CHAPTER 1: INTRODUCTION – JUSTIFICATION

Agriculture holds a pivotal position in human life and society, and in recent years, there has
been a notable upsurge in agricultural production in tandem with the global population
increase [1]. In the realm of agriculture, both water and fertilizers emerge as vital components
for crop production and with this the control of nutrient and water loss has been considered
as a global challenge for the agricultural sector [2].
Water plays a crucial role as a conduit for nutrient transport from the soil to the plant roots.
Nonetheless, in numerous regions, water scarcity and drought pose substantial obstacles, as
there is insufficient water to satisfies food demands[3]. Additionally, crops are dependent on
nutrients for their growth. Urea fertilizer is the most used due to its high nitrogen content
(about 46%) and low cost (Azeem, KuShaari, Man, Basit & Thanh, 2014). However, due to its
high soluble characteristic, it has shown the greatest potential for losses. Leaching and
flooding are normally considered to be the major N loss pathways [4]. Phosphorus is also an
important fertilizer used to stimulate the growth and development of crops. Generally, only
10– 20% of the conventional phosphorus fertilizer applied to soil is absorbed by crops [4].
The low absorption of fertilizers by the soil prompts a tendency to use excessive amounts,
causing pollution; hence, it has become a worldwide issue. Pollution from agricultural
activities is responsible for the contamination of soils, surface water, groundwater and farm
products, among other undesirable environmental and social effects (Ongley et al., 2010; Sun
et al., 2012). In Ecuador, large quantities of inorganic fertilizer such as urea, ammonium
sulfate, super phosphate and diammonium phosphate are applied as routine agricultural
practice [5]. Due to the indiscriminate use of agrochemicals, soils deteriorate and lose their
nutrients (FAO, 2015), additionally, it has the potential to adversely impact the quality of
water, which results in a depletion of natural resources and increasing costs for farmers, since
over-application does not guarantee a proportional increase in productivity. In this context,
it is crucial to promote more balanced and sustainable agricultural practices that minimize
the adverse impacts associated with the overuse of fertilizers.

A solution to overcome the low efficiency in nutrient absorption from fertilizers and the
scarcity of water for irrigation would be the synthesis and evaluation of a biodegradable
chitosan-hydrogel for the controlled and slow release of urea and phosphates over a long
period of time that ensures that the amount of nutrients present in the soil is adequate to
meet the optimal growth needs of crops, thus reducing environmental impact and nutrient
loss through leaching, volatilization and degradation. In addition, hydrogels are extremely
hydrophilic polymers that have the characteristic of absorbing large amounts of water, as an
agricultural input, and make it available to the plants over a long period [6].

The chitosan-hydrogel modification by emulsification using glutaraldehyde as a crosslinker to

form urea-loaded chitosan hydrogels was carried to obtain a material with better properties.
The use of dialdehydes and chitosan (CH) in the creation of hydrogels has been investigated
for the purpose of controlled release of fertilizers into the soil. CH possesses unique
characteristics, including: biocompatibility, biodegradability, mucoadhesion, and broad
antibacterial activity, [7]. By combining chitosan (CH) with different compounds, mechanical
properties and porous structures that allow free diffusion of nutrients can be improved. The
use of dialdehyde resulted in hydrogels with excellent mechanical properties, and an
exceptional degree of swelling. In situ hydrogelation was chosen as the method of urea
encapsulation, targeting its fine dispersion in hydrogels, with potential for slowing release.
In this thesis project, is to demonstrated the effectiveness of urea-loaded chitosan hydrogels
for the controlled release of fertilizers. This will be achieved by creating various materials
containing different proportions of cross-linking agents and additives, such as glutaraldehyde,
hydroxypropyl cellulose and carboxymethylcellulose-Ca (PO ) .
3 4 2

1.1 PROBLEM STATEMENT

Across the globe, agriculture holds a central position, and as agricultural production continues
to rise, the proper utilization of fertilizers and water remains critical for effective crop
cultivation. However, the challenges of fertilizer loss and excessive application not only
imperil crop yields but also pose environmental concerns. To address these challenges, there
is a need to explore sustainable solutions.

The development of a chitosan-hydrogel offers an environmentally friendly and economically

viable means to enhance nutrient retention and water management in agricultural practices.
Additionally, the abundance of shrimp shell waste, approximately 72,000 tonnes generated
annually in Ecuador [8], presents an opportunity to harness chitosan, a component of these
shells, for innovative and cost-effective applications in agriculture.
This thesis intends to explore the practicality and advantages of introducing a bio-hydrogel in
Ecuador's agriculture to facilitate controlled release of fertilizers and enhance water
retention.

1.2 OBJECTIVES
1.2.1 General Objectives
Synthesize and characterize a chitosan-based hydrogel designed for controlled release of urea
and phosphorus in soil, while simultaneously assessing its capacity for water retention.

