Sulfate Sorption Behavior of Two Soils in Ganges Floodplains Anindita

SULFATE SORPTION BEHAVIOR OF TWO SOILS IN GANGES
FLOODPLAINS
COURSE TITLE: PROJECT THESIS

COURSE NO: SS-4106
Soil Science Discipline

Khulna University
Khulna
December, 2014
Page 1 of 57

FLOODPLAINS
COURSE TITLE: PROJECT THESIS

COURSE NO: SS-4106
This project thesis paper has been prepared and submitted to the Soil
Science Discipline, Khulna University for the partial fulfillment of the
four years professional B. Sc. (Hons) degree in Soil Science
Submitted By
Anindita Das
Student ID: 091304
Session: 2012-2013
Page 2 of 57

FLOODPLAINS
Approved as to style and content by
..
Chairman of Examination Committee
Khulna University, Khulna
Bangladesh
______________________________________
Khulna University
Khulna
December, 2014
Page 3 of 57
SULFATE SORPTION BEHAVIOR OF TWO SOILS OF GANGES

FLOODPLAINS
Declaration
This thesis paper is entirely the candidates own investigation
Supervisor
.
Md. Sadiqul Amin
Associate Professor
czn_bd@yahoo.com
Khulna University, Khulna
Candidate
.
Anindita Das
Student ID: 091304
______________________________________
Khulna University
Khulna
December, 2014
Page 4 of 57
DEDICATED TO MY
BELOVED PARENTS AND BROTHER
Whose woes can never be fulfilled
Page 5 of 57
Acknowledgement
All praises belong to the almighty God, who is the most generous and benevolent. The
almighty God gives me the strength and ability to accomplish this thesis in time with
different complexities.
I would like to express the most gratitude to the honorable supervisor Md. Sadiqul
Amin, Associate Professor, Soil Science Discipline, Khulna University, Khulna for his
valuable comments, advice, systematic guideline and co-operation at all stages of this
study. I am also grateful to him for giving his most valuable time and for his sincerity.
I am sincerely thankful to Afroza Begum, Professor and Head, Soil Science Discipline,
Khulna University, Khulna for providing all possible facilities during the course of this
thesis and I am deeply indebted to all other teachers of Soil Science Discipline for their
important advice and suggestion.
Special thanks are extended to Md. Sanaul Islam and Md. Zaber Hossain, Associate
Professor, Soil Science Discipline, Khulna University, Khulna for their constructive
guidance, valuable advice and affectionate feelings throughout the period of study.
Special appreciation goes to my friends Arpita, Reza, Ema and Samiha for their cordial
support to do the best.
This acknowledgement would be incomplete without acknowledging the lab assistant,
Mr. Abdullah and Mr. Mahfuz. Without their support I cant go through this.
Finally, I respectfully remember my parents and brother for their relentless suppo rt for
my higher education and without whose blessing this work would not have been possible.
DECEMBER, 2014
The Author,
Anindita Das
Page 6 of 57
Contents
List of Tables
iv
List of Figures
Chapter One
1-3
1
1. Introduction
1.1. Background of the study
1.2. Objectives of the study
1.3. Limitation of the study
Chapter Two
4-18
4
2. Literature Review
2.1. The functions of sulfur
2.2. Sources and forms of sulfur in soil
2.2.1. Soil organic sulfur
2.2.2. Soil inorganic sulfur
2.3. Sulfur Cycle
2.4. Sulfur sorption and desorption
2.5. Adsorption isotherm
2.6. Factors affecting sulfate sorption in soil
10
2.6.1. Sulfate adsorbed to clay
11
2.6.2. Effects of hydrous oxide
11
2.6.3. Soil pH
12
2.6.4. Presence of Organic Ligands
12
2.6.5. Presence of other Anions
13
2.6.6. Presence of cation
13
2.6.7. Presence of Organic matter in soil
14
2.7. Mechanism of sulfate adsorption
14
2.7.1. Non specific adsorption
15
2.7.2. Specific adsorption
16
Chapter Three
19-23
19
3. Materials and Methods

3.1. Soil sample collection and Preparation
19
3.2. Bajoa series
19
Page 7 of 57
3.3. Gopalpur series
19
3.4. Analytical procedure
20
3.4.1. Physical properties of soils

3.4.1.1. Particle size analysis
3.4.2. Chemical properties of soils
20
20
20
3.4.2.1. Soil pH
20
3.4.2.2. Electrical Conductivity (EC)
21
3.4.2.3. Organic Carbon
21
3.4.2.4. Cation Exchange Capacity (CEC)
21
3.4.2.5. Available Sulfur (S)
21
3.5. Sulfate sorption experiment
21
3.6. Experiment with sulfate and acetate
22
3.7. Statistical analysis
23
Chapter Four
24-33
24
4. Results and Discussion

4.1. Physical and Chemical properties of soils
24
4.1.1. Particle size analysis
24
4.1.2. Texture
24
4.1.3. Soil reaction (pH)
24
4.1.4. Electrical Conductivity (EC)
24
4.1.5. Organic Carbon (OC)
25
4.1.6. Cation Exchange Capacity (CEC)
25
4.1.7. Available sulfur (S)
25
4.2. Sulfate sorption behavior
25
4.3. Freundlich adsorption isotherm
26
4.4. Langmuir adsorption isotherm
27
4.5. Temkin adsorption isotherm
28
4.6. Discussion
31
4.6.1. Adsorption isotherm
31
4.6.2. Effects of chemical parameter on sulfate

sorption
31
Page 8 of 57
Chapter Five
34
34
5. Summary and Conclusion
35-45
References
46
Appendix
Page 9 of 57
List of Tables
Table No.
Titles
Table 3.1
Location and environmental conditions of the soils
20
Table 4.1
Physical and chemical parameters of soils
25
Table 4.2
Freundlich and Langmuir constants of sulfate

sorption
30
Page 10 of 57
List of Figures
Figure No.
Titles
Fig. 2.1
The Sulfur cycle in soils
Fig. 2.2
Basic Adsorption Isotherm
8
9
2+
2-
Fig. 2.3
Cooperative adsorption with Ca and SO4 ion pair
14
Fig. 2.4
Protonation of hydroxyl creates formation of net

positive charges and results in nonspecific adsorption
16
Fig. 2.5
Specific adsorption where (a) sulfate displaces water

from net positive site, or (b) sulfate displaces hydroxyl
from neutral site and (c) the adsorbed sulfate may
displace another hydroxyl or water ligand from the
adjoining metal resulting in a 6-member ring and
neutralization
17
Fig. 4.1
Sulfur sorption capacity of soils with different rates of

sulfate application
26
Fig. 4.2
Freundlich adsorption isotherm for sulfur in Gopalpur

