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HUMAIRA HASAN Student ID: 081321 Session: 2010-11

______________________________________ Soil Science Discipline Khulna University Khulna April, 2012



Course Title: Project Thesis Course No: SS-4106

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

Submitted By ________________________________ HUMAIRA HASAN Student ID: 081321 Session: 2010-11



Approved As To Style And Content By

KHANDAKAR QUDRATA KIBRIA Associate Professor Head & Chairman of Examination Committee Soil Science Discipline Khulna University, Khulna Bangladesh

Soil Science Discipline Khulna University Khulna April, 2012


DECLARATION This project thesis paper is entirely the candidates own investigation.

Supervisor Md. Sadiqul Amin Assistant Professor Soil Science Discipline Khulna University, Khulna

Candidate HUMAIRA HASAN Student ID: 081321

_______________________________________ Soil Science Discipline Khulna University Khulna April, 2012


ACKNOWLEDGEMENT At first I wish to express all my devotion and reverence to almighty Allah, 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 Md. Sadiqul Amin, Assistant professor, Soil Science Discipline, Khulna University, under whose careful supervision and scholastic guidance this thesis has been conducted. I am sincerely thankful to Khandakar Qudrata Kibria, Associate professor and Head 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 cooperation at different stages for accomplishing this study. I convey my respect and gratefulness to Md. Sanaul Islam, Associate professor, Soil Science Discipline, University of Khulna for his cordial co-operation during this study. Special appreciation goes to my friend Falguni Akter for her excellent co-operation during this study. I am also thankful to my senior Sobuj Ahmed and junior Ali Reza, for their cordial co-operation during my work. 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.

April, 2012. Author



DEDICATION To my beloved family


Titles CONTENT LIST OF TABLES LIST OF FIGURES Chapter one: Introduction 1. Introduction Chapter two: Literature review 2. Literature review 2.1. Primary soil minerals 2.2. Secondary soil minerals 2.3. Formation of clay minerals 2.3.1. Formation of Vermiculite Release of Potassium Oxidation of Iron Hydroxyl Orientation 2.3.2. Formation of Smectite Transformation from Mica Environment transformation of mica Formation from Solution 2.3.3. Formation of Kaolinite Equilibrium environment and conditions for synthesis of Kaolinite Kaolinite formation Interlayered Montmorillonite 2.4. Structure of clays minerals 2.4.1. The 1:1 Type Minerals from Hydroxy-Al that promote the 10 11 11 11 11 13 14 17 3 5 6 7 8 8 9 9 10 10 1 Page No. I IV V Transformation from Chlorite


Titles Kaolinite Halloysite 2.4.2. The 2:1 type Minerals Smectite (Montmorillonite) Vermiculite Mica Illite Chlorites 2.4.3. Interstratified Clay Minerals Intergrade Montmorillonite-Vermiculite-Chlorite

Page No. 17 19 20 20 21 23 24 25 26 27 27 28 35 35 36 36 Swelling 2:1 to 2:2 intergrades 2.5. Soil mineral weathering sequences 2.6. Pridiction of clay mineralogy 2.7. Ganges Floodplain soils of Bangladesh 2.8. The agricultural landuse of Ganges Floodplain soils 2.9. Clay mineralogy of the soils of Bangladesh

Chapter three: Materials and Methods 3. Materials And Methods 3.1. Study area 3.2. Collection of soil samples 3.3. Processing of soil samples 3.4. Soil analyses 3.4.1. Particle size analysis 3.4.2. pH 3.4.3. ECe 3.4.4. Organic carbon 41 41 42 42 42 42 42 42 42


Titles 3.4.5. Cation exchange capacity 3.4.6. Exchangeable K+ 3.4.7. Water soluble K+ 3.4.8.Water soluble Mg2+ Chapter four: Results and Discussion 4. Results and Discussion 4.1. Physical Characteristics 4.2. Chemical Characteristics 4.2.1. pH 4.2.3. CEC 4.2.4. K+ content 4.2.5. Mg2+ content 4.2.6. Organic C and humus 4.3. Prediction of clay minerals 4.4. Weathering stability of clay minerals Chapter five: Summary and conclusion Chapter six: References

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44 44 44 44 44 44 46 46 46 46 49 50


LIST OF TABLES Titles Table 2.1 Common primary mineral of soil Table 2.2 Common secondary Minerals in Soils Table 2.3 Types of minerals as indicators for relative degree of soil development (the higher the number, the higher the degree of development Table 2.4 The typical ratio of CEC to clay for some classes of clay mineralogy Table 3.1 General information of sampling sites Table 4.1 Different properties of studied soils Table 4.2 The clay mineralogy of the soil samples Page No. 6 7 30

35 41 45 46

Table 4.3 Pedological indices for studied soil samples Table 4.4 Pedological indices of different clay minerals under equilibrium condition

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LISTS OF FIGURES Titles Fig 2.1 Fig 2.2 Fig 2.3 Fig 2.4 Fig 2.5 Fig 2.6 Fig 2.7 Fig 2.8 Fig 2.9 Fig 2.10 Fig 2.11 Fig 2.12 Fig 2.13 Fig 2.14 Fig 2.15 General conditions for the formation of the various layer silicate clays and oxides of iron and aluminum Composition of solutions equilibrated with montmorillonites Tetrahedron, octahedron and classification of silicate mineral Models of a 1:1 layer structure Schematic structure of Kaolinite Schematic structure of Halloysite Models of a 2:1 layer structure Schematic structure of montmorillonite Schematic structure Vermiculite Schematic structure of Mica Schematic structure of Chlorite Mineral stability sequence. Stability of minerals Relative solubility of a few clay minerals Relative solubility of selected primary and secondary minerals at pH 7.0 A clay mineralogical map of Bangladesh soils Page No. 8 12 16 17 18 19 20 21 22 24 26 29 32 34 40

