CHAPTER TWO

LITERATURE REVIEW
Agriculture marks the back bone of economic development of any country and
sustainability in agriculture sector is a serious concern, which itself is linked with
environmental degradation occurring due to crop husbandry practices. Hence, due
consideration to these two simultaneous aspects needs to be given. This resulted in the
development of many new products designed to meet the requirements of both
sustainability and environmental protection thereby reducing the negative impacts of
conventional fertilizers via their reduced and modified ways of application.

To combat with these both aspects new kind of fertilizers were developed termed
as controlled release fertilizers (CRFs) and slow release fertilizers (SRFs). These
fertilizers (CRFs and SRFs) were prepared to release nutrients gradually to coincide with
the plant nutrient requirements and to reduce the environmental issues. These were
physically prepared, by coating the granules of traditional fertilizers with different methods
to lower the rate of dissolution (Hongfei and Zhenghui, 2005; Shavit et al., 2003).

The terms of SRFs and CRFs are usually used interchangeably but have some
differences. CRF used for those fertilizers, in which the duration, pattern, and rate of
release are well recognized and managed. On the other side, SRFs characterized through
slow release rate of nutrients than usual, but the duration, pattern, and rate of release are
not very well controlled (Cui et al., 2010; Mikkelsen and Bruulsema, 2005).

CRFs and SRFs have been available since1950s but these materials enjoined
their infancy till the 1980s after which real progress in the development of these materials
took place. Initially, SRFs containing nitrogen base materials like urea formaldehyde (UF)
and isobutyldiene urea (IBDU) were available commercially (Mikkelsen and Bruulsema,
2005). UF is prepared by the reaction of urea and formaldehyde under controlled
temperature and pH conditions at varying reaction times and the end product is a blend
of methylene urea with different long chain polymers. The nitrogen releases when
microorganisms break the long chains into smaller units resulting in the release of urea.
Whereas IBDU is a blend of isobutyraldehyde and urea from which nitrogen releases by
hydrolytic cleavage of the molecules. The release of nitrogen is faster as particle size
decreases and soil temperature increases (Guertal, 2009).

In 1960’s the encapsulation of fertilizers were done. Since then, coated fertilizer
products were developed as technology has expanded. The fertilizers are coated with
sulfur, resins, polymer, and hybrids of sulfur and polymers, to reduce leaching losses and
improve the nutrient uptake effectiveness compared to ordinary fertilizers (Hongfei and
Zhenghui, 2005; Rai et al., 2015). These coating materials are discussed briefly one by
one.

In the beginning, elemental sulfur was used in a molten form for coating of urea
pills to synthesize sulfur coated urea, as sulfur is inexpensive and have no injurious
influence on the plant growth. Commercially, the initial sulfur coated urea item was
developed for almost 40 years by the Tennessee Valley Authority (Trenkel, 1997, 2010b).
A layer of wax sealant is used on sulfur coated urea in order to reduce microbial
degradation and seal cracks in the coating. There is, however one demerit of this item, is
no uniformity in its release rate because of development of cracks in the surface coating.
Generally, the product released one- third very quickly (burst) while remaining one-third
released very slowly (Medina et al., 2009). Later sulfur coated urea was covered with
another layer of resin to control the release of nitrogen by the Archer Daniels Midland
company (Shaviv, 2001; Shaviv and Mikkelsen, 1993). This coating technique served as
the platform for a large number of polymer coated fertilizer products that are now available
in the market.

Alkyd-type called Osmocote (OH, Marysville, Scotts-Sierra Horticultural Products)

is another type of resin coating developed in 1967 in California by use of
dicyclopentadiene as copolymer with the blend of glycerol ester (Sartain et al., 2004). The
release rate of nutrients from CRFs was regulated by varying the composition or thickness
of coating materials. By using this technique, different fertilizers such as urea and NPK
etc. were coated by keeping the weight of coating material between 10-20% of the
fertilizer’s total weight (Budai et al., 2014).
 Similarly, thermoplastic resins were also applied as a coating material for coating
of granular fertilizer. The fast-drying chlorinated hydrocarbon solvent was used for the
dissolution of the coatings because of the impermeability of the thermoplastic polymers,
in water. Surfactants and ethylene-vinyl acetate must be included as a release controlling
substances to achieve the desired diffusion properties. Potentially, the degree of release-
controlling agents controls the release pattern and by twisting the talc into the coating,
release rates can also be changed. This coating material could be used for prilled and
granular fertilizers (Sartain and Kruse, 2001).