soil series
27
Fig. 4.3
Freundlich adsorption isotherm for sulfur in Bajoa soil

series
27
Fig. 4.4
Langmuir adsorption isotherm for sulfur in Gopalpur

soil series
28
Fig. 4.5
Langmuir adsorption isotherm for sulfur in Bajoa soil

series
28
Fig. 4.6
Temkin adsorption isotherm for sulfur in Gopalpur soil

series
29
Fig. 4.7
Temkin adsorption isotherm for sulfur in Bajoa soil

series
29
Fig. 4.8
Changes in S sorption as affected by acetate in the

Bajoa series
32
Fig. 4.9
Changes in S sorption as affected by acetate in the

Gopalpur series
33
Page 11 of 57
Chapter One
1. Introduction
Sulfur (S) is increasingly being recognized as the fourth major plant nutrient after
nitrogen, phosphorus and potassium. The importance of sulfur in agriculture is being
increasingly emphasized and its role in crop production is well recognized (Jamal et al.,
2010; Scherer, 2009). Sulfur is best known for its role in the formation of amino acids
methionine and cysteine; synthesis of proteins and chlorophyll; oil content of the seeds
and nutritive quality of forages (Jamal et al., 2009; Tandon, 1986).
Plants absorb sulfur mainly in the form of inorganic sulfate (SO42-) ions through the
roots, thus sulfate sulfur must be present in soils in sufficient amount in order to meet
crop sulfur requirements (Brady and Weil, 2013). Generally sulfate ions are known to be
weakly or moderately retained by soils. Sulfate retention is markedly differing from soil
to soil. The brown latosols and reddish brown lateritic contain higher amount of
sesquioxides and exchangeable aluminum (Chao et al., 1962b) thats why these soils
exhibit much higher adsorption of sulfate than other soils. The capacity for sulfate
adsorption is often greater in subsoil due to the presence of more clay and aluminum/iron
oxides.
Sulfate may be present in the soil solution, adsorbed on soil surfaces, or as insoluble
compounds, such as gypsum (Nelson, 1982) or associated with calcium carbonate
(Roberts and Bettany, 1985). Adsorption of sulfate occurs on positive charges that are
pH dependent and these sites are negligible above pH 6.5 (Tabatabai, 1982). The
insoluble sulfate compounds are probably not taken up directly by the crop. On a
theoretical basis, the solution and adsorbed forms of sulfate are the primary pools of
sulfur in the soil that are immediately available for plant uptake.
Adsorbed sulfate is in equilibrium with sulfate in solution; therefore, increased solution
sulfate will increase adsorbed sulfate. Sulfate is considered to be weakly held on
adsorption site and will easily be displaced with anions such as phosphate. In efforts to
obtain information on the mechanism involved in sulfate adsorption by soils, it is
desirable to first determine the effects of soil constituents. Various soil constituents or
factors have been held responsible for sulfate adsorption in soils including mineralogical
Page 12 of 57
composition, content and nature of organic matter, pH and the presence of other ions
(Alves and Lavorenti, 2004)
The effect of organic ligands on sulfate adsorption/desorption and on its mobility and
availability has received attention. Various organic ligands, such as oxalic, humic, citric
and acetic acid competed with sulfate for adsorption of kaolinite and Fe oxides. Their
competitive ability was related to the type of functional groups (Inskeep, 1998).
Desorption of sulfate is of interest not only from the point of view of plant availability of
adsorbed sulfate, but also in terms of the effect of acid rain on cation leaching from soils.
Unless sulfate is desorbed and is mobile in the soil, inputs of sulfuric acid will not have
any effect on cation leaching. This fact has been demonstrated by Johnson and Cole
(1977) in both laboratory and field studies. It has also been shown that both plant
availability (Barrow, 1961) and leaching of sulfate and removal of cations was reduced in
sulfate adsorbing soil (Singh, 1980). Besides the ability of the soil to adsorb sulfate,
desorption also depends upon a number of other factors, such as nature of adsorption,
type of desorbing ion, soil: solution ratio, pH of the suspension, vigor of shaking, and
time of contact between sulfate ion and the adsorbent. Therefore varying results are
reported on sulfate desorption (Singh, 1984).
1.1. Background of the study
An Adsorption isotherm, which describes the relation between the activity or equilibrium
concentration of the adsorptive and the quantity of adsorbate on the surface at constant
temperature, is usually employed to describe adsorption (Sparks, 1995). Sorption
capacity of the soil provides an accurate estimate of nutrient requirement of soil.
Generally plant nutrients remain in soil solution, exchange sites and interlayer spaces of
silicate mineral maintaining equilibrium. After application of fertilizer in soils, a new
equilibrium is established through adsorption, desorption, precipitation, transformation,
losses, uptake by crops etc. In our country, because of limited knowledge, farmers
generally apply sulfur fertilizer to the field without judging the requirement of sulfur.
They prefer to apply fertilizer in broadcast method, which increase fertilizer and soil
contact and more sulfate sorption is occurred in soils containing higher amount of clay
Page 13 of 57
minerals and Fe and Al oxide. So for assessing the Sulfur availability, this experiment
was undertaken to find out the Sulfate sorption potential in some soils of Bangladesh.
1.2. Objectives of the study
1. To find out the sulfate sorption potential of two soils of Ganges Floodplains.
2. To assess the adsorption equations that best to describe the relationship between
solution sulfur and adsorbed sulfur.
3. To observe the changes in sulfate sorption as affected by the presence of acetate
anion.
1.3. Limitation of the study
Among the Ganges Floodplain soils of Bangladesh, the study areas were selected only
two unions (Batiaghata and Surkhali) of Batiaghata upazila under Khulna district.
Page 14 of 57
Chapter Two
2. Literature Review
Reviewing the literature helps the researcher to develop the thesis paper. This chapter
includes some related and essential information about selected topic that have taken from
books, journals, articles, newspaper, organizational papers and so on.
2.1. The functions of sulfur
Sulfur contains a wide range of biological compounds. Sulfur (S) is found in vitamins,
biotin and thiamine; cofactors Sadenosyl- L-methionine, coenzyme A, molybdenum
cofactor (MoCo), and lipoic acid; and many secondary compounds (Leustek, 2002,
Leustek and Saito, 1999). S is the main component of amino acids formation and these
amino acids are the building block of protein. So it serves important structural, regulatory
and catalytic functions of proteins, and act as a major cellular redox buffer in the form of
the tripeptide glutathione and certain proteins such as thioredoxin, glutaredoxin and
protein disulfide isomerase. Cysteine residues in proteins sometimes form covalent
disulfide bonds. Disulfides can be reduced to the thiol form by glutathione or redox
proteins like thioredoxin (Leustek and Saito, 1999; Saito, 2000). For some enzymes,
disulfide bond formation serves to regulate activity. Many enzymes of carbon dioxide
fixation are regulated in this way as a means to coordinate their activity with the light
reactions of photosynthesis. The regulatory molecule in this case is thioredoxin, which
reduces target enzymes using electrons from ferredoxin (Scherer, 2001; Matsubayashi et
al., 2002). So sulfur is a constituent of all living organisms, where it ranks in importance
with nitrogen as a constituent of protein (Stevenson, 1986).
2.2. Sources and forms of sulfur in soil
Sulfur (S) inputs to soil originate from three major sources: mineral weathering,
atmospheric deposition, and organic matter decomposition (Brady and weil, 2013). Soil
minerals, like
iron, nickel, and copper sulfides, and gypsum (CaSO4), weather and
release into the soils as sulfates and sulfides form (Moss, 1978). Calcium carbonates also
contain S at higher levels than many non calcareous materials, so S is released during
their weathering (Harward and Reisenauer, 1966). In unpolluted natural situations, the
Page 15 of 57
primary source of S in soil is parent material weathering (Hutchinson, 1979). About 95%
of total S content of most soils is contained in organic matter. After decomposition of
organic matter it produce sulfate ion through mineralization and this ion is uptake by
plants (Stevenson, 1986).
The average S content of the earths crust is estimated to be between 0.06 and 0.10
percent (Tisdale et al., 1997). Soils vary widely in their total content of S. Generally, the
total S content of tropical soils is lower because of their lower organic matter content
(Blair, 1979) and higher degree of weathering. In humid temperate soils, the total S
concentration present may range from 100-15,000 g/g, of which 5-500 g/g is typically
soluble in dilute acid or water (Wainwright, 1984). Wainwright (1984) also reported that
in humid to sub humid pastures, the majority of S is in organic forms, where as in drier
soils, it exists mainly as gypsum, epsomite, chalcopyrite and pyrite. In well drained,
temperate agricultural soils, the majority of S present is organically bound. Sulfur can be
grouped into two broad areas: organic and inorganic forms. Most of the total S pool in
soils is composed of organic fractions (Mitchell and Fuller, 1988), primarily due to leaf
litter inputs (Pregitzer et al., 1992).
Human activities account for about 50 percent of current S inputs to the atmosphere
(Kennedy, 1986). Atmospheric sulfur dioxide (SO2) is absorbed by soils and vegetation,
and sulfate (SO42-) aerosols are deposited via wet and dry deposition (Christophersen and
Wright, 1980). Vegetative matter is decomposed by microorganisms, transforming
organic S to other organic or inorganic forms (Tisdale et al., 1997); however, S released
during organic matter decomposition is not considered a major source of S in terms of
total S budgets because it is tightly cycled to meet plant needs (Reuss and Johnson,
1986).
2.2.1. Soil organic sulfur
Up to 98% of the total soil S may be present as organic S compounds and is associated
with a heterogeneous mixture of plant residues, animals and soil microorganisms
(Stevenson, 1986). Soil organic S is divided in two main groups: the first group contains
S atom in the oxidized state and the other group contains S atom in the reduced state.
Page 16 of 57
In soil organic matter Organic S occurs in two primary forms: ester sulfates, which have
C-O-SO3 linkages and carbon-bonded S, which has direct C-S linkages. A few other
organic forms also exist, but they are of comparatively minor importance. Ester sulfates
include
compounds
such
as
cholinesulfate,
phenolic
sulfates,
and
sulfated
polysaccharides. Carbon-bonded S is comprised principally of amino acids such as

methionine and cysteine, and sulpholipids (Harwood and Nicholls, 1979).
Ester sulfates originate predominantly from microbial biomass material (David et al.,
1984; McLaren et al., 1985) and microbial formed materials (Fitzgerald, 1978). Ester
sulfate acts as readily available S stores when needed for plant and microbial nutrition
(Strickland et al., 1987), because it is mineralized faster than C-bonded S (Schindler et
al., 1986). Soil microorganisms and plant roots can hydrolyze ester sulfates when S is
needed to meet immediate nutritional demands (McGill and Cole, 1981). By contrast,
most C-bonded S in soils is derived from litter and dead root inputs (David et al., 1984),
though some is present in microbial biomass (Konova, 1975). Carbon-bonded S is broken
down less easily and, therefore, is less labile and available to plants and microorganisms
(Fitzgerald et al., 1982). Carbon-bonded S is particularly immobile if it is carried alluvial
into mineral soil horizons (Konova, 1975).
2.2.2. Soil inorganic sulfur
Inorganic S is usually much less abundant in most of the agricultural soils than is
organically bound S (Bohn et al., 1986). Sulfate is the most common form of inorganic S
and can be divided into SO42- in soil, adsorbed SO42- and mineral S (Barber, 1995).
Plants absorb S mainly in the form of inorganic sulfate (SO42-) ions through the roots,
thus sulfate S must be present in soils in sufficient amount in order to meet crop S
requirements (Brady and Weil, 2013). Insufficient availability of sulfur to crop plants not
only declines their growth and yield but can also deteriorate nutritional quality. Sulfur
may precipitate in form of SO42- as calcium, magnesium or sodium sulfate. In tidal
marshlands large amounts of sulfide metals like pyrite (FeS2) accumulate. After draining
these areas, the S compounds are oxidized to SO42- accompanied by a decrease in pH. If
adsorbed SO42- in soil is not readily available to plants, any treatment causing a decrease
in retention and a corresponding increase of SO42- in soil solution should increase SO42Page 17 of 57
availability to plants (Elkins and Ensminger, 1971). Therefore, little SO42- adsorption is
to be expected in surface soils which are adequately limed (Evans, 1986) and
consequently the joint application of limestone and gypsum results in an increased
availability of SO42- (Serrano et al., 1999). The higher concentration of SO42- in the soil
solution of the uppermost soil layer (Eriksen, 1996) may also be caused by the
application of S containing fertilizers and other S inputs. Further, it may be assumed that
surface soil material adsorbs less SO42- than does subsoil material, because organic matter
and phosphate accumulations are thought to be major factors, which block SO42adsorption sites (Johnson and Todd, 1983).
Barton et al. (1999) found that deeper profile layers showed less capacity for SO42adsorption. Couto et al. (1979) detected that the adsorption of SO42- is increased with the
depth in the soil profile. According to their results, this difference between the horizons is
assumed to be caused by the higher organic matter content in the topsoil. Johnson and
Todd (1983) found that SO42- adsorption is negatively correlated with the soil organic
matter content as the adsorption sites of Fe and Al hydroxides can be blocked by anionic
groups of organic matter. Further, organic anions in soils, which are derived from
decomposition of organic materials, may affect SO42- adsorption by occupying adsorption
sites (Martinez et al., 1998) by their preferential adsorption based on the number of
oxygen containing functional groups (Inskeep, 1989).
2.3. Sulfur Cycle
Sulfur can appear in many forms in the environment. The major forms of sulfur present in
the atmosphere include sulfur dioxide (SO2) and hydrogen sulfide (H2S). Both forms of
sulfur enter the atmosphere from natural events like volcanic eruptions or manmade
activities such as the burning of fossil fuels. In the soil, S can be found as organic sulfur
compounds, sulfides (S2-), elemental sulfur (S), and sulfate (SO42-), the latter of which is
the form required for plant uptake. Microorganisms also mediate other parts of the sulfur
cycle, particularly S oxidation and reduction. Oxidation and reduction are key processes
in S transformations because the occurrence of SO42- depends on oxidation.
Page 18 of 57
Fig. 2.1. The Sulfur cycle in soils (Brady and weil, 2013)
Completely mineralized S compounds can be transferred to SO42- or H2S by microbes.

Hydrogen sulfide is a common product of mineralization. The reduction step from SO42to H2S is microbially mediated, primarily by bacterial species in the genera
Desulfovibrio, Desulfotomaculum, and Desulfomas (Brady and Weil, 2013; Kennedy
1986) under anaerobic conditions (usually saturation). Thiobacillus, become more
important as an oxidizing bacterium. They obtain their energy from inorganic S and their
C from CO2. Some parts of sulfate are adsorbed with the clay minerals.
2.4. Sulfur sorption and desorption
Sorption phenomenon plays relevant role in the estimation of the solubility, availability,
mobility and tendency of ions (Uzoho et al., 2014). Knowledge of the sulfate sorptiondesorption characteristics are useful for describing, studying and managing the sulfur
status of soils (Das et al., 2009). The adsorption process, which refers to surface S
accumulation on soil components, may, in some cases, be accompanied by penetration of
the adsorbed S by diffusion into the adsorbent body, leading to further adsorption of the
adsorbed species. The general term sorption sometimes used to denote both of these
processes taking place simultaneously. Both adsorption and desorption studies have
indicated the fertility status of soil (Kimsey et al., 2005), particularly under long-term
fertilizer trials dealing with both organic and inorganic materials. The nature of sulfate
Page 19 of 57
adsorption in a system can be known by fitting adsorption data to isotherm equations.

