportedly near
maximum crystallinity. The ∆G values for kaolin precipitated in soils and sediments
at 25°C probably will range from 3.760 MJmol-1 for halloysite to the initial
precipitation level of -3.783 MJ mol-1 for kaolinite (Kittrick 1970).

2.3.3.2. Kaolinite formation from Hydroxy-Al Interlayered Montmorillonite

Kaolinite formation has been induced by hydrothermal treatment of hydroxy-Al
interlayered montmorillonite at 220° C (Poncelet and Brindley 1967). The kaolinite
was expanded to approximately 0.85 nm during the first few days of reaction. After
14 d of hydrothermal treatment or heating at 300° C following hydrothermal
treatment, the kaolinite collapsed to 0.72 nm. The early product had a spacing
suggestive of halloysite or a halloysite-kaolinite interstratified mixture (Dixon and
Weed 1989).

Efforts to synthesize kaolinite from smectite have produced kaolinite-smectite

interstratified. Both tetrahedral and octahedral sheets of smectite were ought to
dissolve, releasing H4SiO4 for reaction with Al3+ to form kaolinite according to the
following equations (2.5 and 2.6): Tetrahedral and octahedral sheets of smectite
dissolve:

(Al,Fe,Mg)2Si4O10(OH)2 + 4H2O + 6H+ 2 (A1,Fe,Mg)3+ + 4H4SiO4 ... [2.5]

24
H4SiO4 and Al3+ react to form kaolinite

2H4SiO4 + 2A13+ + H2O A12Si2O5(OH)4 + 6H+ .. .. [2.6]

The net reaction gives the eq.2.7

(Al,Fe,Mg)2 Si4 O10 (OH)2 + mAl3+ + 6H2O

2Al2Si2O5(OH)4 + 6H+ + aFe3+ + bMg+ [2.7]

Where m = 2 + a + b.
The addition of Al3+ contributed to the progress of the reaction and to kaolinite
production to a limit where smectite appeared to be stabilized. No amorphous silica
product was formed, and the pH declined during the progress of the reaction as
suggested by the equations. Some unreacted smectite remained, and some discrete
kaolinite was formed (Dixon and Weed 1989).

2.4. STRUCTURE OF CLAYS MINERALS

The term clay mineral is commonly used to refer to minerals with the sheet silicate
structures of the phyllosilicates. Phyllosilicates are one of many subclasses of the
silicate mineral class (Fig. 2.3). The basic structural feature of all minerals in these
subclasses is the SiO4 tetrahedron linked by the sharing of three of four O anions to
form sheets with a pseudohexagonal network in the ab crystallographic plane. The
sheet has the composition (Si2O5)2-. The three shared O2- ions are termed basal O2-
ions while the fourth apical O2- is not shared with another SiO4 tetrahedron and may
bond to other structures. The tetrahedra are interconnected in sheet-like structures.
These sheets are commonly referred to as silica or tetrahedral sheets (Fig. 2.3).
Cations in each tetrahedral sheet are in fourfold coordination, i.e., each Si cation is
bonded to four O2- ions arranged in each tetrahedron. Aluminum may replace as many
as half of the Si, producing a formula composition such as (AlSi3O10)5- or
(Al2Si2O10)6-. Minerals in which tetrahedral sheets of silica dominate are often
referred to as layer silicates (Olson et al. 2000).

25
 Nesosilicates Sorosilicates
(SiO4)4- (Si2O7)6-

Tectosilicates
(SiO2)0
Single Chain
Inosilicates
(SiO3)2-

Phyllosilicates Double Chain

(Si2O5)2- Inosilicates
(Si4O11)6-

Fig. 2.3 - Classification of silicate minerals (Schulze 1989)

In most phyllosilicates, the tetrahedral sheet is combined with another sheet-like

grouping of cations such as Al3+, Mg2+, or Fe3+ in sixfold-coordination with O2- and
OH- anions. Sixfold coordination means that the negatively charged anions are
arranged around the positively charged cations in an octahedral pattern; one anion at
each corner of an octahedron surrounding a central cation. Adjacent octahedra share
anions to form a planar network referred to as an octahedral sheet (Schulze 1989).

Phyllosilicates may be structurally classified into dioctahedral and trioctahedral types.

This classification is based on the cation valence and configuration of the octahedral
site in two- or three-layer structures. There are two ways to fill an octahedral site,
depending on the cation valence. A divalent cation (Ca2+, Mg2+) when placed into the
octahedral site produces a trioctahedral arrangement (Olson et al. 2000).

Phyllosilicates strongly influence chemical and physical properties of soils because of

their small particle size, high surface area, and cation exchange properties. Among the
phyllosilicate minerals important to soil development, the most common are discussed
here: mica, vermiculite, chlorite, smectite, interstratified minerals, kaolinite, and talc
and pyrophyllite. Depending on the arrangement of octahedral and tetrahedral sheets

26
the clay minerals can be grouped into 1:1, 2:1 and 2:1:1 (Table 2.3) type clay minerals
(Olson et al. 2000).
TABLE 2.3
Classification of phyllosilicates in soils (Brindley and Brown 1980)
Layer Charge/unit
Group Subgroup Mineral Species
Type formula
Kaolinite
Kaolin 1:1 Kaolin ~0
Halloysite
Pyrophyllite 2:1 Pyrophyllite Pyrophyllite ~0
Talc 2:1 Talc Talc ~0
Montmorillonite
Beidellite
Dioctahedral smectites
Nontronite
Smectite 2:1 0.2- 0.6
Saponite
Trioctahedral smectites
Hectorite
Sauconite
Dioctahedral
Dioctahedral vermiculite
vermiculite
Vermiculite 2:1 0.6 - 0.9
Trioctahedral
Trioctahedral vermiculite
vermiculite
Muscovite
Paragonite
Dioctahedral micas
Celadonite
Mica 2:1 ~1.0
Biotite
Trioctahedral micas
Phlogopite
Lepidolite
Illite Illite Illite ~0.6 - 0.9
Dioctahedral chlorites
Chlorite 2:1:1 variable
Trioctahedral chlorites

27
2.4.1. The 1:1 Type Minerals
The 1:1 layer structure consists of a unit made up of one octahedral and one
tetrahedral sheet, with the apical O2- ions of the tetrahedral sheets being shared with
(and part of) the octahedral sheet. There are three planes of anions. One plane consists
of the basal O2 ions of the tetrahedral sheet, the second consists of O2 ions common to
both the tetrahedral and octahedral sheets plus OH- belonging to the octahedral sheet,
and the third consists only of OH- belonging to the octahedral sheet (Dixon and Weed
1989). The common 1:1 type clay minerals are described bellow.

2.4.1.1. Kaolinite
Kaolinite occurs commonly in soils, often as hexagonal crystals with an effective
diameter of 0.2 to 2 µm. Hydrogen bonding between adjacent unit layers prevents
expansion (swelling) of the mineral beyond its basal spacing of 7.2 Å (Fig 2.4).
Surface area is limited to external surfaces and hence is relatively small, ranging from
10 to 20 m2/g. Kaolinite is coarse clay with low colloidal activity, including low
plasticity and cohesion, and low swelling and shrinkage (Bhon et al. 1979). Kaolinite
is dioctahedral and the layer is electrically neutral. Other kaolin minerals, dickite and
nacrite, have the same basic 0.7-nm unit layer thickness but stacking sequences of
layers along the c axis differ (Olson et al. 2000).

O
H-bonding
between basal planes
C-spacing OH
7.2 Å
Al

O, OH
Si
O
Fig. 2.4 - Schematic structure of Kaolinite Al2 Si2 O5 (OH)4 (Bear 1964)

The ideal unit formula for kaolinite [Al2Si2O5 (OH)4] has an Si/Al ratio of 1 which
suggests little or no isomorphic substitution. Most of the 1 to 10 cmol kg-1 cation

28
exchange capacity of kaolinite has been attributed to dissociation of OH groups on
clay edges. However, if only one Si4+ of every 400 in the silica sheet were substituted
by Al3+, the net negative charge would be cmol kg-1. Chemical analysis of clay
systems is not sufficiently sensitive to prove or disprove this extent of isomorphic
substitution. Such limited substitution is not sufficient to alter the unit cell formula
given for kaolinite. The cation exchange capacity of kaolinite is highly pH-dependent
suggesting that isomorphic substitution is not the predominant source of charge (Bhon
et al. 1979).

Kaolinite in soils is both authigenic (formed in place) and allogenic (formed

elsewhere). It can form from the weathering of primary and secondary minerals,
subsequent to the release of Si4+ and Al3+. In most soils, however, kaolinite is
inherited from the weathering of older sediments (Olson et al. 2000).

Kaolinite particles are often >1 µm in size and have a platy or book-like appearance
when viewed with an electron microscope. Although not considered an expanding
clay mineral, kaolinite will swell with the intercalation of some small polar molecules
such as formamide, hydrazine or urea (Olson et al. 2000).

2.4.1.2. Halloysite
Halloysite is similar in structure to kaolinite except for a layer of water molecules that
is intercalated within the 1:1 layer. It differs in morphology from kaolinite in that it is
often tubular (Singh 1996). Bates (1958) also described lath-shaped and polyhedral
forms of halloysite and a platy halloysite. Fig 2.5 shows the schematic structure of
Halloysite.

Halloysite has water molecules between each 1:1 layer and the ability to adsorb large
quantities of monovalent cations such as NH4+. Drying will cause the water molecules
to be removed and the clay layers to collapse together (Newman and Brown 1966).
Halloysite is also characterized by a tubular morphology, whereas kaolinite, when
examined with microscopic techniques, has a platy structure (Sparks 1995). Halloysite
is found primarily in soils of volcanic origin and typically weathers to kaolinite. If not
properly handled during sampling and analysis, it is difficult to distinguish halloysite

29
from kaolinite; once dehydrated, the layer spacing decreases to close to that of
kaolinite (Olson et al. 2000).

Hydrogen bonding

H 2O
C-spacing Hydrogen bonding
10.25 Å OH
Al
O, OH
Si
O

Fig. 2.5 - Schematic structure of Halloysite Si4 Al4 O10(OH)8.4 H2O (Bear 1964)

2.4.2. The 2:1 type Minerals

The 2:1 layer structure consists of two tetrahedral sheets bound to either side of an
octahedral sheet. There are four planes of anions. The outer two planes consist of the
basal oxygens of the two tetrahedral sheets, while the two inner planes consist of
oxygens common to the octahedral sheet and one of the tetrahedral sheets, plus the
hydroxyls of the octahedral sheet (Dixon and Weed 1989). The common 2:1 type clay
minerals are described bellow.

2.4.2.1. Smectite (Montmorillonite)

The term smectite is a generic name for 2:1 clay minerals that swell or collapse easily
depending on their pressure potential, osmotic potential, and saturating cations
(Sumner 2000). Smectites are 2:1 layer silicates with layer charge of 0.25 to 0.6 per
formula unit. Because of the relatively low layer charge, smectites are freely
expanding. The c-spacing varies with the exchangeable cation and the degree of
interlayer solvation. Complete drying yields a spacing of 9.6 Å, and full hydration can
swell the layer to distance of tens or even hundreds of Angstroms (Bhon et al. 1979).