After application of the single coating, the modification was done in terms of
changing the properties of fertilizers by increasing the number of coating layers. Double
coating of urea was done to improve both the slow release and water retention properties
and named as double coated slow release water retention urea (DSWU). The coating
consisted of three-layers: the outside coating was cross-linked poly (acrylic acid-co-
acrylamide) superabsorbent, the inside coating was ethyl-cellulose and the core was pure
poly (N-vinyl-pyrrolidone) hydrogel consisting of urea in a sodium alginate matrix.
According to the elemental analysis, 21.1% nitrogen content was found in the product
and water absorbency was 70 times of its own weight. After being incubated in soil for a
period of one month, the slow-release experiment outcomes yielded that the efficient
nutrient release ratio was below 75%. The water-retention property of soil and water-
holding capacity can significantly improve through the mixing of DSWU into the soil.
DSWU can be used for horticulture and agriculture, particularly in drought-prone regions
where there is an insufficiency of water (Ni et al., 2009).

2.1 Nano based Slow Release Fertilizers

Nanotechnology has remarked the revolution in fertilizer technology by the

provision of nano sized controlled-release smart materials that provides enhancement in
nutrient release along with significant cost reduction both in aspects of economics and
environmental pollution (Chinnamuthu and Boopathi, 2009). In this context, it provides
the feasibility of exploiting nanomaterials or nanostructures (size less than 100nm) for
development of SRFs or CRFs to enhance nutrient use efficiency through their smart
delivery mechanism of nutrients (DeRosa et al., 2010; Solanki et al., 2015).
 Surface coatings of fertilizers with nanomaterials strongly firm the material
because of a higher surface to volume ratio than existing ones thus enabling controlled
release of nutrients in the much improved way. The nano-fertilizers are stable, more
efficient in the provision of nutrients and less eco toxic than ordinary fertilizers (Ditta and
Arshad, 2016; Medina et al., 2009; Naderi and Danesh-Shahraki, 2013). These nano
based fertilizers are available in many forms when talking with respect to their chemical
nature. These include nanoparticles, oxides of nanoparticles, in combination with
conventional fertilizers and as support materials in nano-composites and are discussed
here one by one briefly.

The nanoparticles significantly improve the germination and plant growth.

According to Shah and Belozerova (2009), that different metal nanoparticles like gold
(Au), copper (Cu), silicon (Si) and palladium (Pd) had a positive effect on the growth of
lettuce seed when applied in different concentrations. The Si and Cu were more effective
at higher concentrations while Pd and Au work very well at low concentrations. Similarly,
the nano crystalline powder of copper, iron, and cobalt applied at very low concentrations
on G.max had a profound affect on the germination as compared to control (Ngo et al.,
2014).

The study of Nair et al. (2010), reported that foliar application of zinc oxide
nanoparticles improve the tomato plant growth. They conducted an experiment in which
tomato plants were grown in pots and different concentrations of zinc oxide nanoparticles
were applied in ranges from 0 – 100 mg/L. The results revealed that maximum biomass
production and growth was recorded at a concentration of 20 mg of zinc oxide
nanoparticle as compared to the control. Similar positive results in respect of germination
and growth of spinach were found when titanium oxide (TiO 2) nanoparticles were added
to the soil. The early germination was detected with enhanced plant growth (Zheng et al.,
2005). As Zhao et al. (2014), studied the comparative effects of zinc oxide and cesium
oxide nanoparticles at a concentration of 400 ppm on fruit quality of Cucumis sativus. The
results showed that fruit quality improved due to increased starch contents and
carbohydrate pattern.
 Combination of different nanoparticles and materials in combination with
conventional fertilizers are also tried to facilitate slow release of nutrients. Chitosan
nanoparticles are stable, cationic and biodegradable material that was assimilated with
NPK fertilizer to estimate the release of nutrients and its effectiveness as CRF or SRF
(Corradini et al., 2010). Likewise, urea-formulated hydroxyapatite nanoparticles prepared
with nitrogen fertilizer, and nitrogen release pattren studied were conducted in lab for 60.
Compared to commercial fertilizers, these nanoparticles subsequently showed the slow
release of nitrogen, after initial bursting up to sixty days. On the other hand, commercial
fertilizer showed the release of nutrients to the level of thirty days only. The stronger
attachment of urea on hydroxyapatite surface is facilitated by large hydroxyapatite area.
The strong interaction between urea and hydroxyapatite nanoparticles added to the
controlled and slow release of urea (Kottegoda et al. 2011).

Similarly, polymers containing mesoporous nanoparticles also proved to be an

effective carrier for agrochemical compounds, which helped in the improvement of
economic utilization and effectiveness. Urea (15.5 %) was entrapped in mesoporous silica
nanoparticles (150 nm) and showed the controlled release of urea in water and soil with
a minimum of fivefold improvement (Wanyika et al., 2012).