The concentration of sulfate in soil solution, as predicted by the sorption-desorption
isotherms, provided valuable information on sulfur availability to crop plants (Reddy et
al., 2001). The sulfate sorption capacity varied widely among the soils and increases with
the increase in S concentration of equilibrium solution. However, the adsorption tends to
reach a maximum limit with increase in the ambient S concentration (Ghosh and Dash,
2012).
2.5. Adsorption isotherm
The process of Adsorption is usually studied through graphs know as adsorption
isotherm. It is the graph between the amounts of adsorbate (x) adsorbed on the surface of
adsorbent (m) and pressure at constant temperature.
Fig. 2.2. Basic Adsorption Isotherm (Sparks, 1995)
From the (Fig. 2.2), it can predict that after saturation pressure Ps, adsorption does not
occur anymore. This can be explained by the fact that there are limited numbers of
vacancies on the surface of the adsorbent. At high pressure a stage is reached when all the
sites are occupied and further increase in pressure does not cause any difference in
adsorption process. At high pressure, adsorption is independent of pressure (Spark,
1995).
The nature of sulfate adsorption in a system can be known by fitting adsorption data to
isotherm equations. The main motivations for describing adsorption curves are: (1) To
Page 20 of 57
identify the soil constituents involved in adsorption (Loganathan et al., 1987), (2) To
predict the amount of fertilizer needs of soil to meet the demand of plant uptake for an
optimum yield (Fox and Kamprath, 1970) and (3) To study the nature of the adsorption
processes to learn more about the mechanism of the process (Harward et al., 1962). A
variety of isotherm shapes are possible, depending upon the affinity of the adsorbent for
the adsorbate. In general, for soil sulfur and phosphorus, Langmuir and Freundlich
adsorption equations have been used extensively by different workers (Reddy et al.,
2001) several factors affect the sulfate sorption by soil. Among these, pH and presence of
complexing anions (Parfitt, 1982), clay content, extractable Fe and Al (Fuller et al., 1985)
soil horizon type (Tisdale et al., 2013), organic carbon, CaCO3 content and native
extractable sulfate (Bhogal et al., 1996) are the most important.
The process of desorption refers to the reversible release of adsorbed sulfur into the soil
solution phase. Desorption of once sorbed sulfur from soil and clays often has been
shown to be irreversible leading to a large hysteresis effect (Reddy et al., 2001). Thus,
the concentration of sulfate in soil solution as predicted by sulfate sorption-desorption
curves provides a valuable information on sulfur availability to crop plants. It indicates
the immediate concentration at which sulfate should be available to plants and
concentration of sulfate in water that drains from a particular horizon. Sorption of sulfate
can result in the release of OH- ions to the bulk soil solution and can increase the cation
exchange capacity (Dolui and Jana, 1997). This aspect of SO42- sorption could be
valuable in acidic red and lateritic soils of tropics due to their low cation exchange
capacities. Information on the sulfate sorption characteristics of acid soils of India is
meager. Hence the present investigation pertaining to study the sulfate sorptiondesorption characteristics has special bearing in acid red and lateritic soils of the region.
2.6. Factors affecting sulfate sorption in soil
The Sulfur sorption capacity of soils varies moderately with the variations in pH, Fe and
Al content, Clay content, available P exchangeable Ca plus Mg, Organic carbon content,
Presence of anions and cations etc (Das et al., 2009). All of these are mentioned here:
Page 21 of 57
2.6.1. Sulfate adsorbed to clay

The sulfate adsorption capacity of soil varies widely and is dependent on a number of soil
properties, clay content and clay types are very much important within these properties.
Sulfate ions are readily adsorbed on clay surface, and this process is reversible and
concentration dependent (Chao et al., 1962b). Soils containing large amount of clays
provide greater tendency to adsorb of sulfate because of their more surface areas.
Harward et al. (1962) proposed that sulfate is adsorbed to the surface of clays coated with
hydrated iron and aluminum. According to Harward et al. (1962) the decreasing order of
adsorption capacity of clays as:
kaolinite> illite>montmorillonite
Aylmore et al. (1967) showed that sulfate, adsorbed to iron and aluminum oxides is held
more firmly than that adsorbed to kaolinites.
2.6.2. Effects of hydrous oxide
The adsorption of sulfate by soils and soil materials occurs by replacement of M-OH2 or
M-OH groups (Parfitt, 1978). In addition, the adsorption of sulfate by clay minerals
occurs by ligand exchange (Aylmore et al., 1967).
Ligand exchange is the dominant mechanism for SO42- adsorption onto Fe and AI
hydrous oxides (Rajan, 1979). Anion adsorption sites lie on the surfaces of colloids, and
these surfaces can have a positive, negative or zero charge depending upon pH. At low
pH, surfaces become positively charged because of H+ adsorption, and anion adsorption
is enhanced. At high pH, surfaces become negatively charged because of H+ dissociation
(or OH- adsorption), and anions may be repelled (Alves and Lavorenti, 2004).
Sulfate is adsorbed at positive and neutral sites by displacing OH2 and OH- groups,
respectively. Adsorption of sulfate occurred predominantly at positive sites at low
solution concentrations, whereas, the proportion of the sulfate adsorbed at the neutral
sites increased at higher solution concentrations. The form of sulfate bonding is
apparently governed by the level of the positive charge on the clay surface. Higher
positive charge at low and intermediate levels of sulfate saturation resulted in the
adsorption of sulfate as a divalent anion by forming a 6-member ring with surface A1.
Page 22 of 57
In comparison, the adsorption of sulfate by hydrous metal oxides is well characterized.

For specific adsorption to occur, an anion must be capable of accepting or donating
protons and that maximum adsorption occurs at pH = pKa (Hingston et al., 1967). With
the adsorption of sulfate by gibbsite, the anion accepts a proton from the positive site (MOH2+) on the surface, and the monovalent species HSO4- is adsorbed by displacing the
resulting OH- ion without creating additional negative charges on the surface. On the
other hand, sulfate adsorption by hydrous alumina, there have quantitative relationships
between the sulfate adsorbed, the ligands displaced, and the changes in surface charge,
that sulfate is most probably adsorbed by bridging across two adjacent A1 surface atoms
to form a 6-member ring (Rajan, 1978). Sulfate is adsorbed on goethite as a binuclear
bridging complex (Parfitt and Smart, 1978).
2.6.3. Soil pH
A greater variation that governs the extent of adsorption reactions in a particular soil is
pH. As well as the adsorption of SO42- by soils is influenced by soil pH (Chao et al.,
1962b; Parfitt, 1980). But it is inversely correlated to SO42- sorption. The researches have
demonstrated that sulfate adsorption increases which decreasing soil pH (Zhang & Yu,
1997). Adsorption of SO42- in soil is favored by strongly acid condition and it become
negligible at pH > 6.5. Anion exchange capacity (AEC) increase with decreasing pH.
Usually, no sorption of sulfate is seen above the point of zero charge of the sorbents
(Pigna and Violante, 2003).
2.6.4. Presence of Organic Ligands
Low molecular mass organic ligands (LMMOLs) such as acetate, oxalate, malate, citrate,
succinate, and tartrate, are commonly present in soil environments, especially at the soil
root interface, and can influence the sorption of sulfate on soil components (Liu et al.,
1999). The competitive sorption of LMMOLs and sulfate are extremely important in
understanding the role of bimolecular present in the rhizosphere on the availability of this
nutrient for plants. More oxalate will be adsorbed when it is added before sulfate than
when added in a mixture with or after sulfate. Furthermore, the effect of low molecular
mass organic ligands (LMMOLs) on the mobility of sulfate in soil environments has
received little attention (Inskeep, 1989). LMMOLs are common in the rhizosphere as
Page 23 of 57
they are secreted by plant roots and produced by bacteria and fungi which are particularly
abundant at plant-soil interface.
2.6.5. Presence of other Anions
The amount of Sulfate sorption decreases in the presence of phosphate, acetate, oxalate,
and malate, because of phosphate and strongly chelating Low molecular mass organic
ligands (LMMOLs) bind more strongly to aluminum or iron than sulfate ions (LopezHernandez et al., 1986) and because of differences in the coordination forms of each
ligand on the surfaces of the sorbents (binuclear and mononuclear, mono or bidentate)
and their relative distribution (Sparks, 1999). The mechanisms of sulfate and acetate
adsorption are similar and both ions compete for the same sorption sites, although
adsorbed acetate does not compete strongly with phosphate. However some studies have
demonstrated that sulfate may be adsorbed mainly by an outer-sphere complexation
mechanism, that is, sulfate is adsorbed on the positive sites by electrostatic attraction
(Turner and Kramer, 1991) in spite of the formation of inner-sphere complexation, which
may be possible under certain conditions (Peak et al., 2001; Pigna and Violante, 2003).
Bhatti et al. (1998) found that oxalate and acetate adsorbed by a soil clay fraction formed
monodentate and binuclear surface complexes at pH 3.5, but binuclear surface complexes
were formed at pH 4.5 and 5.5. Sulfate is considered to be weakly held with the strength
of adsorption decreasing in the order (Tisdal et al., 2013).
OH- > H2PO4- > SO42- > CH3COO- > NO3- = Cl2.6.6. Presence of cation
The amount of sulfate retained is affected by the associated cation or the exchengeable
cation and followed by the lyotropic series: H+ > Ca2+ > Mg2+ > K+ = NH4+ > Na. Both
the cation and the sulfate from a salt may be retained, but the strength of adsorption of
each will likely differ (Tisdal et al., 2013).
Several investigators have observed that SO42- adsorption in acid soils increased in the
presence of added calcium or lime (Marcano-Martinez and McBride, 1989). In cases of
relatively high calcium, specific adsorption processes and precipitation of gypsum alone
could not explain the amount of increase observed. The mechanism of cooperative
Page 24 of 57
adsorption in which Ca2+ and SO42- form an ion pair has been proposed as a possible
mechanism (Marcano-Martinez and McBride, 1989). Sulfate adsorption above predicted
levels is achieved by Ca2+ adsorption onto negative OH-, and the paired SO42- ion
displaces a neighboring water molecule (Fig. 2.3). This mechanism minimizes the
formation of net negative charges at the oxide surface so cation exchange and SO42adsorption simultaneously increase.
Al
OH21/2
O SO33/2
Al
+ CaSO4
Al
OH1/2
Ca
Al
+ OH2
OH1/2
Fig. 2.3. Cooperative adsorption with Ca2+ and SO42- ion pair
(Marcano-Martinez and McBride, 1989)
2.6.7. Presence of Organic matter in soil

