Adsorptive Capability Test of Powdered Eggshell Waste on Copper Sulfate-Induced Water

A Paper presented to
The Senior High School Faculty
Saint Jude Catholic School
Manila

In Partial Fulfillment of the

Requirements in III
Inquiries, Investigations, and Immersions

Sim, Ranielle S.
Co, Daphne Hazel C.
Esteban, Charlene Denise S.
Ong, Elyssia Barrie H.
Tan, Alessandra Grace T.
 ACKNOWLEDGMENTS

We would like to take this opportunity to first thank our research adviser Mr. Mark Gil A.
Vega of the Senior High School department at Saint Jude Catholic School. He was always ready
to provide us direction whenever we had a question about our research or writing. He unfailingly
allowed this paper to become our own work but gave us the needed guidance whenever he
thought that we needed it.
We would also like to thank our Investigations, Inquiries, and Immersion teacher, Mr.
Lodeo Pascual for his unwavering faith in our capabilities to finish our research paper, we would
also like to thank him for being the second reader of our paper; we are gratefully indebted to his
very valuable comments on our research.
This research would not have been achievable without the help of our school, Saint Jude
Catholic School and SGS Philippines Inc., for examining and providing the results for the
samples that we needed to complete this research.
Finally, we express our profound gratitude to our parents and to our beloved Lord, for
providing us with endless support and constant encouragement throughout our months of study
and through the process of researching and writing our paper. All our accomplishments would
not have been possible without them. Thank you.

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 TABLE OF CONTENTS

ABSTRACT 3

Chapter I 4

Chapter II 10

Chapter III 1​​8

Chapter IV 2​​5

Chapter V 2​​9

BIBLIOGRAPHY 3​​1

APPENDICES 3​​6

CURRICULUM VITAE 3​​9

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 ABSTRACT

Chicken eggs have long been utilized for many purposes in terms of human consumption,
with the eggshells often neglected and thrown away. However, these eggshells contain high
calcium carbonate and are porous in structure, making them a candidate for serving as a good
adsorbent for removing heavy metals from contaminated water. In this study, the researchers
aimed to assess the adsorptive capabilities of the said eggshells on water induced with copper
sulfate, testing for the copper content of the solutions in particular. Copper was utilized as the
heavy metal to be adsorb in the distilled water because of it toxicity to human health and
appearance in food products and water. The experiment was tested through four 1L samples of
copper sulfate solution, with one serving as the control and with 2g, 4g, and 6g of crushed
eggshells submerged in the three other samples respectively for 60 minutes. The copper sulfate
solutions were additionally taken to SGS Philippines Inc. for the testing of copper content using
the Inductively Coupled Plasma Method (ICP). The results of the study indicate inconclusive
evidence due to the deviating values that were found in the concluding data of the experiment.

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 Chapter I
INTRODUCTION

This chapter introduces and provides the background of the research topic and the
consequential research problem pertaining to the adsorptive capability of eggshell waste in
response to the issue of wasted eggshells and tap water impurities, which will then be applied
and tested on distilled water induced with copper sulfate.
A. Background of the Study
Eggs are undeniably important in every household, as they have a number of uses
that are significant for human consumption, such as breakfast food and a binder to some
ingredients. More so, the outermost part of the egg—the shell—is often disposed of as a
result since it is usually seen as waste, further eliminating its potential uses. New research
indicates however that they have other possible uses, such as serving as low-cost
adsorbents for the purification of water.

Eggshell waste, and thus eggshells in general, is composed of three layers and can
further be divided into two parts: the mammillary matrix and the spongy matrix. These
matrices are composed of pores that serve as a permeable layer for gas transport.
Furthermore, these porous structures can be ground into powder to serve and function as
a material for adsorption. Similarly, the calcium carbonate content present in its chemical
composition makes it viable as an alternative method for metal adsorption. According to
the review journal written by ​Mittal, Teotia, Soni, and Mittal (2016)​​, eggshells and
eggshell membrane can be used as an efficient low-cost adsorbent for organic and
inorganic materials on wastewater. Moreover, ​Kale et al. ​(2018) ​mentioned that they can
be used for the removal of heavy metals such as lead, zinc, and iron​.

To explain further, the process responsible for such phenomena is adsorption. As

stated by ​Crawford and Quinn (2017); Gupta, Carrott, Ribeiro, and Suhas (2009)​​,
t​his process can be related to ion exchange wherein both processes involving ​the transfer

4
and distribution of resulting equilibrium of solutes occur between a fluid phase and a
solid particle. ​Therefore, it can be said that ​the most effective adsorbents exhibit the
following properties: the high surface area from porous structures and fast adsorption
kinetics. In line with this, it is possible for eggshells to be low-cost adsorbents with
porous structures in its shell membrane.

