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Activated Carbon from Pomelo (Citrus maxima)

Albedo as Adsorbent to Zinc (II) in


Aqueous Solution

Ryan Christian C. Morales


Chyle Keremiah D. Orcullo
Rodith A. Padilla
Stepahnie Suzzane S. Valdez

Academic Track, Baguio City National Science High School

Author Note

Ryan Christian C. Morales, Chyle Keremiah D. Orcullo, Rodith A. Padilla, and

Stepahnie Suzzane S. Valdez are students of the Science, Technology, Engineering,

and Mathematics strand. Correspondence to this paper should be directed to Mr.

Morales at starfishprime25@gmail.com.

Special thanks is expressed to DENR – EMB Region 1 and Ms. Kira Nae

Baguilat for providing assistance during the experimentation and testing stage of this

study. Gratitude is also given to the research adviser, Mr. Edgar Soriano, and Mr. Leo

Peter Dacumos for the guidance.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 2

Abstract

The study tested the adsorptive ability of activated carbon from pomelo albedo (ACPA)

to Zn2+ in aqueous solutions. It determined if there is a significant difference in the Zn 2+

content of the aqueous solution before and after the intervention. Moreover, the effect of

contact time, pH of the aqueous solution, adsorbent dose, and initial concentration of

Zn2+ to the adsorption of ACPA was studied.

The ACPA was prepared through ZnCl2 activation and thermal activation. Afterwards,

effect of contact time was tested from 0-300 minutes, pH studies was done with pH

ranging from 1 to 7, effect of adsorbent dose was tested with 1 g to 5 g of ACPA, and

effect of initial Zn2+ concentration was tested with 1 ppm to 5 ppm of Zn 2+. Each set-up

was stirred for 5 minutes and was left untouched for the time prescribed per treatment.

Activated carbon from coconut husk (ACCH) was chosen as the control during the

experimentation. The amount of Zn 2+ left per treatment was analyzed by an FAAS

machine.

Results showed that for ACPA, the optimum contact time is 180 minutes and the

optimum pH level is 5. Adsorbent dose and initial concentration of Zn 2+ are proportional

and inversely proportional respectively to the adsorption of the adsorbents. Most

importantly, ACPA and ACCH are able to adsorb Zn 2+ through chemisorption in a

monolayer fashion however; ACPA is able to adsorb more Zn 2+ than ACCH.

In conclusion, ACPA can be used by water treatment systems to remove of Zn 2+ in

contaminated water.

Keywords: ACPA, adsorption, pH level, contact time, adsorbent dose,

iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiichemisorption
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 3

Chapter 1

INTRODUCTION

Background of the Study

Zinc is a metallic element that is present in the Earth’s crust and it has been used

by humans in various industries such as in the pharmaceutical industry, mining industry,

and metal electroplating industry. One form of this useful metal is zinc (Zn) dust. Based

from the substance information sheet of Sigma-Aldrich (2018), the average size of Zn

dust is less than 10 micrometers, which is as big as red blood cells. Zinc dust are bluish-

gray in color, odorless, and reacts quickly with the compound that it comes in contact

with. However, it does not dissolve in water (Wiley, 2017). This is supported by the

chemical data sheet of National Oceanic and Atmospheric Administration (n. d.) wherein

they said that, though Zn dust is insoluble in water, it may produce various water-soluble

Zn compounds which could contaminate water with Zn 2+ ions. Zinc is a metal that is

often detected in industrial wastewater, mostly from gold and metal mining industries

(Wan Ngah, Teong & Hanafiah 2007).

Zinc (II) is one of the heavy metals known to contaminate water bodies. Despite

naturally occurring in the environment, Zn 2+ turns into a pollutant if its concentration in

water exceeds water safety standards (Scottish Environmental Protection Agency, n.d.).

For the Philippines, the Department of Environment and Natural Resources [DENR]

(2016) stated that the allowable Zn concentration in freshwater is 2 ppm and below.

Furthermore, marine waters used for ecotourism, recreation, and propagation of marine

food sources should have Zn concentrations ranging from 0.04-1.5 ppm for them to be

deemed safe for their intended uses (DENR, 2016).


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 4

Zinc (II) Environmental Impacts

Zinc (II) has damaging effects to the environment if it is improperly disposed. In

Butuanon River in Cebu, industrial firms nearby have been discharging untreated

wastewater containing Pb, Zn, and Cd compounds as early as 1996 (Vestil, 2016).

Greenspec (2018) warns that an environment with high concentrations of Zn may

produce undesirable effects.