Organic matter content can influence sulfate adsorption through two opposite
mechanisms. Organic matter, however it has a negative influence on sulfate adsorption
(Johnson and Todd, 1983) because organic matter blocked adsorption sites and sulfate
cannot fix on exchange sites. Other studies indicated that organic matter has a positive
effect on sulfate adsorption. The formation of Al and Fe humus complexes (Shoji and
Fujiwara, 1984) and the inhibition of the crystallization of Al and Fe oxides caused by the
organic matter (Huang and Violante, 1986) increase the reactive surfaces toward sulfate
adsorption.
2.7. Mechanism of sulfate adsorption
Sulfate is an essential mineral element for plant growth. Plants adsorb sulfate from the
soil solution, therefore replenishment from organic and adsorbed sources is important in
maintaining sulfate supply to the plant (Sumner, 2000). Hydrous oxides of aluminum and
iron and short-range ordered aluminosilicate materials can retain sulfate in soils against
leaching. Ultisols, Alfisols, and Oxisols have a high sorption capacity due to an
abundance of Fe and Al oxides. Adsorption of sulfate on variable charge minerals and
soils has been studied but the mechanisms for its adsorption and the structures of its
surface complexes are not very simple. The mechanisms proposed for sulfate retention in
soils are:
Page 25 of 57
a. Electrostatic attraction by positively charged sites

b. Specific adsorption through ligand exchange and
c. Formation of aluminum hydroxysulfate precipitates (Pasricha and Fox, 1993).
According to Peak et al. (2001), sulfate form only outer-sphere surface complexes above
pH 6.0 and a mixture of outer- and inner-sphere surface complexes at pH less than 6.0. At
the experimental pH (6.0) studied, the kaolinite edge carried positive sites, as suggested
by the adsorption of C1- ions by the untreated kaolinite, and probably neutral sites. The
existence of negative centers is unlikely because the amount of Na+ adsorbed did not
exceed the aqueous CEC of the sample.
Anion adsorption can be nonspecific or specific. Nonspecific adsorption involves only
electrostatic (Columbic) attraction, while specific adsorption occurs by ligand exchange
(Parfitt and Smart, 1978). All anions are adsorbed nonspecifically, but only a few,
including SO42-, also are adsorbed specifically (Johnson et al., 1979). Specific adsorption
is believed to be the predominant mechanism of SO42- adsorption (Neary et al., 1987).
2.7.1. Non specific adsorption
Nonspecific adsorption of SO42- occurs within the double diffuse layer as a counter ion to
positively charged surfaces on organic matter, layer silicates, or oxide- and hydrous
oxide-dominated surfaces. These materials are amphoteric; they can have positive,
negative, or zero charges-with the net charge being pH-dependent (Bohn et al., 1985).
Positive charges are created on the surfaces by the presence of H+ (Fig. 2.4). As pH
decreases and H+ becomes more available, more positively charged colloidal surfaces are
created. In turn, the number of surfaces available for anion adsorption increases (Johnson
and Cole, 1980). The functional groups of soil components involved with the protonation
are hydroxyl (-OH), carboxyl (-COOH), phenol (C6H5OH), and amine (-NH2) groups
(Bohn et al., 1985). Because only electrostatic attraction is involved in nonspecific
adsorption, desorption can be achieved relatively easily either by increasing solution pH
(Nodvin et al., 1986) or by exchange with other anions that have a greater or equal
affinity for adsorption (Bohn et al., 1985).
Page 26 of 57
Fig. 2.4. Protonation of hydroxyl creates formation of net positive charges and results in nonspecific
adsorption (Bohn et al., 1985)
2.7.2. Specific adsorption

Specific adsorption results in a greater adsorption capacity than would occur by
nonspecific adsorption alone and specifically adsorbed anions are held more tightly. Most
specific adsorption occurs in soils with high levels of free iron and aluminum oxides and
hydroxides (Rajan, 1978; Fuller et al., 1985), though hydroxy-aluminum polymers
bonded to clays and organic matter, and broken bonds on clays also provide surfaces for
specific adsorption (Harward and Reisenauer, 1966). Ligand exchange can occur when a
net negative, positive, or zero charge exists (Bohn et al., 1985).
In specific adsorption, SO42- bounds to the metal oxide within the inner Helmholtz layer
by displacing an H2O or OH molecule (Bohn et al., 1985) (Fig. 2.5) or occasionally other
anions (Harrison et al., 1989). Whether H2O or OH- is displaced depends primarily upon
the concentration of SO42- in solution. At low concentrations, SO42- usually is adsorbed
on positive sites, displacing coordinated water (Fig. 2.5a). With greater SO42concentrations, SO42- increasingly is adsorbed on neutral sites by displacing OH- (Fig.
2.5b) (Rajan, 1978).This concentration dependency results in the activation of new
adsorption sites with increasing SO42- concentrations (Chao et al., 1962a; 1962b).
Page 27 of 57
Fig. 2.5. Specific adsorption where (a) sulfate displaces water from net positive site, or
(b) sulfate displaces hydroxyl from neutral site and (c) the adsorbed sulfate may displace
another hydroxyl or water ligand from the adjoining metal resulting in a 6-member ring
and neutralization (Rajan, 1978).
Specific adsorption effectively increases the negative charge on the adsorbing surfaces
more than non specific adsorption, so nonspecifically adsorbed anions cannot desorbed or
displace those specifically adsorbed (Singh, 1984). Nonspecifically adsorbed anions held
as counter ions in the double diffuse layer are displaced back into soil solution due to
repulsion from the developed negative charges (Hingston et al., 1967). Conversely, the
creation of higher pH and more negative charges from specific adsorption can result in
cation adsorption increase (Couto et al., 1979; Marcano-Martinez and McBride, 1989).
The net negative charge created can be neutralized further by the formation of a 6-
Page 28 of 57
member ring from displacement of another OH- or water ligand from the adjoining metal
(Fig. 2.5c) (Rajan, 1978).
According to, Chao et al. (1962b) possible mechanisms of sulfate adsorption by soils
may be tentatively suggested as follows:
a) Anion exchange due to positive charges developed on hydrous iron or aluminum
oxide or on the crystal edges of clays, especially kaolinite, at low pH.
b) Retention of sulfate ions by hydroxy-aluminum complexes through coordination.
c) Salt adsorption resulting from attraction between the surface of soil colloids and
the salt.
The Amphoteric properties of soil organic matter which develop positive charges under
certain specific conditions.
Page 29 of 57
Chapter Three
3. Materials and Methods
Two soil series of calcareous origin namely Bajoa (Typic Endoaquept) and Gopalpur
(Aquic Eutrochrept) were selected to investigate the sulfate sorption behavior.
3.1. Soil sample collection and preparation
Soil samples were collected at a depth of 0-15 cm from a square area of 1 km2 under a
soil series. Then the samples were mixed together to form a composite sample. After
drying in air, the larger aggregates were broken gently by crushing it in a wooden
hammer, and passed through a 2 mm sieve. The sieved soils were preserved in plastic bag
and labeled properly for determining their various physical and chemical properties.
Two soil series used in the present investigation are described below and general
information of sampling sites is given in Table 3.1.
3.2. Bajoa series
Bajoa soils are developed in Tidal Floodplain basins. They are seasonally shallowly to
moderately deeply flooded, poorly drained soils developed in tidal deposits. It contains a
grey to olive grey silty clay loam subsoil with moderate to strong blocky structure in the
B horizon. They have five phases: highland; medium high land, non-saline; medium high
land, saline; medium lowland; and medium lowland, flood hazard.
3.3. Gopalpur series
Gopalpur series includes poorly drained, seasonally flooded soils developed in
moderately fine textured Gangetic Alluvium of meander floodplain. They are developed
on the summits to upper slopes of gently undulating ridges. Gopalpur soils consist of
olive-brown, friable, calcareous clay loams and silty clay loams usually overlying a
moderately fine textured substratum. They show a weak coarse blocky structure in the
sub soil with patchy coatings on ped faces. They are calcareous and moderately alkaline
in reaction throughout the profile. They have five phases: Highland, smooth relief;
highland, irregular relief; medium highland, irregular relief; medium lowland and
medium lowland, flood hazard.
Page 30 of 57
Table 3.1. Location and environmental conditions of the soils

Soil series
Characteristics feature
Bajoa
Gopalpur
Location
Village: Milemara
Union: Batiaghata
Upazila: Batiaghata
District: Khulna
Village: Dokkhinpara,
Chaderdanga
Union: chaderdanga
Upazila: Batiaghata
District: Khulna
Latitude & longitude
N: 22043.219
E: 89028.256
N: 22040.727
E: 89027.151
Land type
Medium high land
High land
Land use
Fallow- Sesame- T. Aman
Fallow - Sesame - T. Aman
Effervescence
Calcareous
Calcareous
(Soil and land resource utilization guide, SRDI, 2008)
3.4. Analytical procedure

Different physical and chemical parameters of soil were analyzed by following
procedures.
3.4.1. Physical properties of soils
3.4.1.1. Particle size analysis
The particle size analysis of the soils was done by combination of sieving and hydrometer
method as described by Gee and Bauder (1986). Textural classes were determined using
Marshalls Triangular Coordinate systems.
3.4.2. Chemical properties of soils
3.4.2.1. Soil pH
Soil pH was determined electrochemically with the help of glass electrode pH meter as
suggested by Jackson (1973). The ratio of soil to water was 1:2.5 as suggested by Jackson
(1967).
Page 31 of 57
3.4.2.2. Electrical Conductivity (EC)

It was measured at a soil: water ratio of 1:5 with the help of EC meter and converted into
1:1 ratio as USDA (2004).
3.4.2.3. Organic Carbon
The sample organic carbon was determined by Walkley and Blacks wet oxidation
method as outlined by Jackson (1973).
3.4.2.4. Cation Exchange Capacity (CEC)
The CEC of the soils were determined by extracting the soil with 1N KCl (pH 7.0)
followed by the replacing the potassium in the exchange complex by 1N NH4OAc. The
displaced potassium was determined by a flame photometer (Jackson, 1967).
3.4.2.5. Available Sulfur (S)
Extraction of available S was made by 500 ppm P solution from potassium bi phosphate
with a soil extractant ratio of 1: 8. The S content was determined by turbidimetric method
(Hunt, 1980).
3.5. Sulfate sorption experiment
The sulfate sorption capacity of each soil was measured by using a procedure similar to
that describes by Nair et al. (1984). Sulfur sorption isotherms were determine for each
soil by equilibrating 1 g of air dried sieved soil (<2 mm) in 50 ml centrifuge tube (taking
a soil: solution ratio of 1: 20) with 20 ml sulfate solution as Na2SO4 dissolved in a 0.01M
CaCl2 matrix which contain seven initial concentration of 0, 1, 2, 5, 10 and 50 ppm. So
the initial S contents in per gram soil were 0, 20, 40, 100, 200, 500 and 1000 g S. The
suspensions were shaken end-over-end for 16 hours. After passing 16 hour equilibration
period, the solid and liquid phases were separated by centrifuge. Sulfur concentration in
the extract (equilibrium solution) was measured according to Turbidimetric method of
Hunt (1980). The amount of S sorbed by the soil was calculated by subtracting the
concentration of S in the equilibrium solution from the concentration of added S. The S
content of the supernatant solution was measured at spectrophotometer using wavelength
of 420 nm. Each treatment was replicated three times.
Page 32 of 57
3.6. Experiment with sulfate and acetate