Meanwhile, due to the industrialization that resulted in severe pollution present in

the country and lack of clean resources, the access to having clean water has become
difficult. Water remains to be the basic necessity of a human being, and therefore the fact
that this necessity grows scarce as time passes is troubling at best for the society. Taking
this into account, the researchers wanted to test the adsorptive capabilities of eggshell
waste for the purification of water that was induced with copper sulfate to see the
adsorptive capabilities of eggshells on copper, before moving on to the more complex
cases such as wastewater. The general public, especially those without access to clean
drinking water will benefit the most from this study as it produces a low-cost alternative
to water purification.

Tap water refers to the water that is supplied from a valve and this can be seen in
almost every establishment and household as it is commonly used for cleaning, cooking,
and the like. In developed countries, tap water is potable enough to become drinking
water, however, there are still cases wherein tap water is still contaminated. According to
the study conducted by ​Da Silva et al., (2008), ​3​6.4% of the tap water samples displayed
contamination by at least one coliform, pathogenic bacterium or coliform indicator
through the heterotrophic plate count test. Likewise, in the study of ​Abed and Alwakeel
(2007), ​they were able to detect high amounts of sulfate and chloride in tap water, along
with alkaline pH, sodium, and calcium that were above the normal range.

Likewise, the study of ​Ahmad, Kumar, and Haseeb (2012) identified copper as
one of the most toxic metals, proving fatal even in low concentrations. It is commonly

5
 found in food groups and drinking water, which makes it prone to the risk of human
consumption. Significant amounts of copper in the body due to such consumption can
lead to a variety of diseases, including brain, skin, heart, pancreas, and liver diseases, as
well as kidney failure ​(as cited in Veli and Alyuz, 2007; Zheng et al., 2010)​​.

B. Statement of the Problem

According to UE regulations, eggshell waste is considered hazardous, therefore
the different possible applications of eggshell waste to the society must be taken into
consideration. The study has three main variables: the adsorptive capability, the amount
of eggshells, and the amount of copper sulfate. The dependent variable for the study is
the adsorptive capability, the independent variable is the amount of eggshells, while the
constant variable is the amount of copper sulfate.
With these variables in mind, the study aims to complete the following objectives
and thus answer the problem stated in relation to the research topic:
1. To gauge the adsorptive capability of chicken eggshell waste
2. To successfully adsorb copper using eggshells submerged in copper sulfate
solution
3. To identify and use the proper formulas for calculating the adsorptive capability
of eggshells, percentage of copper adsorbed, and adsorption capacity
C. Hypothesis
The study mainly involved two hypotheses, with the null hypothesis denoted by
H​​o being
​ that the eggshell waste was incapable of adsorbing copper from the copper
sulfate solution, and the alternative hypothesis denoted by ​H​a being
​ that the eggshell
waste was capable of adsorbing copper from the copper sulfate solution.

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D. Conceptual Framework

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E. The Significance of the Study
With the focus of testing the adsorptive capability of eggshell waste on the
purified water that will be induced with copper sulfate, the results of the research study
will benefit the following:

First Responders. ​The study will aid them in improving and widening the access
of Filipinos to clean water, most especially in times of disasters and emergencies.

Filipino Consumers. ​The data from the research will allow Filipino consumers to
be more aware of tap water and its contents, which will be beneficial to their health,
hygiene, and lifestyle.

Future Researchers. ​Other researchers expressing similar interests in researching

the adsorptive capability of eggshell waste in water may use this study for more
information, guidance, and literature to support their research endeavors.

F. Scope and Limitations

The study focused on the adsorptive capability of eggshell waste, meaning only
the eggs from that of the common chicken was used and involved in the experiment
conducted for data, as chicken eggs are the ones that are commercially available for the
widespread consumption of Filipinos.

Additionally, due to the time constraints and limitations in the available

equipment, facilities, and abilities of the researchers, conducting the adsorptive capability
test of eggshell waste was limited on distilled water that will be induced with copper
sulfate. The experiment was thus conducted within the premises of the said school,
utilizing the Research Hub that is located on the fourth floor of the researchers’ school,
Saint Jude Catholic School; meanwhile, the sample solutions of copper sulfate was taken

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 to the laboratory of SGS Philippines Inc. in Makati for the measurement of copper
content only.

G. Definition of Terms

Adsorptive Capability. ​It is intended used for solutes with limited

solubility. The adsorption capacity of an adsorbent can be measured by the value
of the amount of adsorbed substance which has reached its saturated solution. The
research revolved around the testing of the adsorptive capability of eggshell waste
on the tap water of SJCS.

Eggshell Waste. ​The main variable utilized in the research. Eggshells

contain pores which allow adsorption processes or gas exchange to occur. For this
research, chicken eggshell waste was tested for its adsorptive capabilities in tap
water.

Copper sulfate (CuSO4). ​The solute used to mix with water and produce
the solution needed for the research. It is an inorganic compound that is
comprised of copper and sulfur.

Inductively Coupled Plasma (ICP) Method. ​The method used to

determine the amount of copper found in the solution after the submersion of
powdered eggshell.