One effect is that, the abundance of Zn 2+ in water bodies destroys aquatic

ecosystems. It is because Zn2+ is toxic to zooplanktons, the primary diet of most marine

organisms (Ismail & Adnan, 2016). An increase in the amount of Zn compounds in water

bodies means the reduction of population of zooplanktons which could significantly

disrupt the food chain. Other than that, ingestion of too much Zn 2+ damages the gills of

fishes. As a result, it disables their ability to take in dissolved oxygen from water

(Kamaruzzaman, Ong & Jalal, 2008). Bioaccumulation of Zn toxins could also occur in

marine organisms intended for human and commercial consumption, putting their

consumers at risk (Paler & Ancog, 2014).

Researchers obtained samples of catfish caught from a major river in Cebu City

to study their Zn2+ concentrations. It was found out that fish samples obtained from the

upstream, midstream, and downstream of Butuanon River contain 60-90 ppm of Zn2+ on

average (Oquiñena and Ancog, 2016). Oquiñena and Ancog (2016) stated that this

exceeds the safe concentration of at most 50 ppm of Zn2+ in aquatic organisms intended

for human and commercial consumption as determined by the European Union.

Effects of Zn Compounds to Human Health

With regards to human health, exposure to too much Zn compounds is

dangerous. Mayo Clinic (2018) stated that the allowable intake of Zn substances in the

human body is 11 mg/day for men and 8 mg/day for women. In addition, the World
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 5

Health Organization (2017) recommends that at most 2 ppm of Zn 2+ ions should be

present in drinking water for it to be safe for consumption.

According to the Agency for Toxic Substances and Disease Registry [ATSDR]

(2005), excessive intake of Zn 2+ and other Zn compounds for long periods of time could

suppress copper and iron absorption in the body, affecting many metabolic processes.

Furthermore, ingesting high levels of Zn for several months may cause anemia, skin

irritation, and can damage the pancreas. On the other hand, short term exposure to

huge amounts of Zn dust could lead to an illness called “metal fume fever” (ATSDR,

2005). Zinc and its compounds are useful to many industries; however, too much

exposure to it is dangerous to human health.

Effects of Zn Compound Contamination to Communities

The degradation of the environment due to rapid industrialization has become a

major concern today. Many factories and industries have been established and

developed, one of which is the mining industry. It is known that mining uses different

heavy metals and chemicals such as cyanide, borax, lime, Hg, and Zn in order to

process and extract valuable metals like gold and silver. The destruction of the

environment due to mining is a major problem in many countries around the world

(Engels, 2002). Zinc contaminants have been found in at least 985 of the 1,662 current

and former hazardous waste sites in the United States and these may cause harm to

people (ATSDR, 2005). In China, rivers near major metropolitan areas contain high

concentrations of lead (Pb), arsenic (As), mercury (Hg), cadmium (Cd) and Zn (Hu, Jian

& Kavan, 2014). The Chinese Ministry of Ecology and Environment (2018) traced the

sources of the pollutant Zn to mining sites and factories near the river systems. It was

found out that Zn and other heavy metals used in industrial processes are discharged

without any treatment by these industries in rivers.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 6

Likewise, the Philippines has been facing the negative impact to the environment

of irresponsible mining practices. Contamination of water sources by Zn has affected the

safety of agricultural food sources in the Philippines. A study by the Philippine Rice

Research Institute discovered that irrigation water of rice fields in several provinces in

the country are deposited with high concentrations of chromium (Cr), Zn and Hg

(Magahud, Badayos, Sanchez & Santa Cruz, 2015). These heavy metals were also

present in trace amounts in rice samples taken from those fields. Magahud et al. (2015)

stated that the heavy metal contaminants were identified to have originated from

industrial wastes that were poorly processed and were dumped in lakes and rivers used

for irrigation.