There are hosts of organic acids occurring widely in soils, stemming from plant roots and
produced through the decomposition of plant residues. Acetic acid was chosen to observe
its effects on S availability or sorption, as it is very common in the soil system. The
concentration of acetic acid ranges from 2.65 - 5.7 m mol/L (Stevenson, 1967; Rao and
Mikkelson, 1977). Acetic acid concentration chosen for application was 5 m mol/L.
Sulfate and acetate ions were added to soil in different sequences. The sequences
followed are given below1) Simultaneous application of sulfate and acetate ions.
2) Application of acetate ions 2 hour before addition of sulfate ions.
In these experiments S concentration varied from 0-50 g/ml like that of sulfate sorption
experiment. Three replications were given for each treatment.
The amount of S sorbed was determined by following adsorption equation:
X= (Ci-Cf) / (V/W)
Where, X is the change of the S in soil solution. Positive X values sorption of S by the
soil solid phase whereas negative values indicate desorption by the soil. Ci is the initial S
concentration added and Cf final equilibrium concentration of S in solution. V is final
volume and W is soil mass.
The S sorption capacity was interpolator from the S sorption isotherm. S sorption data
were fitted into following sorption equation according to Freundlich, Langmuir and
Temkin equation.
Freundlich equation
LogX = Logk + 1/n LogC
Where X or x/m = the amount of S sorbed (mg/kg) or (g/g).
C = the equilibrium concentration of S (mg/L) or (g/ml) in solution.
N or 1/n = the empirical constant.
K = the proportionality constant (mg/kg) or (g/g).
Page 33 of 57
A plot of LogX (y-axis variable) against LogC (x-axis variable) will yield a
straight line with slope N and a y intercepts Logk.
Langmuir equation (1918)
CX-1 = (KLbL)-1 + C bL-1
C = the equilibrium concentration of S (mg/L) or (g/ml) in solution
KL = the binding energy constant (L/mg) or (ml/g).
bL= S sorption maximum(mg/kg) or (g/g) soil.
A plot of CX-1 (y-axis variable) against C (x-axis variable) will yield a straight
line with slope bL-1 and a y intercept (KLbL)-1. The maximum sulfur buffering
capacity of the soil was estimated from the product of KL and bL.
Temkin equation (1926)
X = a + b LogC
C = the equilibrium concentration of S (mg/L) or (g/ml) in solution.
a and b = constants.
A plot of X (y-axis variable) against LogC (x-axis variable) will yield a straight
line with slope b and a y intercept a.
3.7. Statistical analysis
Regression curve fitting equations were drawn by the Microsoft Office Excel program.
Suitability of different adsorption equations were studied by calculating the R2 values of
the respective equations.
Page 34 of 57
Chapter Four
4. Results and Discussion
Many soils have little reaction with the sulfate ion. In others, however, reactions do occur
and the sulfate ions distribute themselves between the solid phase and the soil solution
that is some of the ions become sorbed. The present investigation was conducted to study
sulfate sorption in Gopalpur and Bajoa soil series. The study results and discussion are
presented in this chapter.
4.1. Physical and Chemical properties of soils
4.1.1. Particle size analysis
The sand percentage of Gopalpur and Bajoa soil series were 12% and 5% (Table 4.1). So
Gopalpur soil was contained the higher amount of sand. Besides this the silt percentage
of Gopalpur and Bajoa soil series were 57% and 60% as well as the clay percentage were
31% and 35% (Table 4.1).
4.1.2. Texture
The texture of both Gopalpur and Bajoa soil series were silty clay loam (Table 4.1). This
result resembles to several findings by many other researchers. SRDI staff (2008) found
that on the Ganges meander floodplain, soils of ridges and inter-ridges depressions are
silt loam to silty clay loam; and on the Tidal floodplain, soils of ridges and depressions
are silty clay loam in subsoil texture.
4.1.3. Soil reaction (pH)
The pH of the Gopalpur and Bajoa soil series were 7.9 and 6.9 indicating the Gopalpur
soil series was moderately alkaline and the latter was slightly acidic to neutral (Table
4.1). This is a common feature of the Ganges floodplains soil of Bangladesh (Brammer,
1971).
4.1.4. Electrical Conductivity (EC)
The EC value of the Gopalpur and Bajoa soil series were 2.4 and 5.52 dSm-1 (Table 4.1).
These results indicate that the Gopalpur and Bajoa soil were slightly to moderately saline.
Page 35 of 57
This may be due to the land type of our investigated areas which were situated near and
within Tidal floodplain.
4.1.5. Organic Carbon (OC)
The organic carbon percentage of the Gopalpur and Bajoa soil series were 0.46% and
0.70% (Table 4.1) indicating the lower amount of organic carbon in Gopalpur soil series
(BARC, 2005).
4.1.6. Cation Exchange Capacity (CEC)
The CEC of the Gopalpur and Bajoa soil series were 17 Cmol(+)kg-1 and 22 Cmol(+)kg-1 of
soils (Table 4.1). Hossain et al. (2012) reported that CEC varied from 9.22 to 24.4
Cmol(+)kg-1, which is similar to this finding. CEC varies with the type of clay minerals
depending on the clay content, types of clay and organic matter content. Each clay type
has different types of CEC of soils (Tan, 1994).
4.1.7. Available sulfur (S)
Available sulfur content of the Gopalpur and Bajoa soil series were 21 ppm and 230 ppm
(Table 4.1), which indicates higher level of sulfur in Bajoa soil (SRDI, 2008). The high
content of sulfur may be due to recent application of sulfur fertilizer or any other sort of
input of sulfur.
Table 4.1. Physical and chemical parameters of soils
Soil
series
Sand
(%)
Silt
(%)
Clay
(%)
Gopalpur
12
57
31
Bajoa
60
35
Textural
Class
Silty
Clay
Loam
Silty
Clay
Loam
pH
EC
(dS/m)
OC
(%)
Available
S (ppm)
CEC
Cmol(+)
kg-1
7.9
2.4
0.46
21
17
6.9
5.52
0.70
230
22
4.2. Sulfate sorption behavior

Soils were equilibrated with 0.01 M calcium chloride solution containing graded
concentrations (0 to 50 g mL-1) of Na2SO4 solution. Sulfate was sorbed at different
amounts and proportions by the soils in present study except 0 g mL-1 sulfur application
Page 36 of 57
(Fig. 4.1). In the present study, sulfate sorption increased gradually with increasing
sulfate application in both soil series. The data related to the sulfate sorption pattern of
soils studied containing various amount of sulfate (0 to 1000 g S per 20 mL) for 16
hours is shown in (Fig. 4.1 and Appendix Table 1).
700
Sulfur Sorbed
(g g-1 soil)
600
500
400
300
200
Adsorbed S in Bajoa
100
Adsorbed S in Gopalpur
0
0
500
1000
Sulfur Application (g mL-1)
1500
Fig. 4.1. Sulfur sorption capacity of soils with different rates of sulfate application
At 0 g mL-1, there were occurred no sorption in both soil series. The sorption of sulfate
in soils increased with increasing levels of the added sulfur is reported by Ghosh and
Dash (2012). The sorption of sulfate in soil was higher in Bajoa (645.12 g/g soil) when
sulfate was applied at the rate of 50 g S mL-1 and lower in Gopalpur (550.76 g/g soil).
So depending on their sulfate sorption capacity, the soils can be arranged in the following
order: Bajoa>Gopalpur. It is interesting to note that the adsorption though gradually
reduced but not in proportion following the trend of more adsorption with increase in
sulfate concentration of equilibrium solution. The sorption curve (Fig. 4.1) indicates that
sorption tends to reach a maximum limit with increasing in the ambient sulfate
concentration. Therefore, continuous application of sulfur may lead to considerable build
up of residual sulfur whatever sulfate would have left following the fate of fixation or
adsorption.
4.3. Freundlich adsorption isotherm
The sorbed data was fitted to the Freundlich Equation. The Freundlich adsorption
isotherm fit better in the studied soil. The R2 value of the Freundlich equation of
Page 37 of 57
Gopalpur and Bajoa soil series were 0.997 and 0.958, where higher value 0.997 was
observed in Gopalpur soil (Fig. 4.2 and 4.3). The intercept of Gopalpur and Bajoa soil
series were 1.466 and 1.854. The slopes of the sorption curves show that the amount of S
sorbed by the soils differed among various soil series. The higher slope of 0.963 was
observed in Gopalpur soil.
Log of sulfur sorbed

(g g-1soil)
4.5
4
3.5
3
2.5
2
1.5
1
0.5
0
-2
y = 0.963x + 1.466
R = 0.997
-1
0
1
2
Log of equilibrium sulfur conce.(g ml-1)
Fig. 4.2. Freundlich adsorption isotherm for sulfur in Gopalpur soil series
Log of sulfur sorbed

(g g-1soil)
3
2.5
2
1.5
y = 0.375x + 1.854
R = 0.958
1
0.5
0
-0.5
0.5
1.5
Log of equilibrium sulfur conce.(g
2.5
ml-1)
Fig. 4.3. Freundlich adsorption isotherm for sulfur in Bajoa soil series
4.4. Langmuir adsorption isotherm

The Langmuir adsorption isotherm explains the adsorption maxima and energy of
adsorption. The R2 value of the Langmuir equation of Gopalpur and Bajoa soil series
were 0.993 and 0.991, where higher value 0.993 was observed in Gopalpur soil (Fig. 4.4
and 4.5). The intercept of Gopalpur and Bajoa soil series were 0.015 and 0.011. The slope
of the both soil series showed 0.001. The good fit of Langmuir adsorption isotherm
Page 38 of 57
explained that the sorption affinity of soils remains constant with increasing surface
Cx-1
saturation (Mead, 1981).
-100
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
-0.1 0
y = 0.001x + 0.015
R = 0.993
100
200
300
400
500
Equilibrium sulfur conce.(g ml-1)

Fig. 4.4. Langmuir adsorption isotherm for sulfur in Gopalpur soil series
Cx-1
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
-0.1
-50
0
y = 0.001x + 0.011
R = 0.991
50
100
150
200
250
300
-1
Equilibrium sulfur conce.(g ml )
350
400
Fig. 4.5. Langmuir adsorption isotherm for sulfur in Bajoa soil series
4.5. Temkin adsorption isotherm

The R2 value of the Temkin equation of Gopalpur and Bajoa soil series were 0.974, 0.837
(Fig. 4.6 and 4.7). The slope of Temkin equation of Gopalpur and Bajoasoil series were
0.005 and 0.004. The intercept of Temkin equation was the higher for Gopalpur and the
lower for Bajoa soil series. The soil series showed the poorest fit to the Temkin
adsorption isotherm, meaning that these soils adsorption capacities did not decrease
linearly with an increase in surface saturation.
Page 39 of 57
Log C
3
2.5
2
1.5
1
0.5
0
-0.5 0
y = 0.005x - 0.207
R = 0.974
100
200
300
400
-1
Sorbed amount (g g soil)
500
600
Log C
Fig. 4.6. Temkin adsorption isotherm for sulfur in Gopalpur soil series
3.5
3
2.5
2
1.5
1
0.5
0
-0.5 0
y = 0.004x - 0.042
R = 0.837
200
400
600
800
Sorbed amount (g g-1 soil)