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 Chapter II
REVIEW OF RELATED LITERATURE

Eggs have long been a common food resource taken from poultry; oftentimes its contents
have made their way onto breakfast plates as well as dish recipes where they serve as a binder of
ingredients. While the importance of eggs and their contents is sure to persist for generations to
come, the same cannot be said for the outermost part of the egg—the shell. These eggshells are
seen as nothing more than waste and thus end up in the trash, throwing away the possibility of
other potential uses.

This chapter provides a rundown of previous research which has indicated some of these
potential uses, including the capability of the adsorption of certain contents. With the thrust of
technological advancement and modernization, issues of pollution and lack of clean resources
remain at large to this day and so does the issue of difficult accessibility to clean water, which is
most prevalent in poorer areas and slums. Taking such into account, it becomes essential to test
the capabilities of eggshell waste in adsorbing the contents of substances as simple as tap water
before moving on to the more complex cases of wastewater.

ADSORPTION

Adsorption, as defined in the work of ​Crawford and Quinn (2017), ​is a process where a
material, called the adsorbate, travels from a gas or liquid phase and forms a monomolecular
layer on a solid or liquid condensed phase. The study of ​Gupta, Carrott, Ribeiro, and Suhas
(2009) ​shown on the article ​‘Low-Cost Adsorbents: Growing Approach to Wastewater
Treatment-A Review’ from the book ‘Critical Reviews in Environmental Science and
Technology’, further defines adsorption as the process where there is concentration of a material
at a solid surface from its liquid or gaseous environment. The study separated adsorption into
two types mainly being, physical and chemical. Physical adsorption, also called physisorption,
occurs through the physical attraction between the adsorbed molecules and the solid surface.

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Here, it is observed that the force of attraction between these molecules are weak, hence,
resulting in the bond being reversible. The attractive forces that are responsible for this
phenomena are called the van der Waals forces. Conversely, chemical adsorption or
chemisorption occurs when the attraction of the adsorbed molecules and the solid surface is due
to chemical bonding. These attractive forces are stronger compared to the van der Waal forces,
therefore, the process is difficult to reverse and the chemisorbed species are a challenge to
extract from the solid surface.

Ion exchange, along with adsorption share common aspects and can be organized
together as “sorption processes.” This process happens when an ion coming from a solution is
switched for an ion with the same charge affixed to a fixed solid particle. Similarly, both the
adsorption and ion exchange includes the interaction between a fluid phase and solid particles
wherein the transfer and distribution of resulting equilibrium of solutes occurs.

These, therefore, led to the development of various adsorbents used for the removal of
solutes from a solution by adsorption or ion exchange, also, it is used for the adsorption of gases.
Good adsorbents have the following characteristics: high surface area resulting from structures
with a number of pores and fast adsorption kinetics. There are a number of possible adsorbents
used by industries and for pollution control, such as alumina and bauxite, silica gel, zeolites and
ion exchange resin, and activated carbon. However, adsorbents such as activated carbon proved
to be high in cost, therefore, low-cost alternative adsorbents had been produced. These LCAs are
from either low-cost natural abundant materials or industrial wastes and byproducts.

The main goal of this development is to be able to lessen the cost of these adsorbents and
to lessen the need for regeneration. These resources are also currently underused and unrecycled.
They also consist of little to no pretreatment beforehand, therefore small industries from all over
the world, even non-industrialized ones can manufacture these. The production of these products
can prove to be useful to the community in the long run as it aids the treatment of the water and
pollution control and in return, can contribute to their economic and social growth.

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 At the same time, ​Wang, et al. (2010) was able to conclude that natural zeolites are
abundant and low-cost resources with a porous structure that is inhabited by water, alkali and
alkaline earth cations. They also exhibit a high cation exchange, making them good adsorbents.
Zeolites thus exhibit high adsorptive capability in aqueous solutions with cations such as heavy
metals. However, this resource exhibited varying selectivity to some materials. Therefore,
surface modification through cationic surfactant was used in order for the adsorption of organics
and anions to be possible. Further modification of these natural zeolites with the use of some
heavy metals by surface precipitation can also be done for a stronger adsorptive capability with
inorganic anion adsorption.

Furthermore, as stated by ​Bhatnagar et al., (2015), ​various agricultural “waste peels”

can be used as low-cost adsorbents for water and wastewater treatment. These “waste peels”
include citrus waste peels, particularly orange, pomelo, grapefruit, and lemon peels, banana
peels, cassava peels, jackfruit peels, pomegranate peels, garlic peels. These are natural,
nature-friendly and economic sourced adsorbents that can improve and treat the current
wastewater quality system. Such “waste peels” could also undergo different modification
methods for it to develop modified peel-based adsorbents, most of which are chemical
modification processes. The mechanisms which allow the adsorbents to remove pollutants
include ion exchanges and sorption processes. The agricultural “waste peels” also have a high
adsorption capacity for many pollutants, and they are also biocompatible and non-toxic to the
environment. All in all, these biosorbents display much more advantages in the area of pollution
control over expensive activated carbons and can provide strategies for overall waste
minimization.

