ZINC REMOVAL BY IRON NANOPARTICLE SYNTHESIZED USING

MANGIFERA INDICA SEED KERNEL AS CAPPING AGENT

A Thesis Presented to
The Faculty of the College of Engineering and Technology
University of Saint La Salle
Bacolod City

In Partial Fulfilment
of the Requirements for the Degree
Bachelor of Science in Chemical Engineering

SHAUN M. BAUTISTA
EMERALD GRACE D. PARCON
ERASMO P. TAN JR.
JOSHEIL G. VILLANUEVA

October 18, 2019

 2

APPROVAL SHEET

This thesis entitled “ZINC REMOVAL BY IRON NANOPARTICLE

SYNTHESIZED USING MANGIFERA INDICA SEED KERNEL AS CAPPING
AGENT” presented by SHAUN M. BAUTISTA, EMERALD GRACE D. PARCON,
ERASMO P. TAN JR. and JOSHEIL G. VILLANUEVA, in partial fulfilment of the
requirements for the degree Bachelor of Science in Chemical Engineering of the
University of St. La Salle has been evaluated and approved by the panel of evaluators.

PANEL OF EVALUATORS

FELIX R. QUERUBIN, RChE, MEE

Chair

MARY ANN T. PANDAN, RChE, PhD

Member

MARIE THERESE BERNADETTE F. SALES, RChE, PhD

Member

MA. JUNALLIE F. POMPERADA, RChE, PhD

Adviser
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ACKNOWLEDGEMENT

We would like to express our sincerest and deepest gratitude to the people who have
journeyed with us as we finish this paper. It could not have been completed without the
help of the following people

To our family and loved ones, our inspirations, for supporting us and
understanding us when we go home late at night just to finish this study.

To our beloved thesis adviser, Ma. Junallie F. Pomperada, PhD, for her
immense knowledge, guidance and motivation which prepared us to be in our best
always.

To our research professor, Rendell C. Barcimo, MEE, for being patient in

correcting our papers and as being our second thesis adviser.

To the members of the panel, Felix R. Querubin, MEE, Mary Ann T. Pandan,
RChE, PhD and Marie Therese Bernadette F. Sales, RChE, PhD for the time and
effort in giving comments, knowledge and constructive criticism that have moulded the
content of this study.

To ADMATEL, for their time in accommodating us for the analysis of our

sample and for their fast response to our queries about the result.

To Miss Jennibeth Alojado and Miss Checkee Ordon of the Chemical

Engineering and Science Laboratory, for always being patient with us when we request to
use the equipment and apparatuses in the laboratory.

To our friends and classmates, ENCH5 Batch 2020, for all the help and words of
encouragement.

Lastly, to our dear Lord Jesus Christ, for giving us wisdom, strength and
knowledge to finish this paper.
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TABLE OF CONTENTS

Page
TITLE PAGE i
APPROVAL SHEET ii
ACKNOWLEDGEMENT iii
TABLE OF CONTENTS iv
LIST OF TABLES v
LIST OF FIGURES vi
LIST OF EQUATIONS vii
ABSTRACT viii
INTRODUCTION 1
Background of the Study 1
Statement of the Problem 5
Scope and Limitations
6
Significance of the Study 7
Definition of Terms 9
Review of Related Literature 10
MATERIALS AND METHODS 21
Research Design 21
Research Methodology 22
Statistical Treatment 25
RESULTS AND DISCUSSION 26
CONCLUSION 37
REFERENCES 39
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APPENDICES 45
Appendix A: Documentation of the Research Process 45
Appendix B: Result of FESEM Analysis 49
Appendix C: Statistical Analysis and Calculations 53
Appendix D: Grammarian’s Certification 68
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LIST OF TABLES

Table Page
1. Total Phenolic Content of Various Plants 15

2. Particle Size of Iron Nanoparticles using Field Emission Scanning 30

Electron Microscopy (FESEM), analyzed using ImageJ Application

3. F-Test for the Determination of the Variances of the Percent Removal 35

4. t-Test result for the Percent Removal of Zinc with and without FeNPs 35
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LIST OF FIGURES

Figure Page
1. Tube A - Ferric Chloride, Tube B - Mango Leaf Extract, Tube 17
C - Iron Nanoparticle Synthesized Solution

2. FESEM of Magnetite Nanoparticle 18

3. Schematic Diagram of the Experimental Procedure 22

4. Tube A - 0.1 M Ferric Chloride, Tube B - Mangifera indica seed 27

kernel extract, Tube C - Iron Nanoparticle Synthesized Solution

5. FESEM Image of the Synthesized Iron Nanoparticles 29

6. Clustered Bar for Percent Removal of Zinc at various pH and 32

Constant Contact Time of 5 minutes

7. Clustered Bar for Percent Removal of Zinc at various Contact Time 33

and Constant Contact pH of 6

8. Percentage Removal Comparison between using Iron Nanoparticle 34

at Optimum Contact time and pH with and without Iron Nanoparticle

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LIST OF EQUATIONS

Equation Page
1. Area of Nanoparticle 20

2. Percent Yield of Iron Nanoparticles 24

3. Percent Removal of Zinc 25

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ABSTRACT

Presence of heavy metals in landfill leachate poses a risk to the environment especially in
unlined landfills where infiltration of leachate into ground water might occur. The recent
increase in the disposal of electronic devices raises the question on the presence of Zinc
in disposal sites, since exposure to this heavy metal causes adverse health effect.
Recently, studies on nanoparticles for wastewater treatment have gained attention due to
their excellent properties which makes it effective for treatment of complex wastewater
like landfill leachate. In this study, iron nanoparticles (FeNPs) were synthesized using the
phenolic compound extracted from Mangifera indica seed kernel as the capping agent and
utilized in the removal of Zinc in synthetic leachate wastewater. FeNPs formed where
characterized using Field Emission Scanning Electron Microscopy (FESEM). Physical
and chemical properties of the sample confirmed the presence of iron nanoparticle
exhibiting the following results: jet black in color, insoluble in water at room
temperature, and showed attraction to magnet. Photomicrographs and FESEM analysis
showed that FeNPs produced were quasi spherical in shape with an average diameter of
32.503 nanometres and with mean surface area of 3318.849 square nanometres analysed
using ImageJ software. In the removal of Zinc from the synthetic leachate wastewater
using EDTA titration, it showed that the highest percent removal was attained at a pH of
6 and at a contact time of 5 minutes. Based on the results of the statistical analysis, it
proved that the iron nanoparticle has significantly reduced the amount of Zinc in the
leachate wastewater resulting a percent removal of 95.07% as compared to the 7.17%
removal without iron nanoparticle. Further experiments could be done by using a sand
filter and the use of UV-Vis Spectroscopy as an alternative in determining the removal
efficiency of Zinc in the leachate wastewater.
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INTRODUCTION

Background of the Study

Landfilling is the primary option for waste disposal all over the world. According

to Soumyadeep (2014), most of the landfill sites across the world are too old and are not

engineered correctly to prevent contamination of the underlying soil and groundwater by

the toxic leachate. Moreover, according to Encyclopedia of Ecology (2008), landfill

leachate is formed when rainwater infiltrates and percolates through the degrading waste.

Landfill leachate is characterized by high organic and inorganic pollutant concentrations

and is extremely toxic to the environment. The significant impacts of landfill

leachate could be eutrophication of aquatic systems and has toxic effects on fauna

(Stefanakis, 2014).