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1. Introduction Bangladesh is the largest deltaic floodplain in the world with a total area of 147570 km2 of which 88892 km2 is occupied by major rivers and estuaries. The great delta is flat throughout and sketches from near the foothills of the Himalayas Mountain in the north to a southern irregular deltaic coastline that faces the Bay of Bengal. The major portion of the Bengal basin of the Sindhu-Ganges depression lies in Bangladesh (Saheed, 2010). 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 tertiary formation. The soil 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 of the other. These 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, Psamments, Orthents, Aquepts, Ochrepts, Umbrepts, Aquolls, Udalfs, Ustalfs, Udults and Ustults and also may be some Uderts. Among them the Aquepts are by far the most dominant soil covering about 60% of the area (Saheed, 1985). In Bangladesh, some data on both sand and clay mineralogy are available but they are not adequate. 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 (Saheed, 1985). Recently formed delta and alluvial plains of the Ganges, Brahmaputra and Meghna rivers are the most extensive area of cropping practices. Pedological indices for determination of the weathering stability of soil mineral could be influenced by different type cropping pattern. The objectives of this study is To predict the mineralogy of some soils of Ganges floodplain of Bangladesh under different cropping pattern. To describe the weathering stability of the clay minerals. - 12 -

2. Literature Review 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 (<2m) 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 for plants, and create the water-and air-filled pores that make plant growth possible.

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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 350C 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

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kaolinite or pyrophyllite can develop in the presence of an excess of K 2O, depending on the temperature, the amount of K2O and the Al2O3:SiO2 ratio (Grim, 1986). 2.1. Primary soil minerals The mineral which has not been altered chemically since its deposition and crystallization from molten lava is called primary mineral (Brady and Weil, 2002). Most common primary minerals in soils are 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.

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

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).

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Table 2.2 Common secondary Minerals in Soils Name Clay minerals Kaolinite Montmorillonite Vermiculite Chlorite Allophane Imogolite Goethite Hematite Maghemite Ferrihydrite Bohemite Gibbsite Pyrolusite Gypsum Chemical formula Si4Al4O10( OH)8 MX (Al, Fe , Mg)4Si8O20 (OH)4 [M = interlayer metal cation] 3+ (Al, Mg, Fe )4 (Si, Al)8O20(OH)4 [M Al (OH)6](Al, Mg)4(Si, Al)8 O20(OH, F)4

Si3Al4O12 . nH2O Si2Al4O10 . 5H2O FeOOH -Fe2O3 -Fe2O3 Fe10O15 . 9H2O -AlOOH Al (OH)3 -MnO2 CaSO4 . 2H2O Source: Sparks, 1995

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.

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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). The alteration of micas to vermiculites may be subdivided into separate steps, or factors affecting alteration: (i) release of K, (ii) oxidation of Fe 2+and

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(iii) OH orientation. These reactions may be mitigated by the presence of organic acids (Robert et al., 1979). 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 (Bassett, 1959; Roux et al., 1963) micavermiculite 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). 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 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 tetrahedral 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 or a crystalline external phase of -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; the decrease in surface charge is minimal and vermiculite is formed (Farmer et al., 1971). Hydroxyl Orientation

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In trioctahedral micas OH- ions sit in a hole above three divalent (Fe 2+ 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 (Al 3+), 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). 2.3.2. Formation of Smectite In the environment smectite can form by the transformation of mica, chlorite and solution. 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 + 0.5Si4+ + 0.25Ca2+ (Si 3.5Al0.5)(Mg3)O10(OH)2Ca0.25 + 0.5Al3+ + K+ 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

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Without these extensive changes, micas do not have the low-charge characteristics necessary for them to exhibit the properties of smectites. 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 pHs 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). 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 100C (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). 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 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.

- 21 - Equilibrium environment and conditions for synthesis of Kaolinite Formation of kaolinite in the presence of smectite at 25C 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.

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 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 2Al3+ + 2H4SiO4 + H2O 6H+ + Si2Al2O5(OH)4(kaolinitic) . [2.1]

The equilibrium constant, K, for the reaction is

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An activity of unity is assumed for kaolinite and H2O. Taking log on both sides. [Eq. 2.2] log K = -6pH 2log Al3+ - 2log H4Sio4 Dividing by 2 and rearranging gives [Eq.2.3] log Al3+ + 3pH = -log H4Sio4 log K [2.3] .. [2.2]

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 H 4SiO4- 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). 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] Gr = G (kaolinite) - 2G3+Al - 2G 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 25C. Hence G (kaolinite) = -3.783 MJ mol-1.

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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 25C 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) Kaolinite formation from Hydroxy-Al Interlayered Montmorillonite Kaolinite formation has been induced by hydrothermal treatment of hydroxy-Al interlayered montmorillonite at 220 C. The kaolinite was expanded to approximately 0.85 nm during the first few days of reaction. After 14d 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+ H4SiO4 and Al3+ react to form kaolinite 2H4SiO4 + 2Al3+ + H2O The net reaction gives the Eq.2.7 (Al,Fe,Mg)2Si4O10(OH)2 + m Al3+ + 6H2O Al2Si2O5(OH)4 + 6H+ + aFe3+ + bMg2+ 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 .. [2.7] Al2Si2O5(OH)4 + 6H+ . [2.6] 2(Al,Fe,Mg)3+ + 4 H4SiO4 [2.5]

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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 oxy 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 SiO 4 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 (AlSi 3O10)5- or (Al2Si2O10)6-. Minerals in which tetrahedral sheets of silica dominate are often referred to as layer silicates (Olson et al. 2000).