Jin et al. (2010), prepared a novel insoluble SRF, biuret poly phosphoramide
(BPAM) by mixing urea, phosphoric acid (H3PO4) and ferric oxide (Fe2O3) coated with
active carbon, acrylic acid, acrylamide, and carboxymethyl chitosan materials. BPAM
compositional analysis confirmed the elemental composition to be 5.66% of nitrogen and
11.7% of phosphorus. The results of studies revealed that BPAM own excellent capacity
for water retention and the tendency for the steady release of phosphorus along with
better cation absorption capacity in saline soil.

Another kind of slow release membrane-encapsulated urea fertilizer with 26.74%

N, moisture preservation and superabsorbent was prepared. Urea granules were the core
of it, and the copolymers of cross-linked starch (the first layer) and AM and AA (the second
layer) were the membrane materials. Compared to its own weight in tap water, its water
absorption rate was around 80 (g/g) times. According to the water-retaining potential
experiment, the greatest water-retaining ratio 12.45% compared to when the SMUSMP
mass ration to soil was 1: 100. As per the water retention and slow release experiments,
it not only had good moisture retention capacity in soil but also had to batter slow release
property. The utilization of water resources and fertilizer can be improved efficiently
through it (Guo et al., 2005).

Urea granules, under the current study, were layered with ethyl cellulose and
polyhydroxy butyrate with differing circumstances while the emulsifiers are present. The
final products and the original granules were featured, and the interaction between the
rates of mass change, and the coating and the granules. In distilled water, commercial
enzyme kit is used to measure the rates of urea release, thereby presenting a more
uniformity. Also, it is observed that there is a reduction of urea portions dissolution in
water by effectively coating the granules with those polymers (Costa et al., 2013).

The clay based nano-composites are also used as SRFs, in which mostly
montmorillonite or zeolite used as a support matrix. Clay particles have adsorptive pores
which carry nutrients and release them slowly. The results of the study revealed that clay
based nanocomposite (30-40 nm) released nutrients especially nitrogen for a longer
duration than ordinary fertilizers (Subramanian et al., 2015).

Pereira et al. (2012), reported that urea augmented with montmorillonite clay
nanocomposite, was prepared by an extrusion process with different urea contents (50 to
80%) by weight at room temperature and characterized by XRD, DTA, and SEM-EDX
techniques. The diametric comparison test showed that the prepared nanocomposite is
deformable, and dissolution rate of urea was slowed in water which verified it as effective
slow release nano-composite with a low amount of montmorillonite (10% in weight).

Introduction of organic material into kaoline clays using exfoliation process under
definite pressure and temperature to prepare nano- subnanocomposite. This material was
used for coating of CRFs and SRFs because of its thickness and potential for adsorption
of organic carbon and macro nutrients. The application of this nano-subnanocomposite
improve the soil conditions and enhance the plant growth (Xiumei et al., 2005).
 In recent years, use of zeolite and biochar gained much attraction in the
agriculture. These are renewable materials, have numerous beneficial properties and
potential for providing a solution to the environmental problems caused due to
conventional fertilizers. Their unique physiochemical properties like porous structure, high
cation exchange capacity, large surface area and excellent adsorption capacity made
them more appropriate materials as fertilizer carriers. Past studies had proved that
adsorbed nutrient was found in biologically available forms and had suggested the
potential uses and benefits of nutrient doped biochar and zeolite as SRFs in agricultural
production (Ramesh et al., 2011; Verheijen et al., 2014). So this research work focuses
on the use of zeolite and biochar as support material for impregnation of nutrients.

2.2 Zeolites and Nanoporous Zeolites

Zeolites are inorganic porous minerals, have unique physio-chemical properties

which make them the most popular class of minerals after their identifications in 1756 by
a Swedish mineralogist, Alex Fredrik Cronstedt. He gave a Greek name zeolite, ‘Zeo’
means boil and ‘lite’ means to boil, because of their property to boiled and frothed when
heated due to water loss. Later in 1862, St.Claire Deville claimed the synthesis of zeolite
in the laboratory. The real progress in zeolite synthesis had begun in the 1940s, when
Richard Barrer and Robert Milton have made significant efforts for zeolite synthesis and
study its all aspects of practical applications (Polat et al., 2004; Sangeetha and Baskar,
2016).
 Zeolites are crystalline aluminosilicate minerals, having a three-dimensional
tetrahedral arrangement of TO4 (T= tetrahedrally coordinated atom, usually Si4+, Al3+),
linked with each other by oxygen sharing to form a stable honey comb like structure with
open voids and negative charge (Figure 2.1). Zeolite is attracted to cations of alkali and
alkaline metals because of negative charge, which can easily move in and out of voids
(Preetha et al., 2014).These cations may be Na+ (sodium), K+ (potassium),
Rb+(rohbdium), Mg2+(magnesium), Ca2+(calcium) ,NH4+(ammonium), TMA+
(Tetramethylam-monium) and other nitrogen containing organic cations. Further, these
cations are bounded by removable water molecules which are exchanged through other
sorbates by ionic redox reactions or ionic migration (Rehakova et al., 2004). The internal
surface area of these channels increases due to the exchange of ions, which make zeolite
an effective ion exchanger (Ramesh et al., 2011).