Fig. 4.7. Temkin adsorption isotherm for sulfur in Bajoa soil series
Among the three adsorption equations, Freundlich equation was best fitted to the
equilibrium S sorption data R2 = 0.997, 0.958. The sulfate sorption data was fitted to the
Freundlich and Langmuir equations and plotted in Table 4.2.
Page 40 of 57
Table 4.2. Freundlich and Langmuir constants of sulfate sorption
Freundlich constants
Langmuir constants
Soil
series
Log X = log
Kf + N logc
Kf
(g/g)
BI
CX-1 = (KL bL)-1

+ cbL-1
bL
(g/g)
KL
(ml /g)
MBC
(ml /g)
Gopalpur
Y = 0.963x +
1.466
0.96
28.84
27.67
Y = 0.001x +
0.015
550
0.12
66
Bajoa
Y = 0.375x +
1.854
0.38
71.44
27.15
Y = 0.001x +
0.011
645
0.14
90.3
X: Total sorbed S; C: Equilibrium S concentration in solution; Kf and N are empirical constants; BI:
Buffering Index; bL: Sulfate sorption maximum; KL: S binding strength; MBC: The Maximum Buffering
Capacity of the soil.
The Langmuir sulfate sorption maxima (bL) and the constant relating to binding energy
(KL), calculated from the Langmuir equation are presented in Table 4.2. Results clearly
indicate that Bajoa soil had the higher sulfate adsorption capacity (645 g S g-1 soil). It
should be noted that the bL values are more empirical curve-fitting parameters than true
sorption maxima, since input concentration were not sufficient to saturate the soil
(D'Angelo et al., 2003). The Langmuir sorption maxima (bL) will decrease with the
increasing sulfur level in soil. This may be due to the fact that at higher dose of sulfur
application the availability of exchange sites on clay micelle may be low for adsorption
of added sulfur in soil. The sulfur binding energy KL of the gopalpur and Bajoa soil series
were 0.12 ml /g and 0.14 ml /g. The Maximum Buffering Capacity (MBC) was found
to be higher in the soil of Bajoa 90.3 ml/g. The sulfur constant value kf derived from the
Freundlich equation showed 28.84g/g and 71.44g/g for Gopalpur and Bajoa. The
values of N were 0.96 and 0.38 for Gopalpur and Bajoa. The values of N or 1/n are less
than unity indicating that the amount of sulfate adsorbed increased more rapidly than its
concentration in soil solution.
Page 41 of 57
4.6. Discussion
4.6.1. Adsorption Isotherm
On the following study, among the sorption equations, Freundlich equation was best
fitted to the sorption data. Similar results have been reported for Freundlich equations by
other scientists as well (Bolan et al., 1988, 1993; Aves and Lavorenti et al., 2004). Based
on R2 values, the Freundlich equation was better in predicting the sulfate sorption
capacity of soils than the other two equations (Ghosh and Dash, 2012). Beside this,
Langmure was also good fitted to the sorption data next Freundlich equation. The good
fit of the Langmuir adsorption equation indicates that the sulfate sorption affinity of soils
remained constant with increasing surface saturation (Mead, 1981).
The Bajoa soil series had the highest KL values. Ghosh and Dash (2012) suggested that
high KL value indicates strong bonding of sulfur by soil particles. As a result, due to the
highest KL values, the Bajoa soil series probably retain sulfate better than Gopalpur soils
and possibly be the better sink at similar sulfur adding rates.
The Maximum Buffering Capacity (MBC) was found to be higher in the soil of Bajoa
90.3 ml /g. The results suggest that for supplying the same amount sulfur to soil, the soil
will require higher amount of sulfur as fertilizer. Higher values of MBC of soil suggest a
concomitant greater degree of resistance to changes in concentration of sulfur in soil
solution (Ghosh and Dash, 2012).
4.6.2. Effects of chemical parameter on sulfate sorption
The percent clay content of soils was of decisive importance for the adsorption of sulfate
and it could be the considered as a parameter of capacity or quantity for the fixation of
sulfate. The higher clay content provides the greater surface areas also contribute to the
sulfate adsorption. Harward et al. (1962) proposed that sulfate is adsorbed to the surface
of clays coated with hydrated iron and aluminum. In this study, the Bajoa soils containing
large amounts of clay (35%) than Gopalpur (31%) and probably that is the cause for
adsorbing more sulfate in Bajoa soil series (Table 4.1).
The higher sulfate sorption capacity of the Bajoa soil series might be attributed to its high
organic carbon content (0.70 %) and CEC (22 Cmol(+)kg-1) (Table 4.1). The direct
Page 42 of 57
relationship between sulfate sorption and soil organic carbon can be due an increase in
reactive surfaces caused by either formation of Al- and Fe- humus complexes (Shoji and
Fujiwara, 1984). Fine texture soils usually have a higher CEC and can hold more
exchangeable sulfate.
Several researchers have demonstrated that sulfate adsorption increases with decreasing
soil pH (Zhang & Yu, 1997). In this present investigation, it was noticed (Table 4.1) that
the soils (Bajoa) with relatively low pH (6.9), adsorbed more sulfate than Gopalpur
similar to the study of Aves and Lavorenti (2004).
The strength of bonding of the anions with the adsorption surface determines the
competitive ability of that anion. The acetate anion competes with sulfate on the
exchange site of soil although this effect is not so stronger (Tisdal et al., 2013; Bhatti et
al., 1998).
Adsorbed so4-s (g g-1soil)
700
600
Sulfate adsorption
500
400
Sulfate +Acetate
adsorption
300
200
100
0
-100 0
500
1000
Sulfate +Acetate (2
hours before
Acetate application)
1500
Applied S concentration (g ml-1)

Fig. 4.8. Changes in S sorption as affected by acetate in the Bajoa series
The data presented in the Fig. 4.8 showed changes in sulfate adsorption when acetate was
added to the soil in different sequences with sulfur solution in comparison to that when
sulfur solution was applied alone. When acetate was applied to the soil simultaneously
with sulfur solution a decrease in sulfate sorption was observed. At the first stage 64%
sulfate was adsorbed in addition with single sulfur solution. But at application of sulfate
with acetate solution, this sorption range was decreased 4-5% which is similar to the
study of Anar (2007). Alejandra et al. (2006) also found a decrease in sulfate adsorption
when they applied sulfur solution with oxalate or citrate simultaneously. They used
Page 43 of 57
synthetic and natural allophonic compounds as the adsorbent of sulfate. Liu et al. (1999)
also found oxalate to prevent sulfate adsorption.
Adsorbed SO4-S (g g-1 soil)
600
500
400
Sulfate adsorption
300
200
Sulfate + Acetate adsorption
100
Sulfate + Acetate adsorption (2

hours before Acetate application)
0
0
500
1000
1500
Applied S concentration (g ml-1)

Fig. 4.9. Changes in S sorption as affected by acetate in the Gopalpur series
In Gopalpur soil there was not found any noticeable change in sulfate sorption (55%)
when sulfate and acetate was applied simultaneously. Although, 2 hours before acetate
application had decreased sorption range 55% to 50% (Fig. 4.9). This result is similar to
the study of Anar (2007).
Page 44 of 57
Chapter Five
5. Summary and Conclusion