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( e)
Fig. 2.3. (a) Tetrahedron [TO4]; (b) tetrahedral sheet. Oa and Ob refer to apical and basal oxygen atoms, respectively. a and b refer to unit-cell parameters; (c) O oct (OH, F, Cl) orientation in cis-octahedron and trans-octahedron; (d) location of cis- and trans-sites in the octahedral sheet. O a and Ob refer to apical and basal oxygen atoms, respectively. a and b refer to unit cell parameters (Brigatti et al., 2006); (e) classification of silicate mineral (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

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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). In the octahedral sheet, connections between each octahedron, M, to neighbouring octahedra are made by sharing edges. The edge-shared octahedra form sheets of hexagonal or pseudo-hexagonal symmetry (Fig. 2.3). Common tetrahedral cations are Si4+, Al3+, and Fe3+. Octahedral cations are usually Al3+, Fe3+, Mg2+, and Fe2+, but other cations, such as Li+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, V3+, Cr3+, and Ti4+ were identified. Octahedra show two different topologies related to hydroxyl position, i.e., the cis- and the trans-orientation (Fig. 2.3). 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 (Ca 2+, 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 the clay minerals can be grouped into 1:1, 2:1 and 2:1:1 type clay minerals (Olson et al., 2000). 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 (fig. 2.4). One plane consists of the basal O2 ions of the tetrahedral sheet, the second consists of O 2 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).

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Fig. 2.4. Models of a 1:1 layer structure. Oa, Ob, and Ooct refer to tetrahedral apical, tetrahedral basal, and octahedral anionic position, respectively. M and T indicate the octahedral and tetrahedral cation, respectively (Brigatti et al., 2006).

The common 1:1 type clay minerals will be described. Kaolinite Kaolinite occurs commonly in soils, often as hexagonal crystals with an effective diameter of 0.2 to 2 m. Hydrogen bonding between adjacent unit layers prevents expansion (swelling) of the mineral beyond its basal spacing of 7.2 (Fig 2.5). 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).

Fig. 2.5. Schematic structure of Kaolinite Al2Si2O5 (OH)4 (Bear, 1964)

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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 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 m 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). 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). Fig 2.6 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 from kaolinite; once dehydrated, the layer spacing decreases to close to that of kaolinite (Olson et al., 2000).

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Fig. 2.6. Schematic structure of Halloysite Si4Al4O10(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 (fig. 2.4). 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 will be discussed.

Fig. 2.7. Models of a 2:1 layer structure. Oa, Ob, and Ooct refer to tetrahedral apical, tetrahedral basal, and octahedral anionic position, respectively. M and T indicate the octahedral and tetrahedral cation, respectively(Brigatti et al., 2006) Smectite (Montmorillonite)

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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 , and full hydration can swell the layer to distance of tens or even hundreds of Angstroms (Bhon et al., 1979). 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 Si 4+ and the octahedral cations are Al3+, Fe2+ and Mg2+ (Fig 2.8). 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).

Fig. 2.8. 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

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octahedral sheet. Nontronite also is a Fe-bearing mineral with Fe 3+ 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 m 2/g, with as much as 80% of the total due to internal surfaces. Montmorillonite has high colloidal activity, 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 m. Smectites are common in Vertisols and are especially common in soils of alluvial plains (Bhon et al., 1979). 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 or more, so as to accommodate interlayer water and interlayer exchangeable cations (Bear, 1964). Fig. 2.9 shows the schematic structure Vermiculite.

Fig. 2.9. Schematic structure Vermiculite Mgn(H2O)6(Mg,Fe++)3Si4-n AlnO10(OH)2 (Bear, 1964)

The general formula for vermiculite is M x-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

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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). 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 ) 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). 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

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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. 2.10). 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 monovalent cations, usually K+, occupying interlayer sites between two tetrahedraloctahedral- tetrahedral layers. The general formula is Mx(R(2+)3-y, R(3+)y) (Si4X

,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 Fe 2+ 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+, particularly in biotite mica (Olson et al., 2000).

Fig. 2.10. 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 m 2/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).

- 34 - 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 Earths 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). 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 illiteshave NH4+ rather than K+ in the interlayer space (Moore and Reynolds, 1997). TheNH4+ 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). 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 Al 4.4(OH)12. (Al1.2, Si6.8) Al4O20(OH)4 also occurs (Bear, 1964).

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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. 2.11). This sheet is positively charged because there are fewer than 3OH - per Al3+ in the 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).

Fig. 2.11. Schematic structure of Chlorite [AlMg2(OH)6] [Mg3Si3AlO10(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, - 36 -

or (2) diagenesis. 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. MontmorilloniteVermiculiteChlorite 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 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 gibbsitelike 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). 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

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2:2 intergrades. A sharp 18 peak with Mg saturation and glycerol solvation, and a greatly broadened 10 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 montmorillonitechlorites 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 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 hydroxyl 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 data, (Goldich, 1938) proposed a mineral stability sequence (Fig. 2.12) 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.

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Furthermore, secondary minerals that are weathering products of the preexisting minerals are not considered (Dixon and Weed, 1989).

Fig. 2.12. 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 about these changes, or whether a given soil under a specific weathering environment will proceed through all stages.