Figure 2.1: Structure of Zeolite showing tetrahedral arrangement

Source: (Querol et al., 2002)

Generally, zeolites are characterized by this empirical formula that was proposed
by Barrer in 1982 as:

(Mx+, My2+)[Al(x+2y)Sin-(x+2y)O2n].mH2O.
Where atoms in the tetrahedral framework structure are symbolized within the brackets,
M+ and M2+ are (monovalent and the divalent) cations that balanced negative charge of
structure and water molecules indicate the adsorbed or zeolitic water (Englert and Rubio,
2005).

Zeolite has the potential to hold water molecules up to 60% of their own weight
due to interconnected voids and pores crystalline structure. Consequently, water
molecules could be absorbed or evaporated from the pores without altering and damaging
the zeolite structure (Polat et al., 2004). Hence enabling zeolites to store water and
provides water for a prolonged period of time in dry and drought lands (Tan et al., 2010).

Zeolite has complex crystalline structure and have around 193 structure types,
which can be classified by three letter codes on the basis of silica to aluminum ratio as:
low Si : Al ratio (1.0 to 1.5), intermediate Si : Al ratio (2 to 5) and high Si: Al ratio (10 to
several thousands) (Flanigen, 1980). So, the Zeolite categorized with low Si: Al ratio,
represented by letter A and X have high cations and have highest ion-exchange capacity.
Zeolite having intermediate Si: Al ratio, are denoted by Y and zeolite that have lower Si:
Al ratios are known as ZSM-5.The Si: Al ratio is an important property of zeolite, as it
determines the ion exchange potential of zeolite. Si: Al ratio is directly linked to the thermal
stability and inversely linked to the cation content. The Si: Al ratio increase the zeolite’s
surface selectivity alter to hydrophobic from hydrophilic. Because of these properties, the
zeolite is used in different industries as a catalyst, ion exchanger and for water softening
(Saadat et al., 2012).

Zeolite found in abundance both in natural and synthetic form, having different
structures with varying pores sizes. Which can be categorized into three classes:
mesoporous, microporous and nanoporous (Li, 2003). In the 1970s, first nano-sized
zeolite (NZ) particles were synthesized in the Lab (Mintova et al., 2006). Which exhibited
new interesting properties because of their small size to volume ratio and enhanced
surface activity. NZ can be synthesized by both tops down and bottom up approaches
using ball mining (Wang and Peng, 2010), sol-gel, hydrothermal (Wang et al., 2012a) and
microwave methods (Sathupunya et al., 2002). The synthesized zeolite are characterized
using different techniques like fourier transform infrared spectroscopy (FTIR), energy-
dispersive X-ray spectroscopy (EDX), x-ray diffraction (XRD), scanning electron
microscope (SEM), atomic force microscopy (AFM), thermal gravimetric analysis (TGA)
etc. for determination of crystallinity, particle size, morphology and thermal stability.

Zeolite (both natural and synthetic) are frequently used in agriculture as soil
amendments due to its unique molecular sieve structure, high surface to volume ratio,
adsorption, and cation exchange capacity. Thus, application of zeolite improves the
growth of plant and consequently increased the crop yield (Leggo, 2000; Leggo et al.,
2006). The zeolite not only used as fertilizer in agriculture but also can also act as carrier
or support material for SRF, helps in minimization of leaching loss and sustainable
agriculture (Manik and Subramanian, 2014).

Some of the natural zeolites like Clinoptilolite, Phillipsite, Chabazite, and Mordenite
have been extensively used in agriculture as SRF to improve the soil quality, water
retention and plant growth (Bansiwal et al., 2006). The study of Khan et al. (2008),
revealed that application of zeolite on the soybean planting leads to early stimulation of
vegetative stage on the allophonic soil. Similar results were reported for tomato when
zeolite was added to the soil, in the ratio of one fifth of soil weight (Unlu et al., 2004).

The reason for this enhanced growth is usually attributed to improved soil
conditions with respect to cation exchange capacity and pH, which ultimately enhance
the availability of nutrients to plants (Ramesh et al., 2011). The addition of zeolite in the
soil, helped in managing and controlling the valuable nutrient, by preventing release and
their harmful impacts to the environment. There are many studies in the literature
showing that zeolite application in soil with nitrogen source can enhance the nitrogen use
efficiency. So the use of zeolite as fertilizer reduce environmental issues and also improve
fertilizer competence (Millán et al., 2008). It has been reported that zeolite when used as
SRFs in combination with nitrogen, phosphorus, and potassium compounds, augments
the action these compounds (Naderi and Danesh-Shahraki, 2013).