30
Clay minerals in the smectite-saponite group are characterized by a layer charge of
0.2-0.6 per half-cell formula unit. The group includes the subgroups dioctahedral
smectites and trioctahedral saponites. The dioctahedral smectites are represented by
montmorillonite, beidellite, and nontronite. The ideal half-cell chemical formula for
montmorillonite is M0.33, H2OAl1,67 (Fe2+, Mg2+)0.33 Si4O10(OH)2, where M refers to a
metal cation in the interlayer space between sheets. The tetrahedral cations are Si4+
and the octahedral cations are Al3+, Fe2+ and Mg2+ (Fig 2.6). One can calculate the
negative charge in the tetrahedral sheet as 0 and in the octahedral sheet as - 0.33.
Thus, the net negative charge is - 0.33 that is balanced by exchangeable cations
represented by M0.33. The other feature that characterizes montmorillonite is the
presence of water molecules in the interlayer space. This causes montmorillonite to
take on shrink-swell characteristics (Spark 1995).
Si
O
Na
O
C-spacing Si
9.6 to 18
Å O, OH
Al, Mg
O, OH
Si
O
Fig. 2.6 - Schematic structure of montmorillonite Nax(Al2-xMgx)Si4O10(OH)2 (Bear
1964)

The major difference between montmorillonite and the other two dioctahedral
smectites, beidellite and nontronite is that isomorphous substitution in these minerals
occurs in die tetrahedral sheet (i.e., Al3+ Substitutes for Si4+) rather than in the
octahedral sheet. Nontronite also is a Fe-bearing mineral with Fe3+ being the
predominant element in the octahedral sheet (Sparks 1995).

Typical cation exchange capacities for montmorillonite range from 80 to 120 cmol kg-1.
The cation exchange capacity is only slightly pH-dependent. The low layer charge
allows the mineral to expand freely, exposing both internal and external surfaces.
Such expansion yields a total surface area of from 600 to 800 m2/g, with as much as
80% of the total due to internal surfaces. Montmorillonite has high colloidal activity,

31
including high plasticity and cohesion, and high swelling and shrinkage.
Montmorillonite normally occurs as a fine clay with irregular crystals having an
effective diameter of 0.01 to 1 µm. Smectites are common in Vertisols and are
especially common in soils of alluvial plains (Bhon et al. 1979).

2.4.2.2. Vermiculite
Vermiculite occurs extensively in soils. It forms as a product of weathering or
hydrothermal alteration of micas and possibly also of chlorites. The weathering or
alteration of micas has replaced the potassium by predominantly exchangeable
magnesium and has expanded the interlayer space to yield a unit cell c-spacing of 14
Å or more, so as to accommodate interlayer water and interlayer exchangeable cations
(Bear 1964). Fig. 2.7 shows the schematic structure Vermiculite.

The general formula for vermiculite is Mx-y(R(2+)3-y, R(3+)y) (Si4-x, Alx)O10 (OH)2 +
H2O, where x represents the tetrahedral substitution and y, the octahedral substitution
and M is most often Mg2+. In ambient conditions, 6 water molecules, arranged in two
sheets, form an octahedron around each Mg2+. Vermiculites saturated with Ca2+ or
Mg2+ and equilibrated at 54% relative humidity expands to a lesser degree than
smectites, i.e., X-ray diffraction (XRD) d-spacing are about 1.4 nm rather than 1.7 nm
(Olson et al. 2000).

Si

H2 O

H 2O
C-spacing O
10.15 Å Al, Si
O, OH
Mg, Fe2+
O, OH
Al, Si
O

Fig. 2.7 - Schematic structure Vermiculite Mgn (H2O)6 (Mg, Fe++)3 Si4-n Aln O10(OH)2
(Bear 1964)

32
Isomorphic substitution in the tetrahedral sheet yields an excess negative charge of
1.3. Isomorphic substitution in the octahedral sheet yields an excess positive charge of
0.6. So the net charge is -0.7 per unit formula. The layer charge in vermiculite gives
rise to a cation exchange capacity of from 120 to 150 cmol kg-1, which is considerably
higher than the exchange capacity of montmorillonite. As with montmorillonite, the
cation exchange capacity is only slightly pH-dependent. Vermiculite swells less than
montmorillonite because of its higher layer charge. The mineral is nonswelling (with
a c-spacing of 10 Å) when saturated with K+ or NH4+ ions. Such ions are commonly
termed fixed and cannot be exchanged with ordinary salt solutions. Total surface
areas of vermiculite, when not K+ or NH4+ saturated, range from 600 to 800m2/g
(Bhon et al. 1979).

2.4.2.3. Mica
Micas occur in almost any geologic environment and are abundant in many rocks
including shales, slates, phyllites, schists, gneiss, granites, and in sediments derived
from these rocks. As clay minerals, they can be derived from preexisting micas by
mechanical fragmentation but may also form in situ. Micas are 2:1 phyllosilicates
having a charge imbalance that is satisfied by a tightly held, nonhydrated, interlayer
cation (Olson et al. 2000).

The idealized end member micas are dioctahedral muscovite- K2Al2,Si6Al4O20(OH)4,

and its isomorphous analogue paragonite Na2Al2,Si6Al4O20(OH)4, and trioctahedral
biotite- K2Al2Si6 (Fe2+, Mg)6O20(OH)4 and phlogopite- K2Al2,Si6Mg6O20(OH)4. A
variety of additional ion substitutions, beyond those indicated for the end members,
such as Li for Mg, more Al for Si, F or O for OH, and possibly OH for O, can occur
in micas. Layer charge, represented equivalent to K, in the end-members, decreases in
some biotites because of substitution of Al for Mg, or Fe3+ for Fe2+ in the trioctahedral
layer. The layer charge is extremely high in margarite-Ca2Na2Al2,Si6Al4O20(OH)4
which is representative of the “brittle” micas (Bear 1964).

Micas have an octahedral sheet sandwiched between two tetrahedral sheets (Fig. 2.8).
One of the 4 tetrahedral sites typically contains Al3+ rather than Si4+. This results in
excess negative charge per formula unit. The negative charge is balanced by

33
monovalent cations, usually K+, occupying interlayer sites between two tetrahedral-
octahedral-tetrahedral layers. The general formula is Mx(R(2+)3-y, R(3+)y) (Si4-X,
Alx)O10(OH)2 where M is usually K+ or Na+. Micas can be either dioctahedral or
trioctahedral. The mica group consists of many species because Fe2+ and Fe3+
substitute for Mg2+ and Al3+ in octahedral sheets and Na+ and Ca2+ may substitute for
K+. Occasionally, Ba2+, Rb2+, Cs, Sr+, or NH4+ also substitute for K+ (Nettleton et al.,
1970; Speer, 1984), particularly in biotite mica (Olson et al. 2000).

O
K
O
Si, Al
C-spacing
10 Å O, OH

O, OH
Si, Al
O

Fig. 2.8 - Schematic structure of Mica K[Al2 (Si3Al) O10(OH)2] (Bear 1964)

Although micas may be either dioctahedral or trioctahedral, isomorphic substitution in

the tetrahedral layer creates negative charge close to the unit layer surface. This
charge strongly retains the K+ ion. Such interlayer K+ is so strongly adsorbed that it is
not exchanged in standard cation exchange capacity determinations. Thus despite the
relatively large layer charge (about -1 for many micas), the CEC is only 20 to 40 cmol
kg-1. Total surface area is about 70 to 120 m2/g and is restricted to external surfaces.
Micas are nonswelling and are only moderately plastic. So-called fixed K+ is released
slowly during weathering and is an indigenous source of K+ for many soils (Bhon et
al. 1979).

2.4.2.4.1. Illite
Illite is found in the clay fraction of soils and sediments and mainly forms from mica.
It is the most abundant clay mineral in sedimentary rock. Illite forms and is stable at
the Earth’s surface. Shales have both diagenetic and detritally recycled illitic
components. Illite also forms during surficial weathering, as well as in hydrothermal
and in metamorphic environments (Olson et al. 2000).

34
Although illite is usually dioctahedral, it differs from muscovite in that the octahedral
sheet of illite contains more Fe2+ and Mg2+ in place of Al3+ than muscovite. The
overall layer-charge density of illite is less than that of either biotite or muscovite. In
the tetrahedral sheet of illite Al3+substitutes less for Si4+. The K+ content of illite is
also lower due to the lower negative layer charge that must be countered. Some illites
have NH4+ rather than K+ in the interlayer space (Moore and Reynolds 1997). The
NH4+ found in rocks with high organic matter contents (e.g., shales), the assumed
source of the N (Olson et al. 2000).

Illite has a layer charge of about 0.8 per half-cell formula unit, intermediate between
smectite and mica. Grim et al. (1937) developed the term illite to describe clay-size
mica that was found in argillaceous rocks. Other terms that have been used for illite
are hydromica, hydromuscovite, hydrous illite, hydrous mica, K-mica, micaceous
clay, and sericite. Illite has more Si4+, Mg2+ and H2O but less tetrahedral Al3+ and K+
and water than muscovite. While K+ is the predominant interlayer ion along with
divalent ions such as Ca2+ and Mg2+, NH4+ can also occur in illite (Sparks 1995).

2.4.2.5. Chlorites
Chlorite occurs extensively in soils, mainly inherited from mafic rocks, serpentine,
and other rocks, but to some extent formed in soils. This mineral is a 2:1:1 or 2:2
layer silicates. A hydroxide interlayer (sometimes termed the “brucite” layer) of
composition such as Al2Mg4(OH)122+, is sandwiched between negatively charged
mica-like layers as a replacement for K+ in the mica structure. A type formula for
trioctahedral chlorite is (Al2Si6)Al2Mg10O20(OH)14, in which Fe2+ and other divalent
cations may replace Mg, and Fe2+ and other cations may replace Al. This formula may
be written as AlMg6(OH)12. (Al2Si6)AlMg6O20(OH)4. Chlorite is usually trioctahedral,
but dioctahedral chlorite, which may be represented by the formula Al4.4 (OH)12.
(Al1.2, Si6.8) Al4O20(OH)4 also occurs (Bear 1964).

Chlorites are often referred to as 2:1:1 clays since they are 2:1 clays with a hydroxide
interlayer, either gibbsite-like [Al(OH)x] or brucite-like [Mg(OH)x] where x is <3, that
is continuous across the interlayer sheet and is octahedrally coordinated (Fig. 2.9).
This sheet is positively charged because there are fewer than 3OH- per Al3+ in the

35
sheet. The interlayer sheet is bound to the 2:1 clay electrostatically and the tetrahedral
layer is bonded to the interlayer sheet by hydrogen bonding (Sparks 1995). Cation
exchange capacities range from 10 to 40 cmol kg-1, and total surface area values from
70 to 150m2/g (Bhon et al. 1979).