AGRICULTURAL WASTE

Agricultural waste has become one of the most urgent problems in the food industry
because of the cost it takes in order to dispose of it. This, however, can open another avenue in

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which new uses for these residual materials can be found. According to the Bureau of
Agriculture and Statistics (2011)​​, the Philippines produced 4.24 Metric Tons of chicken and
duck eggs in 2010. Eggshells, considered as a hazardous waste by UE regulations, are often
discarded, leading to an amount of hundreds of thousands of tonnes worldwide. A recent study
was done by ​Laca, Laca, and Diaz (2017) ​showcased that eggshells may be employed as an
environment-friendly catalyst such as the synthesizing of biodiesel, bioactive compounds, and
wastewater treatment. It was able to conclude that green eggshell-derived catalysts can be
employed to develop materials such as nanocomposites that can be used in the sorption process
for wastewater treatment.

EGGSHELL WASTE

In the research study of ​Tsai, et al. (2006)​​, the chicken eggshell structure is comprised of
three layers, with the cuticle on the outer surface, the spongy (calcareous) layer, and the inner
lamellar (or mammillary) layer ​as cited by Tullett (1987); Stadelman (2000)​​. Similarly, ​Tsai et
al. (2008) ​further notes that the eggshell can also be divided into two parts, which are the
mammillary matrix (i.e., eggshell membrane) and the spongy matrix (i.e., calcified eggshell),
where the latter takes up 10% of the total mass of the egg (​ca. 60g), and its chemical composition
in terms of weight is as follows: calcium carbonate (94%), magnesium carbonate (1%), calcium
phosphate (1%) and organic matter (4%), ​as cited by Tsai et al. (2006); Stadelman (2000)​​. Due
to its high content in the aforementioned chemical compounds, it has become suitable for use as
a fertilizer, a soil conditioner, and an additive for animal feed as mentioned by ​Tsai et al., (2008)
and as ​cited by Christmas and Harms (1976)​​. ​Rohaizar, Hadi, and Sien (2013) additionally
emphasize an environmentally-friendly particular, makes the eggshell considerable as an
alternative method for metal adsorption.

Additionally, according to ​Tsai et al., (2008), ​the eggshell is notable for having several
openings that are circular in shape (pores), which are found in the spongy and mammillary
layers. These structures are what allow the exchange of gases in and out of the shell. The cuticle,

13
on the other hand, is covered with a mucin protein that served as a soluble plug for the pores, but
it is permeable to the transmission of gases as well. It is these porous structures found in the
eggshell that unlocks the possibility of grinding it into powder and thus function as a material for
adsorption.

Following along the review journal written by ​Mittal, Teotia, Soni, and Mittal (2016)
on the capability of eggshells and eggshell membranes as an adsorbent, it has been determined
that eggshells and eggshell membrane can be an efficient and low-cost adsorbent for organic and
inorganic materials, primarily on wastewater. Previous research that was conducted with the
purpose of decreasing the amount of eggshell waste has also been used as references to conclude
that eggshells and eggshell membrane can be used as an adsorbent. More importantly, both
eggshells and eggshell membrane can be used to extract various classes of dyes, oxalic acid,
phenol, pesticides, humic acid, pharmaceutics, surfactants, polycyclic aromatic hydrocarbons
(PAHs); heavy, precious, and light metals; actinides, fluorides, etc.

Moreover, the research conducted by ​Kale et al. ​(2018) has also revealed that low-cost
adsorbents such as eggshells can be used to remove ​heavy metals such as lead, zinc, and iron. In
another study done by ​Zahkir and Sheriff (2014)​​, low-cost adsorbents such as papaya seeds,
eggshells, and coconut leaf powder can be used to remove heavy metals from wastewater.
Hence, the team of ​Kale et al​​. ​(2018) ​tested chicken eggshells and removed 85%, 82% and 86 %
of chromium, lead, and cadmium respectively. Coconut leaf powder was then tested and it
removed 87%, 90% and 85% of chromium, lead, and cadmium respectively. Papaya seed powder
then managed to remove 80%, 85% and 79% of chromium, lead, and cadmium respectively from
wastewater with the initial metal ion concentration of 100 ppm solution. ​Abdulrahman et al.
(2014)​​ also found that the rate of adsorption increased with the increase of contact time.

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TAP WATER

Based on the results gathered from a study of Microbial and Mineral Contents of Bottled
and Tap Water conducted by ​Abed and Alwakeel (2007)​​, using the method of inductively
coupled plasma mass spectrometry (ICP-MS) and the pH of water showed that the mineral
content of tap water contained an amount of aluminum that was considered below toxic range, as
well as high amounts of sulfate and chloride. All of the samples that were tested also contained
alkaline pH, sodium, and calcium that were already above the acceptable range of pH level
7.2–7.4.