The results of this study revealed that zeolite (clintopillolite) charged with
ammonium, have the ability to rapidly solubilize the phosphate minerals, leading to
enhanced phosphorus uptake and concurrent positive effect on crop yield (Hua et al.,
2006). Sheta et al. (2003), reported that natural zeolite like clintopillolite had a high
potential for iron and zinc sorption which made it suitable for SRFs. The sequestration
impact of exchange and sparingly solubility of minerals caused the slow release of zine
and transmit to zeolite exchange sites the trace nutrients where plants can use them more
readily for uptake (Broos et al., 2007). Zeolite also used to minimize ammonia
volatilization due to surface application of urea, as zeolite had high CEC and more
attraction for NH4 ions (Haruna et al., 2008).

The natural zeolite has some impurities that may affect the availability and release
of nutrients which might hinder or inhibit the plant growth. However, the synthetic zeolites
are used as an alternative to a natural zeolite having the advantage of no impurities and
have definite crystalline structure (Rehavoka et al., 2004). Busaidi and his coworkers
analyzed the effect of synthetic zeolite on the development of crop and on soil
functionality. They conducted experiment in both pots and plot on barley crop by irrigating
with saline water in greenhouse. The outcomes of the experiment showed that zeolite can
amend salinity stress in sandy soil and effectively improve nutrient balance (Busaidi et
al., 2008).

Another experiment was conducted to analyze nitrogen use worth of urea using
microporous natural zeolite (Z) and nanoporous zeolite (NZ) as substrate. According to
the data results, the release of N from urea mixed with NZ (1:1) was 48 days while urea
with a conventional zeolite having the same ratio (1:1) in the mixture, was up to 34 days
and nitrogen released from urea was finished in just 4 days. So this study suggests that
zeolite based fertilizers can be used for improving crop production as an alternate strategy
(Manik and Subramanian, 2014). Similar results were reported by Rahale, (2010) which
showed that absorption processes are facilitated by NZ due to a wide surface area for
anionic nutrients and cationic nutrients. The stability of the system was indicated by the
value of zeta potentials of the particles ranging from - 30 to - 65.

The research on zeolite based SRF is very limited with respect to loaded nutrients,
in their cationic forms like ammonium (NH4+) and potassium (K+). While the loading of
nutrients on unmodified zeolite, in the anionic forms like phosphate (PO43-), nitrate (NO3-
) and sulfate (SO42-) is hardly reported (Hidayat et al., 2015). Therefore, to load the anionic
nutrients onto the zeolite, the modification of its surface becomes imperative which
enhance anionic affinity to promote the loading of anionic nutrients thereby facilitating its
use as SRF.

During last fifteen years, extensive studies have been conducted on surface
modified zeolite by Li et al. (2007), to improve its adsorption capacity. Surface
modification enables the adsorption of the anions, into the surface of zeolite through anion
exchange process as reported in the literature (Bowman, 2003; Faghihian and Bowman,
2005; Vujaković et al., 2000). For surface modification of zeolite, a cationic surfactant
Hexadecy-ltrimethylammonium bromide (HDTMABr) was used and results represent that
application of HDTMA bromide enhanced the 200 % of the CEC of zeolite (Salonki,
2015).Bilayers on zeolite external surfaces were formed by the surfactant molecules
(HDTMABr) with the lower layer occupied by electrostatic interaction between and the
positively charged surfactant head groups and the negatively charged zeolite surface,
while the hydrophobic forces bound the upper and lower layers together and these forces
existed between the surfactant tail groups in both the layers (Bowman, 2003).

The studies revealed that surface modified zeolite, showed positive results related
to retention of phosphate (Bansiwal et al., 2006) and chromate (Krishna et al., 2001). The
study conducted by Bansiwal et al. (2006),in which he used the constant flow percolation
reactor to examine the release behavior of phosphorus in field conditions and the
comparative analysis of the release mechanism of phosphorus from pure fertilizers,
surface modified zeolite and fertilizer-loaded unmodified zeolite. The results showed a
continuous release of phosphorus from surface modified zeolite loaded with fertilizer for
1080 h, whereas phosphorus release was exhausted within 264 h from KH2PO4. For PO43-
, surface modified zeolite is a fine sorbent and potentially strong as a fertilizer carrier that
helps in slow release of the phosphorus.