The present study was conducted to show the sulfate sorption capacity within two soil
series by comparing their best suitability in different adsorption isotherm and the effects
of acetate anion on sulfate sorption. Between two soil series, Bajoa soil possessed the
greater sorption (645.12 g/g soil) with increasing the sulfur concentration. Beside this,
the Gopalpur soil series showed sulfate sorption (550.76 g/g soil) probably due to its
higher pH (7.9); lower CEC (17 Cmol(+)kg-1), organic C (0.64%) and clay content (31%)
than Bajoa (pH 6.9; CEC 22 Cmol(+)kg-1; Organic C 0.70%; clay content 35%). On the
other hand, at the presence of acetate anion, the amount of sulfate sorption in both soil
series was decreased due to the competition between the sulfate and acetate anion on the
exchange site.
The Frundlich equation showed the best fit with higher value of coefficient followed by
Langmuir and Temkin. The Langmuir equation has explained the Maximum Buffering
Capacity (MBC) and the binding energy (kL) of sulfate ion on the Bajoa soil series.
So the overall results of this study indicate that the sulfate sorption capacity of Bajoa soil
series was at a higher degree of magnitude. For this reason, to maintain the optimum soil
solution sulfur to meet the crop requirements, more sulfur should be applied in Bajoa soil
series.
Page 45 of 57
References
Adams, W.A.; Gafoor, S.N. and Karim, M.I. 1987. Composition and properties of poorly
ordered minerals in Welsh soils. Part . Phosphate adsorption and reactivity
towards NaF solution. Journal of Soil Science, 38: 95-103.
Alejandra, A.J.; Antonio, V.; Massimo, P. and Maria, L.M. 2006. Mutual interaction of
Sulfate, Oxalate, Citrate, and Phosphate on Synthetic and Natural Allophanes.
Soil Science Society of America Journal, 70: 337-346.
Alves, M.E. and Lavorenti, A. 2004. Sulfate adsorption and its relationships with
properties of representative soils of the Sao Paulo State, Brazil. Geoderma, 118:
89-99.
Anar, J.M. 2007. Sulfate sorption behavior of some Bangladesh soils. M.Sc. Thesis
(unpublished), Department of Soil, Water and Environment, Dhaka University,
Dhaka, Bangladesh.
Aylmore, L.A.G.; Karim, M. and Quirk, J.P. 1967. Adsorption and desorption of sulfate
ions by soil constituents. Soil Science, 103: 10-15.
Barber, S.A. 1995. Soil Nutrient Bioavailability. 2nd Edition. John Wiley and Sons, New
York.
BARC, 2005. Fertilizer Recommendation Guide. Soils Publication No. 45, Bangladesh
Agricultural Research Council, Dhaka, Bangladesh.
Barton, D.; Gammack, S.M.; Billet, M.F. and Cresser, M.S. 1999. Sulfate adsorption and
acidification of Calluna heathland and Scot pine forest podzol soils in north-east
Scotland. Forest Ecology and Management, 114: 151-164.
Bhatti, J.S.; Comerford, N.B. and Johnston, C.T. 1998. Influence of soil organic matter
removal and pH on oxalate sorption onto spodic horizon. Soil Science Society of
America Journal, 62: 152-158.
Bhogal, N.S.; Choudhary, K.C. and Sakal, R. 1996. Kinetics of sulphate adsorption in
calcareous soil. Journal of the Indian Society of Soil Science, 44: 70-73.
Blair, G.J. 1979. Sulfur in tropics. International Fertilizer Development Center, Muscle
Shoals Albama. 69 pp.
Page 46 of 57
Bohn, H.L.; Barrow, N.J.; Rajan, S.S. and Parfitt, R.L. 1986. Reactions of inorganic
sulfur in soils. pp. 233-249. In: Tabatabai, M.A. (ed.), Sulfur in Agriculture,
Agronomic Monogram, volume 27: CSSA, and ISSSA, Madison, WI.
Bohn, H.L.; Mcneal, B.L. and OConnor, G.A. 1985. Soil chemistry. 2nd Edition. New
York: John, Wiley and Sons.
Bolan, N.S.; Syers, J.K. and Sumner, M.E. 1993. Calcium-induced Sulfate adsorption by
soils. Soil Science Society of America Journal, 57: 691-696.
Bolan, N.S.; Syers, J.K.; Tillman, R.W. and Scotter, D.R. 1988. Effect of liming and
phosphate additions on sulphate leaching in soils. Journal of Soil science, 39:
493-504.
Brady, N.C. and Weil, R.R. 2013. The Nature and Properties of Soils. 14th Edition.
Prentice Hall, Upper Saddle River, New Jersey, USA.
Brammer, H. 1971. Bangladesh: Soil resources. AGL: SF/PAK-6, Technical report no. 3,
FAO, Rome.
Chao, T.T. 1964. Anionic effects on sulfate adsorption by soils. Soil Science Society of
America Proceedings, 31: 581-583.
Chao, T.T.; Harward, M.E. and Fang, S.C. 1962a. Adsorption and desorption phenomena
of sulfate ions. Soil Science Society of America Journal, 26: 234-237.
Chao, T.T.; Harward, M.E. and Fang, S.C. 1962b. Soil constituents and properties in the
adsorption of the sulfate ion. Soil Science, 94: 286-293.
Chao, T.T.; Harward, M.E. and Fang, S.C. 1962c. Movement of
35
S-tagged sulfate
through soil columns. Soil Science Society of America Proceedings, 26: 27-32.
Christophersen, N. and Wright, R.F. 1980. Sulfate flux and a model for sulfate
concentrations in stream water at Birkenes, a small forested catchment in
southernmost Norway. Swiss Natinal Science Foundation-Project IR 70/80. 52 pp.
Couto, W.; Lathwell, D.J. and Bouldin, D.R. 1979. Sulfate sorption by two oxisols and an
alfisol of the tropics. Soil Science, 127: 108-116.
Curtin, D. and Syers, J.K. 1990. Mechanisms of sulfate adsorption by two tropical soils.
Journal of Soil Science, 41: 295-304.
Page 47 of 57
D'Angelo, E.M.; Vandiviere, M.V.; Thorn, W.O. and Sikora, F. 2003. Estimating soil
phosphorus requirements and limits from oxalate extract data. Journal of
Environmental Quality, 32: 1082-1088.
Das, I.; Datta, A.; Ghosh, K.; Chatterjee, S. and Chakraborty, A. 2009. Sulfate
sorption/desorption behavior vis--vis thermodynamic characteristics of some
sulfur deficient soils of West Bengal. Agronomy and Soil Science, 55(1): 35-50.
David, M.B.; Mitchell, M.J. and Schindler, S.C. 1984. Dynamics of organic and
inorganic sulfur constituents in hardwood forest soils and their relationship to
nutrient cycling. pp. 221-245. In: Stone, E.L. (ed.), Forest soils and treatment
impacts. Proceedings 6th North American Forest Soils Conference, 1983 June,
Knoxville, The University of Tennessee.
Dolui, A.K. and Jana, S.C. 1997. Sulphate sorption-desorption characteristics of some
Inceptisols. Journal of the Indian Society of Soil Science, 45: 265-270.
Elkins, D.M. and Ensminger, L.E. 1971. Effect of soil pH on the availability of adsorbed
sulfate. Soil Science Society of America Proceedings, 35: 931-943.
Eriksen, J. 1996. Incorporation of S into soil organic matter in the field as determined by
the natural abundance of stable isotopes. Biology and Fertility of Soils, 22: 149155.
Evans, A.J. 1986. Effects of dissolved organic carbon and sulfate on aluminum
mobilization in forest soil columns. Soil Science Society of America, 50: 15761578.
Fitzgerald, J.W. 1978. Naturally occurring organosulfur compounds in soils. pp. 391-443.
In: Nriagu, J.O. (ed.), Sulfur in the environment, Part II. New York: John Wiley
and Sons, Inc.
Fitzgerald, J.W.; Strickland, T.C. and Swank, W.T. 1982. Metabolic fate of inorganic
sulphate in soil samples from undisturbed and managed forest ecosystems. Soil
Biology and Biochemistry, 14: 529-536.
Fox, R.L. and Kamprath, E.J. 1970. Phosphate sorption isotherms for evaluating the
phosphate requirements of soils. Soil Science Society of America proceedings, 34:
902-907.
Page 48 of 57
Fuller, R.D.; David, M.B. and Driscoll, C.T. 1985. Sulfate adsorption relationships in
forested Spodosols of the northeastern USA. Soil Science Society of America
Journal, 49: 1034-1040.
Gee, G.W. and Bauder, J.W. 1986. Particle size analysis. pp. 383-411. In: Klute A. (ed.),
Methods of Soil Analysis, Part I, Physical and Mineralogical Methods. Agronomy
Monograph No.9 (2nd edition). American Society of Agronomy, Madison,
Wisconsin.
Ghosh, G.K. and Dash, N.R. 2012. Sulphate SorptionDesorption Characteristics of
Lateritic Soils of West Bengal, India. International Journal of Plant, Animal and
Environmental Sciences, 2(1): 167-170.
Harrison, R.B.; Johnson, D.W. and Todd, D.E. 1989. Sulfate adsorption and desorption
reversibility in a variety of forest soils. Journal of Environmental Quality, 18:
419-426.
Harward, M.E. and Reisenauer, H.M. 1966. Reactions and movement of inorganic soil
sulfur. Soil Science, 101: 326-335.
Harward, M.E.; Chao, T.T. and Fang, S.C. 1962. Soil properties and constituents in
relation to mechanisms of sulphate adsorption. Reprinted from Radioisotopes in
Soil-Plant Nutrition Studies, International Atomic Energy Agency, Vienna.
Harwood, J.L. and Nicholls, R.G. 1979. The plant sulpholipid -a major component of the
sulphur cycle. Biochemistry Society Transactions, 7: 440-447.
Hingston, F.J.; Atkinson, R.J.; Posner, A.M. and Quirk, J.P. 1967. Specific adsorption of
anions. Nature, 215: 1459-1461.
Hossain, M.E.; Hoque, S. and Osman, K.T. 2012. Phosphate sorption in some
representative soils of Bangladesh. Archives of Agronomy and Soil Science, 58
(9): 959-966.
Huang, P.M. and Violante, A. 1986. Influence of organic acids on crystallization and
surface properties of precipitation products of aluminum. pp. 159-221. In: Huang,
P.M. and Schnitzer, M. (eds.), Interactions of soil minerals with natural organics
and microbes. Special Publication, volume 17, SSSA, Madison.
Page 49 of 57
Hunt, J. 1980. Determination of total sulfur in small amount of plant material. Analyst,
105: 83-85.
Hutchinson, T.C. 1979. Sulphur in soil and vegetation. pp. 428-442. International
symposium sulphur emissions and the environment, May 8-10, London, UK.
Inskeep, W.P. 1989. Adsorption of sulfate by kaolinite and amorphous iron oxide in the
presence of the organic ligands. Journal of Environmental Quality, 18: 379-385.
Jackson, M.L. 1967. Soil Chemical Analysis. 2nd Edition. Prentice Hall of India Pvt. Ltd.
New Delhi.
Jackson, M.L. 1973. Soil Chemical Analysis: Advanced Course. Prentice Hall of India
Pvt. Ltd. New Delhi.
Jamal, A.; Ko, K.; Kim, H.S.; Cho, Y.K. and Joung, H. 2009. Role of genetic factors and
environmental conditions in recombinant protein production for plant molecular
biofarming. Biotechnology Advances, 27: 914-923.
Jamal, A.; Moon, Y.S. and Abdin, M.Z. 2010. Enzyme activity assessment of peanut
(Arachis hypogea) under slow-release sulphur fertilization. Australian Journal of
Crop Science, 4(3): 169-174.
Johnson, D.W. and Cole, D.W. 1977. Sulfate mobility in an outwash soil in western
Washington. Water Air and Soil Pollution, 7: 489-495.
Johnson, D.W. and Cole, D.W. 1980. Anion mobility in soils: relevance to nutrient
transport from forest ecosystems. Environment International, 3: 79-90.
Johnson, D.W. and Todd, D.E. 1983. Relationship among iron, aluminum, carbon, and
sulfate in a variety of forest soils. Soil Science Society of America Journal, 47:
792-800.
Johnson, D.W.; Cole, D.W. and Gessel, S.P. 1979. Acid precipitation and soil sulfate
adsorption properties in a tropical and in a temperate forest soil. Biotropica, 11:
38-42.
Kennedy, I.R. 1986. Acid soil and acid rain: The impact on the environment of nitrogen
and sulfur cycling. New York: John Wiley and Sons, Inc.
Page 50 of 57
Kimsey, M.; McDaniel, P; Stwawn, D. and Moore, J. 2005. Fate of applied sulfate in
volcanic ash-influenced forest soils. Soil Science Society of America Journal, 69:
1507-1515.
Konova, M.M. 1975. Humus of virgin and cultivated soils. pp. 475-526. In: Geisking,