1.2.2 Specific Objectives

CHAPTER 2: THEORETICAL FOUNDATIONS

2.1 Fertilizers
8
CHAPTER 3: METHODOLOGY
3.1 Materials and Reagents
The reagents used in this work were supplied from

• Carboxymethyl cellulose (CMC), Urea, Glutaraldehyde, Hydroxypropyl cellulose (HPC),

Phosphoric acid (H3PO4), calcium carbonate (CaCO3), Chitosan (Ch)

Furthermore, in the execution of the characterization methods, this study utilized the
subsequent laboratory apparatus:
3.2 Hydrogel synthesis
For the synthesis of the hydrogel, the method by Iftime [9] was adapted and modified. A series
of essential solutions were prepared. These included a 2% chitosan solution, dissolved in a 2%
acetic aqueous solution, serving as the foundational component. Additionally, a 2%
Hydroxypropyl cellulose solution was crafted to complement the chitosan matrix. To facilitate
the crosslinking process, a 10% glutaraldehyde solution was prepared. Furthermore, a unique
solution comprising urea and glutaraldehyde at a 10% concentration was created, with the
urea content carefully varied at 50, 25, and 75 mg. To enhance the hydrogel's performance,
a 2% Carboxymethyl cellulose solution was prepared with calcium nanoparticles. The
preparation of calcium nanoparticles, involved H3PO4 and calcium carbonate. This process
was ejecuted with the gradual addition of calcium carbonate, followed by the introduction of
acid after 12 hours, culminating in a week-long stirring process. The result was a 1% CMC-
Ca3(PO4)2 solution.
The formulation of the hydrogels involved the sequential addition of the previously prepared
solutions in specific quantities. The order of introduction was as follows:
1. Chitosan (Ch),
2. Hydroxypropyl cellulose (HPC),
3. Urea + glutaraldehyde solution
4. CMC-Ca3(PO4)2 solution.

It is crucial to emphasize that, following the addition of solutions 2, 3, and 4, it is essential to

stir for 5 minutes to each addition to ensure proper homogenization of the resulting mixture.
After achieving homogenization, the solutions were poured into approximately 20 ml plastic
containers and allowed to air dry in a cool environment for one week. Once the hydrogels
were completely dried, they were then subjected to a freezing process. The nomenclature
and detailed composition of the resulting hydrogels are comprehensively documented in
Table.
 Nomencla Muestra Chitos HPC Urea(m Urea+ CMC- Método de
ture an (ml) g) Glutaralde Ca3(PO4) secado
(2%) (2%) hido 2 (ml)
(ml) (10%) (ml) (1%)
ChL 1 20 2.5 50 2 5 Ambiente
ChH 1 20 2.5 50 2 5 Ambiente
ChL 2 20 2.5 25 2 5 refri/ambiente
ChH 2 20 2.5 25 2 5 refri/ambiente

ChL 3 20 2.5 75 2 5 refri/ambiente

ChH 3 20 2.5 75 2 5 refri/ambiente

ChL 1 20 5 50 2 10 refri/ambiente

ChH 1 20 5 50 2 10 refri/ambiente

ChL 2 20 5 25 2 10 refri/ambiente

ChH 2 20 5 25 2 10 refri/ambiente

ChL 3 20 5 75 2 10 refri/ambiente

ChH 3 20 5 75 2 10 refri/ambiente

ChL 1 20 2.5 50 2 15 refri/ambiente

ChH 1 20 2.5 50 2 15 refri/ambiente

ChL 2 20 2.5 25 2 15 refri/ambiente

ChH 2 20 2.5 25 2 15 refri/ambiente

ChL 3 20 2.5 75 2 15 refri/ambiente

ChH 3 20 2.5 75 2 15 refri/ambiente

3.3 Hydrogel characterization

3.4 Swelling Of Chitosan Hydrogel

The hydrogel swelling test was carried out to evaluate how much the material expands or uptakes
water. In this test, a pre-weighed small hydrogel sample is immersed in distilled water, and its capacity
to absorb and retain the liquid is assessed over a period of time. The moisture content of the hydrogel
was measured with equation x at time intervals. Dried hydrogel samples were weighed initially (Wd)
and then at different times during swelling (Ws) in distilled water.
Porcent mouisture= Ws-Wd/Wd *100

3.5 Water -Holding capacity (WH) and Water -retention ratio (WR) of hydrogel

The WH and WR study for the hydrogel is to show the efficiency of the prepared hydrogel to hold
water in soil [10-11-12]. For the WH study, certain weights of the soil ( 4 x 3.00 g) were prepared. A
hydrogel with a weigh of 0.05 g were mixed with each of the soil samples to obtain a 2% (w/w)
samples. Two of the soil samples was kept blank (no hydrogel). The soil samples were placed into
plastic pipes of 10 ml supported in 50ml Erlenmeyer flasks., the bottom of each pipe was sealed by
filter paper and weighed. After that, 2 ml of water was slowly poured from the top of the pipe. The
erlenmeyer was weighed again when no water was dripping and the WH % was calculated using the
following equation.

The obtained wet samples from WH study were used for WR study. The samples were kept at room
temperature and weighed for 1 month. From the equation below, WR % was determined:

%WR= (WT-W1)/(W2-W1) *100

where the W1 is the weight of each sample without water, W2 is the weight of each sample after
water stop seeping, and the Wt refers to the weight of sample after specified time intervals.

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