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Table 2.3 Types of minerals as indicators for relative degree of soil development (the higher the number, the higher the degree of development Relative degree of soil development 1 2 3 4 5 6 7 8 9 10 11 12 13 Prominent minerals in soil clay fraction Gypsum, and other soluble salts Calcite, dolomite, and apatite Olivine-hornblende minerals Biotite, glauconite, ferromagnesian chlorite Feldspars Quartz Muscovite-illite Interstratified 2:1 layer silicates and vermiculite Montmorillonites Kaolinite and halloysite Gibbsite and allophane Hematite-goethite Anatase-leucoxene Source: Jackson and Sherman, 1953

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 25C and pH 5 for 1-mm crystals of albite and enstatite, respectively, 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 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). - 40 -

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 + 6H+ 2Al3+ + 2H4SiO40 + 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

log k = 2 log (Al3+) + 2 log (H4SiO40)- 6 log (H+)



Simplifying, rearranging, and substituting the above equation (Eq. 2.8), eq.2.9 derived log (Al 3+) + 3pH = 3.4 log (H 4SiO40) . [2.9]

This algebraic manipulation of the equilibrium constant (Eq. 2.9) permits a graphic representation of this solubility reaction, as shown in fig. 2.13. Similarly, gibbsite, amorphous silica, and montmorillonite solubilities are also plotted in fig. 2.13.

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Fig. 2.13. 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. 2.13 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 pFe 3+ 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 Al 3+ 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 (H 4SiO2) activity of -3.0, the montmorillonite line (pH 6, pMg 3.7) is below the metastable extension of the logAl 3+ + 3 pH 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 (H4SiO4 0) of -3.0 and pH 7.0. At log (H4SiO40) of -6.0, their relative solubilities are reversed (Dixon and Weed, 1989).

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The two montmorillonite stability lines (contours) in fig. 2.13 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 silicagibbsite 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. 2.13 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. 2.14. 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. 2.14. 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 (H 4SiO40) 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 -

Fig. 2.14. Relative solubility of selected primary and secondary minerals at pH 7.0 when log Mg 2+= 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 H 4SiO40 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 H 4SiO40 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 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.

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2.6. Pridiction of clay mineralogy The ratio of CEC by ammonium acetate at pH 7 to clay can be used to predict clay mineralogy. If the ratio is multiplied by 100, the product is cmol(+)/kg clay (Soil Survey Staff, 2006). The typical ratio for some classes of clay mineralogy are mentioned in Table 2.4
Table 2.4 The typical ratio of CEC to clay for some classes of clay mineralogy Typical ratio of CEC to clay <0.2 0.2-0.3 0.3-0.5 0.5-0.7 >0.7 classes of clay mineralogy Kaolinitic Kaolinitic or mixed Mixed or illitic Mixed or smectite Smectite

Source: Soil Survey Staff, 2006

These ratios are more valid when some detailed mineralogy data are available. If the ratio of 1500 kPa water to clay is 0.25 or less or 0.6 or more, the ratio of CEC by ammonium acetate to clay is not valid. Ratios of 1500 kPa water to clay of 0.6 or more are typical of poorly dispersed clays, andic and spodic materials with an isotic mineralogy class, and ratios of less than 0.3 are common in some soils that contain large amounts of gypsum ((Soil Survey Staff, 2006)). A ratio of CEC at pH 8.2 to 1500 kPa water of more than 1.5 and more exchange acidity than the sum of bases plus KCl extrctable Al imply a soil with a high pHdependent charge. Along with bulk density data, they help to distinguish soils that have andic and spodic materials or soils that have materials with an isotic mineralogy class from soils with materials that are more crystalline (Soil Survey Staff, 2006). 2.7. Ganges Floodplain soils of Bangladesh - 45 -

Floodplain constituents about 80% of the total land surface of Bangladesh. It is formed by the sediments deposited by the major rivers of Tista, Brahmaputra, Jamuna, Ganges, Meghna, Surma-Kushiara, Karotoa-Bangali, Atrai, Punarvaba and other small rivers. Ganges Floodplain has characteristically two landscape units: The High Ganges Floodplain and the Low Ganges Floodplain (Rahman, 2005). High Ganges Floodplain is often termed as Mouribad Gangetic delta where flow of the river is practically cut off from their parent river.this area has a complex relief of broad and narrow ridge and inter-ridge depressions, separated by areas of smooth, broad ridges and basins. About more than half of area is above the normal flood level whereas the rest of the area is shallowly flooded. Soils of this area are calcareous, permeable silt loam to silty clay loams (Rahman, 2005). Low Ganges Floodplain has a typical meander landscape of broad ridges and deep basins. Differences in elevation between ridges tops and basins centres are generally in the range of 3-5 meters. In this floodplain area, about 2/3 of the land is either moderately deeply or deeply flooded. Only a small portion of the land is above normal flood-depth and the rest is shallowly flooded (Rahman, 2005). Highland soils are permeable, calcareous sandy and the lowland soils are heavy clayey. Heavy clay soils in the basins stay wet in the early dry season and then quickly become dry. Land preparation is difficult because of heavy consistency of clay soil, which makes ploughing difficult for dry land crops or puddle hardly satisfactory for transplanted rice crops (Rahman, 2005). 2.8. The cropping pattern of Ganges Floodplain soils On permeable highlands, aus or jute followed by rabi crops such as wheat, tobacco, spices, vegetables or sugar-cane are the principle crops grown; on impermeable highlands and medium highlandsm, aus or jute followed by transplanted amon are the principle rainfed crops but with irrigation, HYV boro followed by rainfed transplanted amon are the principle crops grown. On medium lowlands and lowlands, mainly mixed with aus and amon or jute followed by khesari are grown in the slow draining areas. In the quick draining areas, mustard, wheat and other early dryland rabi crops are grown. Where irrigation are available, HYV boro is grown in the rabi season (Rahman, 2005). 2.9. Clay mineralogy of the soils of Bangladesh - 46 -