The research study of ​Da Silva et al., (2008) ​likewise stated that ​the evaluation of the
bacteriological quality of tap water from municipal water systems has presented that 36.4% of
the samples displayed contamination by at least one coliform, pathogenic bacterium or coliform
indicator. These were enumerated through the heterotrophic plate count test and has revealed the
following pathogenic bacteria and coliforms in the samples: ​Total ​coliforms​, thermotolerant
coliforms, ​Escherichia coli​, fecal ​streptococci​, Pseudomonas aeruginosa, Staphylococcus spp.
Therefore, it is recommended that along with the routine data tests performed, municipal water
systems perform the Pseudomonas test regularly in order for the bacteria and coliform count to
be properly monitored and maintained.

Consequently, ​De Angelis, et al., (2017) ​concluded that ​the synthesis of hydroxyapatite
eggshell waste was made to be used as an adsorbent for the removal of Nickel from aqueous
solutions. The characterization of this material includes the use of X-ray diffraction, ​scanning
electron microscopy with the energy dispersion ​spectrum analysis​, and ​Fourier transforms
infrared spectroscopy​. The adsorption kinetic process with regards to the contact time and the
initial nickel concentration was investigated. The investigation resulted in the adsorption
equilibrium being achieved within 80 minutes. The application of the tests namely,
pseudo-first-order, pseudo-second-order, and intraparticle diffusion kinetics models, was used
for the further study on the kinetics of this process. The results displayed that the

15
pseudo-second-order kinetic model had the best description of the adsorption process with a high
correlation coefficient. 109 mg/g was the acquired maximum adsorptive capacity of nickel and it
was higher than other adsorbents of the same kind. This process was best fitted with the
Langmuir equation as compared to the other adsorption equations. Also, the removal mechanism
of nickel from this synthesized hydroxyapatite could result in the formation of a nickel-bearing
phosphate. This is made possible by the ion exchange with calcium, and the dissolution or
precipitation of the hydroxyapatite, thus resulting in the phosphate formed. In conclusion, this
study confirmed the hypothesis that the synthesized hydroxyapatite from eggshell waste serves
as an exceptional low-cost adsorbent for the removal of nickel from contaminated waters​.

COPPER

Copper is characterized by the atomic number 29 and an atomic mass of 63.546. Placed
at the third transition series of metals on the periodic table, it is a common metal that can be
found in a wide range of food groups as well as drinking water, and exhibits properties that allow
it to switch between oxidation states as copper(I) (cuprous ion) and copper(II) (cupric ion)
(Stern, 2010)​​, capable of serving as both an electron donor or an electron recipient ​(as cited in
Ralph and Mcardle, 2001)​​.

According to ​Ahmad, Kumar, and Haseeb (2012)​​, copper is one of the most toxic
metals when it comes to not only the environment but also human health, especially when it
becomes involved in human consumption, as a substantial amount ending up in the human body
can result to many harmful effects such as brain, heart, pancreas, and skin diseases ​(as cited in
Veli and Alyuz, 2007)​​, as well as liver disease and kidney failure ​(Zheng, et al., 2007)​​.

METHODOLOGY

Renge, Khedkar, and Pande (2012) conducted research to determine the capability of
using eggshells as low-cost adsorbents. Eggshells are characterized as largely-crystalline calcium

16
carbonate. In conducting the experiment, the researchers used hen and duck eggshells that were
cleansed with tap water repeatedly, they were left to cool through the air. Because the protein
component of eggshells can be altered om high temperatures ( > 40 °C), the eggshells were also
incubated in a hot air oven at 40 °C for 30 minutes. After that procedure, the eggshells were then
ground to a powder in a grinder and sieved to obtain between 60-100 mesh (0.25-0.104 mm) size
particles. Also, it was elaborated that the adsorption process that was utilized for this research
was the Langmuir Isotherm.

The study of ​Kanyal and Bhatt (2014) ​showcased a different method. In order to
prepare a 1000 ppm stock solution of copper sulfate, they added 3.93g of copper (II) sulfate in
1L of deionized water. The researchers collected around 20 eggshells from their daily kitchen
waster and were washed in tap water followed by distilled water. They were left to dry on
blotting paper and were then subjected to the oven at 50℃ for 2 days. Once done, the eggshells
were pulverized with the use of a mortar and pestle followed by a mixed in order to get fine
particles. To obtain a homogenous size, the pulverized adsorbent was later sieved.

17
 Chapter III
METHODOLOGY

This chapter presents the main processes and the data gathering procedures that the study
employed. These are the measures taken by researchers to properly obtain information and
thoroughly answer the research questions. Also discussed here will be the research method,
research locale, procedures, statistical treatment of data.

I. Research Method

As described by ​Lewis (2015)​​, the qualitative research process allows researchers

to utilize “interpretive and theoretical frameworks”, integrating their worldviews. At the
same time, assumptions, paradigms, and frameworks are created on the basis of research
inquiry, and it is through these that researchers are guided accordingly in producing a
proper qualitative research.

Moreover, ​Yilmaz (2013) ​defines the quantitative research method as “research

that explains phenomena according to numerical data which are analyzed by means of
mathematically based methods”, which makes use of statistical analysis in the testing and
interpretation of numerical data, the main feature that sets it apart from the qualitative
method.