O
OH
Al, Mg
OH
C-spacing O
14 Å Si, Al

O, OH
Mg
O, OH

Si, Al
O

Fig. 2.9 - Schematic structure Chlorite [Al Mg2 (OH)6] [Mg3 Si3 Al O10(OH)2] (Bear
1964)

2.4.3. Interstratified Clay Minerals

Since the 2:1 and 1:1 layers of clays are strongly bonded internally but are weakly
bonded to each other, layers can stack together to form interstratified clays. Examples
include interstratified smectite with talc-type units and smectite and mica units such
as 1:1 mica-dioctahedral smectite or hectorite. Another example would be
interstratifications of smectite or vermiculite with chlorite. For example, a 1:1
regularly interstratified chlorite-smectite structure would contain four tetrahedral
sheets, two in each of the 2:1 layers, three octahedral sheets, one in each of the 2:1
layers and the other in the hydroxidic interlayer, and one expanding interlayer space
containing the exchangeable cations. Interstratification of smectite with kaolinite can
also occur (Newman and Brown 1966). Carroll (1970) suggests that mixed-layering
occurs in two ways: (1) degradation due to weathering of rocks, sediments, and soils,
or (2) diagenesis.

36
Similarly, Sawhney (1989) states that naturally occurring mixed-layer minerals form
by
1. Hydrothermal alteration,
2. Weathering involving partial removal of interlayer K from mica or removal of
a hydroxide-interlayer from chlorite, or
3. Uptake of K and
4. Formation of a brucite-like or gibbsite-like interlayer in expanding layer
silicates.

2.4.3.1. Montmorillonite–Vermiculite–Chlorite Intergrade

Precipitation of coatings of hydrous, positively charged sesquioxides on the negative
surfaces of layer silicates has long been recognized as a phenomenon characteristic of
soils, as has their fundamental influence on soil chemical properties such as phosphate
fixation. Precipitation of hydroxy-aluminum, hydroxy sesquioxides, and possibly
magnesium hydroxide as gibbsite-like (or brucite-like) structures in the interlayer
spaces of montmorillonite and vermiculite produces structures the properties of which
are intergradient between those of the expansible mineral and those of chlorite. Most
natural clay intergrades so far described have shown 14 Å diffraction spacing and
have been termed “dioctahedral vermiculite”, “vermiculite”, “chlorite-like” or
chlorite, according to the end-member to which they are compared. The interlayers
are heterogeneous with respect to islands of the “brucite-like” structures or “gibbsite-
like” structures which are distributed in interlayer spaces otherwise filled with water
and exchangeable cations, as is characteristic of vermiculite or montmorillonite. The
cation exchange capacity is consequently decreased to the extent of the positive
charge of the nonreplaceable hydroxy cation interlayers. The interlayer specific
surface is also decreased. The interlayer space becomes increasingly resistant to
collapse by heating as hydroxy interlayers become more extensive. The products have
appropriately been designated as inter- gradient 2:1 to 2:2 layer silicates or
intergradient montmorillonite-vermiculite-chlorite (Bear 1964).

37
2.4.3.2. Swelling 2:1 to 2:2 intergrades
“Swelling chlorite” has been described as having one surface of the brucite-like layer
unattached to a silicate layer, the interlayer positions thus would be heterogeneous
with respect to brucite and water-cation layers, and the complex is a swelling 2:1 to
2:2 intergrades. A sharp 18 Å peak with Mg saturation and glycerol solvation, and a
greatly broadened 10 Å peak with K saturation and 500° C heating, characterize the
expanding montmorillonite-chlorite intergrade type of clay (Bear 1964).

In alkaline soils of arid regions, montmorillonite is relatively stable to weathering and

so has a high frequency distribution. Characteristically, it is partially interlayered. The
weathering mechanism by which swelling intergradient 2:1 to 2:2 montmorillonite-
chlorites is formed appears to arise from the swollen character of montmorillonite
when moist. The presence of abundant montmorillonite creates moist conditions and,
as a result, the clay in the soil is kept swollen to 20 to 40 Å spacing. Intercalated
hydroxyaluminum sheets can attach to only one layer of montmorillonite so long as
the layers are widely separated. In a feldspar rich mantle, alkalinity and hydrolysis
yield a plentiful supply of freshly precipitated aluminum hydroxide, which has a
positive charge when below pH 8.3. The (+) valence charges on the hydroxy
sesquioxide inter- layer cations attach to (-) exchange sites. Laboratory syntheses also
have involved attachment of gibbsite interlayers to one surface while the
montmorillonite is in a swollen state. The cation exchange capacity was considerably
lowered by the introduction of hydroxyaluminum interlayers in synthetic preparations
(Bear 1964).

2.5. SOIL MINERAL WEATHERING SEQUENCES

Soil mineral weathering has been studied for many decades; most of the available
information, however, is empirical in nature and cannot be used for quantitative
predictions. In this section some of the available empirical weathering sequences
along with the predictions based on thermodynamic data have discussed (Dixon and
Weed 1989).

Although there are exceptions, minerals that are far removed from their formation
environment tend to be the least stable. Based on generalizations from accumulated

38
data, (Goldich 1938) proposed a mineral stability sequence (Fig. 2.10) that supports
the above hypothesis, in which the least stable minerals (in an aqueous environment)
are the first to crystallize during cooling of magma, and the most stable minerals
crystallize last. Because weathering (in this case, essentially the rate of dissolution) is
highly dependent on the nature of the weathering environment, however, the main
drawback of this sequence is that it does not consider the weathering environment.
Furthermore, secondary minerals that are weathering products of the preexisting
minerals are not considered (Dixon and Weed 1989).
Olivine
Calcic Plagioclase
Augite
Calci-Alkalic Plagioclase
Hornblende Alkali-Calcic Plagioclase Increase
Alkalic Plagioclase Stability
Biotite

Potash Feldspar

Muscovite

Quartz

Fig. 2.10 - Mineral stability sequence. Stability of minerals increases as one proceeds
towards quartz, and as a group, salic minerals (plagioclases, feldspars, etc.) are
more stable than mafic minerals (olivine, augite, etc.) (Goldich 1938)

Jenny (1941) considered soil development to be a function of five factors: parent

material, topography, biosphere, climate, and time. The resultant weathering therefore
was considered to be a function of these factors.

Jackson and Sherman (1953) related the relative degree of soil development to the
types of minerals present in the clay fraction (Table 2.4). The explicit assumption in
this sequential development is that there is a continuous leaching of the soil profile
with time. Although, in general, the sequence is applicable to all soils and can be used
to categorize the soils according to their degree of development, this sequence cannot
be used to determine the specific chemical environmental conditions needed to bring

39
about these changes, or whether a given soil under a specific weathering environment
will proceed through all stages.

TABLE 2.4
Types of minerals as indicators for relative degree of soil development (the higher
the number, the higher the degree of development) (Jackson and Sherman 1953)
Relative degree of Prominent minerals in soil clay fraction
soil development
1 Gypsum, and other soluble salts
2 Calcite, dolomite, and apatite
3 Olivine-hornblende minerals
4 Biotite, glauconite, ferromagnesian chlorite
5 Feldspars
6 Quartz
7 Muscovite-illite
8 Interstratified 2:1 layer silicates and vermiculite
9 Montmorillonites
10 Kaolinite and halloysite
11 Gibbsite and allophane
12 Hematite-goethite
13 Anatase-leucoxene

Numerous other researchers have identified the weathering products of various rocks
and minerals and have proposed empirical weathering sequences. In general, it is
recognized that the weathering of a mineral is affected by its composition, coefficients
of expansion, cleavage, and original defects in the crystals, hardness, and specific
surface. Additional external factors are the physical, biological, and chemical
(oxidation/reduction, hydration, hydrolysis, pH, chelation, cation exchange,
carbonation) conditions of the weathering environment (Dixon and Weed 1989).

The rate of weathering of primary minerals (e.g., 80,000 and 8800 years) of mean
lifetime at 25°C and pH 5 for 1-mm crystals of albite and enstatite, respectively
(Lasaga 1984), as well as the rate of formation of crystalline clay minerals, is so slow
that the bulk mineralogy of any given soil is not expected to change considerably in
the lifetime of any given individual. Therefore, it is easy to analyze the sample
mineralogically and find the exact distribution of the minerals. In the case of trace

40
elements or hazardous elements, however, the type or sequence of mineral formation
is very important because it may control the concentrations of these elements in
groundwaters (Dixon and Weed 1989).

Thermodynamic data can be used to predict the formation and weathering of minerals,
and perhaps the sequence of mineral weathering, because the of a mineral is
dependent on the composition, crystallinity, nature of chemical bonds, etc., and
because the precise weathering environment can be quantified in terms of activities of
constituent ions (Dixon and Weed 1989).

Most major soil minerals contain one or more elements in common. Rarely, if ever,
can these minerals all be in equilibrium with one another. Within the group competing
for common elements, individual minerals are usually stable (least soluble) over a
rather narrow range of solution compositions. Thus, it is possible to understand the
soil system over a small portion of its solution composition range by considering the
stabilities of only a few of its minerals (e.g., gibbsite, kaolinite, montmorillonites, and
amorphous silica) (Dixon and Weed 1989).

The use of thermodynamic data in making graphs to portray mineral weathering

sequences or stability sequences has been discussed by many authors (Garrels and
Christ 1965). As an example, the following reaction describes the equilibrium
between kaolinite and its dissolved species:

Al2Si2O5(OH)4 + 6 H+ 2 Al3+ + 2 H4SiO40 + H2O

Kaolinite and H2O have unit activity and thus can be ignored in the equilibrium
expression. The equilibrium constant (K) for the above reaction is therefore

(Al3+)2(H4SiO40)
K =
( H+)6
log K = 2 log (Al3+) + 2 log (H4SiO40) - 6 log ( H+) … [2.8]

Simplifying, rearranging, and substituting the above equation (Eq. 2.8), eq.2.9 derived

log (Al3+) + 3pH = 3.4 - log (H4SiO40) … [2.9]

41
This algebraic manipulation of the equilibrium constant (Eq. 2.9) permits a graphic
representation of this solubility reaction, as shown in fig. 2.11. Similarly, gibbsite,
amorphous silica, and montmorillonite solubilities are also plotted in fig. 2.11.

10
Kaolinite
Gibbsite
8
log Al3+ + 3 pH

6 a
Montmorillonite b
a = pH 6, pMg 3.7
4 b = pH 7, pMg 3.7

-7 -6 -5 -4 -3 -2
0
log (H4 SiO4 )

Fig. 2.11 - Relative solubility of a few clay minerals. Solubility lines for Belle
Fourche montmorillonite assume equilibrium with hematite and Na as the
exchangeable ion when log Na = -3. The data for SiO2 (am) are from Kittrick (1969);
for gibbsite, from Kittrick (1966a); for kaolinite, from Kittrick (1966b); and for
Belle Fourche montmorillonite, from Kittrick (1970)

Fig. 2.11 is a two-dimensional graph with a two-ion parameter on the ordinate and a
single illustrative contour line. Three ion variables are shown in this graph, with pH
and pMg (-log Mg2+) fixed at selected levels of interest (pMg 3.7 is the average
content of natural waters) and pFe3+ assumed to be fixed by hematite equilibrium and
pH. Only four minerals are considered explicitly, yet the graph appears to explain the
formation of gibbsite, kaolinite, and montmorillonite, and their control of Al3+ as a
function of H4SiO40. As the H4SiO40 concentration increases, first gibbsite, then
kaolinite, and finally montmorillonite become, in turn, the most stable mineral of the
group (Dixon and Weed 1989).