The leachate problem is worsened by the fact that many landfills lack an

appropriate bottom liner or collection system, increasing the possibility of infiltration of

leachate through the landfill layers to contaminate groundwater. The presence of heavy

metals in landfill leachate poses a risk to the environment especially in unlined landfills

where dissipation of leachate into ground water might occur. There is a growing concern

regarding the build-up of heavy metals in soil and groundwater. Different kinds of wastes
 11

are responsible for the presence of heavy metals in the landfills such as electronic waste,

painting waste and used batteries which increase heavy metals content in landfills (Al

Raisi et al., 2014).The main threats to human health are associated with the exposure to

heavy metals like lead, cadmium, zinc, manganese, copper, nickel, chromium, mercury

and arsenic (Br. Med, 2003). Even though adverse health effect due to heavy metals is

known, still exposure continues in most of the developing countries (Tchounwou et al.,

2014).

The recent increase in use and disposal of electronic devices like cell phones and

computers raise the question about the quantity of metals they contain in waste disposal

sites and their fate in the environment especially because such devices mainly contain

lead, cadmium, mercury, arsenic, copper, zinc and others (Al Raisi et al., 2014).

Nowadays, nanotechnology had gained its reputation because of its various

applications. According to Tiwari et al. (2008), it offers the possibility of an efficient

removal of pollutants. Moreover, it is being used for detection and removal of chemical

and biological substances including heavy metals such as zinc.

Nanoparticles are typically defined as materials smaller than 100 nm in at least

one dimension scale which result in larger specific surface area, higher surface activity

and active center that make it possible and effective for treatment process of complex

wastewater like landfill leachate (Andas et al., 2015). Nanoparticles due to small size,

high surface area, crystal form, unique network order, and highly reactivity can be used

for purification and treatment of pollutants. Small size of iron nanoparticles makes easy

and effective subsurface distribution,while their large cross-section makes high reactivity
 12

and rapid destruction of the pollutants. There are many reports about the use of

nanoparticles as a purification process for removal pollutants from the environment.

Researches indicate that nanoparticles of iron can act as a reducing agent and catalyst in

detoxification of a large number of pollutants in the environment, such as organic

pesticides, Trinitrotoluene (TNT), heavy metals, nitrates, and polychlorinated biphenyls

(PCBs).

In recent years, iron nanoparticle has attracted a great deal of attention due to their

efficiency in removal of different types of contaminants from aqueous solutions

(Fazlzadeh et al., 2017). These iron nano particle can be produced in various ways such

as the traditional synthesis of using a variety of organic solvents and reducing agents like

sodium borohydride (NaBH4). However, these reducing agents pose great risks to the

environment and also creates harmful byproducts to human health. One of the alternative

methods to this traditional synthesis is the use of plant extracts with high phenolic content

which is cost effective, simple and environmentally friendly (Sunardi et al.,2017).

Mango (Mangifera indica L.) is the most important tropical fruit crop after

bananas and plantains (Araya, 2015). It has been grown and cultivated in over 100

countries with tropical or subtropical climate. About 1-2% of mango production is

processed to make products such as juices, concentrates, jams, dried fruits etc and is often

consumed fresh. Mango processing yields about 40-50% of byproducts. These

byproducts include mango seed which represent from 20-60% of the whole fruit and

mango seed kernels which represent from 45-75% of the whole seed (Suska, 2019). The

residue of mango processing industries, the seed in particular, is not being utilized to its

full commercial potential (Kasas et al).

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Since the major use of mango is the consumption of the sour-sweet pulp being

eaten raw or for different kinds of food preparation and processes, the seed and the skin

are typically treated as waste and immediately disposed without further utilization.

However, in recent years, efforts to find ways in utilizing the wastes have been made.

Research shows that mango seed kernel can be used for the extraction of edible oils. It

also has a potential antioxidant properties and high phenolic content of 16.93 mg/g

(Kasas et al). With the antioxidant or reducing properties of some plant extracts, they are

usually responsible for the reduction of metal compounds into their respective

nanoparticles (Dhuper, 2012).

A study of the synthesis of iron nanoparticles from the leaf extract of Mangifera

indica of Dhuper and his team showed a successful reduction of iron (III) to zero valent

iron nanoparticle. However, it is not considered to be one of the efforts in utilizing mango

wastes since the leaves are needed for the photosynthesis of the plant. Using the mango

seed kernel for the synthesis of iron nanoparticle does not only add to the pool of waste

utilization but also gives an alternative to the traditional synthesis that uses reducing

agents that causes harmful by-products to human.

In general, metal based nanoparticle become of particular interest among the

researcher. Thus this study wasconducted by the researchers to provide a way of treating

the leachate wastewater that might contaminate our ground water source and water cycle

by using phenolic compound that will be extracted from the Mangifera indica seed

kernel.
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Statement of the Problem

The study aimed to synthesize iron nanoparticle from FeCl3 using Mangifera

indica seed kernel as capping agent, for leachate treatment. Specifically, this study sought

to answer the following queries:

1. What will be the percent yield of iron nanoparticles from FeCl3 using

Mangifera indica seed kernel as the capping agent?

2. What are the characteristics of the synthesized iron nanoparticles from FeCl3

using Mangifera indica seed kernel as the capping agent in terms of the

following:

a. Specific Surface Area;

b. Average Primary Particle Size;

c. Particle Shape;

d. Color; and

e. Solubility in water?

3. Which pH value will yield the highest zinc removal using the synthesized iron

nanoparticle at a constant contact time of 5 minutes?

 15

a. pH=5

b. pH=6

c. pH=7

4. Which contact time will yield the highest zinc removal using the synthesized

iron nanoparticle at a constant pH value that yields the highest zinc removal?

a. 4 minutes

b. 5 minutes

c. 6 minutes

5. What is the percent removal of Zn in the synthetic landfill leachate using the

iron nanoparticle at contact time and pH value that yields the highest removal of

zinc (II)?

6. Is there a significant difference on the removal of zinc (II) from the synthetic

leachate wastewater between with and without Mangifera indica synthesized iron

nanoparticle?

Scope and Limitations

This study focused on investigating the different characteristics of iron

nanoparticles, namely: the zero valent iron, iron (II) oxide, and iron (III) oxide derived

from Mangifera indica seed kernel and its removal of harmful zinc (II) from the synthetic

leachate wastewater. The Mangifera indica seed kernel was collected from the local

market, and the specie of mango was not determined by the researchers. The synthesis of
 16

iron nanoparticles was conducted at the Chemical Engineering Laboratory of University

of St. La Salle. Field Emission Scanning Electron Microscopy (FESEM) is the test to be

used to confirm the presence of iron nanoparticles which was conducted at the DOST-

ITDI (ADMATEL) in Bicutan, Taguig City. The physical and chemical characteristics of

the synthesized iron nanoparticles such as the specific surface area, average particle size,

particle shape, and solubility in water at room temperature was evaluated. The leachate

treatment process included the preparation of synthetic leachate wastewater samples with

zinc (II) at a room temperature of 25 degree Celsius. The treatment of synthetic leachate

wastewater using the synthesized iron nanoparticle was done using eighteen 18 trials.