When the qualitative and quantitative research methods are used in joint
combination, the mixed research method becomes the result of such. This is further
supported by the research study of ​Östlund, Kidd, Wengström, and Rowa-Dewar
(2011)​​, which describes mixed methods research as research wherein the researchers
gather and process data through the two approaches of qualitative and quantitative
methods. In line with this information, the study thus implemented the mixed research
method, beginning with the application of the qualitative research method and then

18
 transitioning into the quantitative research method for the gathering and analysis of data.
This proved to be the most appropriate at each step of the research process for the study
involves either one method or the other.

II. Research Design

As described by ​White, H., and Sabarwal, S. (2014)​​, experimental designs and

quasi-experimental designs are similar in a number of ways. Both quasi-experimental
designs and experimental designs evaluate a causal hypothesis. A causal hypothesis tests
the interaction of variables, specifically its cause and effect interactions, to have a theory
on how one variable causes an effect to another variable. Also, they both test how an
‘intervention’ is effective such that it is able to attain its objectives, measured by a certain
set of indicators.

The design of the study defines the study type which is experimental.
Experimental research as defined by Harland (n.d.) ​is a study that strictly adheres to a
scientific research design, which our research implements. The scientific research
includes a hypothesis, a variable that can be manipulated by the researchers, and
variables that can be measured, calculated, and compared. Moreover, the experiment is
completed in a controlled environment. The researcher collects the data and the following
results will either support or reject the hypothesis. It should determine the relationship
between two variables: the independent variable and dependent variable.

The sub-type that the research will be implementing is the quasi-experimental

designs. This type of research design determines comparison groups that are close to the
treatment group in terms of its pre-intervention characteristics. Comparison groups are
groups that do not receive the intervention given to the treatment group for the purpose of
comparison. Treatment groups are groups that receive the intervention or the independent

19
variable. Therefore, in the comparison of the two groups, it is possible for the
independent variable to be tested in terms of a difference in the outcomes of both groups.

Since this type of research design may be more susceptible to bias, various
techniques may be done in order to maintain the validity of the data and reduce the risk of
bias. These techniques are the regression discontinuity design (RDD) or the propensity
score matching (PSM). In the data analysis of a study with a quasi-experimental design,
the methods, ex-post single difference or double difference can be used.

This research design is most commonly used when it is not possible to randomize
variables to treatment and control groups. As is with the case of ex-post impact
evaluation designs, the counter-factual assessment of poverty impact of assigned
programs and ex-ante impact evaluations, the analysis of important policy initiatives,
where it is not possible to randomize the variables.

In line with this information, the study thus utilized this research design as it
proved to be the most appropriate research design. With the development of the causal
hypothesis, the effectivity of eggshell waste in being a low-cost adsorbent that brings the
removal of copper sulfate from copper sulfate-induced water leads to the testing of the
quality of the aforementioned water after the experiment using the indicators relevant to
the study. The condition used was chosen by the researchers, wherein they chose to
induce copper sulfate to purified drinking water as the treatment group and to use purified
water as the baseline standard for their research to be able to test whether or not the
adsorptive capability of eggshell could be used as a low-cost adsorbent and use it to
remove copper sulfate from water.

20
III. Materials

The main materials needed for the experiment of the study are that of eggshell
waste and purified drinking water.

The eggshell waste was obtained and collected from the from each of the
researchers’ own households. The eggshells were collected at the end of each day, with
the whole process carried out over a span of three weeks.

The water used, on the other hand, was Absolute distilled water, bought from
groceries near the school. The water was distributed evenly in amounts of 1L among
three identical beakers for the experiment proper.

IV. Data Gathering Procedure

PREPARATION OF EGGSHELL

In accordance with the journal “Modified Eggshells as Cost-Effective Absorbent

for the Treatment of Arsenic (III) Contaminated Industrial Effluents” written by
Mubarak, ​Zia-Ur-Rehman, and Chaudhry (2015)​​, the researchers started with the
collection of poultry eggshell waste coming from the researcher’s own homes and
respective school. These eggshells were washed and cleaned with distilled water to
remove impurities left in the eggshell waste. The eggshells were then heated at 105℃ for
around 3 hours and grounded into a fine powder with a blender and left for further
treatment.

PREPARATION OF SOLUTIONS
In consonance with the journal of Bioremediation and Biodegradation, “Removal
of Heavy Metals from Water (Cu and Pb) Using Household Waste as an Adsorbent”

21
 written by ​Kanyal and Bhatt (2015), ​the researchers made use of self-contaminated
copper sulfate (CuSO​4​2+​) induced water solutions as their samples. For the preparation of
the samples, four 1L purified water samples (three for the samples and one for the
stocked solution) were taken from Absolute distilled water, then placed into respective
beakers. Afterward, 3.93g of copper sulfate (CuSO​4​2+​) were each induced into the four
purified water samples in order to complete the stock solution.