Bangladesh is apparently flat alluvial plain with apparent homogenous land and soil condition and it, in fact, has a complex land pattern and soil condition. It has three distinct land system: Floodplain, Terrace and Hill (Rahman, 2005). Huizing (1971) made a reconnaissance study on the sand mineralogy of Bangladesh soils and reported that hill and terrace soils Contained low feldspathic and micaceous minerals while floodplain soils were rich in feldspar, mica and amphiboles. Hasibullah et al. (1971) studied the clay mineralogy of Nunni series of_Northern and Eastern Piedmont Plains, Borda series of Middle Meghna River Floodplain and Noadda and Chhiata series of terrace areas. They reported that all these soils were dominated by mica and kaolinite except for Borda series. Vermiculite was dominant in the two floodplain soils while randomly interstratified minerals dominated the two terrace soils. Hassan and Razzq (1981) studied four soil profiles from the Sunderban forest area on Ganges Tidal Floodplain and found that all soils were dominated by mica and smectite with some katolinite, chlorite; vermiculite and interstratified minerals. white (l985) reported qualitative estimates of clay mineralogical composition of a large number of soils and opined that mica (muscovite) and kaolinite were the predominant minerals in the clay fraction of most floodplain soils. He speculated that mica was transformed to vermiculite under acidic condition, in the BrahmaPutra, Meghna and Tista floodplain soils; while under neutral to alkaline reaction and poor drainage conditions mica was transformed tosmectite (montmorillonite). He also reported the occurrence of halloysite in the surface and smectite in the lower horizons of some terrace soils. Saheed (1985) reported three groups of mineralogical association in Bangladesh soils mica, vermiculite and kaolinite in most floodplain soils; smectite along with mica in Gangeas floodplain soils; and mica and halloysite in terrace soils. Mineralogy of silt, and fine and coarse clays of four soil profiles was studied by Islam and Lotse (1986). Using X-ray dilfraction (XRD), ion exchange and selective dissolution techniques. Mica and smectite were found to be dominant in Batra and Ghior series of Ganges River Floodplain, whereas mica and kaolinite were dominant in Naraibag and Ghatail series of Old Meghna Estuarine Floodplain and Old BrahmaPutra Floodplain, respectively.

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Islam et al. (1988) reported the clay mineralogical composition of 18 soil profiles and found that mica was dominant in all soils, kaolinite and vermiculite in almost all soils, while halloysite in terrace soils and smectite in Ganges floodplain soils. His description has similarity with the reports of White (1985) and Saheed (1985). Egashira (1988) studied the mineralogical composition of five soil profiles from terrace areas and reported that the clay fractions were dominated by mica and kaolinite while the sand and silt fractions were mostly by quartz. In addition, some interstratified funerals like mico-vermiculite-smecectite and kaolinite-smectite were detected. The transformation sequence of mica in terrace soils was outlined as follows: mica kaolinite-smectite interstratified mica-vermiculite-smectite kaohinite. interstratified

Mia (1990) reported the mineralogical composition of forty-seven soil profiles and found that mica and kaolinite were the major clay minerals in most soils and that the proportion of kaolinite was highest in hill soils; smectite was present in Ganges floodplain soils, while vermiculite and chlorite were present sporadically in different soils. Egashira and Yasmin (1991) reported that mica arnd chlorite were found to be dominant in Tista and Old Brahmaputra floodplain soils, and the latter also contained large amounts of vermiculite; the calcareous part of Ganges floodplain soils was composed of smectite and mica while the noncalcareous or decalcified part contained mica and chlorite. A terrace soil was dominated by mica and interstratified kaolinitesmectite and mica-vermiculite-smectite. Hassan (1991) reported the clay mineralogical composition of four floodplain soils, two terrace soils and two hill soils. Hill and terrace soils were dominated by mica and kaolinite; Ganges floodplain soil by mica and smectite, and Brahmaputra, Meghna and Tista floodplain soils by mica and vermiculite . Ali (1994) reported that Ganges floodplain soils contained smectite as the predominant mineral with some mica, chlorite and kaolinite, while in Brahmaputra floodplain soils mica, knolinite and chlorite were the major minerals. Alam et al. (1993a, b) and Alam (1994) reported that hilt soils were dominated by mica and hydroxy-Al interlayered vermiculite with low smectite, vermiculite, kaolinite and chlorite contents. Terrace soils had higher mica and kaolinite but trace amounts of smectite, chlorite and vermiculite. All floodpiain soils were rich in mica and contained kaolinitc and chlorite; the mica content was higher in noncalcareous soils

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than in calcareous soils; calcareous soils contained smectite in large quantities while noncalcareous soils were rich in vermiculite. Mazumder (1996) reported the clay mineralogical composition of seven soil profiles of Brahmaputra floodplain and found that all soils were rich in mica, kaolinite and vermiculite while chlorite was identified in some soils. Aramaki (1996) studied 11 soil profiles for the clay mineralogical composition and reported that mica was dominant in all soils, smectite in Ganges floodplain soils, interstratified mica-vermiculite-smectite and interstratified kaolinite-smectite or kaolinite in terrace soils. kaolinite was rich in hill soils and even greater than mica, while Old Brahmaputra and Meghna floodplain soils contained good amounts of chlorite and vermiculite. Khan et al. (1997) studied five benchmark sail profiles from different floodplain of Bangladesh and found that mica was the dominant mineral in all soils. Smectite was dominant in Ganges floodplain soils only. Varing amounts of kaolinite and vermiculite were present in all soils. Idenification of kaolinite as a dominant mineral in most floodplain soils was a matter of great controversy among the reports. Mia (1990), White (1985), Saheed (1985), Ali (1994), Islam and Lotse (1986), Mazumder ( 1996), and Khan et al. (1997) reported high quantity of kaolinite in different floodplains soils while others found smaller amounts of kaolinite in those soils. The clay mineralogical map of Bangladesh (Fig. 2.15) was prepared by Hussain et al. (1999).