The most stable mineral also is the least soluble. At a log (H4SiO2) activity of -3.0, the
montmorillonite line (pH 6, pMg 3.7) is below the metastable extension of the

42
kaolinite stability line (dashed), which is below the metastable (dashed) extension of
the gibbsite stability line. Because the pH of the system is fixed, the lowest value of
log Al3+ + 3pH is the lowest value of Al3+. Gibbsite supports almost 10,000 times as
much Al3+ as montmorillonite at log (H4SiO40) of -3.0 and pH 7.0. At log (H4SiO40) of
-6.0, their relative solubilities are reversed (Dixon and Weed 1989).

The two montmorillonite stability lines (contours) in fig. 2.11 indicate that
montmorillonite becomes more stable as the pH increases and as pMg decreases. This
increased montmorillonite stability comes at the expense of kaolinite, whose stability
range is correspondingly restricted. The point where the montmorillonite and kaolinite
stability lines intersect defines the chemical conditions under which these two
minerals can be in equilibrium with each other. Montmorillonite-amorphous silica and
kaolinite-gibbsite are also compatible pairs. Incompatible pairs are amorphous silica-
gibbsite and montmorillonitc-gibbsite (unless solution conditions are such that
montmorillonitc becomes sufficiently stable to eliminate the kaolinite stability field
entirely). Perhaps the most important insight to be gained from fig. 2.11 is an
appreciation that a variety of minerals can be formed in soils in response to a variety
of soil-solution environments and that the chemical weathering environment can be
quantified (Dixon and Weed 1989).

The relative solubility of selected primary and secondary minerals is Plotted in fig.
2.12. It should be emphasized that the accuracy of the stability of a given mineral
depends on the conditions assumed for the diagram as well as on the accuracy of the
thermodynamic data used in the calculations. These diagrams can be extended to
include other minerals for which thermodynamic data are available and other
environmental conditions not considered in fig. 2.12. In these diagrams, the mineral
that maintains the lowest log Al3+ + 3pH activity at a given H4SiO40 activity is the
most stable. For example, at log (H4SiO40) of -7.0, the minerals in order of increasing
stability are Na-glass, K-glass, vermiculite, low albite, Ca-glass, analcime (same as
Ca-glass), microcline, pyroxene, montmorillonite, anorthite, chlorite (same as
anorthite), kaolinite and gibbsite (Dixon and Weed 1989).

43
 20

18

16

14

12
log Al3+ + 3 pH

10

SiO2 (am)
2

0
-7 -6 -5 -4 -3
0
log (H4 SiO4 )

Fig. 2.12 - Relative solubility of selected primary and secondary minerals at pH 7.0
when log Mg2+ = log Na+ log K = -3, log Ca2+ = -2.5, and log Fe3+ is in equilibrium
with hematite (Kittrick 1970)

The stability sequences based on thermodynamic data depend on the chemical

conditions in the weathering environment, such as H4SiO40 activity, pH, and the
precise activities of other ions; by contrast, the empirical sequences are fixed, and
thus changes in weathering environment cannot be taken into consideration. In
general, however, the thermodynamic data support the empirical observations,
namely: (Dixon and Weed 1989)
1. The primary minerals dissolve to form clay minerals
2. Montmorillonites are stable in solutions with high H4SiO40 activity (poorly
drained conditions)
3. Kaolinites are stable in solutions of moderate H4SiO40 activity (well drained)
and
4. Gibbsite is stable only under conditions where H4SiO40 activity is very low

44
In addition to the relative stabilities of minerals, information regarding environmental
conditions needed for the possible formation of these minerals also can be obtained
from the stability diagrams.

2.6. X-RAY DIFFRACTION ANALYSIS

In x-ray diffraction analysis, x-rays are used to determine crystalline compounds in
soils. The analysis is based on the principle that x-rays will be diffracted by crystal
planes. Soil minerals can be identified by measuring this diffraction at several
different angles (Tan 1996).

X-rays are generated after ejection of an electron from the K- shell of an atom by
bombardment with a highly energetic electron beam. Continuous X-ray radiation is
emitted after the subsequent transition of orbital electrons from states of high to low
energy levels. If the transition takes place with an electron from the L-shell, K-α
radiation is emitted. When an electron from the M-shell occupies the vacated position
in the K-shell, K-β is emitted. Therefore, the emitted X-ray is composed of both K-α
and K-β radiation. For X-ray diffraction analysis the K-α radiation is used, and the K-
β is blocked by a filter system. When a beam of X-rays hits a sample, absorption,
scattering or fluorescence of the X -rays may occur. The scattering effect is the basis
for X -ray diffraction analysis. The interaction of X-ray with an electron of an atom in
the sample may result in an incoherent or coherent scattering of the X-ray. The
scattering is said to be incoherent, if energy is lost in the collision or interaction. The
latter will especially take place if the electron is loosely bound. The scattering is
considered coherent, if no energy is lost in the collision. The coherently scattered X-
ray exhibits the same wavelength as the incident X-ray (Tan 1996).

2.6.1. Sources of X-Ray Radiation

The primary source unit consists of a vacuum-sealed X-ray tube, contained in a water-
cooled housing unit. The tube contains an anode, which is called the target, and a
cathode. Numerous metals have been used as target materials. The most common
target elements are Cu, Fe, Mo and Cr. Most X-ray diffraction spectrometers are
supplied with a Cu-tube. When a high voltage is applied across the cathode and

45
anode, the electrons, released from the cathode, strike the surface of the target. Upon
impact, energy is transferred to the metallic surface of the target, which then emits
radiation in the 0.1 - 100 Å region. The wavelength of the x-ray emitted by the target
depends upon the metal used and the applied voltage [eq. 2.10-2.12](Tan 1996).

When energy (E) of the electrons is converted into radiant energy, the following
condition holds (Tan 1986).
Eelectrons = Eradiation …. …. [2.10]
Eelectrons = eV and Eradiation = hv
Where, e = valence, V = applied voltage, h = Max Planck’s constant,
and v = frequency.
v = c/λ …. …. [2.11]
In this equation, c = the velocity of light in vacuum and λ = the wavelength.
Therefore:
hv = eV
h(c/λ) = eV
λ = hc/eV …. …. [2.12]
Since h, c and e are known, hce = 12,400. The final equation, characterizing the
emitted x-rays, is then:
λ = 12,400/V

2.6.2. Principles of X-Ray Diffraction

When such a beam of X-rays hits a crystal, X-rays are scattered among other things.
A crystal plane is composed of a systematic and periodic arrangement of atoms in
space. This kind of arrangement of atoms is called a crystal lattice. Each atom in the
lattice serves as a scattering point. The coherently scattered waves may constructively
interfere with each other, producing diffraction maxima. In order to meet the
requirement for constructive interference, the scattered waves from each atom must be
in phase. As illustrated in fig. 2.13, wave II must travel longer than wave I to leave
the crystal plane (Tan 1996).

46
 I
Diffracted
Incident beam beam
II

θ θ A θ
Lattice
spacing
d θθ
C D
Lattice B
spacing d
Crystal plane

Fig. 2.13 - The conditions for diffractions of x-rays from crystal planes. The
difference in path length between wave I and II is CBD=CB+BD. Since CB=BD,
therefore CBD=2CB, Reinforcement occurs when 2CB=nλ (integral numbers of
wavelengths). Since CB=ABsinθ, hence 2CB=2ABsinθ. Since AB=d, therefore,
nA=2dsinθ (Tan 1996)

To ensure that the two waves remain in phase (or for reinforcement to occur), the path
length difference between the two waves must equal a whole number (n) of
wavelengths (λ). Commonly known as Bragg’s law, this relationship may be
expressed as:
nλ = 2d sinθ
in which n = integral numbers, λ = wavelength (Å), d = interplanar or lattice spacing,
and θ = angle of incidence beam or angle of diffraction. Sometimes the lattice spacing
is identified by the indices hkl. In this case, Brag’s law changes to:
nλ = 2hkl d sinθ
The symbols hkl may refer to the 001, 010, 100 crystal planes, hence to the d001, d010,
or d100 spacings.

Thus, X-ray diffraction will occur only if the Bragg’s law is obeyed. The angle of the
incidence beam (θ) is changed during analysis. When n = 1, the diffraction is called
the first-order diffraction. By changing the angle of the incidence beam, n becomes 2
or 3, corresponding then to the second-order and third-order of diffractions,

47
respectively. In clay mineral analysis, the X-ray spectrum, called x-ray diffractogram,
is composed only of first- and second-order diffraction maxima (Tan 1996).

Diffraction of X-rays from a succession of regularly spaced atoms produces a

diffraction maximum, which is recorded. Because the interatomic distances in space
are not the same between two minerals, the angles of diffraction will be very
distinctive for a particular mineral. The interatomic distances in a crystal usually
produce an array of diffraction maxima, which is used to identify the mineral (Tan
1996).

2.6.3. Pretreatment of soil samples

For the identification of clay minerals, it is required to analyze the samples both in
their original state and after they have been subjected to such pretreatments as
deferration, saturation with K, saturation with Mg and glycolation, and heating at
500°C. Potassium saturation and glycolation of Mg-saturated samples are used to
distinguish between expanding and non-expanding minerals (Table 2.6). Saturation
with K will normally effect a collapse of intermicellar spacings, and the value for d-
spacings of 20 - 17 Å exhibited by smectite may collapse to 10 Å. Reconstitution of
the d-spacing to 17 Å is achieved by the glycolation procedure. None of these
treatments will have any effect on the d-spacings of non-expanding minerals, e.g.,
kaolinite (Tan 1996).

2.6.3.1. K-Saturation
50 mg of clay was weighted in a polyethylene centrifuge tube. 10 ml of distilled water
was added and a few drops of 0.5 M NaOH, and the clay was dispersed with a hand
shaker. 10 ml, 2 M KCl was added to flocculate the clay and centrifuged. The clay
was washed for two times with 10 ml 1 M KCl to insure complete saturation with K.
Again the sample was centrifuged and discarded. The excess KC1 was washed once
with 50% methanol and once with 95% acetone. The methanol and acetone was
centrifuged and discarded. The clay was dispersed again ultrasonically with distilled
water. A glass slide sample was prepared for X-ray diffraction analysis (XRD) (Tan
1996).