METHOD
After preparing the copper sulfate solutions, crushed eggshells with differing
weights, 2g, 4g, and 6g, were placed and secured into three separate sheets of thin cloth,
which are tied up into small bags, respectively. The samples were all labeled properly and
the eggshells were applied to their respective beakers with 60 minutes as their contact
time. Subsequently, the adsorbents were then taken out and then the mixture was filtered
using filter paper.

TESTING
The four samples were sent to the laboratory of SGS Philippines, Inc. for the
analysis of their copper content through the use of Inductively Coupled Plasma Method
(ICP).

V. Data Analysis

In the case of equilibrium studies, this will be carried out using the Langmuir and
Freundlich adsorption isotherm equations.
The Langmuir equation, which depicts the relationship between the number of
active sites of a surface undergoing adsorption, is represented as:

22
where ​' q e ' is the mg of metal adsorbed per g of adsorbent at equilibrium, C e is the metal
ion concentration at equilibrium. ' Q0 ' and 'b' are the constants and can be determined
from the graph.
​ ​e r​ esulted in a straight line. The slope is Q​0 ​and intercept is b.
A plot of C​e​/q​e ​vs C

The Freundlich isotherm, representing the variation of adsorption of a quantity of

gas adsorbed by a unit mass of the solid adsorbent with pressure, and expressed by
Freundlich as:

where ​'x' is the amount of solute adsorbed, m is the weight of adsorbent, C​e ​is the solute
equilibrium concentration. K and 1/n are the constant characteristics of the system.

The Freundlich parameters were obtained by fitting the experimental data to the
linearization of the equation to be written in the logarithmic form:

where ​(Q​e =
​ x/m). Plotting log Q​e ​against log C​e​, resulted in a straight line graph. The
slope of the straight line is '1/n' and intercept is equivalent to log K.

The adsorption capacity of metal ions by eggshell waste was calculated by the
following equation:

where C o and C e are the initial and equilibrium concentrations (ppm) of metal ions in
solution respectively, is the volume of solution and is the quantity of adsorbent.

23
 Finally, to answer the question posed in the hypothesis, the formula for the
percentage of the removal of copper sulfate from an aqueous medium will be utilized. To
reiterate, the null hypothesis (​H​o​)​ is that the treated eggshell waste was incapable of
adsorbing copper sulfate from the copper sulfate-induced water solution, while the
alternative hypothesis (​H​a )​ is that the treated eggshell waste was capable of adsorbing
copper sulfate from the copper sulfate-induced water solution. The equation to calculate
the percentage of copper removed is as follows:
Ci − Ceq
Removal of Copper (%) = Ci × 100
where C​i ​is the initial ion concentration in mg L​-1​, C​eq ​is equilibrium (or final) ion
concentration in solution in mg L​-1​.

24
 Chapter IV
DATA ANALYSIS

This chapter presents the data gathered by the researchers through experimentation and
testing; with the use of several tables and charts. It would also provide a corresponding
discussion of the aforementioned results from the lab.

I. Introduction
This research paper suggests that eggshells have the capability to adsorb copper sulfate
on copper sulfate-induced water. This is to gauge the adsorptive capability of eggshell waste and
to be able to adsorb mainly copper and other harmful substances that may be found in water.

II. Results
Results were gathered through tests done by SGS Philippines, Inc. This action was done
to show the copper contents left on the solutions to determine the adsorptive capability of
powdered eggshell waste on copper sulfate-induced water.

Table 1. Copper contents of the four solutions used to identify the adsorptive capability of
powdered eggshell waste on copper sulfate-induced water

Analysis Name Powdered Unit Results Unit

Eggshell
Waste

Stock Solution 0 grams 982 mg/L

2g Eggshell 2 grams 968 mg/L

4g Eggshell 4 grams 983 mg/L

6g Eggshell 6 grams 974 mg/L

25
Table 2. Copper contents of each solution presented in a bar graph

Table 3. Metal removal percentage of the results

Metal removal % = | C oC− oC e | × 100%

Analysis Name Percentage

2g Eggshell Less 1.43%

4g Eggshell Added 0.10%

6g Eggshell Less 0.71%

26
Table 4. Adsorption capacity of q
mg V
q( g )​ = | C o − C e × m
|

mg
Analysis Name q( g )

2g Eggshell 3.56

4g Eggshell 0.25

6g Eggshell 2.04

III. Discussion
As shown in Table 1 and Table 2, the setups that were done in determining the adsorptive
capability of powdered eggshell waste on copper sulfate-induced water solution are as follows: a
stock solution with 0g of powdered eggshell, with 2g of powdered eggshell, with 4g of powdered
eggshell, and with 6g of powdered eggshell.

These parameters for each setup was decided upon by the group of researchers in
accordance with a previous research that is similar to the topic at hand. The materials needed for
the lab testing—specifically the solutions—were done in the laboratory of Saint Jude Catholic
School. In creating the solutions, the researchers used a constant solution consisting of 1 liter of
distilled water with 3.93g of copper sulfate for each. Afterwards, varying amounts of powdered
eggshell waste was added to the mixture to determine whether the amount of eggshell hinder or
affect its capability to adsorb copper from the solution.