Monitoring and detection of zinc (II) levels was determined using EDTA Titration

Method at the Chemical Engineering Department of University of St. La Salle. Moreover,

this study focused on the percentage removal of zinc using the synthesized iron

nanoparticle from the phenolic compound of Mangifera indica seed kernel and the

determination of the optimum pH value and contact time.

Significance of the Study

The results of this study could be beneficial to the following sectors:

Environmental sector. This study may be considered to be an environment-

friendly solution to landfill leachate by designing a treatment that will use iron

nanoparticles that will be synthesized from the reaction of phenolic compound extracted

from Mangiferaindica seed kernel with FeCl3. This study will not use toxic chemicals in

the synthesis of nanoparticle and also it would lessen the production of production of

waste, resulting to lesser environmental impact.

Mango farmers. This study may provide mango farmers an additional source of
 17

income. This may also, give them knowledge and awareness about the viability of the

other uses of Mangifera indica seed kernel which they have already considered a waste.

Local government agencies. This study may help the local government agencies

in campaigning for both waste management and utilization by using the mango seed

kernel. This study may also implement a new process of leachate treatment that will bring

out a low-cost, culturally acceptable, environment-friendly, and appropriate leachate

treatment and sanitation technology. Moreover, this may help manage and sustain landfill

leachate generation that can help lower the significant threat to surface water and

groundwater in different communities, nationwide.

Community. This study may provide a big help in the community by reducing

health issues in communities from poor management of wastewater. It may reduce the

groundwater and surface water pollution by improving the sanitation, and by treating the

landfill leachate before it will be disposed to bodies of water via filters with mango seed

kernel-synthesized iron nanoparticles in an economical, effective, and environment-

friendly process.

Industries. This study may help various industries that uses mango as their raw

material in production of goods. Mangifera indica seed kernel is considered to be a waste

in processing industries and thus, this study may provide them with additional knowledge

on the further uses of seed kernel. This may provide them extra income and may help in

the waste disposal of these by products.

Future researchers. The information presented in this study may provide

significant data for future researchers in formulating another novel strategy to address

problems caused by leachate. The results of this study can be a basis for further
 18

researches to increase the efficiency and further optimization by improving existing

methodologies related to this study.

Definition of Terms

For further understanding of the study, the following terms are defined;

Iron Nanoparticle. It refers to nanoscale iron particles which will be synthesized

using phenolic compounds from Mangifera indica Seed Kernel and Ferric Chloride

solution. It will be used to remove Zinc from wastewater.

Landfill Leachate. It Landfill leachate is consist of many different organic and

inorganic compounds that are either dissolved or suspended in the wastewater including

Zinc.

Mangifera Indica Seed Kernel. It refers to the source of phenolic compound

Nanoparticle – particulates with diameter between 1 to 100 nanometers

Phenolic Compound. It refers to the reducing agent that will be used in this study

to synthesize iron nanoparticles. It will be extracted from Mangifera indica Seed Kernel.

Synthetic Leachate Wastewater. It refers to the leachate that the researchers are

going to treat using the iron nanoparticle.

Zinc. It refers to the component of leachate wastewater which will be filtered out.
 19

Review of Related Literature

The review includes the conceptualization and research literature which are

related to the study.

Landfill Leachate.

Landfills are an indispensable part of the everyday living, they may present long

term threats to groundwater and also to surface waters that are hydrologically connected

(Subramani et al., 2015). According to Megan Lynch, Landfill leachate can be

categorized into four groups: Dissolved organic content, inorganic macro component,

heavy metals, and xenobiotic organic compounds.

Heavy metals pollution has raised serious environmental concerns worldwide

because of the bioaccumulation of living organisms which pose long term risk to the

earth’s ecosystem. The main flows of heavy metals to the environment are from

industrial and municipal wastes (Charusiri et al., 2008).

According to Christensen (2001), landfill leachate is generally found to have a pH

of 4.5 to 9. Moreover, a study on the Environmental Sampling and Analysis for Metals by

Csuros M. and Csuros C. shows that common heavy metals in leachate has a

corresponding mean values of concentration; copper (5 ppm), zinc (50 ppm), lead (0.30

ppm), and mercury (60 ppb).

Zinc in landfill leachate and its effect to ground water.

 20

Zinc was considered to be one of the most important heavy metals used in various

industrial processes for the production of corrosion-resistant alloys and brass, and for

galvanizing steel and iron products. On the other hand, zinc was considered to be toxic

even at very low concentrations that result from domestic and industrial discharges in the

water environment that result to one of environmental pollutants. Moreover, urban runoff,

mine drainage, and municipal and industrial effluents made considerable contribution to

the zinc load of surface water (New Technologies of Zinc Removal in Wastewater, n.d).

According to the World Health Organization (WHO) in 2003, the levels of zinc in

surface water and groundwater normally do not exceed 0.01mg/litre and 0.05 mg/litre,

respectively. A study conducted by Adarna and Castañares in 2013 on the sediments of

Butuanon River, Cebu, Philippines showed that the upper, middle, and downstream

sampling sites of the river is heavily polluted with zinc and copper based on US

Environmental Protection Agency sediment quality guidelines.  Another study conducted

by Adarna et al. (2011) showed that lead and zinc in guppy fish in the Butuanon River,

Cebu, Philippines exceeded the Food and Agriculture Organization or World Health

Organization (2011) acceptable limit of 30 and 50 ppm, respectively.

Nanoparticles and their wide range of advantages.

Nanotechnology has emerged as a state-of-the-art and cutting edge technology

with various applications in a wide array of fields in recent years. Nanotechnology can be

defined as the manipulation of matter through certain chemical or physical processes to

create materials with specific properties, which can be used in particular applications.

Among broad area comprising nanomaterials, nanotools, and nanodevices; nanoparticles

 21

have become the main focus of researchers because of their ease in production and

manipulation (Herlekar et al., 2014). Nanoparticles possess unique physical and chemical

properties due to their high surface area and nanoscale size. Due to these characteristics,

they are suitable candidates for various commercial and domestic applications, which

include catalysis, imaging, medical applications, energy-based research, and

environmental applications (Khan et al., 2017).

Iron nanoparticles: its properties and some applications.

Iron nano-materials are significantly important for abatement of environmental

pollution such as degradation of organic dyes, chlorinated organic pollutants, and heavy

metals removal (Saif et al., 2016). It is said that iron nanoparticles, namely: nano zero-

valent iron (nZVI), magnetite (Fe3O4) and maghemite (Fe2O3) are widely used in the field

of environmental remediation. This is mainly due to their very efficient pollutant removal

capacity, fast reaction kinetics and most importantly due to magnetism which enables its

easy recovery (Tang & Lo, 2013). In general, nanomaterials are materials whose external

dimensions are in the nanoscale (usually 1–100 nm) or those who have a nanoscale

internal structure/surface. Under the nanoscale, nanomaterials often exhibit some special

properties, such as a surface effect, small size effect, quantum effect, and macro quantum

tunnel effect. These properties contribute to their extraordinary adsorption capacity and

reactivity, both of which are favorable for the removal of heavy metal ions (Bi et al.,

2019). They have attracted so much attention not only because of their magnetic

properties but also because they have been shown to be associated with low toxicity in

the human body. Studies have shown that these particles are efficient adsorbents because

they combine magnetic separation with ionic exchange capacity for heavy metals
 22

removal. Also, magnetic properties of iron oxide nanoparticles allow, for simple

dispersion, the removal from an aqueous system. Specifically, magnetite (Fe3O4) and

maghemite (γ-Fe2O3) nanoparticles have been used in the adsorption of arsenic and

chromium due to their surface properties (Velez, 2016).