48
 TABLE 2.5
Effect of parameters on the d-spacing of selected Clay Minerals (Tan 1996)
d-spacing
Clay minerals
Å nm
K-saturated sample
14 1.4 Vermiculite, Chlorite
10 – 12 1.0 – 1.2 Smectite, Illite
7.2 – 7.5 0.72 – 0.75 Halloysite, Metahalloysite
7.15 0.715 Kaolinite, Chlorite
Mg-saturated sample
Vermiculite, Chlorite, Smectite, and
14 1.4
Illite
10 – 12 1.0 – 1.2 Illite, Halloysite
7.2 – 7.5 0.72 – 0.75 Kaolinite, Chlorite
Mg-saturation + glycolation
17 – 18 1.7 – 1.8 Smectite
14 1.4 Vermiculite
10 – 12 1.0 – 1.2 Illite, Halloysite
7.15 0.715 Kaolinite
Heating at 500°C (773K)
14 1.4 Chlorites
10 1.0 Vermiculites
Chlorites (Kaolinite and sesqui-
7.0 0.7
oxides become amorphous)

2.6.3.2. Mg-saturation and glycolation

Fifty mg of clay was weighted in a polyethylene centrifuge tube. Ten ml of distilled
water was added and a few drops of 0.5 M NaOH, and the clay was dispersed with a
hand shaker. 0.2 N HCl was added dropwise under constant stirring to adjust the pH
to 3.5-4.0. Ten ml 10 N Mg(OAc)2 was added and shaked with a handshaker and
centrifuged. The clay was washed two more times with Mg(OAc)2, followed by a
washing with 1 N MgCl2 to insure complete saturation. The excess salts were washed
out once with 50% methanol and once with 95% ethanol. The clay was dispersed

49
again ultrasonically with distilled water. A slide sample was prepared and the slide
was dried over CaCl2 in a desiccator for analysis by XRD or for glycolation. The glass
slide was placed with the dry Mg-saturated clay upside down over ethylene glycol in a
desiccator overnight. As soon as the dry color changes into a slightly moist color, the
sample is ready for analysis by XRD (Tan 1996).

2.6.3.3. Heating at 500°C

After performing XRD of the K-saturated sample, the slide is heated in a muffle
furnace at 500°C for at least 15 m. Cool, and store the slide over CaCl2 in a
desiccator. Kaolinite, halloysite, gibbsite, hematite, goethite and some HIV become
amorphous to X-rays as a result of heating at 500°C. Frequently, heating is performed
to distinguish between vermiculite, chlorite and illite. Vermiculite has interlayer
hydroxy alumina complexes in its structure. These layers will be destroyed by heating
at 500°C, with the consequent collapse and shift of the d-spacing of vermiculite from
14 Å to 10 Å. On the other hand, heating at 500°C will have no effect on chlorite, but
will, however, produce a second-order 7.2 Å diffraction peak. The latter can be
mistaken for kaolinite. However, heating at 500°C will make kaolinite amorphous to
XRD, as indicated above, and both the 7.13 Å and 3.56 Å peaks of kaolinite will
disappear (Tan 1996).

2.6.4. Preparation of slides

Many methods have been developed for the preparation of samples for analysis by
XRD. Examples are the random powder method, random-orientated rod method, the
wedge method, the glass slide method, and the ceramic plate method (Tan 1996).

2.6.4.1. Random Powder Sample

In the random powder sample, the crystals lie in a random position to each other. In
this method, the sample can be placed in a capillary tube, or with the aid of glycerol
and gum tragacanth, the clay sample can also be made into a paste, and rolled into a
rod of 0.3 to 0.5 mm thickness, which is analyzed by XRD. In the wedge method, the
paste is pressed into specially designed wedge holders. These types of random powder
samples are usually analyzed by a powder camera X-ray diffraction unit (Tan 1996).

50
2.6.4.2. Random-Oriented Samples
Currently, the porous ceramic tile and the random-oriented glass slide method are
preferred for mounting XRD samples. However, if sufficient amounts of samples are
available, a random powder type of mounting using Al sample holders, instead of
capillary tubes, may also be used, which is perhaps the most rapid and simple method.
In the ceramic tile method, a tile is placed in a clay suspension, and the liquid is
removed by suction so that the surface of the tile is covered by a thin layer of oriented
clay. The clay can also be deposited on the tile surface by centrifugation. However, a
more rapid and simple method is the oriented glass slide method. The specimens,
mounted by these methods, are analyzed with a XRD unit that records the results as a
graph, called previously a diftractogram. The procedures for mounting samples by the
oriented glass slide method and random powder method are presented below in more
details (Tan 1996).

2.6.5. Diffractograms of Clay Minerals

The diffractogram is composed of a series of diffraction peaks printed with the 2θ
angles in the abscissa and radiation counts or peak intensities in the y-axis. The
position of the diffraction peaks corresponds directly to the d-spacings. The common
unit for lattice spacing is the angstrom unit (1 Å = 10-10 m), which corresponds to the
unit of X-ray wavelength. The SI system requires the use of nanometers (1 Å = 0.1
nm). The value d(001)/n, called lattice spacing, can be measured from the results. If n
= 1, the d(001)/1 represents the first-order diffraction spacings. If n = 2, then d(001)/2
represents the second-order diffraction spacing. The series of d/n values obtained,
together with the intensities of the XRD peaks, serve as fingerprints for the
identification of the mineral species. Highest intensity of diffraction maxima is
obtained from d(001) planes. The first-order d(001) diffraction peak, and in many
cases together with the second-order diffraction peak, identify the mineral species
(Tan 1996).

51
2.7. CLAY MINERALOGY OF SOILS OF BANGLADESH
Physiographically, Bangladesh is divided into three major units: northern and eastern
hills of Tertiary formations, Pleistocene terraces of the Madhupur and Barind tracts,
and recent floodplains. Floodplains, mainly comprising alluvial sediment of the
Ganges, Brahmaputra and Meghna river systems, which occupy 80% of the country.
Clay and sand mineralogy of floodplain soils is summarized as follows (Ahsan and
Karim 1988, Islam et al. 1988): Tista and Brahmaputra river sediment contains large
amounts of mica and feldspars but no calcium carbonate, and clays are mixed,
kaolinite, mica, vermiculite, and chlorite. Ganges river sediment contains clay and
sand minerals similar to sediment from the other two rivers, but in addition it contains
calcium carbonate and smectite clay; piedmont sediment derived from the eastern
hills has small amounts of weatherable minerals and contains mixed kaolinite, mica,
vermiculite and chlorite clays.

The clay fraction of the terrace soils were dominated by mica and kaolinite. In
addition to these minerals, interstratified minerals of mica-vermiculite-smectite
(Mi/Vt/Sm) and of kaolinite-smectite (K/Sm) were detected, and following sequence
of the transformation was proposed: mica Mi/Vt/Sm-Kt/Sm kaolinite (Brammer
1996).

2.7.1. Tertiary sediments

The northern and eastern hills, which occupy about 12 percent of Bangladesh. The
higher hill ranges in the Chittagong Hill Tracts, Chittagong and Sylhet regions are
underlain by rocks of the Surma and Tipam formations. These are regarded as late
Oligocene to mid-Miocene in age. They mainly comprise sandstones, shales and
siltstones which have been consolidated to varying degrees, and which locally contain
lime or pyrites. Lower hills are mainly underlain by little-consolidated sands and
shales of the Dupi Tila formation, which may be late-Miocene in age. Small, areas are
occupied by unconsolidated sands and boulder beds of the Dihing formation, which
may be late-Pliocene or Pleistocene in age (Brammer 1996).

The sand fraction of these rocks is dominated by quartz (70-90 percent of the total). In
most places, the contents of feldspars (mainly alkali) and mica are low (1-10 and <5

52
percent respectively) and heavy mineral contents do not exceed 3 percent, comprising
varying proportions of zircon, tourmaline, kyanite, staurolite and epidote. In these
areas, the total content of easily-weatherable minerals (feldspars and biotite) generally
is less than 10 percent (Brammer 1996).

Exceptionally, in some younger rocks along the northern border of Mymensingh and
Sylhet regions, higher contents of feldspars (up to 15 percent) are found, and
relatively high amphibole and biotite contents occur amongst the heavy minerals. The
total content of easily-weatherable minerals in such rocks generally exceeds 15
percent. The source of these minerals is presumed to be the occasional boulders of
basalt and gneisses present in Dihing rocks in these areas (Brammer 1996).

2.7.2. Madhupur clay

The Madhupur and Barind Tracts, which together occupy about 8 percent of the
country, are underlain by the Madhupur Clay. The Madhupur Clay was earlier called
the ‘older alluvium’ and was regarded as Pleistocene in age. The 1964 Geological
Map of Pakistan gave the formation the name Madhupur Clay, and suggested that it
might correlate with the Dupi Tila formation, regarded as of Mio-Pliocene age
(Brammer 1996).

The Madhupur Tract and the eastern part of the Barind Tract are similar in mineral
content to most of the Tertiary sediments: i.e., high in quartz; relatively low in
feldspars and micas; and with zircon, tourmaline, kyanite, staurolite, sillimanite and
epidote dominating the heavy mineral fraction. The content of easily-weatherable
minerals ranges from 4-9 percent. The western half of the Barind Tract has a slightly
higher content of easily-weatherable minerals (8-14 percent) and a different heavy
mineral assemblage: garnet occurs in addition to kyanite, staurolite, sillimanite and
epidote in the south; in the north, sillimanite is dominant and epidote contents are
small. Clay mineral data for unweathered Madhupur Clay near Dhaka indicate that it
comprises illite, kaolinite and a trace of montmorillonite (smectite). This
mineralogical composition suggests that the Madhupur Clay is similar in origin to the
Tertiary hill rocks. The low feldspar and mica contents are in marked contrast with
adjoining floodplain sediments (Brammer 1996).

53
2.7.3. Tista floodplain
In the Kaunia and Gangachara series, mica and chlorite were predominant clay
minerals followed by kaolinite, vermiculite, and mixed-layer minerals. Smectite was
not detected. The Palashbari series showed the same mineralogical composition as the
Kaunia and Gangachara series but having the somewhat higher vermiculite and lower
chlorite contents. The high vermiculite and low chlorite contents of the Palashbari
series relative to the Kaunia and Gangachara series suggest that chlorite was
progressively transformed into vermiculite in the Palashbari series, and hence the
Palashbari series is at an advanced stage of mineral weathering. Interstratified mica-
chlorite (Mi/Ch) of the Kaunia and Gangachara series was altered to interstratified
mica-vermiculite. (Mi/Vt) in the Palashbari series. Thus, it was considered that the
Kaunia, Gangachara, and Palashbari series were originally the same in the clay
mineralogical composition, dominated by mica and chlorite, and that the Palashbari
series has been subjected to weathering for longer time or more intensively, indicated
by a greater extent of transformation of chlorite into vermiculite (Brammer 1996).

2.7.4. Old Brahmaputra floodplain

The Silmondi and Sonatala series were dominated by mica, chlorite, and vermiculite,
with a small quantity of kaolinite and mixed-layer minerals. Essentially no smectite
was included. The clay mineralogical composition of the Old Brahmaputra floodplain
soils was similar to that of the Tista Floodplain soils, except relatively large quantities
of vermiculite and very small amounts of Mi/Cl. Vermiculite of the Old Brahmaputra
floodplain soils was found in the silt as well as the clay fractions and seems to be
inherited, for the most part, from the sediment (Brammer 1996).

2.7.5. Ganges river floodplain

Among the Ganges river floodplain soils, the Ghior and Ishurdi series contained large
amounts of smectite in addition to mica, chlorite, kaolinite and vermiculite. The
Darsona series, on the other hand, was essentially devoid of smectite and contained
larger amounts of chlorite and Mi/Ch instead. The Darsona series resembled the
Kaunia and Gangachara series of the Tista floodplain, and the remaining of Mi/Ch
along with large amounts of chlorite suggested that the Darsona series was at an early
stage of mineral weathering. Consequently, it is difficult to consider that smectite was

54
leached away from the upper layer of the Darsona series during or after
decalcification. The Ganges river floodplain seems to include at least two kinds of soil
different in the clay mineralogy: one is calcareous in nature and contains smectite; the
other is noncalcareous and lacks smectite (Brammer 1996).