Compared to nitrate, the loading capacity of sulfur on surface modified zeolite can
be owing to the anions’ change impact. One positive charge is contributed by each
HDTMABr molecule and it takes only one negative charge to neutralize. Sulfate needs
two HDTMABr molecules to balance because it is divalent. Meanwhile, there is no rigidity
in the surface configuration of the HDTMABr sue to the surfactant tail-to-tail interaction.
Therefore, in comparison with 1:1 neutralization of HDTMABr by nitrate, favorability of 2
HDTMABr molecules with one sulfate can be less (Li, 2004; Li, 2003).

The charge generated owing to the hydrogen bonding with the surface and by the
exchange of cations in the pores generates the electrical field which ultimately influences
the nitrogen adsorption on such modified zeolites. Because of the higher cation exchange
capacity, shorter diffusion path lengths, and unique surface qualities, nanoporous zeolites
have drawn much attention in the present context (Ramesh et al., 2011).

According to Jha and Hayashi (2009), there may be a free and slow release of
ammonium covering the internal zeolite channels, thereby allowing the crop to progress
absorption which can be observed in higher dry matter crop production. Zeolite mixed
with Urea may be applied as SRF which aids the carrying and releasing of nitrogen from
nanozeolite and reduces the nitrogen losses (Ahmed et al., 2010).

2.3 Biochar

Biochar is the porous carbonaceous solid, formed in an oxygen free atmosphere

by thermochemical conversion of organic materials. Biochar is a versatile material and
composed of ash, sulfur (S), oxygen (O), hydrogen (H), nitrogen (N), and carbon (C) in
varying proportion depending upon feedstock material (Chan et al., 2008; Ding et al.,
2016; Tang et al., 2013). Thus, biochar is considered a significant tool, for addressing
various important concerns of food insecurity, soil degradation, agricultural problem,
waste management, climate change and as a source for energy production (Hunt et al.,
2010; Kwapinski et al., 2010; Mukome et al., 2013).

Generally, agricultural crop residues are burned in the field for their disposal and
land preparation. Due to this practice, a lot of pollutants emitted into the atmosphere and
become a source of environmental pollution which ultimately led to global warming issue.
Although these crop residues are rich in carbon content that is abundantly available, so
these can be used as biochar source and have potential applications in agriculture (Sun
et al., 2014).

The biochar research gained much importance now a days, because use of
biochar not only reduces the burden of solid waste produced from the different sources
like agriculture, wood etc. (Sohi, 2012) but also indicating better plant growth (Chan et
al., 2008; Singh et al., 2010), enhanced nitrogen retention (Steiner et al., 2008), and
increased bioavailability and plant uptake of supplemented nutrients (Atkinson et al.,
2010; Major et al., 2009).

Different agricultural by-products or residues have been utilized for the production
of biochar like corn cob and corn stalk (Liu et al., 2014; Shariff et al., 2016), sugar beet
tailing (Yao et al., 2011), rice straw (Demirbas et al., 2006; Peng et al., 2011), waste wood
(Abdullah and Wu, 2009; Brown et al., 2006; Chun et al., 2004; Lucchini et al., 2014) and
wheat residues (Chun et al., 2004; Mohanty et al., 2013). Many researchers are taking
interest in the use of biochar for amending the soil because soil quality improved by the
use of biochar. The addition of biochar to the soil also helpful for carbon sequestration,
thus facilitate in mitigation of climate change globally (Laird, 2008; Laird et al., 2009; Woolf
et al., 2010; Akbari et al., 2011).It is estimated that conversion of plant biomass to the
stable carbon rich biochar, has the hypothetical potential of 24 gigatons of carbon
absorption from the atmosphere per year; which is 20% of the total CO2 taken by
photosynthesis process (Wang et al., 2012; Wu et al., 2013).

Biochar is not only helpful in CO2 sequestration but also have a profound effect on
the reduction of other greenhouses gas. According to Renner (2007), emissions of
methane and nitrous oxide were reduced up to 80% in both greenhouse study and field
trials by the use of biochar in Columbia.

Biochar application typically in the Midwestern United States soils resulted in

enhanced water retention, cation exchange capacity and high pH. Moreover, biochar
addition in the soil also decreased the leaching of magnesium (Mg), nitrogen, and
potassium (Laird et al., 2010). According to Altland and Locke (2012), almost 10% v/v
additions of biochar minimized phosphorus and nitrate leaching by reducing their release
over time. So, it follows that due to the biochar’s capacity to slow down the release of
Nitrate to the roots of the plant, it may be utilized less often. In addition, there can be a
reduction in the application of potassium and phosphorus because biochar retains these
nutrients and release them over time (Altland and Locke, 2012). Fertilizer potential of
biochar has also been indicated by the field studies (Glaser et al., 2001).