Conventional nanoparticle synthesis methods like attrition and pyrolysis have

drawbacks such as defective surface formation, low production rate, high cost of

manufacturing, and large energy requirement, and chemical and physical processes have

of hazardous byproducts, and contamination from precursor chemicals. Hence, there is a

growing need to develop clean, nontoxic, and environment-friendly procedures for

nanoparticle synthesis (Herlekar et al., 2014). Thus iron nanoparticles have promising

advantages that can combat environmental pollution. The interest in nanoscale zero-

valent iron in environmental remediation is increasing due to the reactivity of nanoscale

iron having a large surface area to volume. The production of iron nanomaterials, such as

metallic iron and oxide of iron via a more convenient greener route, is a great step

forward in the development of nanomaterials (Saif et al., 2016). Furthermore because of

the simple synthesis and natural occurrence of iron nanoparticles, the ZVI is considered

to be a low cost material for the adsorption of noxious metals. ZVI is an eco-friendly

material which possesses less chance of secondary contamination when used in

contaminated environment (Anjum et al., 2016).

Synthesis of Iron nanoparticles (FeNPS) using plant extracts.

FeNPs of various dimensions and morphologies have been manufactured using

aqueous tea extracts. According to previous research, the polyphenol compounds and the
 23

water soluble constituents are mainly accountable for the reduction of metal ions and

stabilization of the nanoparticles, respectively. During the synthesis, reducing agent

converts metal ions to nanometal via reduction process. On the other hand, capping agent

is a compound which helps in the stabilization of nanoparticles as it protects the

agglomeration of nanoparticles from combining themselves. Also, capping agents prevent

the particle from growing beyond the nanometric size of interest (Okoth, 2016). Green

tea-catechins (GTCs) are groups of Polyphenols compounds belonging to the flavonoid

family. They include; (-)-epigallocatechin (EGC), (-)-epigallocatechin-3- gallate

(EGCG), epicatechin (EC), (-)-epicatechin-3- gallate (ECG) and possesses various

biological activities. The synthesized iron nanoparticles using tea extracts were found to

be nontoxic and more effective as a Fenton-like catalyst (Okoth, 2016). The reaction for

the synthesis of iron nanoparticles (FeNPs) is shown below:

nFe3+ + 3(Ar-OH)n -> nFe + 3n(Ar=O) + 3nH+

Mangifera indica Seed Kernel.

Mangifera indica (MI) occupies the second position as a tropical crop with global

production of exceeding 35 million tons. Mango seed kernel represents about 20% of the

whole mango fruit (Abdel-Aty, 2018) and contains a considerable amount of phenolic

about 16.93 mg per g of seed and includes rich levels of health-enhancing compounds

and natural antioxidants (Maisuthisakul, 2018). As seed kernel is not currently utilized

for any commercial purposes, it is discarded as a waste and becomes a source of

pollution. This waste should be treated as a specialized residue due to the high levels of

phenolic compounds and stable fat rich in saturated fatty acids (Maisuthisakul, 2008).
 24

Table 1 shows the total phenolic content of various plants.

Table 1.

Total Phenolic Content of Various Plants

Plant Source Total Phenolic Content Reference

(mg/g)

Mango Kernel Oil 9.87 Kittiphoom and Sutasinee

(2013)
Mango Kernel 16.93 Maisuthisakul (2008)
Chia Oil 3.62 Ullah et al. (2016)
Olein Fraction of Chia Oil 4.25 Ullah et al. (2016)
Stearin Fraction of Chia Oil 2.57 Ullah et al. (2016)
Almond Peel 3.82 Nadeem et al. (2014b)
Moringa Oleifera Oil 7.1 Nadeem et al. (2013)
Sesame Cake 1.84 Nadeem et al. (2014c)
Chia Seed Extract 7.6 Azeem et al. (2015a.b)
Sugarcane Juice 6.19 Ullah et al. (2016)
Date Fruit Extract 5.19 Rahman et al. (2015)
Tamarind Seed 9.45 Soong and Barlow (2006)
Longan Seed 6.26 Soong and Barlow (2006)
Avocado Seed 8.82 Soong and Barlow (2006)
Jackfruit Seed 2.77 Soong and Barlow (2006)
 25

A source from Promising features of mango (Mangifera indica L.) kernel oil: a

review shown in Table 1 concluded that mango kernel has the highest phenolic content

compared to other plant seeds and extracts.

An example of plant extract, green tea extract, in a study of iron nanoparticles

showed that green tea can be a reducing agent for the synthesis of the different

morphology of iron oxide nanoparticles because of its high amount of polyphenols and

other organic groups in it. It has been found out that about 4000 species are present out of

which 1/3rd of the total is polyphenols that help in the reduction of the salt precursors

like FeCl3 to nanoparticles. With the antioxidant and reducing properties of plant extracts

from their high phenolic content, they could be responsible for the reduction of metal

compounds into nanoparticles. Therefore, mango seed kernels being high in phenolic

content, could also be a reducing agent for the synthesis of iron nanoparticles.

A study was conducted at De La Salle University determined that there is

241.0835 mg/g of phenolic that can be extracted from Mangifera indica seed kernel

(Sanchez et al., 2015)

Ferric Chloride and Phenolic Compound.

In the study of Dhuper et al (2012), it was reported that for the synthesis of green

iron nanoparticles using leaf extracts of the plant – Mangifera indica and aqueous Ferric

Chloride (FeCl3) solution led to rapid formation of highly stable, crystalline iron

nanoparticles. The rate of nanoparticle synthesis was very high, which justifies the use of

plants over microorganisms in the biosynthesis of metal nanoparticles through greener

and safer methods.

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Ferric Chloride Test.

In determining the presence of phenols in a sample, ferric chloride test is used.

The classical way of the test was applied by Al-Jumaily et al (2014). An intense green,

purple, blue or black colours in the solution of 5 mL skin grape extract with 1% aqueous

or alcoholic ferric chloride indicates the presence of phenols.

Characterization of iron nanoparticles (iron oxide (II,III) magnetite, nanoscale zero

valent).

Figure 1 shows the mixing of plant extract with 0.1 M FeCl3 solution which

resulted in a reduced black solution. A change in color was obtained by nanoparticle

synthesis, an indication of the formation of iron nanoparticles (Dhuper, 2012). The

natural synthesized magnetite nano-scale crystals possess metallic luster and opaque jet

black color, according to Lee (2007).

Figure 1. Tube A - Ferric Chloride, Tube B

- Mango Leaf Extract, Tube C – Iron

Nanoparticle Synthesized Solution

A FESEM image from Figure 2 shows that iron nanoparticles appear quasi-
 27

spherical with a mean particle size of about 20.5 nm, determined by Image J Software.

The scale bar on the image represents 200 nm, and the field of view is approximately 1.38

µm (Taimoory & Trant, 2017).

Figure 2. FESEM of

magnetite nanoparticle

Another result of FESEM Analysis by Abong et. al (2018), observed that

nanoparticles were quasi spherical in shape, have rough surfaces and are varying in sizes.

The average particle diameter for the synthesized magnetite nanoparticle is 44.2860 nm

that used rice hull extract which falls within the range of nanoparticles being 1-100 nm.

The average surface area in sq. nm is 2060.80735.