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Fig. 2.15 A clay mineralogical map of Bangladesh soils. Dots indicate location of soil sampling sites. Legends: 1. mica-chlorite suite; 2. mica-smectite suite; 3. mica- vermiculite- kaolinite suite; 4. micachlorite- vermiculite suite; 5. mica -mixed-layer-minerals- kaolinite suite; 6. kaolinite -mica suite; 7. mica kaolinite- vermiculite suite; and 8. mica-kaolinite- vermiculite suite ( Hussain et al., 1999).

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3. Material And Methods A study was conducted to asses the mineralogy of some soils of Ganges river floodplain area in the south-western region of Bangladesh. 3.1. Study area The samples were collected from different locations of Jessore and Satkhira district. General information of sampling sites are presented in Table 3.1
Table 3.1 General information of sampling sites Sample No. Address Village: Mohakal Union: Noapara Thana: Avoynagar District: Jessore Village: Ghoragasa Union: Norendropur Mouza: Ghoragasa District: Jessore Village: Ramnagar Union: Ramnagar Mouza: Sutigata District: Jessore Village: Teghori Union: Deora Mouza: Teghori Thana: Kotowali District: Jessore Village:Meghla Union:Chachra Thana:Kotowali Dist:Jessore Village: Navaron Union: Navaron Mouza: Jhikorgacha Thana: Jhikorgacha District: Jessore Village: Jhapaghat Union: Helatola Mouza: Brozobaksha Thana: kolaroa District: Satkhira Village: Jhapaghat Union: Helatola Mouza: Brozobaksha Thana: Kolaroa Physiography Ganges Tidal Floodplain Agricultural Land Use


Ganges Meander Floodplain


Ganges Meander Floodplain

Teak plants

Ganges Meander Floodplain

Amon-Jute -Pulses

Ganges Meander Floodplain


Ganges Meander Floodplain


Ganges Meander Floodplain


Ganges Meander Floodplain


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District: Satkhira

3.2. Collection of soil samples A total of 8 soil samples were collected for laboratory analysis. Representative soil samples were collected from surface only. The samples were placed in plastic bags. 3.3. Processing of soil samples The collected soil samples were dried in air by spreading on separate sheet of papers after it was transported to laboratory. After drying in air, the larger aggregates were broken gently by crushing in a wooden hammer. A portion of the crushed soil was passed through a 2.0 mm sieve. The sieved soil were then preserved in plastic bag and labeled properly. These were later used for various chemical analyses. The chemical analyses were carried out on those collected soil samples in the laboratory of the Soil Science discipline in Khulna University. 3.4. Soil analyses Different parameters of soil were analyzed by following the available procedures. 3.4.1. Particle size analysis The particle size was determined by hydrometer method presented by Gee and Bauder (1986). 3.4.2. pH
Soil pH (1:2.5) was determined electrochemically by using of glass electrode with the procedure of Jackson (1973).

3.4.3. ECe The ECe of the soil was measured at a soil water ratio of 1:1 by EC meter (USDA, 2004) 3.4.4. Organic carbon Soil organic carbon was determined by of Wakley and Blacks (1934) wet oxidation method as described by Jackson (1973). 3.4.5. Cation exchange capacity

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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). 3.4.6. Exchangeable K+ For the determination of exchangeable K+ soil was extracted with 1N NH4OAC solution of pH 7.0 as described by Piper (1950) and Jackson (1973). 3.4.7. Water soluble K+ Water soluble K+ was determined after extraction with distilled water as described by Jackson (1973). 3.4.8.Water soluble Mg2+ Water soluble Mg2+ was determined in a combination determination process of Ca2+and Mg2+, after extraction with distilled water as described by Piper (1950).

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4. Result and Discussion The results obtained from laboratory analysis will be discussed in this section. 4.1. Physical Characteristics The texture of the samples varied from loam to clay loam (Table 4.1). This result resembles to several findings by other researches. SRDI staff (1965-86) found that on the young Ganges meander floodplain, soils of ridges and inter-ridges depressions are silt loam to silty clay; and on the old Ganges meander floodplain, soils of ridges and depressions are loamy to clay in texture. Highest value of sand percentage was observed in sample no. 1 (51%) and lowest value of sand percentage was in sample no. 2 (19%) (Table 4.1). Highest value of silt percentage was in sample no. 5 (60%) and lowest in sample no. 6 (38%) (Table 4.1). Highest value of clay percentage was observed in sample no. 6 and 7 (Table 4.1) and lowest in sample no. 1 (10%) (Table 4.1). 4.2. Chemical Characteristics 4.2.1. pH Among the samples pH values were varied from 5.9 to 7.22 (Table 4.1). pH 5.9 was found in sample no. 4 whereas 7.22 was found in sample no. 7. 4.2.2. EC EC values were varied from 0.59 dS/m (sample no. 5) to 3.84 dS/m (sample no. 1) among the samples (Table 4.1). 4.2.3. CEC CEC values were varied from 42.56 cmolc/Kg (sample no. 7) to 10.92 cmolc/Kg soil (sample no. 3) among the samples (Table 4.1). 4.2.4. K+ content Water soluble K+ content were varied from 0.04 cmolc/Kg (sample no. 6) to 0.10 cmolc/Kg (sample no. 8) among the samples (Table 4.1). Exchangeable K+ content were varied from 0.04 cmolc/Kg (sample no. 5) to 0.32 cmolc/Kg (sample no. 7) among the samples (Table 4.1).