The pyrolysis process greatly affects both physical and chemical properties of
biochar material. Based on the feedstock material and pyrolysis process, there can be a
significant variation in the chemical and physical properties of biochar (Spokas, 2010).
Consequently, the performance of biochar is closely related to both composition of the
source material and production methods used. The feedstock is important in terms of
evaluating the biochar role in the soil. However, there is no mutual opinion as regards
optimal feedstock in respect of both energy production and soil use, largely owing to the
fact that commercial pyrolysis plants were less frequently available, and those that are
available are connected and used in the processing of particular waste streams. The
currently used feedstock at research and commercial facilities includes sewage sludge
(Shinogi et al., 2003), dairy manure, chicken litter (Das et al., 2008), olive waste (Yaman,
2004), distillers grain, sugarcane bagasse, organic wastes inclusive of paper sludge,
switch grass, nut shells, rice hulls, corn cobs, crop residues including straw, tree bark,
wood pellets, and wood chip (Kwapinski et al., 2010; Sohi et al., 2010).

As appeared from the results of various research works, decrease observed in the
yields of biochar with the increase in temperature (Collins, 2008; Keiluweit et al., 2010;
Ding et al., 2016b). Angin (2013), reported that biochar yields at 400 oC varied from
34.18% to 29.70% (4.48% changes) with a change in heating rate from 10 to 50 oC/min.
Nevertheless, there was 1.76% decrease in biochar yield occurred at 600 oC with same
heating rates.

Heating rate and temperature not only impact the yield but also greatly influence
the chemical properties of biochar. pH values of the biochar also increase with the
increase in temperature (Liang et al., 2006; Inyang et al., 2010; Angın, 2013) due to the
separation of alkali salts separate from organic materials (Yuan et al., 2012). Increase in
carbon content of biochar also results with an increase in pyrolysis temperature, while the
hydrogen and oxygen content reduces in relation to carbon content (Chun et al., 2004;
Chen et al., 2011).

On the other side, the porosity of biochar increases due to increase in temperature.
When the temperature rises, dehydroxylation of water molecules occurred very speedily
and that results in the porous structure of biochar (Demirbas et al., 2006). Cation
exchange capacity is also interlined with the temperature at which the biochar is
produced, that is, cation exchange capacity increases significantly with the increase in
the temperature (Lehmann, 2007).

Owing to various properties of biochar like high surface charge density and high
surface area, it's being exclusively used in soil quality enhancement applications (Liang
et al., 2006). The ability of the soil to reserve plant available water and retain nutrients is
increased with the use of biochar which minimizes leaching of agricultural chemicals and
nutrients (Glaser et al., 2001; Lehmann et al., 2006; Laird et al., 2010;).

When biomass is harvested, most of the nutrients are removed, but soil biochar
applications recycle those nutrients. Biomass comprises of base cations (primarily K, Mg,
and Ca) which are converted during pyrolysis into carbonates (ash), hydroxides, and
oxides that are blended with the biochar. Mostly biochar act as a liming agent during its
application to the soil because of the existence of these bases. Soil bulk density is
reduced by biochar because it is a low-density material (Laird et al., 2010; Rogovska et
al., 2012) and as a result, it increases soil aeration, root penetration, and water infiltration.
Moreover, there has been seen an increase in the soil aggregate stability when biochar
is applied (Glaser et al., 2002) however, there is as yet no clarity as to this effect
(Brodowski et al., 2006).

Additional advantage of using biochar for soil enrichment is that facilitates

prolonged water retention because of the porous structure (Dugan et al., 2010; Glaser et
al., 2002; Liang et al., 2006; Sohi et al., 2010). This directly cuts the cost involved in the
irrigation by reducing its frequency and intensity. Further, this also helps in maintaining
the soil pH which directly impacts soil fertility and nutrient availability. Application of
biochar e.g.; rice husk and maize cob reported to enhances soil pH by 20% and 23% on
average, respectively which is as good as caused by the lime use of fertilizer (Nurhidayati
and Mariati, 2014).

Zhang et al. (2009), suggested that the increase in the soil pH suppresses the
activity of the enzyme(s) involved in the conversions of nitrite to nitrous oxide thereby
increasing nitrogen availability in the soil. The application of biochar in soil resulted, in
increased CEC which in turn reduced the loss of nutrients through leaching (Lehmann,
2007). Since the biochar possesses high CEC it has the capacity to hold the nutrient
present in the soil, therefore it increases the nutrient use efficiency of the soil which
otherwise get washed away due to precipitation. Fifty percent of carbon in the biomass
retained in its structure during the conversion of biomass into biochar which is more stable
in nature as compared to the biomass which on degradation releases the carbon back
into the atmosphere. Thus, biochar production and its application to soil, later on, create
a carbon sink (Kwapinski et al., 2010).