J.E. (ed.), Soil components, organic components, Volume one: New York.
Langmuir, I. 1918. The adsorption of gases on plane surfaces of glass, mica and
platinum. Journal of American Chemical Society, 40: 1361-1403.
Leustek, T. 2002. Sulfate metabolism. In: Somerville, C.R. and Meyerowitz, E.M. (eds.),
The Arabidopsis Book. American Society of Plant Biologists, Rockville, MD.
Leustek, T. and Saito, K. 1999. Sulfate transport and assimilation in plants. Plant
Physiology, 120: 637-643.
Liu, F.; He, J.Z.; Colombo, C. and Violante, A. 1999. Competitive adsorption of sulfate
and oxalate on goethite in the absence or presence of phosphate. Soil Science,
267: 180-189.
Loganathan, P.; Isirimah, N.O. and Nwachuku, D.A. 1987. Phosphorus sorption by
Ultisols and Inceptisols of the Niger delta in southern Nigeria. Soil Science, 144:
330-338.
Lopez-Hernandez, D.; Siegert, G. and Rodriguez, J.V. 1986. Competitive adsorption of
phosphate with malate and oxalate by tropical soils. Soil Science Society of
Marcano-Martinez, E. and Mcbride, M.B. 1989. Calcium and sulfate retention by two
Oxisols of the Brazilian Cerrado. Soil Science Society of America Journal, 53: 6369.
Marsh, K.B.; Tillman, R.W. and Syers, J.K. 1987. Charge relationships of sulfate
sorption by soils. Soil Science Society of America Journal, 51: 318323
Martinez, C.E.; Kleinschmidt, A.W. and Tabatabai, M.A. 1998. Sulfate adsorption by
variable charge soils: effect of low molecular- weight organic acids. Biology and
Fertility of Soils, 26: 157-163.
Page 51 of 57
Matsubayashi, Y.; Ogawa, M.; Morita, A. and Sakagami, Y. 2002. An LRR receptor
kinase involved in perception of a peptide plant hormone, phytosulfokine.
Science, 296: 1470-1472.
Mcgill, W.B. and Cole, C.V. 1981. Comparative aspects of cycling of organic C, N, S
and P through soil organic matter. Geoderma, 26: 267-286.
Mclaren, R.G.; Keer, J.J. and Swift, R.W. 1985. Sulphur transformations in soils using
sulphur-35 labeling. Soil Biology and Biochemistry, 17: 73-79.
Mead, J.A. 1981. A comparison of the langmuir, freundlich and Temkin equations to
describe phosphate adsorption properties of soils. Australian Journal of soil
research, 19: 333-342.
Mitchell, M.J. and Fuller, R.D. 1988. Models of sulfur dynamics in forest and grassland
ecosystems with emphasis on soil processes. Biogeochemistry, 5: 133-163.
Mora, M.L.; Shene, C.; Violante, A.; Demanet, R. and Bolan, N.S. 2005. The effect of
organic matter and soil chemical properties on sulfate sorption in Chilean
volcanic soil. pp. 223-244. In: Huang, P.M.; Violante, A.; Bollag, J.M. and
Vityakon, P. (eds.), Soil abiotic and biotic interaction and the impact on the
ecosystem and human welfare. Science Publishers (Enfield, NH USA).
Moss, M.R. 1978. Sources of sulfur in the environment, The global sulfur cycle. In:
Nriagu, J.O., (ed.), Sulfur in the environment. Part I. The atmospheric cycle. New
York, John Wiley and Sons.
Nair, P.S.; Logan, T.J.; Sharpley, A.N.; Sommers, L.E.; Tabatabai, M.A. and Yuan, T.L.
1984. Interlaboratory comparison of a standardized phosphorus adsorption
procedure. Journal of Environmental Quality, 3: 591-595.
Neary, A.J.; Mistry, E. and Vanderstar, L. 1987. Sulphate relationships in some central
Ontario forest soils. Canadian Journal of Soil Science, 67: 341-352.
Nelson, R.E. 1982. Carbonate and Gypsum. pp. 181-197. In: Page, A.L.; Miller, R.H. and
Keeney, D.R. (eds.), Methods of soil analysis. Part II. Chemical and
microbiological properties. 2nd Edition. American Society of Agronomy,
Madison, WI.
Page 52 of 57
Nodvin, S.C.; Driscoll, C.T. and Likens, G.E. 1986. The effect of pH on sulfate
adsorption by a forest soil. Soil Science, 142: 69-75.
Parfitt, G.D. 1982. Adsorption from aqueous solutions. Journal of Colloid and Interface
Science, 89: 596-597.
Parfitt, R.L. 1980. Chemical properties of variable charge soil. pp. 167-194. In: Theng,
B.K.G. (ed.), Soils with Variable Charge. New Zealand Society of Soil Science,
Lower Hutt, New Zealand.
Parfitt, R.L. and Smart, S.C. 1978. The mechanism of sulfate adsorption on iron oxides.
Soil Science Society of America Journal, 42: 48-50.
Pasricha, N.S. and Fox, R.L. 1993. Plant nutrient sulfur in tropics and subtropics.
Advances in Agronomy, 50: 209-269.
Peak, D.; Elzinga, E.J. and Sparks, D.L. 2001. Understanding sulfate adsorption
mechanisms on iron (III) oxides and hydroxides: Results from ATR-FTIR
Spectroscopy. pp. 167-190. In: Selim, H.L. and Sparks, D.L. (eds.), Heavy metals
release in soil Lewis Publication.
Pigna, M. and Violante, A. 2003. Adsorption of sulfate and phosphate on Andisols.
Communications in Soil Science and Plant Analysis, 23: 432-436.
Pregitzer, K.S.; Burton, A.J.; Mroz, G.D.; Liechty, H.O. and macdonald, N.W. 1992.
Foliar sulfur and nitrogen along a 800-km pollution gradient. Canadian Journal of
Forest Research, 22: 1761-1769.
Rajan, S.S.S. 1978. Sulfate adsorbed on hydrous alumina, ligands displaced, and changes
in surface charge. Soil Science Society of America Journal, 42: 39-44.
Rajan, S.S.S. 1979. Adsorption and desorption of sulfate and charge relationships in
allophonic clays. Soil Science Society of America Journal, 43: 65-69.
Rao, D.N. and Mikkelson, D.S. 1977. Effect of rice straw additions on production of
organic acids in flooded soil. Plant Soil, 47: 303-311.
Reddy, K.S.; Tripathi, A.K.; Singh, M.; Rao, S. and Anand, S. 2001. Sulphate sorptiondesorption characteristics in relation to properties of some acid soils. Journal of
the Indian Society of Soil Science, 49: 74-80.
Page 53 of 57
Reuss, J.O. and Johnson, D.W. 1986. Acid deposition and the acidification of soils and
waters. 119 pp. New York: Springer-Verlag.
Roberts, T.L. and Bettany, J.R. 1985. The influence of topography on thr nature and
distribution of soil sulfur across a narrow environmental gradient. Canadian
Saito, K. 2000. Regulation of sulfate transport and synthesis of sulfur-containing amino
acids. Current Opinion in Plant Biology, 3: 188-195.
Sanyal, S.K.; De Datta, S.K. and Chan, P.Y. 1993. Phosphate Sorption-Desorption
behavior of some acidic soils of South and Southeast Asia. Soil Science Society of
Scherer, H.W. 2001. Sulphur in crop production - invited paper. European Journal of
Agronomy, 14(2): 81-111.
Scherer, H.W. 2009. Sulfur in soils. Journal of Plant Nutrient Soil Science, 172: 326-335.
Schindler, S.C.; Mitchell, M.J.; Scott, T.J.; Fuller, R.D. and Driscoll, C.T. 1986.
Incorporation of 35S-sulfate into inorganic and organic constituents of two forest
soils. Soil Science Society of America Journal, 50: 457-462.
Serrano, R.E.; Arias, J.S. and Fernandez, P.G. 1999. Soil properties that affect sulphate
adsorption by palexerults in western and central Spain. Communications in Soil
Science and Plant Analysis, 30: 1521-1530.
Shoji, S. and Fujiwara, Y. 1984. Active aluminum and iron in the humus horizons of
Andisols from Northeastern Japan: their forms, properties, and significance in
clay weathering. Soil Science, 137: 216-226.
Singh, B.R. 1980. Distribution of total and extractable Sand adsorbed SO42- in some acid
forest soil profiles of southern Norway. Actaagriculturae Scandinavia, 30: 357363.
Singh, B.R. 1984. Sulfate sorption by acid forest soils: 3. Desorption of sulfate from
adsorbed surfaces as a function of time, desorbing ion, pH, and amount of
adsorption. Soil Science, 138: 346-353.
Sparks, D.L. 1995. Sorption phenomena on Soils. Environmental Soil Chemistry, pp. 99104.
Page 54 of 57
Sparks, D.L. 1999. Kinetics and mechanisms of chemical reactions at the soil
mineral/water interface. pp. 135-191. In: Sparks, D.L. (ed.), Soil Physical
Chemistry. 2nd Edition. CRC Press, Boca Raton.
SRDI, 2008. Soil and land resource utilization guide, Batiaghata upazilla, Khulna
districts. Soil Resources Development Institute, Dhaka.
Stevenson, F.J. 1967. Organic acids in soil. pp. 119-146. In: Mclearn, A.D. and Peterson,
G.H. (Eds.), Soil Biochemistry. New York, Wiley.
Stevenson, F.J. 1986. Cycles of soil. 1st Edition. John Wiley and sons. New York.
Strickland, T.C.; Fitzgerald, J.W.; Ash, J.T. and Swank, W.T. 1987. Organic sulfur
transformations and sulfur pool sizes in soil and litter from a southern
Appalachian hardwood forest. Soil Science, 143: 453-458.
Sumner, M.E. 2000. Handbook of Soil Science. 2nd Edition. CRC Press, Boca Raton, FL.
Tabatabai, M.A. 1982. Sulfur. pp. 501-538. In: Page, A.L.; Miller, R.H. and Keeney,
D.R. (eds.), Methods of soil analysis. Part II. Chemical and microbiological
properties. 2nd Edition, Agronomy No. 9. American Society of Agronomy,
Madison, WI.
Tan, K.H. 1994. Environmental Soil Science. Marcel Dekker, Inc. 270 Madison Avenue,
New York
Tandon, H.L.S. 1986. Sulfur Research and Agricultural Production in India. 2nd Edition.
Fertilizer Development and Consultation Organization, New Delhi.
Temkin, M.I. and Pyzhev, V. 1940. Kinetic of ammonia synthesis on promoted iron
catalysts. Actaphysiochim, 12: 327-356.
Tisdale, S.L.; Nelson, W.L.; Beaton, J.D. and Havlin, J.L. 1997. Soil fertility and
fertilizers. 5th Edition. New York: Macmillan publishing Company, Inc.
Tisdale, S.L.; Nelson, W.L.; Beaton, J.D. and Havlin, J.L. 2013. Soil Fertility and
Fertilizers. 8th Edition. Prentice Hall of India Private Ltd., New Delhi.
Turner, L.J. and Kramer, J.R. 1991. Sulfate ion binding on goethite and hematite. Soil
Science, 152: 226-230.
Page 55 of 57
USDA (United States Department of Agriculture). 2004. Soil Survey Laboratory Manual,
Soil Survey Investigation Report No. 42, version 4.0, USDA-NRCS, Nebraska,
USA.
Uzoho, B.U.; Obasi, S.N. and Iwuanyanwu, U.P. 2014. Sulphate sorptivity in relation to
land use types of soils of the humid tropical rainforest, Southeastern Nigeria.
International Journal of Environment and Pollution Research, 2(1): 1-8.
Violante, A.; Rao, M.A.; De Chiara, A. and Gianfreda, L. 1996. Sorption of phosphate
and oxalate by a synthetic aluminium hydroxysulphate complex. European
Wainweight, M. 1984. Sulfur oxidation in soils. Advances in Agronomy, 37: 349-396.
Zhang, G.Y. and Yu, T.R. 1997. Coordination adsorption of anions. pp. 175-218. In: Yu,
T.R. (ed.), Chemistry of Variable Charge Soils. Oxford University Press, New
York.
Zhang,
P.C. and Sparks, D.L. 1990. Kinetics and
mechanisms of sulfate
adsorption/desorption on goethite using pressure-jump relaxation. Soil Science

Society of America Journal, 54: 1266-1273.
Page 56 of 57
Appendix Table 1. Adsorbed sulfate (g g-1 soil) in soils treated with different concentration of sulfur
g S per 20 ml
0
20
40
100
200
500
1000
Adsorbed amount of
S in Bajoa series
(g g-1 soil)
0
50
70
110.22
170.43
360.28
645.12
Page 57 of 57
Adsorbed amount of
S in Gopalpur series
(g g-1 soil)
0
29.57
54.36
90.79
160.61
330.64
550.76

Sulfate Sorption Behavior of Two Soils in Ganges Floodplains Anindita

Transféré par

Informations du document

Copyright

Formats disponibles

Partager ce document

Partager ou intégrer le document

Options de partage

Avez-vous trouvé ce document utile ?

Ce contenu est-il inapproprié ?

Droits d'auteur :

Formats disponibles

Sulfate Sorption Behavior of Two Soils in Ganges Floodplains Anindita

Transféré par

Droits d'auteur :

Formats disponibles

SULFATE SORPTION BEHAVIOR OF TWO SOILS IN GANGES

COURSE TITLE: PROJECT THESIS

Soil Science Discipline