2.7. 6. Northern and eastern piedmont plains

The Nirsaral and Karnaphuli series of the northern and eastern piedmont plains
contained mica, kaolinite, chlorite, vermiculite, smectite, vermiculite-chlorite
intergrade and mixed-layer minerals. The smectite found in the Nirsaral and
Karnaphuli series was originated from mica and existed as a discrete phase and a
component of interstratified mica-vermiculite-smectite. The clay mineralogical
composition of the piedmont soils is common in principle to that of the meander
floodplain soils, but features of more or less intensive weathering of minerals are
obvious. The Pahartali series was dominated by mica and chlorite and was identical
with the Palashbari series of the Tista floodplain (Brammer 1996).

2.7. 7. Barind tract

The Amnura series contained mica, kaolinite, vermiculite, chlorite, vermiculite-
chlorite intergrade and considerable amounts of mixed-layer minerals (Brammer
1996).

2.8. MINERAL WEATHERING OF SOIL OF BANGLADESH

In Bangladesh, most of the soil parent materials are of alluvial origin it appears that
the dominant parent material of the clay fraction is muscovite mica, along with
moderate amounts of kaolinite. The mica appears to be weathered to vermiculite
under moderately acidic conditions; under these conditions aluminum hydroxy
polymers, which result from the dissolution and decomposition of the mineral phases,
may be exchanged onto the expanded mica or vermiculite. This may reduce the
capacity of the weathered micaceous minerals to fix potassium. If the pH of soils
containing significant amounts of interlayer aluminum hydroxy polymers is raised
above a pH of 6.5, there is a possibility that the aluminum polymers will be
neutralized and expelled into the soil solution. This produces high surface aluminum
hydroxide which is capable of fixing large amounts of phosphorus. The activity of

55
aluminum on the surface of the freshly precipitated aluminum hydroxide may be
sufficiently high to produce aluminum-toxicity in sensitive crops (Brammer 1996).

Under neutral or basic conditions in soils that are poorly drained, the mica weathers to
smectite (montmorillonite) such weathering trends are characteristic in the Ganges
River alluvium group of soils. In order to better understand the nature of the mica
weathering sequence in Bangladesh soils, some scientists utilized the concept of a
mica ‘weathering index’ to estimate the extent to which potassium has been removed
from the 10 Å mica components in soil clays. The ratio of the intensities of the 10 Å
(001 d-spacing) and 5 Å (002 d-spacing) diffraction peaks of mica is a direct function
of the amount of potassium in the interlayer sites in the mica structure. Thus, a
muscovite mica with a full complement of potassium will have a 001/002 ratio of
about 2. If approximately one-half of the potassium has been removed by weathering,
the 001/002 ratio will be around 5 to 6. It appears that under extremely intense
weathering conditions a process designated as “ferroelysis” can become a dominant
factor in the weathering trend. The process of “ferroelysis” is characterized by
alternating cycles of oxidation and reduction of iron. Extremely low pH values are
produced and all but the most resistant muscovite mica particles are destroyed. It is
suggested that the highly resistant muscovite mica, which has a 001/002 ratio of about
2, would have a relatively low “potassium-supplying power”; soils which contain this
form of mica as the only possible source of potassium will probably respond to
potassium fertilization. In the intense weathering environment characteristic of the
“ferroelysis” process, large amounts of halloysite appear to form in situ (White 1985).

Soils in which the clay fraction has a high 001/002 mica intensity ratio should have
the inherent capacity to supply adequate amounts of potassium for normal plant
growth. The presence of high charge vermiculite phases with the capacity to fix
appreciable amount of potassium could prevent the equilibrium potassium level in the
soil solution from reaching the range required for normal plant growth (White 1985).

Some mica minerals have been weathered to a vermiculite phase which gives a d-
spacing of 12.6 Å instead of the normal 14.2 Å spacing; it may be designated that the
12.6 Å phase as “high charge” vermiculite. It is thought that the charge of this phase

56
is equivalent to about 150 meq/100 g. This high charge vermiculite has the potential
to fix large amounts of potassium (White 1985).

2.7.4. NEEDS FOR CLAY MINERALOGYCAL STUDY AND WORK

Bangladesh has a wide range of mineral soils developed in parent materials derived
from various sources ranging from fresh alluvial deposits of recent origin to strongly
weathered old alluvium and sedimentary rocks of the Tertiary formations. The soils
formed under varied topographic and hydrological, conditions include poorly to very
poorly-drained, strongly gleyed hydromorphic. soils of, the young alluvial lands on
one hand and well drained, red brown, deeply weathered and leached latosolic soils of
the upland terrace and hills an the other. Theses soils are tentatively correlated in the
USDA Soil Taxonomy with Entisols, Inceptisols, Mollisols, Alfisols, Ultisols and also
may be with some Vertisols, encompassing about 512 soil series altogether. At the
sub-order level they are: Aquents, Psamnents, Orthents, Aquepts, Ochrepts,
Umbrepts, Aquolls, Udlfs, Ustalfs and Ustults and also may be some Uderts. Among
them the Aquepts are by far the most dominant soil covering about 60 percent of the
area. The Ochrepts and the Aquents occupy about 20 and 10 percent of the area
respectively, and the remainder covers the rest (White 1985).

The soils of these 512 series have very tentatively been classified at the sub-group
level, but their final correlation even at the series level could not be made
conclusively mainly due to the want of adequate mineralogical data. Some data on
both sand and clay mineralogy are available, but they are not adequate for the present
need. After the reconnaissance soil survey it has become apparent that for a more
efficient use of the soil survey information a further comprehensive grouping of these
soils series is needed at the family level. For this a systematic mineralogical study is
urgently required (White 1985).

57
3.1. MATERIALS AND METHODS
Soil samples of Barisal series were collected from Moshinardanga village of
Batiaghata thana in Khulna district. The GPS coordinates were 22.64452ºN and
89.51864ºE. According to USDA soil taxonomy, the subgroup level classification of
this series was Typic Endoaquepts. The physiography of sampling area was Ganges
Tidal floodplain. The landscape was nearly leveled basin and poorly drained. Present
land use pattern was Fallow-Fallow-T.Aman. For description of soil properties and
sample collection, 1m × 1m × 1m pit was excavated. Samples were collected carefully
from each horizon for physical, chemical and mineralogical analysis.

3.1.1. Methods of Analysis

Among all physical and chemical analysis PSA, pH, ECe, OC, CEC, Exchangeable
and water soluble Na+, K+, Ca2+ and Mg2+ were determined.

3.1.1.1. Particle size analysis

The particle size was determined by a combination of hydrometer and sieving method
presented by Gee and Bauder (1986).

3.1.1.2. pH
Soil pH (1:2.5) was determined electrochemically by using of glass electrode with the
procedure of Jackson (1973).

3.1.1.3. ECe
The ECe of the soil was measured at a soil water ratio of 1:1 by EC meter (USDA
2004)

3.1.1.4. Organic carbon

Soil organic carbon was determined by of Wakley and Black’s (1934) wet oxidation
method as described by Jackson (1973).

3.1.1.5. Cation exchange capacity

CEC was determined by method as described by Jackson (1973); extracting the soil
with 1N NH4OAc solution of pH 7 followed by replacing ammonium from the
exchange site by 2N KCl (Jackson 1973).

58
3.1.1.6. Exchangeable Na+, K+, Ca2+ and Mg2+
For the determination of exchangeable Na+, K+, and Mg2+ soil was extracted with 1N
NH4OAC solution of pH 7.0 as described by Piper (1950) and Jackson (1973). The
exchangeable Ca2+ was determined by atomic absorption spectrophotometer.

3.1.1.7. Water soluble Na+, K+, Ca2+ and Mg2+

Water soluble Na+, K+, and Mg2+ were determined after extraction with distilled water
as described by Jackson (1973). The water soluble Ca2+ was determined by atomic
absorption spectrophotometer.

3.1.2. Preparation of Sample for X-Ray Diffraction Analysis

Various steps were followed for the preparation of sample for XRD. They are disused
bellow.
3.1.2.1. Removal of salts and cementing materials
The salts and cementing materials of the soil sample were removed by the following
procedure as described by Jackson (1975).
3.1.2.1.1. Removal of soluble salts and/or carbonates
Reagents: 1N Sodium Acetate (NaOAc) of pH 5.
Procedure:
a) 10g soil was mixed with 100 ml NaOAc and stirred.
b) The suspension was warmed for half an hour near boiling point.
c) Until clear supernatant was obtained, the suspension was centrifuged.
d) Centrifuge was repeated for 2 times.

3.1.2.1.2. Removal of organic matter

Reagents: 30% Hydrogen Peroxide (H2O2), 1N Sodium Acetate (NaOAc) and 95-
99% methanol (CH3OH).
Procedure:
a) Moist soil was mixed with 5 ml H2O2 and stirred for 5-10 minutes.
b) As the reaction completed the mixture was warmed in hot-plate at 60-70º C for
10-20 minute.
c) Additional 5 ml H2O2 was added and stirred.
d) More 10 ml H2O2 was added and covered with cover glass.

59
 e) The mixture was digested at 60-70º C for 2 hours until the pest condition
appeared.
f) Dark color disappeared, which was the indication of completely removal of
organic matter.
g) The mixture was washed with NaOAc solution for 3 times.
h) After that mixture was washed with 95-99 % methanol.

3.1.2.1.3. Removal of free iron oxide

Reagents: 0.3M Sodium Citrate, 1M Sodium bi Carbonate (NaHCO3), solid Na2S2O4.
Procedure:
a) Soil was added with 40 ml Na citrate and 5 ml NaHCO3 and warmed at 80º C
in water bath.
b) 1 g solid Na2S2O4 was added.
c) The suspension was stirred for 1 minute and warmed at 80º C for 15 minutes.
d) For flocculation, 10 ml of saturated NaCl solution was added.
e) The suspension was centrifuged at 1600-2200 rpm for 10-15 minutes.
f) The sample was finally washed with sodium citrate solution.

3.1.2.2. Separation of sand and silt

The process of separating sand and silt included three steps. They are discussed bellow.
3.1.2.2.1. Separation of sands up to 50 µm from silts and clays
The sands particles of the soil sample were removed by the following procedure as
described by Jackson (1973).
Reagents: Sodium Carbonate (Na2CO3) solution of pH 9.5.
Procedure:
a) Soils in centrifuge tube were dispersed in beaker thoroughly and stirred
freshly.
b) Settling time was 40 sec for each 10 cm.
c) Suspension was decanted to 600 ml beaker through 50 µm sieve.
d) Beaker was stirred vigorously with distilled water and sample was taken at 4
sec cm-1 settling time. The sample was again decanted thorough 50 µm sieve.
e) Particles were washed in the sieve by coarse jet and finally washed with
acetone.
f) Silts and clays remained in the suspension.