Additionally, based on Table 1, it can be said that the stock solution without eggshell
contained 982 mg/L, the 2g eggshell solution contained 968 mg/L, 4g eggshell solution
contained 983 mg/L, and the 6g eggshell solution contained 974 mg/L. Based on these gathered
results, it can be inferred that the presence of powdered eggshell alone results in an adsorption of

27
copper, hence resulting in fewer amounts as compared to the control. A supposed trend can also
be seen, where the ​lesser amount of powdered eggshell results in a greater amount of copper it
can adsorb from a solution. ​However, there is one result that deviated from the other data, which
happens to be the amount of copper found in the 4g eggshell solution that resulted in 983 mg/L,
an amount that is greater than the stock solution with 982 mg/L of copper.

Based on Table 3, the metal removal percentage of each parameter was calculated using
the formula given. The result for 2g of eggshells is that the overall copper content decreased by
1.43% as compared to the stock solution. For the 4g of eggshells, the amount of copper was
increased by 0.10%, while for the 6g of eggshells, the amount of copper only decreased by
0.71%.

Furthermore, as shown in Table 4, the adsorption capacity of the eggshells was also
calculated. The results were that in 2g of eggshells, the adsorption capacity is 3.56; in 4g of
eggshells, the adsorption capacity is 0.25; and in 6g of eggshells, the adsorption capacity is 2.04.

28
 Chapter V
CONCLUSIONS AND RECOMMENDATIONS

As the consumption of eggs in a daily perspective continues to grow, it is more than an

understatement to say that several to hundreds of eggshells are being thrown in a matter of
seconds. Issues involving the increase in waste pollution and in the lack of clean resources
remain to be an unsolvable challenge to most. In line with this, countries all over the world have
tried to look for several alternatives that could produce and obtain accessible clean water in a
mass perspective but unfortunately, no one have yet to succeed in doing so.

In this experiment, the researchers formulated the solutions in the Research Hub located
on the 4th floor vicinity of Saint Jude Catholic School’s laboratories. In creating the samples, the
researchers used three constant solutions of 1 liter of distilled water induced with 3.93g of copper
sulfate. After creating the solutions, the powdered eggshells with varying weights of 2g, 4g, and
6g were placed and wrapped into three separate sheets of thin cloth, which were then tied into
small bags with a string attached for each bag. The sample solutions were then properly labelled
before the eggshells were submerged into their respective beakers. After 60 minutes of contact
time, the researchers removed the adsorbents and the solutions were filtered using filter paper.
Eventually, the researchers poured and sealed the sample solutions inside water bottles before
sending it to the laboratory for testing.

After delivering the tests to SGS, results show that the stock solution without eggshell
contained 982 mg/L of copper, the 2g eggshell solution contained 968 mg/L, the 4g eggshell
solution contained 983 mg/L, and the 6g eggshell solution contained 974 mg/L. Based on these
gathered results, the trend of that the lesser amount of powdered eggshell to be submerged into a
solution leads to a greater amount of copper it can adsorb from a solution can be observed.
However as mentioned before, a result from our experiment turned out to be different from the
other data, which is the amount of copper found in the 4g eggshell solution that resulted in 983
mg/L, a value that is greater than the stock solution, with 982 mg/L of copper. Thus ​producing

29
results showing that in 2g of eggshells, the adsorption capacity is 3.56; in 4g of eggshells, the
adsorption capacity is 0.25; while in 6g of eggshells, the adsorption capacity is 2.04.

In conclusion, the adsorption of copper from copper sulfate-induced water using eggshell
waste has been studied and found feasible, but has also produced inconclusive results. The
adsorption increased with an increase in temperature, adsorbent concentration, and time of
agitation along with its time of submersion. The use of eggshell adsorbent presents operational
simplicity and adsorption capacity for the removal of metals from aqueous solutions.

Having the said results, the researchers came up with the following recommendations for
the future researchers who plan to continue the said experiment. First, the researchers suggest
that future researchers need to compute for the proper measurements and molarity of all the
variables before performing the experiment to attain the expected results. Second, future
researchers are recommended to immerse the glassware to be used for the experiment in a 6 M
HCl solution to remove organic residue on the glassware. Third, future researchers should verify
with the institute regarding the minimum amount of the materials needed and the proper
procedures that will be applied to avoid misunderstanding. Additionally, researchers are
recommended to perform multiple trials that are to be tested in different laboratories to compare
and see if the equipment used within the laboratories lead to similar outcomes. Lastly, the
present researchers suggest that the future ones should also try to use different kinds of eggshell
with higher absorptive capabilities and other compounds like heavy metals to experiment on
which may result in higher absorptive percentage results.

30
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 APPENDICES

APPENDIX A

Claim stub of samples at SGS Philippines Inc. Laboratory

36
37
 APPENDIX B

Results of Copper Content Analysis performed by SGS Philippines Inc. Laboratory

38
CURRICULUM VITAE

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