According to Kimetu et al. (2008), biochar addition affects the yield positively who
led to the observation that the non-nutrient improvement to soil function partially inspired
the effects. In Amazonia after clearance of forests, due to biochar enhanced fertilizer use
efficacy was light lighted, which maintain the crop yields, basically a restoration of
terrapreta (Steiner et al., 2008). The sustained and better crop yield was observed in
plots having biochar and NPK as compared to control plots. As in semi-arid soils of
Australia, results showed that application of biochar mixed with fertilizers have better
plant growth in pot trials (Chan et al., 2008), similarly in Indonesia peanut and maize crop
yields were improved, when combination of nitrogen fertilizer and bark charcoal was
applied (Yamato et al., 2006).

The presence of nutrients in soil and their management estimated the response of
crop to biochar was supported through rice experiment (Asai et al., 2009), thereby
suggesting that statistically higher first-season performance was recorded only when in
low yielding crop variety, biochar was applied combined with N fertilizer; based on a high-
yielding (and thus N-demanding) variety, there was a lower yield compared with the
control in a similar assessment. Nevertheless, no appealing yield response is obtained
according to some studies, for instance, Australian study at wheat at low rates of
application (Blackwell et al., 2007).

Many positive results of biochar have been obtained on crop productivity and soil
quality, derived from researches conducted on greatly degraded tropical soils. For
example, in a charcoal kiln sites increase in both biomass yield (44 percent) and corn
grain (91 percent) were noticed relative to control Ghana sites (Oguntunde et al., 2004).
Major et al. (2009), obtained the same results and observed 189% increment in
aboveground biomass after application of 23 t/acre of biochar (measured five months
after) to Typic Haplustox in Columbia. Thus, the effect of biochar application on plants
nutrient uptake and their availability is not completely clear as few reports showed that
nutrient uptake is increasing while in others decreasing. According to Lehmann (2007),
biochar addition limits the nitrogen availability in soils which are nitrogen deficient
because of biochar high C/N ratio which decreases crop productivity temporarily. This
holds true for the biochar having high volatile matter content and low fixed carbon which
is biologically available.

Some studies had shown that foliar application of nitrogen concentrations have
reduced when biochar was put to soils. For instance, seventy percent increase in cowpea
biomass production was observed by Lehmann and colleagues (2003), on highly
weathered soil when mixed with ten percent (w/w) biochar in comparison with control.
This research observed significant increase in CEC (from 54.0 to 285.5 mmol kg-1);
potassium content (from 28.1 to 258.3 mmol/kg); nitrogen content (from 3.2 to 4.0 g/kg);
carbon content (from 40.0 to 159.4 g/kg); and soil pH (from 5.1 to 5.9).

In the applied biochar, according to the authors, a portion of the carbon was
available for microbial decomposition, which leads to immobilization of nitrogen in soils
which had limited portion of nitrogen. Soils were amended by application of phosphorus
and nitrogen fertilizers on biochar, by contrast, bringing an important yield feedback that
could be ascribed to lead towards more effective application of applied nutrients by
reducing leaching (Ahmad et al., 2014; Xie et al., 2015). Similar positive relations
persisting between fertilizers and biochar additions have been observed by several other
studies (Chan et al., 2008; Kimetu et al., 2008; Zwieten et al., 2010).

Li et al. (2007), reported that field experiments of four biochar (organic /inorganic)
pyrolyzed fertilizers by several bio-wastes as compared to conventional chemical fertilizer
in rice, substantiated that at a much lower rate of N input, biochar compound fertilizer
application reduced greenhouse gases emission and improved nitrogen use efficiency in
rice production, thereby ensuring high rice productivity. For organic/inorganic compound
fertilizer, the application of biowaste biochar can be an alternative to achieve low carbon
intensity and high productivity along with preserving nitrogen fertilizer use in rice sector
of Chinese agriculture (Qian et al., 2014).

As Deenik et al. (2016), conducted three experiments in the greenhouse to assess

the effects of sewage sludge and corn cob biochar on plant growth and soil properties in
an infertile Oxisol with their anaerobically treated counterparts. The greatest
concentration of bioavailable essential nutrients was shown by the anaerobically treated
sewerage sludge biochar, but in the first crop, the treatment only aggravated yields for
the sewage sludge biochar that was without fertilizer. In combination with fertilizer, both
sewage sludge and corncob biochar doubled plant development in comparison with the
control in the first crop cycle, giving no significant outcome for the second and in the third
cycle, more than tripled plant development for the sewage sludge biochar.

A persistent liming effect and high ash material with great nutrient amendment
(particularly P) elaborate the sewage sludge biochar’ benefits in respect of plant growth.
The negative impacts of soil manganese toxicity, as was promised by sewage sludge
biochar, were mitigated and cadmium bioavailability was reduced by sewage sludge,
having no prominent influence upon the bioavailability of other potentially toxic materials
than from the control (Wang et al., 2012; Deenik and Cooney, 2016).