It has also been noted that the adsorption capacities of adsorbents rely largely on

the available surface areas, and the increase of the surface area is normally obtained by

the decrease of the particle size of adsorbents. As a result, there is a need to synthesize

such absorbents with proper particle sizes for the removal of heavy metals from industrial

wastewater (Cheng et al., 2012). 

 28

Optimum pH for the removal of zinc (II).

According to the study “Removal of Zinc from Aqueous Solutions by Magnetite

Silica Core-Shell Nanoparticles”, the optimum pH for removal of zinc (II) using

magnetite silica core-shell nanoparticles is 6. (Emadi et al., 2012)

Effect of Contact Time and the Metal Sorption Kinetics.

In the initial 5 minutes, the adsorption of Zn(II) is very rapid so that more than

90% of Zn(II) ions are adsorbed during this period. However, in the interval between 5 to

20 min, the adsorption kinetics slow down and gradually tends to level off. At times

greater than 20 min the adsorption reaches its maximum value and becomes independent

of contact time, illustrating that adsorption equilibrium is achieved.(Emadi et. al, 2012)

Efficiency of Iron in removal of zinc.

Based on the study entitled “The Removal of heavy metals from wastewater using

magnetic nanocomposites: Analysis of the experimental conditions”, the efficiency of

iron nanoparticle in the removal of zinc (II) in wastewater has an absorption amount of

70 – 87 mg/g (Horst M., 2015).

Techniques for the monitoring and detection of zinc (II).

According to Professor Cindy Mehlenbacher from Mohawk College Chemical,

Environmental, and Biotechnology Department, EDTA has the ability to “wrap” itself

around positive metal ions in water solution. This process is called chelation or complex

formation. Using this property, zinc content can be monitored using EDTA titration with

xylenol orange as the indicator. Xylenol orange is red when complexed with zinc and it is
 29

yellow when it has been displaced from the Zinc by EDTA at the end-point of the

titration. The determination of the final concentration of zinc was done by by using

EDTA titration with xylenol orange as an indicator. It was prepared by dissolving 500 mg

EDTA in 1 liter of distilled water. Then, add three (3) drops of xylenol orange. Titrate the

synthetic leachate wastewater with EDTA solution and when the solution turns from red

to yellow, it indicates that zinc has been displaced by EDTA.

Determining the particle size using Image J software.

Particle size will be determined from the area number alone if one assumes the

particles are roughly spherical. In this case, the area will be converted to an effective

radius using excel or another spreadsheet program according to Eq. (1):

(1)

Where r is the radius of the nanoparticle and A is the area. The diameter (D=2r)

will then be averaged for all of the particles being analyzed (Dune Sciences, Inc., 2011).
 30

MATERIALS AND METHODS

This section explains the details and the procedures for the synthesis of the iron

nanoparticle used for the removal of zinc in the synthetic leachate wastewater.

Research Design

This study is conducted to determine the physical and chemical characteristics of

the synthesized iron nanoparticles by using a descriptive and experimental research

design. Experimental methods were done for the preparation of the synthetic leachate

wastewater. Experimental research was employed to determine the percentage removal of

zinc by varying contact time (3, 4 and 5 minutes) and a pH (5, 6, and 7) in synthetic

leachate wastewater. The treatment of the synthetic leachate wastewater was done by

using eight set-ups. The eight set-ups were done at room temperature. Set-up 1, 2 and 3

for the determination of the pH value with the highest percentage of zinc (II) removal had

a constant contact time of 5 minutes. In each setup, 0.1 g of synthesized iron nanoparticle

is introduced in every trial. The determined pH value with the highest percentage of zinc

(II) removal was used to determine the optimum contact time in treating the synthetic

leachate wastewater in the next three set-ups. For the last two set-ups, the determined pH

and contact time with the highest percentage of zinc (II) removal was used to determine

the efficiency of zinc (II) removal between with and without iron nanoparticle. The
 31

percent removal of zinc (II) in the synthetic leachate wastewater was evaluated using

experimental method. Percent removal served as the dependent variable while the

independent variables that the researchers controlled are the contact time and pH of the

prepared set-ups.

Research Methodology

This section explains the details and procedures for the synthesis of iron

nanoparticles from FeCl3 using Mangifera indica seed kernel as the capping agent and for

the removal of zinc (II) in the synthetic leachate wastewater.

Figure 3 shows the flow diagram of the experimental procedure that was

employed in this study.

Extraction of
Preparation of the Phenolic
Synthesis of Iron
Mangifera indica Compound from Nanoparticle
Seed Kernel Mangifera indica
seed kernel

  Physical and
Chemical
Preparation of
Calculation of Characterization of Synthetic Leachate
Percent Yield the Iron nanoparticle Wastewater

  
Determination of Testing of the
Zinc in Synthetic Treatment of
Synthetic Leachate Treated Synthetic
Leachate Leachate
Wastewater using the
Wastewater Iron Nanoparticle Wastewater

  
Calculation of
Percent Removal of
Zinc
 32

Figure 3. Schematic diagram of the experimental procedure

Preparation of the Mangifera indica seed kernel. Mangifera indica seed kernel

was collected from the waste of the vendors of a local public market in Bacolod. The

collected seed kernel was then washed with distilled water to remove the impurities. The

cleaned seed kernels were subjected to size reduction using a food processor.

Extraction of Phenolic compounds. 100 grams seed kernels were boiled in a 240

mL of distilled water for 30 minutes with continuous stirring using a hot plate magnetic

stirrer at 50 0C (Abong et al., 2018). The resulting concentrate was then allowed to cool

before it was filtered. After extraction, it was centrifuged for 30 minutes and the resulting

liquid after the centrifuge was then the Mangifera indica seed kernel extract.

Phenolic compound content test. The phenolic content was determined using

the procedure of the ferric chloride test. It was done by dropping 4 drops of 1% aqueous

ferric solution into the Mangifera indica seed kernel extract. The presence of phenolic

compounds was then identified by the appearance of intense green, purple, blue or black

colors of the solution. (Al-Jumaily et al., 2014).

Synthesis of iron nanoparticles (FeNPs). Iron nanoparticle was prepared using

0.1 M FeCl3 solution and seed kernel extracts (2:1 volume ratio). The mixture was then

shaken using a shaker for 1 minute and allowed to stand at room temperature for 1 hour.

The mixture was centrifuged for 30 min and the supernatant was poured out. The black

paste obtained was re-dispersed in 98% ethanol followed by purified water to remove

excess impurities three times to completely purify the nanoparticles. The light black paste

was oven dried at 60oC for 8 hours (Okoth, 2016). After drying, the sample obtained was
 33

weighed.

Calculation of % yield of iron nanoparticles (FeNPs). The procedure in

calculating % yield of iron nanoparticles was calculated using Eq. (2). The actual yield is

the amount of the synthesized iron nanoparticle while the theoretical yield is the amount

of the iron nanoparticle solved through stoichiometry.

(2)

Physical and chemical characterization of the iron nanoparticles. The Iron

nanoparticle was characterised in terms of its specific surface area, particle diameter,

particle full range, particle shape, and image using a Field Emission Scanning Electron

Microscopy (FESEM). The color and solubility to water of the iron nanoparticles was

observed and recorded.The synthesized iron nanoparticles were sent to DOST-ITDI

(ADMATEL) at Bicutan, Taguig City.