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Table 4.1 Different properties of studied soils

Soil Property Sand (%) Physical PSA Silt (%) Clay (%) Texture pH EC (dS/m) CEC (cmolc/Kg) Chemical Exchangeable Water soluble Water soluble 1 51 39 10 Loam 6.9 3.84 19.10 0.11 0.07 1.43 0.78 1.34 2 19 61 20 Silt loam 6.1 0.69 18.75 0.10 0.05 0.41 0.62 1.08 3 27 58 15 Silt loam 7.1 0.94 10.92 0.20 0.07 0.34 0.64 1.11 4 28 48 24 Loam 5.9 0.77 15.04 0.12 0.05 1.19 0.60 1.04 5 27 60 13 Silt loam 6.76 0.59 17.04 0.04 0.03 0.58 0.53 0.91 6 27 38 35 Clay loam 6.67 0.73 31.91 0.05 0.04 1.50 0.41 0.71 7 21 44 35 Clay loam 7.22 0.98 42.56 0.32 0.07 1.77 0.90 1.55 8 24 42 34 Clay loam 7.02 1.37 27.17 0.23 0.10 0.72 0.47 0.81

K content (cmolc/Kg) Mg content (cmolc/Kg)

Organic C (%) Humus (%)

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4.2.5. Mg2+ content Water soluble Mg2+ content were varied from 1.77 cmolc/Kg (sample no. 7) to 0.34 cmolc/Kg (sample no. 3) among the samples (Table 4.1). 4.2.6. Organic C and humus Highest value of Organic C (0.90%) and humus (1.55%) was found in sample no. 7 and lowest value of these was 0.41% and 0.71%, respectively in sample no. 6 (Table 4.1). 4.3. Prediction of clay minerals The clay mineralogy of the soil samples was predicted from the ratio of CEC by ammonium acetate at pH 7 to clay (Soil Survey Staff, 2006) and the result is presented in Table 4.2.
Table 4.2 The clay mineralogy of the soil samples Samples No. 1 2 3 4 5 6 7 8 Ratio of CEC to clay 1.91 0.94 0.73 0.63 1.31 0.91 1.22 0.799 Probable Clay Mineralogy Smectitic Smectitic Smectite Mixed or Smectitic Smectitic Smectitic Smectitic Smectitic

4.4. Weathering stability of clay minerals According to Faure (1992), pedological indices for studied soil samples are shown in Table 4.3.

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Table 4.3 Pedological indices for studied soil samples Samples No. 1 2 3 4 5 6 7 8 log [K+]/[H+]env 3.74 2.80 3.95 2.60 3.24 3.27 4.06 4.02 Log [Mg2+]/[H+]2env 11.65 9.50 11.43 9.57 10.98 11.21 12.39 11.60

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 4.4).
Table 4.4 Pedological indices of different clay minerals under equilibrium condition Minerals Illite-Muscovite1 Kaolinite-Mg montmorrillonite2 Illite- Mg montmorrillonite3 Mg montmorrillonite-Chlorite4 log [K+]/[H+]eqi 4.10 log [Mg2+]/[H+]2eqi 6.42 3.29 11.36 Source: Faure, 1992

The equilibrium equations (Faure, 1992) were: 1. log [K+]/[H+] = 1.48 log log [Mg2+]/[H+]2eqi 5.52 2. log [Mg2+]/[H+]2eqi = +6.42 3. log [K+]/[H+] = 0.14 log [Mg2+]/[H+]2eqi + 3.96 4. log [Mg2+]/[H+]2eqi = +11.36 The values of log [K+]/[H+]env in all soil samples varied from 2.60 to 4.06 (Table 4.3) which were lower than the value of log [K+]/[H+]eqi (4.10). According to Le Chatelirs - 57 -

principle the following equilibrium reactions of [Eq. 4.1] Illite Muscovite will shift to left hand side. As a result Illite can form in the environment. 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 . [4.1] In all soil samples, the highest value of log [Mg 2+]/[H+]2env was 12.39 and lowest was 9.57(Table 4.3) which were higher than the value of log [Mg 2+]/[H+]2eqi (6.42). According to Le Chatelirs principle the following equilibrium reactions [Eq. 4.2] of Kaolinite Mgmontmorillonite 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+ .. [4.2]

The values of log [Mg2+]/[H+]2env in all soil samples were varied from 12.39 to 9.57 (Table 4.3) whereas the value of log [Mg2+]/[H+]2eqi was in Faure (1992) equilibrium equations was 3.29. So the following equilibrium reaction [Eq. 4.3] of Illite Mgmontmorillonite will shift to right hand side. 1.013[(Al1.08Mg0.25)(Si3.50Al0.50)O10(OH)2]K0.60 + 0.1245SiO2 (amorphous) + 0.781H+ [(Al2.00) (Si3.67 Al0.33)O10(OH)2] Mg0.167 + 0.086 Mg2+ +0.405 H2O [4.3] Among all the soil samples, the values of log [Mg 2+]/[H+]2env varied form 12.39 to 9.57 (Table 4.3). according to Faure (1992), the equilibrium value of log [Mg 2+]/ [H+]2eqi was 11.36 (Table 4.4). The higher log[Mg 2+]/[H+]2env value indicates the possibility of formation of Chlorite from Mg-montmorillonite. The values of log [Mg2+]/[H+]2env was higher than 11.36 in sample no. 1 (11.65), 7 (12.39) and 8 (11.60). The equilibrium reaction [Eq. 4.4] of Mg-montmorillonite Chlorite is [(Al2.00)(Si3.67 Al0.33)O10(OH)2] Mg0.167 + 5.658 Mg2+ + 9.32 H2O 1.165 Mg5Al2Si3O10(OH)8 + 0.175 SiO2 + 11.316 H+ .. [4.4]

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5. Summary and Conclusion

The physiography of studied soil samples were both Ganges Tidal and Meander floodplain. The landscape was nearly leveled basin and poorly drained. The mineralogical property and weathering stability of minerals were studied in laboratory.