60
3.1.2.2.2. Separation of the coarse silt (50-20µm)
Reagents: Sodium Carbonate (Na2CO3) solution of pH 9.5.
Procedure:
a) Suspension left in 600 ml beaker was stirred and allowed to sand for 5-7 min
for each 10 cm.
b) Supernatant liquid was decanted to 1L beaker by siphoning.
c) The sediment portion was transferred to 100 ml beaker with Na2CO3.
d) Suspension in 100 ml beaker was allowed to stand for 3 min and supernatant
liquid was transferred to 1 L beaker.
e) The sediment was dispersed again with Na2CO3 to 5 cm depth and settled for 2
min 5 sec and decanted to 1 L beaker.
f) This suspension was washed for 2 times with distilled water at same depth and
time and the sample decanted.
g) Fine silt and clays remained in the suspension.

3.1.2.2.3. Separation of silt from clay (<20 µm)

Reagents: Sodium Carbonate (Na2CO3) solution of pH 9.5.
Procedure:
a) Suspension in 1L beaker (<20 µm) was allowed to stand for 8 hours for each
10 cm depth.
b) The supernatant liquid was siphoned to a flask labeled at <2µm.
c) This process was repeated for 5 times.

3.1.2.3. Separation of clay and slide preparation

Reagents: 1M Potassium Chloride (KCl) solution, 0.5 M Magnesium Chloride
(MgCl2) solutions and glycerol solution.
Procedure:
a) The supernatant liquid from the previous step was centrifuged for 28 min 18
sec in 2400 rpm and supernatant solution was decanted.
b) Clays found from centrifuge tube were divided in two parts. First part was
washed with 8ml of 1M KCl solution for 3 times. Second part was washed
with 8ml of 0.5M MgCl2 solution for 3 times. Finally two parts were washed
with distilled water and ethanol to remove excess salts.

61
 c) Clays were transferred in 3 glass slides from KCl saturated clay. 2 glass slides
were heated at 300 and 500º C in muffle furnace.
d) Clays were transferred in 2 glass slides from MgCl2 saturated clay. One was
saturated with glycerol solution.

3.2. RESULTS AND DISCUSSION

3.2.1. Morphological Characteristics
A 1m3 pit was excavated to describe the soil profile. Different horizons were
identified depending on observable and measurable properties. The horizons were
Ap1, Ap2 and cambic horizon Bw. The Bw horizon was further divided in to Bw1,
Bw2 and Bw3 horizons.

The matrix color of Ap1 horizon was dark gray (5Y 4/1) in moist condition (Table
3.1). Yellowish brown color mottles were present. Soil boundary was clear smooth.
The soil was noncalcareous. The texture of the soil was silty clay. The percentage of
sand, silt and clay were 10.00%, 46.00% and 44.00%, respectively (Fig. 3.1).

The matrix color of Ap2 horizon in moist condition was dark gray brown (5Y 4/2)
(Table 3.1). Yellowish brown color mottles were present. Soil structure was massive.
Soil boundary was clear smooth. The soil was noncalcareous. The texture of the soil
was silty clay. The percentage of sand, silt and clay were 7.50%, 46.00% and 46.35%,
respectively (Fig. 3.1).

The matrix color of cambic horizon Bw was dark gray brown in moist condition. It
varied from 2.5Y 4/2 to 2.5Y 4/1 among three horizons (Table 3.1). Mottle color
varied from yellowish brown to dark yellowish brown. Soil structure was mainly very
coarse prismatic breaking into angular blocky which indicates the immaturity of soil.
Continuous, moderately thick dark grey cutans were present along the vertical and
horizontal ped faces. This clay skin caused by seasonal flooding and it is also called
flood coating. Soil boundary varied from clear smooth to smooth. The soil was
noncalcareous through the profile. The texture of the soil was mainly clay, but it
varied from silty clay to clay. The percentage of sand, silt and clay varied from 9.00-
15.00%, 35.00-50.03% and 40.97-50.00%, respectively (Fig. 3.1).

62
63
Fig. 3.1. Particle size distribution of Barisal series at i) 0-13 ii) 13-18 iii) 18-36 iv) 36-
62 v) 62-76 cm depth

64
3.2.2. Chemical characteristics
There was little variation in soil pH among all five horizons. In Ap1 horizon pH value
was 6.52, which was the lowest value in relation with other horizons. The highest pH
value was found in Bw1 horizon (Table 3.2).

Highest value of ECe was observed in Ap1 horizon (14.57 dSm-1) and lowest in Ap2
horizon (4.25 dSm-1) (Table 3.2). The salinity occurred due to sea water intrusion. At
the surface, salinity was highest due to evaporation of water. In other horizons salinity
remained low but in Bw3 horizon salinity was higher which was caused by ground
water salinity.

There was a regular decrease in soil organic matter percentage from Ap1 to Bw1
horizon. Then a regular increase occurs from Bw1 to Bw3 horizon. The highest and
lowest values were 4.70 % and 0.96 % in Bw3 horizon and Bw1 horizon, respectively
(Table 3.2). This irregular variation of soil organic matter was due to the
heterogeneity of fluvial deposits.

Cation exchange capacity was highest (28.24 cmol kg-1) in Bw2 and Bw3 horizons
(Table 3.2). The lowest value was 18.41 cmol kg-1 that was found in Ap2 horizon.

Water soluble Na+ content was highest in Bw3 and lowest in Ap2 horizon. The
highest and lowest values were 0.69 and 0.169 cmol kg-1, respectively (Table 3.2).

Water soluble K+ content was highest in Ap1 and Bw2 horizons. The highest value
was 0.018 cmol kg-1. The lowest value was 0.01 cmol kg-1 which was observed in Ap2
horizon (Table 3.2).

Water soluble Ca2+ content was highest (2.20 cmol kg-1) in Ap1 horizon. The lowest
value was found in Ap2 horizon (0.50 cmol kg-1) (Table 3.2).

The water soluble Mg2+ was highest (1.14 cmol kg-1) in Ap1 and lowest in (0.34 cmol
kg-1) in Bw2 horizon (Table 3.2).

65
66
The highest value of exchangeable Na+ (0.174 cmol kg-1) was observed in Bw3
horizon and the lowest value was observed in Ap2 horizon (0.105 cmol kg-1) (Table
3.2).

The value of exchangeable K+ was highest (0.025 cmol kg-1) in Bw2 horizons.
Whereas the lowest value was observed in Ap2 horizon (0.011 cmol kg-1) (Table 3.2).

The highest value of exchangeable Ca2+ was 14.35 cmol kg-1 which was found in Bw2
horizon and lowest value was 10.12 cmol kg-1 in Ap1 horizon (Table 3.2).

The highest value of exchangeable Mg2+ content was 10.88 cmol kg-1 in Bw3 horizons
whereas lowest value was 7.03 cmol kg-1 in Ap1 horizon (Table 3.2).

Exchangeable sodium percentage was highest (0.66 cmol kg-1) in Ap1 horizon. The
lowest value was 0.55 cmol kg-1 that was found in Bw2 horizon (Table 3.2).

All these values of pH, ECe, soluble organic matter, ESP, water soluble and
exchangeable Na+, Ca2+, Mg2+, K+ corroborated with SRDI (2003).

3.2.3. Identification and Quantification of Clay Minerals

X-ray diffraction analysis of Barisal series is presented in Fig. 3.2. The identified clay
minerals were illite (mica), kaolinite, smectite, chlorite and vermiculite. The HIV
(hydroxy-interlayered vermiculite) and interstratified minerals such Mc/Vt/St and vt-
ch were also found (Fig. 3.2). Fig 3.2A showed that peaks of 10.10 Å at 2 Theta (deg)
8.74, remain unchanged in all treatments. This was the indication of illite. Peaks of 7 Å
at 2 Theta (deg) 11 to 12 remain unchanged in all treatments except 500ºC. This was
the indication of kaolinite. Peaks of 18.11 Å at 2 Theta (deg) 4.78 in glycerol
saturation treatment indicated about smectite. Vermiculite was identified by the peaks
of 14.23 Å at 2 Theta (deg) 6.20 in glycerol saturation treatment. At Fig 3.2B the
peaks of 7 Å at 2 Theta (deg) 11 indicated about chlorite. This way all clay minerals
were identified from X-ray diffractogram.

67
Peaks at 10 Å in K saturation and after heating at 500ºC which gave peak at 14 Å in
Mg-glycerol saturation indicated the presence of vermiculite. The 10 Å peak which
increases to 17 Å in Mg-glycerol saturation indicated the presence of smectite (Tan
1996). HIV gave peak at 14 Å after Mg-glycerol saturation. X-ray diffraction analysis
showed peak at 10 Å and this peak was unchanged after heating at 500º C. This was
obviously peak of illite (mica). The 7 Å peak disappeared at 500º C which confirmed
the presence of Kaolinite. However, some 7 Å peaks remained unchained at 500º C.
These may be lack of chlorite.

(a)

(b)

(c)

(d)

(e)

Fig. 3.2A. X-ray patterns for Ap1 horizon (0-13cm) of Barisal soil series (a) K
saturation (b) Mg saturation-glycerol solvation (c) Mg saturation (d) K saturation
heating at 300ºC (e) K saturation heating at 500ºC.

68
 (a)

(b)

(c)

(d)

(e)

Fig. 3.2B. X-ray patterns for Ap2 horizon (13-18cm) of Barisal soil series (a) K
saturation (b) Mg saturation-glycerol solvation (c) Mg saturation (d) K saturation
heating at 300ºC (e) K saturation heating at 500ºC.

69
 (a)

(b)

(c)

(d)

(e)

Fig. 3.2C. X-ray patterns for Bw1 horizon (18-36cm) of Barisal soil series (a) K
saturation (b) Mg saturation-glycerol solvation (c) Mg saturation (d) K saturation
heating at 300ºC (e) K saturation heating at 500ºC.

70
 (a)

(b)

(c)

(d)

(e)

Fig. 3.2D. X-ray patterns for Bw2 horizon (36-62cm) of Barisal soil series (a) K
saturation (b) Mg saturation-glycerol solvation (c) Mg saturation (d) K saturation
heating at 300ºC (e) K saturation heating at 500ºC.

71
 (a)

(b)

(c)

(d)

(e)

Fig. 3.2E. X-ray patterns for Bw3 horizon (62-76cm) of Barisal soil series (a) K
saturation (b) Mg saturation-glycerol solvation (c) Mg saturation (d) K saturation
heating at 300ºC (e) K saturation heating at 500ºC.

72
The illite content varied from 46 to 61% in all horizons (Table 3.3). The percentage of
illite was highest in Bw3 and lowest in Bw2 horizon. In Ap1 horizon the percentage
of illite, vermiculite, kaolinite, smectite and chlorite were 51.40%, 1.05%, 6.36%,
0.45% and 0.009%, respectively (Table 3.3).

In Ap2 horizon the percentage of illite, kaolinite, smectite and chlorite were 58.65%,
7.48%, 0.26% and 0.008%, respectively (Table 3.3 and appendix).