Determination of solubility to water. This process was based from the solubility

test conducted at the University of Delaware (2011). At 25ºC, three (3) mg of the

synthesized iron nanoparticles was placed in a test tube. Ten (10) mL of water was added

and the mixture was agitated by shaking the bottom of the test tube back and forth for a

minute. Particles in the test tube after stirring was observed whether it is soluble or not.

Preparation of Synthetic Leachate Wastewater. The stock solution of Zn (II)

containing concentration of 50 ppm (Csuros M., nd) was prepared by dissolving 0.333 g

of Zinc Sulfate, ZnSO4 analytical grade, in 2700 mL of distilled water. The pH of the

synthetic leachate wastewater was decreased by adding Sulfuric Acid until the pH meter

reads a pH of 5, 6 and 7 (James, nd).

 34

Determination of Optimum pH and contact time. Based on the study of Horst

(2015), the absorption capacity of zinc ranges from 70 – 87 mg/g of iron nanoparticle. In

this study, the caculated amount of iron nanoparticle that was introduced in 50 ppm zinc

concentration (Csuros M, nd) of synthetic leachate wastewater is 0.1 g. The first three

set-ups had a constant contact time of 5 minutes (Emadi et al., 2012) and varying pH

value. The pH value (5,6,7) with the highest percentage removal of zinc in the synthetic

leachate wastewater had the pH value that was carried to the next to set up in order to

determine the optimum contact time (between 3,4,5 minutes) in the treatment of the

synthetic leachate wastewater. The determination of the final concentration of zinc was

done using EDTA Titration with Xylenol Orange as the indicator. The researchers

prepared the EDTA solution by dissolving 500 mg of EDTA in 1 liter of distilled water.

The researchers then added three (3) drops of xylenol orange. The researchers then

titrated the synthetic wastewater leachate with the EDTA solution. When the solution

turns from red to yellow, it indicates that zinc has been displaced by EDTA at the end of

the titration. Calculation for the concentration of Zn (II) in the treated synthetic leachate

wastewater was done by observing 1:1 ratio of EDTA to Zn (II) in the solution.

Calculation of % Removal of Zinc. The procedure in calculating % removal of

zinc was calculated using Eq. (3). Where, Zf is the zinc (II) concentration after adsorption

in the eight set-ups made and Z0 is the initial concentration of zinc.

(3)

Statistical Treatment. T-test for two independent means at 0.05 α will be used in the

analysis of the data that will be gathered in the removal of zinc and the significant

difference in the adsorption with and without iron nanoparticle (Entrata et al., 2017)
 35

RESULTS AND DISCUSSION

This section presents the data, analysis and interpretation based on the results

from the determination of physical and chemical characteristics of iron nanoparticles

synthesized from the reaction of the phenolic compound extracted from Mangifera indica

seed kernel and FeCl3. The experiment consisted of post-test analysis having three trials

for each set-up. The results obtained were analyzed using statistical tool and presented in

this chapter.

Preparation of Mangifera Indica Seed Kernel.

The obtained seed kernel from the mango collected by the researchers was

reduced into smaller size using a blender.

Extraction of phenolic compounds.

The solution from which the phenolic compound was extracted is a mixture of

Mangifera indica seed kernel and water. At first the solution was transparent in color and

after continuous stirring and heating, the solution turned into colloidal form. It was

centrifuged and there has been a separation of solids from the liquid. After cooling, the

solution changed from transparent to golden yellow. The change in the color of the

solution to golden yellow was the same as the result in the study of Dhuper et al. (2012)

showing that phenolic compound indeed is present in the solution.

Phenolic compound content test.

After dropping 4 drops of 1% aqueous ferric solution into 10 mL of the

Mangifera indica seed kernel extract, the solution changed its appearance into intense
 36

black. The change in the color of the solution signified the presence of phenolic

compounds in the solution. The result holds true based on the procedure of Al-Jumaily et

al. (2014) in determining phenolic compound.

Figure 4 shows the resulting liquid of phenolic compound extracted from

Mangifera indica seed kernel and that of the ferric chloride solution.
 37

Figure 4. Tube A - 0.1 M Ferric Chloride, Tube B - Mangifera indica seed kernel
extract, Tube C - Iron Nanoparticle Synthesized Solution
Synthesis of iron nanoparticles (FeNPs).

A bright yellow 0.1 M FeCl3 solution is mixed with 1.92 L of phenolic extract, the

mixture turned into intense black solution demonstrating the synthesis of iron

nanoparticles. The rapid rate of nanoparticle synthesis justified the use of plants over

microorganisms in the biosynthesis of metal nanoparticles through greener and safer

methods (Dhuper et al., 2012). Phenolic compounds in the Mangifera indica seed kernel

extract acted as capping agent and stabilizing agents in the synthesis of iron nanoparticles

(Al-Jumaily et al., 2014).

After the solution was shaken and centrifuged, a centrifugate of black paste was

obtained. During the synthesis, reducing agent converts metal ions to nanometal via

reduction process whereas capping agents prevent the particle from growing beyond the
 38

nanometric size of interest (Okoth, 2016). So, in this study, the Mangifera indica seed

kernel extract acted as the capping agent for the synthesis of iron nanoparticles. After

drying the obtained product was an opaque jet black crystalline in form weighing 8.71

grams.

Calculation of % yield of iron nanoparticles (FeNPs).

Using the Eq.(2), the percent yield of the iron nanoparticles obtained is 27.98%

(see Appendix for calculations).

Physical and Chemical Characterization of the Iron nanoparticle.

Physical and chemical characteristics of the sample in terms of its specific surface

area, particle size, color and solubility at 25-30°C, confirmed the presence of iron

nanoparticles. The physical characteristics of the sample observed during the experiment

became the basis for the confirmation of the presence of iron nanoparticles. This includes

the change in the color of the solution into intense black paste after mixing. The oven

dried sample obtained had a jet black colored crystals which is a characteristic of iron

nanoparticle according to Lee (2007).

One gram sample of the obtained iron nanoparticle was sent to the DOST-ITDI

(ADMATEL) at Bicutan, Taguig City to determine the range of the sizes of the produced

iron nanoparticles by the use of Field Emission Scanning Electron Microscopy (FESEM).

The imaging of iron nanoparticles was done using a Dual Beam Helios Nanolab 600i

with a FESEM accelerating voltage of 5kV and a beam current of 0.34 nA. Figure 5

shows the result of the FESEM analysis of the synthesized iron nanoparticles using

Mangifera indica seed kernel as capping agent. It can also be observed that the
 39

nanoparticles were quasispherical in shape and are varying in sizes having the same

results to that of the study of Abong et al. (2018).

Figure 5. FESEM image of the synthesized iron nanoparticles.

The area was obtained using the ImageJ application while the particle size was

calculated using Eq. (1). Table 5 shows the area and particle size of the synthesized iron

nanoparticles, with the largest being 70.784 nm and the smallest, 9.083 nm. On average,

the particle diameter for the synthesized magnetite nanoparticle is 32.503 nm, which falls

within the established range of nanoparticles being 1-100 nm and the average surface

area is 3318.849 nm2 (ISO, 2008). Since the particle size falls within the range of 1-100

nm, the nanoparticle exhibits extraordinary adsorption capacity and reactivity, both of
 40

which are favorable for the removal of heavy metal ions (Bi et al., 2019). Moreover, the

variations in mean particle diameters with other studies may be caused by the differences

in process chosen, purpose of the product, and the kind and amount of reagents added.