From the ratio of CEC to clay percentage the clay minerals presented in the soils were predicted. The dominant clay mineral in almost all the soils were Smectitic. Only Teghori soil (sample no. 4) contained mixed or Smectitic dominant clay mineral.

Almost all the studied soils had the tendency to transform into Mgmontmorrillonite. In illite-muscovite system, illite is more stable than muscovite. Muscovite was more stable than illite in Jhapaghat soil (sample no. 7 and 8). In Mg-montmorrillonite-chlorite system, chlorite was more stable than Mg-montmorrillonite for Jhapaghat soil (sample no. 7 and 8). Different cropping pattern had relatively same weathering stability of the minerals, thus it can be said that stability of minerals was not affected significantly by cropping pattern of the soils.

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5. References Adams, W.A.; Evans, L.J. and Abdulla H.H. 1971. Quantitative pedological studies on soil derived from Silurian mudstones. . Laboratory and in situ weathering of chlorite. Soil Science, 22: 158-165. Alam, M.L. 1994. Studies on Clay Mineralogical Characteristics and Their Effects on K Release and Fixation Behaviors of Bangladesh Soils. Dissertation to The United Graduate School of Agriculture Sciences, Kagoshima University, pp. 151. Alam, M.L., Miyauchi, N. and Shinagawa, A. 1993a. Study on clay mineralogical characteristics of calcareous and noncalcareous soils of Bangladesh. Clay Science. 9: 81-97. Alam, M.L., Miyauchi, N. and Shinagawa, A. 1993b. Study on clay mineralogical characteristics of hill and terrace soils of Bangladesh. Clay Science. 9: 109121. Ali, M.L. 1994. Effect of Alternate Wetting and Drying Cycles on Pedogenic Processes of Some Representative Bangladesh Soils. Ph.D. Thesis, University of Bangladesh, Dhaka, Bangladesh. Armaki, K. 1996. Mineralogical Composition of Main Bangladesh Soils. Graduation Thesis, Faculty of Agriculture, Kyushu University, pp. 38. Bassett, W.A. 1959. The origin of vermiculite deposits at Libby, Montana. American Mineralogist, 44: 282-299. Bear, F.E. 1964. Chemistry of The Soil. 2nd Edition. Oxford and IBH Publishing Co. Pvt. Ltd., New Delhi. Bhon, H.L.; McNeal, B.L. and OConnor, G.A. 1979. Soil Chemistry. John Wiley and Sons. Inc., Canada. Borchardt, G.A.; Jackson, M.L. and Hole, F.D. 1966. Expansible layer silicate genesis in soils deplicted in mica pseudomorphs. In: Heller, L. and Weiss, A. (eds.), Israel Program of Scientific Translations . Proceedings of the International Clay Conference, Volume 1, 20-24 June 1966, Jerusalem, Israel.

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Brady, N.C. and Weil, R.R. 2002. The Nature and Properties of Soils . 13th Edition. Pearson Education (Singapore) Pvt. Ltd., India. Brigatti, M.F.; Galan, E. and Theng, B.K.G. 2006. Structures and mineralogy of clay minerals. pp. 20-21. In: Bergaya, F.; Theng, B.K.G. and Lagaly, G. (eds.), Handbook of Clay Science, Developments in Clay Science Series , Volume 1. Elsevier Ltd., Amsterdam. Carroll, D. 1970. Clay mineral. A guide to their X-ray identification. Geological Society of America, Special Paper, pp. 126. Churchman, G.J. 2000. The Alteration and Formation of Soil Minerals by Weathering. In: Sumner, E.M. (ed.), Handbook of soil science. CRC press Boca Raton London, New York, Washington D.C. Chute, J.H. and Quirk, J.P. 1967. Diffusion of potassium from mica-like clay minerals. Nature (London), 213: 1156-1157. Crawford, T.W.; Whittig, Jr.L.D.; Begg, E.L. and Huntington, G.L. 1983. Eolian influence on development and weathering of some soils of Point Reyes Peninsula, California. Soil Science Society of America Journal, 47: 1179-1185. Dixon, J.B.; and Weed, S.B. 1989. Minerals in soil environments. 2nd Edition. Soil Science Society of America, Madison, Wisconsin. Egashira, K. and Yasmin, M. 1990. Clay mineralogical composition of floodplain soils of Bangladesh in relation to physiographic units. Bulletin of the Institute of Tropical Agriculture Kyusho University, 13: 105-126. Essington, M.E. 2004. Soil and Water Chemistry. CRC press LLC., Florida, U.S.A. Farmer, V.C.; Russell, J.D.; McHardy, W.J.; Newman, A.C.D.; Ahlrichs, J.L. and Rimsaite, J.Y.H. 1971. Evidence of loss of protons and octahedral iron from oxidized biotites and vermiculites. Mineralogical Magazine, 38: 121-137. Faure, G. 1992. Principles and Applications of Inorganic Geochemistry. Macmillan Publishing Company Ltd., New York. Garrels, R.M. and Christ, C.L. 1965. Solutions, minerals and equilibria. Harper and Row, Publishing, New York.

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