In Bw1 horizon the percentage of illite, kaolinite and smectite were 46.07%, 7.55%,
and 0.34%, respectively (Table 3.3 and appendix). Chlorite and vermiculite were
found in minor amounts. The presence of interstratified minerals like vermiculite-
chlorite and mica/vermiculite/smectite were 2.42% and 3.09%, respectively.

In Bw2 horizon the percentage of illite, kaolinite, vermiculite and chlorite were 41.49
%, 4.28%, 0.28% and 0.004%, respectively (Table 3.3 and appendix).

In Bw3 horizon the percentage of illite, kaolinite, vermiculite and chlorite were
61.73%, 8.79%, 4.00% and 0.006%, respectively (Table 3.3 and appendix). Small
percentage of HIV was also found.

73
74
3.2.4. Weathering Stability of Clay Minerals
Morphologically the studied pedon of Barisal series (Typic Endoaquepts) was
relatively immature. The ratio of fine silt to total silt can be used to evaluate the in situ
clay formation (Langley-Turnbaugh and Bockheim 1997). The calculated ratio varied
from 0.69 to 0.89 (Table 3.4). This consistent ratio throughout the profile indicated
that there was no evidence of in situ clay formation. All clays are generally alluvial in
nature. Pedological indices for different horizons are shown in Table 3.4 and appendix.

TABLE 3.4
Pedological indices for different horizons of Barisal series (Faure 1992).
Horizon Depth Fine silt/total silt log [K+]/[H+]env log [Mg2+]/[H+]2 env
Ap1 0-13 0.77 2.78 10.80
Ap2 13-18 0.69 3.54 12.31
Bw1 18-36 0.80 3.87 13.11
Bw2 36-62 0.72 3.61 12.26
Bw3 62-76 0.89 3.17 11.73

By using equilibrium reactions and stability diagram of minerals the equilibrium

values of log [K+]/[H+]eqi and log [Mg2+]/[H+]2eqi of different minerals were
calculated according to Faure 1992 (Table 3.5).

TABLE 3.5
Pedological indices of different clay minerals under equilibrium condition (Faure
1992).
Minerals log [K+]/[H+]eqi log [Mg2+]/[H+]2eqi
Illite – Muscovite1 4.10 –
Kaolinite – Mg-montmorillonite2 – 6.42
Illite – Mg-montmorillonite3 – 3.29
Mg-montmorillonite – Chlorite4 – 11.36

Equilibrium equations (Faure 1992)

1. log [K+]/[H+] = 1.48 log [Mg2+]/[H+]2 – 5.52
2. log [Mg2+]/[H+]2 = +6.42
3. log [K+]/[H+] = –0.14 log [Mg2+]/[H+]2 + 3.96
4. log [Mg2+]/[H+]2 = +11.36

75
The values of log [K+]/[H+]env in all horizons varied from 2.78 to 3.87 (Table 3.5)
which were lower than the value of log [K+]/[H+]eqi (4.10). According to Le Chatelir’s
principle the following equilibrium reactions of [Eq. 3.1] Illite – Muscovite will shift
to left hand side.
1.3 [(Al1.80 Mg0.25) (Si3.50 Al0.50) O10 (OH)2]K0.60 + 0.22K+ + 0.43H+
KAl2Si3AlO10(OH)2 + 1.55 SiO2 (amorphous) + 0.325 Mg2+ + 0.5H2O …(3.1)
As a result Illite can form in the environment.

In all horizons, the values of log [Mg2+]/[H+]2env varied form 10.80 to 13.11 (Table
3.5) which are higher than the value of log [Mg2+]/[H+]2eqi (6.42). According to Le
Chatelir’s principle the following equilibrium reactions [Eq. 3.2] of Kaolinite – Mg-
montmorillonite will shift to right hand side and as a result formation of Mg-
montmorillonite may be possible in environment.
7 Al2Si2O5(OH)4 + 8 SiO2 (amorphous) + Mg2+
6[(Al2.00) (Si3.67 Al0.33)O10(OH)2] Mg0.167 + 7H2O + 2H+ … … … (3.2)

The values of log [Mg2+]/[H+]2env varied from in all horizons were 10 to 13 (Table
3.5) whereas the value of log [Mg2+]/[H+]2eqi is 3.29. So the following equilibrium
reaction [Eq. 3.3] of Illite – Mg-montmorillonite will shift to left hand side. Here
Mg-montmorillonite is less stable whereas illite is more stable clay minerals.
1.013[(Al1.08 Mg0.25) (Si3.50 Al0.50)O10 (OH)2 ]K0.60 + 0.1245 SiO2 (amorphous) +
0.781H+ [(Al2.00) (Si3.67 Al0.33)O10(OH)2] Mg0.167 + 0.086 Mg2+ +
0.405 H2O … … … (3.3)

In all horizons, the values of log [Mg2+]/[H+]2env varied form 10.80 to 13.11. The
equilibrium value of log [Mg2+]/[H+]2eqi is 11.36 (Table 3.5). As a result the
following equilibrium reaction [Eq. 3.4] of Mg-montmorillonite – Chlorite will shift
to left hand side.
[(Al2.00) (Si3.67 Al0.33) O10(OH)2] Mg 0.167 + 5.658 Mg2+ + 9.32 H2O
1.165 Mg5Al2Si3O10(OH)8 + 0.175 SiO2 + 11.316 H+ … … … (3.4)
Mg-montmorillonite is stable in Ap1 horizon. However the higher log [Mg2+]/[H+]2env
value indicates the possibility of formation of Chlorite from Mg-montmorillonite.

76
4. SUMMARY AND CONCLUSION

The physiography of Barisal series was Ganges Tidal floodplain. The landscape was
nearly leveled basin and poorly drained. The morphological, physical, chemical and
mineralogical proportions were studied in field and laboratory.

• The soil was alluvium in nature. The matrix color of soil varied from dark
gray brown to gray brown. The texture of the soil varied from silty clay to clay. The
structure of the cambic Bw horizon was massive and very coarse prismatic breaking
in to angular blocky which indicates the immaturity of the soil. Soil boundary varied
from clear smooth to smooth. Continuous, moderately thick dark grey cutans were
present along the vertical and horizontal ped faces. These clay skins were caused by
seasonal flooding. Whole the profile was noncalcareous.

• The pH of the soil was almost neutral. The highest value of pH was 7.09 and
the lowest was 6.52. The highest value of EC was 14.57 dsm-1. The value of cation
exchange capacity varied between 28.24 and 18.41cmol kg-1. The highest value of soil
organic matter was 4.70%. Exchangeable sodium percentage was almost equal within
all horizons and varied form 0.55 to 0.66 cmol kg-1. Extractable Na+ and K+
percentage was almost equal within all horizons. Water soluble Ca2+ and Mg2+
percentage were highest in uppermost horizon. Water soluble Na+ and K+ percentage
was almost equal within all horizons.

• From the X-ray diffraction analysis the clay minerals presented in the soil
were identified and quantified. Illite was the dominated clay mineral and varied from
41-61%. Percentage Kaolinite and Montmorillonite varied from 4-8% and <1-4%,
respectively. Chlorite and Smectite percentage was <1%.

77
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83
6. APPENDIX
6.1. Clay mineral percentages calculation:
6.1.1. Peaks for calculation:
d-spacing (Å)
Symbols
Mg-Glycerol K-Saturated (air) K-Saturated (550°C)
A 18
B 14
C 12
D 10
E 8
F 7
G 6.27
H 4.25
I 4.18
J 3.2
K 4.84
L 14
N 10
1/P 3.57-3.54

6.1.2. Weight proportions

Mica Wmc = D
Smectite Wst = A/3
Vermiculite Wvt = (B-L)/1.5
Chlorite Wch = FP/2(1+P)
Kaolinite Wkt = F/2(1+P)
Vermiculite-Chlorite Wvt-ch = {L-1.5FP/2(1+P)}/1.5
Mica/ Vermiculite Wmc/vt = C/1.5
Mica/Chlorite Wmc/ch = C/1.5
Mica/ Vermiculite/Smectite Wmc/vt/st = {N-D-B-A/3+1.5FP/2(1+P)-C}/1.5
Kaolinite/Smectite Wkt/st = E/1.5
Lepidocrocite Wlp = G
Quartz Wqr = 6H
Goethite Wgt = I
Feldspar Wfd =2j
Gibbsite Wgb = K

84
6.1.3. Mineral percentages calculation of Ap1 horizon:
6.1.3.1. Integrated intensity calculation (from XRD analysis)
A B C D E F G H I J K L N 1/P
129 151 0 4932 0 1223 0 464 199 562 319 0 4517 719

6.1.3.2. Calculation of weight proportions

Wmc = D = 4932
Wst = A/3 = 43
Wvt = (B-L)/1.5 = 100.66
Wch = FP/2(1+P) = 0.8549
Wkt = F/2(1+P) = 610.58
Wvt-ch = {L-1.5FP/2(1+P)}/1.5 = – 0.8549
Wmc/vt = C/1.5 = 0
Wmc/vt/st = {N-D-B-A/3+1.5FP/2(1+P)-C}/1.5 = – 405.1451
Wkt/st = E/1.5 = 0
Wqr = 6H = 2784
Wfd =2j = 1124
Total weight proportions = 9595.09

Zero and negative values were excluded.

6.1.3.3. Percentages calculation

4932 × 100
Mica percentages is = = 51.4 %
9590.09

By calculating this way

mc = 4932 = 51.4 %
st = 43 = 0.45 %
vt = 100.66 = 1.05 %
kt = 610.58 = 6.36 %
ch = 0.8549 = 0.009 %
qr = 2784 = 29.02 %
fd = 1124 = 11.71 %

85
By calculating this way following table was found
Clay Percentages (%)
minerals Ap1 horizon Ap2 horizon Bw1 horizon Bw2 horizon Bw3 horizon
mc 51.4 58.56 46.07 41.49 61.73
st 0.45 0.26 0.34 – –
vt 1.05 – – 0.28 4.00
kt 6.36 7.48 7.55 4.28 8.79
ch 0.009 0.008 – 0.004 0.006
qr 29.02 29.61 24.49 34.91 25.47
fd 11.71 4.09 16.04 19.02 –
vt-ch – – 2.42 – –
mc/vt/st – – 3.09 – –

6.2. Calculation of log [K+]/[H+]env and log [Mg2+]/[H+]2 env

By using pH and water soluble values of and Mg2+, log [K+]/[H+]env and log
[Mg2+]/[H+]2 env were calculated.

In Ap1 horizon pH = 6.52, K+ = 0.018 cmolkg-1 and Mg2+ = 1.14 cmolkg-1

So [H+] = –1/log (6.52) = 3.01995172 × 10-7 molL-1
[K+] = 0.018 / 100 = 1.8 × 10-4 molL-1
log [K+]/[H+] = 2.78
Again, [Mg2+] = 1.14/2 = 0.57/100 = 5.7 × 10-3 molL-1
log [Mg2+]/[H+] = 10.80

By calculating this way following table was found,

Horizon Depth log [K+]/[H+]env log [Mg2+]/[H+]2 env
Ap1 0-13 2.78 10.80
Ap2 13-18 3.54 12.31
Bw1 18-36 3.87 13.11
Bw2 36-62 3.61 12.26
Bw3 62-76 3.17 11.73

86