Table 2.

Particle Size of iron nanoparticles using Field Emission Scanning Electron Microscopy
(FESEM), analyzed using ImageJ application.

Particle no Area (nm2) Particle size(nm)

1 259.158 9.083

2 278.818 9.421

3 377.12 10.956

4 554.062 13.28

5 593.383 13.743

6 791.773 15.875

7 941.906 17.315

8 1170.68 19.304

9 1603.206 22.59

10 1678.272 23.113

11 1783.723 23.828

12 2212.674 26.539

13 2255.569 26.795

14 3374.417 32.774

15 3839.115 34.976

16 5302.911 41.085

17 5731.863 42.714

18 7081.272 47.477
 41

19 7093.783 47.519

20 7261.789 48.078

21 15740.728 70.784

Mean 3318.849 32.503

The solubility of the iron nanoparticles was tested by adding 10 mL of water to a

test tube containing 3 mg of the iron nanoparticles particles and was shaken vigorously

based from the test of University of Delaware (2011). No dissolution of the nanoparticles

was observed. The obtained sample also showed attraction to a strong magnet, which is

also another confirmation that it is magnetite in form. Therefore, the use of Mangifera

indica seed kernel extract as capping agent for the synthesis of iron nanoparticles was

successfully showed.

Preparation of Synthetic Leachate Wastewater.

The resulting solution from the dissolution of Zinc Sulphate was clear. The pH of

the solution was adjusted and maintained to 5, 6 and 7 (Christenen, 2001) using Sulphuric

Acid. The solution was homogenous and clear.

Treating of Synthetic Leachate Wastewater using Iron Nanoparticle.

No observable changes were seen upon addition of iron nanoparticles in the

solution.

Testing of Zinc content in the treated synthetic leachate wastewater.

Addition of Xylenol orange to the treated synthetic leachate wastewater turned the

solution into red. At the endpoint of titration, the color turned to yellow indicating the

displacement of Zinc by EDTA.

Calculation of % Removal of Zinc in the synthetic leachate waste water.

Figure 6 shows the percent removal of Zinc at various pH while maintaining a

 42

constant contact time of 5 minutes.

98.00%
96.27%
96.00% 95.07%
93.88%
94.00%
92.38%
92.00%
90.59%
Percent 90.00% 89.40%
89.10%
Removal Trial 1
88.05% Trial 2
88.00% 87.01% Trial 3
86.00%

84.00%

82.00%
5 6 7
pH

Figure 6. Clustered Bar for percent removal of zinc at various pH and constant contact
time of 5 minutes.
For a constant contact time of 5 minutes and pH of 5, 6 and 7 the % removal of

Zinc is shown in the Figure 6. For a pH of 5, Trial 1 has an average percent removal of

88.50%. For a pH of 6, the average percent removal is 95.07% and for a pH value of 7,

the average percent removal is 90.34%. The figure shows that the adsorption of Zn(II) is

maximum at a pH value of 6 at a constant contact time of 5. Based on the results, pH is

an important parameter affecting adsorption of heavy metal ions and it follows that the

iron nanoparticle is most effective in removing Zn(II) in the synthetic leachate

wastewater in acidic condition (pH 6). Lower adsorption percentage of Zn(II) on iron

nanoparticle at highly acidic conditions (pH<= 5) is probably due to presence of high

concentration of H+ ions on the adsorbent surface competing with Zn(II) for adsorption

sites. With an increase in the solution pH to 6, the iron groups become deprotonated and,
 43

consequently increased the removal efficiency. As to the result of increasing the pH to 7,

the efficiency decreases and may be due to the presence of hydroxide ions which coould

react with the Zn(II) present in the synthetic leachate wastewater.

120.00%

100.00% 96.27%
95.07%
93.88%
82.68%
80.00% 77.30% 75.96%

Percent 60.00%
Removal 48.03% Trial 1
44.00% 46.24% Trial 2
40.00% Trial 3

20.00%

0.00%
3 4 5
Contact time (mins)

Figure 7 shows the percent removal of Zinc at various contact time while

maintaining a constant pH of 6.

Figure 7. Clustered Bar for percent removal of zinc at various contact time and constant
contact pH of 6
For a constant pH of 6 at varying contact time of 3, 4 and 5 minutes the %

removal of Zinc is shown in the Figure 7. For a contact time of 3 minutes, it has an

average percent removal of 46.09%. For a contact time of 4 minutes, its average

percentage removal is 79.98% while in a contact time of 5 minutes, it has an average

percent removal of 95.07%. This shows that the highest removal of Zinc occurred at a

contact time of 5 minutes at constant pH of 6. Based on the results, the sorption kinetics
 44

of the iron nanoparticles at constant pH of 6, when contact time is less than 5 minutes is

slow.

Figure 8 shows the percentage removal of zinc using iron nanoparticles at

optimum contact time of 5 minutes and a pH of 6 in comparison to percentage removal of

zinc without iron nanoparticles.

120

100 96.27 95.07 93.88

80

Trial 1
60
Percent Removal Trial 2
Trial 3
40

20
8.91 7.41
5.17
0
With FeNPS Without FeNPS

Figure 8. Percentage Removal Comparison between using Iron Nanoparticle at 5 minutes

and pH of 6 with and without Iron Nanoparticle.
Based on the figure, it shows that the percent removal of Zn (II) using the iron

nanoparticle at the determined optimum contact time of 5 minutes and optimum pH value

of 6. The trials with iron nanoparticle has an average removal of 95.07% while the one

without the iron nanopartcile has 7.17%. It shows that indeed iron nanoparticle is an

effective capping agent.

Table 3 shows the F-Test to determine if they have equal variance.

 45

Table 3
F-Test for the determination of the variances of the percent removal
(F-Test Two-Sample for Variances)

  With FeNPS Without FeNPS

Variance 1.428033333 3.542533333

Based on the table, the variance of the one with the FeNPS and without FeNPS is

not equal. This signifies that the type of T-test to be used by the researchers is Two-

Sample Assuming Unequal Variances.

Table 4 shows the t-Test to determine if the null hypothesis is valid or not.

Table 4.
t-Test result for the percent removal of zinc
with and without FeNPS (t-Test: Two-Sample
Assuming Unequal Variances)

  With FeNPS Without FeNPS

Mean 95.07333333 7.163333333
Variance 1.428033333 3.542533333
Observations 3 3
Hypothesized Mean Difference 0
Df 3
t Stat 68.29610811
P(T<=t) one-tail 3.45874E-06
t Critical one-tail 2.353363435
P(T<=t) two-tail 6.91748E-06
t Critical two-tail 3.182446305  

Since, t Stat is greater than the t Critical two-tail, 68.29610811 > 3.182446305,

the null hypothesis is rejected. Therefore, there is a significant difference in using FeNPS

and without using FeNPS.It follows that treating the the one with the iron nanoparticle is

efficient in removing the Zn (II) of synthetic leachate wastewater.

 46

CONCLUSION

This section presents a summary of findings in the experimentation of this study.

In addition, this section offers recommendations for further research in a similar field.

The Mangifera indica seed kernels contained phenolic compounds which acted as

the capping agent in the synthesis of the nanoparticles. The presence of the iron

nanoparticle was indicated by the change in color (black) of the Mangifera indica seed

kernel upon the addition of 1% aqueous FeCl3. The iron nanoparticle produced had a

percent yield of 27.98%.

The iron nanoparticles produced by the researchers were characterized according

to specific surface area, average primary particle size and particle shape using Field

Emission Scanning Electron Microscopy at ADMATEL. The mean surface area was
 47

analysed to be 3318.849 square nanometers and the mean particle size was 32.503

nanometers which falls within the acceptable range of nanoparticles. Its shape was

identified to be quasispherical based on the iamge results from the FESEM analysis

The result for the optimum pH for the removal of Zinc was 6, which is in

accordance to the study of Emadi et al. (2012) “Removal of Zinc from Aqueous Solutions

by Magnetite Silica Core-Shell Nanoparticles”, that the optimum pH for removal of zinc

(II) using magnetite silica core-shell nanoparticles is 6. The result for the optimum

contact time for the removal of Zinc was 5 minutes which has the same result also with

Emadi et al. with a very removal of Zinc at a contact time of 5 minutes.

Using T-test for two independent means at 0.05 α, the results shows that the mean

percent removal of Zinc with Iron nanoparticle was 95.07%, whereas the mean percent

removal of Zinc without Iron nanoparticles was 7.17%. Using F-test for solving if there is

any significant variance between the percent removal of Zinc with and without Iron

nanoparticle, it showed that the t-Stat is greater than the t Critical two-tail, 68.29610811

> 3.182446305, the null hypothesis is rejected. Therefore, there is a significant difference

in using FeNPS and without using FeNPS.

The phenolic compound from Mangifera indica seed kernel can be a reducing and

capping agent for the synthesis of iron nanoparticle. The use of iron nanoparticle has

found to effectively remove a significant amount of zinc from the synthetic leachate

wastewater. This concludes that iron nanoparticle can therefore be a medium for the

treatment of leachate wastewater which is a big environmental problem nowadays.

The researchers wish to make the following recommendations which if taken into

considerations may bring some more positive effects to the current results; addition of
 48

set-ups such as varying amounts of iron nanoparticles may be done to determine their

effects on percent removal, the use of medium such as sand filter and the use of UV-Vis

Spectroscopy may be used as an alternative method of determining the removal effiency

of Zn(II) in the leachate wastewater.

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 54

APPENDIX A

Documentation of the Research Process

Mango seeds collected by the researchers Washing of the mango seeds

 55

Separating Seed Kernel Grinding of mango seed kernel

44

Grinded Mango seed kernel Extraction of Phenolic Compound

 56

Preparation of 1% FeCl3 solution Testing of the formation of iron nanoparticle

45

Phenolic Compound Extracted Mixing of Phenolic and 0.1 M FeCl3

 57

Iron nanoparticle Settling of iron nanoparticle after centrifuge

46

Preparation of EDTA solution Checking of pH of synthetic Leachate

 58

Titration of Synthetic Leachate Iron Nanoparticle

APPENDIX B

Result of FESEM Analysis 49

 59

APPENDIX C

Statistical Analysis and Calculations

Table 3

F-Test for the determination of the variances of the percent removal

(F-Test Two-Sample for Variances)

  With FeNPS Without FeNPS

Mean 95.07333333 7.163333333
Variance 1.428033333 3.542533333
Observations 3 3
Df 2 2
F 0.403110768
P(F<=f) one-tail 0.287297894
F Critical one-tail 0.052631579  

Table 4.

t-Test result for the percent

removal of zinc with and

without FeNPS (t-Test: Two-

Sample Assuming Unequal

Variances)

  With FeNPS Without FeNPS

Mean 95.07333333 7.163333333
Variance 1.428033333 3.542533333
Observations 3 3
Hypothesized Mean

Difference 0
Df 3
t Stat 68.29610811
P(T<=t) one-tail 3.45874E-06
t Critical one-tail 2.353363435
P(T<=t) two-tail 6.91748E-06
 60

t Critical two-tail 3.182446305  

Calculation of % yield.

Mass of bottle = 3.25 grams

Mass of bottle with FeNPS= 11.96 grams

Actual mass of the iron nanoparticle = (mass of the bottle with iron nanoparticle –

mass of the bottle)

Actual mass of the iron nanoparticle = 11.96 – 3. 25 = 8.71 grams

For optimum pH Determination at time = 5 minutes

Calculation of % Removal by EDTA Titration

For pH= 5

Trial Initial Volume of Final Volume of Volume of EDTA

EDTA Solution (ml) EDTA Solution (ml) Solution used in the
Titration (ml)

1 50 42.9 7.1

2 50 42.7 7.3

3 50 41.3 8.7
 61

For Trial 1:

For Trial 2:

For Trial 3

For pH= 6

Trial Initial Volume of Final Volume of Volume of EDTA

 62

EDTA Solution (ml) EDTA Solution (ml) Solution used in the

Titration (ml)

1 50 47.5 2.5

2 50 46.7 3.3

3 50 45.9 4.1

For Trial 1:

For Trial 2:

For Trial 3
 63

For pH= 7

Trial Initial Volume of Final Volume of Volume of EDTA

EDTA Solution (ml) EDTA Solution (ml) Solution used in the
Titration (ml)

1 50 42 8

2 50 44.9 5.1

3 50 43.7 6.3

For Trial 1:

For Trial 2:

For Trial 3
 64

59

For optimum contact time at pH of 6

Calculation of % Removal by EDTA Titration

For time = 3

Trial Initial Volume of Final Volume of Volume of EDTA

EDTA Solution (ml) EDTA Solution (ml) Solution used in the
Titration (ml)

1 50 12.5 37.5

2 50 15.2 34.8

3 50 14 36

For Trial 1:

For Trial 2:
 65

For Trial 3

For time=4 minutes

Trial Initial Volume of Final Volume of Volume of EDTA

EDTA Solution (ml) EDTA Solution (ml) Solution used in the
Titration (ml)

1 50 34.8 15.2

2 50 38.4 11.6

3 50 33.9 16.1

For Trial 1:
 66

For Trial 2:

For Trial 3

For time = 5 minutes

Trial Initial Volume of Final Volume of Volume of EDTA

EDTA Solution (ml) EDTA Solution (ml) Solution used in the
Titration (ml)

1 50 47.5 2.5

2 50 46.7 3.3

3 50 45.9 4.1

For Trial 1:
 67

For Trial 2:

For Trial 3

No Iron Nanoparticle
 68

Calculation of % Removal by EDTA Titration

For pH= 6 and time 5 minutes

Trial Initial Volume of Final Volume of Volume of EDTA

EDTA Solution (ml) EDTA Solution (ml) Solution used in the
Titration (ml)

1 100 36.5 63.5

2 100 39 61

3 100 38 62

For Trial 1:

For Trial 2:

For Trial 3
 69

APPENDIX D

October 11, 2019

To Whom It May Concern,

This is to certify that the undergraduate thesis titled “Zinc Removal by Iron Nanoparticle
Synthesized Using Mangifera Indica Seed Kernel as Capping Agent” by Shaun M.
 70

Bautista, Emerald Grace D. Parcon, Erasmo P. Tan Jr., Josheil G. Villanueva for the
degree in Bachelor of Science in Chemical Engineering has been edited by the
undersigned faculty member of the University of St. La Salle, Bacolod City.

Thank you very much,

Truly yours,

Annabelle A. Chavez, Ph. D