In the Cordillera Administrative Region, the Benguet people have experienced

the disruption of agricultural economies and displacement from their homes due to the

contamination of land caused by large-scale corporate mining (Cordillera People’s

Alliance, 2009). Mining activities have a destructive effect on the environment, such as

the devastation of landscapes and the natural habitat of wild animals. Mining sites also

produce harmful by-products, such as mine tailings, that can cause ecological damage

to the environment and water resources. A notable incident was the breach in one of the

containment dams of Philex Mining Corporation, which lead to the spillage of Zn 2+ and

other mine tailings into water bodies (AGHAM, 2013). In addition, small scale mining

industries in the region employ the use of heavy metals in processing ores. However, the

inadequate processes involved in doing so could lead to the deposition of these heavy

metals to soil and water sources nearby these mining sites (Lu, 2012). These events

negatively affected the lives and livelihood of people residing near the mining sites, as

well as the communities that are dependent on the watersheds affected by the pollutants

from mining.
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 7

These incidents would have been prevented if wastewater treatments were

efficient and economical for use of every industry that utilizes heavy metals (Geetha &

Belegali, 2013). Unfortunately, common methods of wastewater treatment, such as ion

exchange, chemical precipitation, reverse osmosis and membrane separation, are found

to be costly and inefficient especially when it comes to treatment of wastewater with low

yet dangerous quantities of heavy metals (Gratao et al., 2005). However, researchers

discovered that adsorption technique using organic materials was more efficient than

conventional methods in treating wastewater with heavy metals (Rashed, 2013). This

means that adoption of the adsorption technique using organic materials is a promising

approach in treating water polluted with heavy metals.

Bioremediation

Bioremediation is the process by which living organisms or materials recovered

from them are used to clean up contaminated air, soil, or water sources (Cornell

University & Penn State University, 2009). The use of fruit peelings in removing heavy

metal ions and chemicals polluting water sources have been studied by numerous

researches. A study conducted by researchers from the National University of Singapore

took advantage of the adsorptive properties of tomato and apple peelings in removing

phosphate and chromate ions from water (Casey 2013). According to Bioremediation -

Advantages of Bioremediation (2018), some of the benefits in using bioremediation to

decontaminate environmental mediums, such as soil and water, are: equipment

requirements are minimal, no secondary wastes are produced in most occasions, and

the cost of treatment per unit volume of soil or groundwater is lower compared to other

remediation techniques.
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 8

Adsorption

Adsorption is defined by the International Union of Pure and Applied Chemistry

(1997), as the increase in concentration of a substance at the surface of another

material due to surface forces. These surface forces, which could be van der Waals

forces or intramolecular forces, are the ones responsible in binding particles to the

surface of a material. Basically, adsorption occurs when molecules in liquid stick to a

surface of another material due to chemical bonding or the work of intermolecular forces

(Barakat, 2011).

Factors Affecting the Adsorption Process

The adsorption capacity of any material to solid adsorbates is influenced by key

factors namely: surface area, adsorbent dose, temperature, chemical composition of the

adsorbent, and pH level of the aqueous solution (Helmenstine, 2018). Surface area is

defined as the total measure of how much exposed area an object has (Surface Area,

2017, para. 1). During adsorption process, materials that have more surfaces exposed

can attract and adsorb more molecules. This is the reason why efficient adsorbents have

adsorption pores in them ranging from 0.25 mm to 5 mm in order for the material to have

enough sites to facilitate adsorption (Helmenstine, 2018).

The second factor that affects the adsorption of heavy metals is the adsorbent

dose. Adsorbent dose is the amount of adsorbents used to remove a particular

adsorbate in an aqueous solution (Charles & Odoemelam, 2010). Considering the actual

concentration of heavy metals, adsorbent dose is directly proportional to the amount of

heavy metal contaminants removed up until an equilibrium point is reached

(Padmavathy, Madhu & Haseena, 2015). This means that increasing the mass of

adsorbents used would also increase the concentration of adsorbates removed from an

aqueous solution.
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 9

Meanwhile, temperature dictates the rate at which the adsorption process

happens and increase in temperature indicates an increase in the internal energy

present in a system. Robb (1989) stated that adsorption is an exothermic reaction

because the process itself releases energy. Thus, the magnitude of adsorption should

increase with the decrease of temperature. An increase in temperature would mean that

the molecules adsorbed would have greater movement due to the input of additional

energy, making it easier for them to detach from the surface they cling unto. Generally

speaking, an increase in temperature decreases the adsorbing capacity of a material.

The adsorptive ability of any material is inversely proportional to the temperature of the

liquid or solid adsorbents, while it is directly proportional to the surface area of the

adsorbent.

The presence of the functional groups also adds to the adsorptive ability of the

adsorbent. Since pomelo albedo contains pectin and other functional groups capable of

binding with Zn2+ ions, it has the potential to bind with Zn 2+ and reduce the concentration

of Zn2+ in the aqueous solution (Majeed, 2017). Furthermore, the activated carbon would

have a greater surface to give more regions for Zn2+ to be adsorbed.

However, the pH level of the aqueous solution has variable effects on the

adsorption process depending on the material which the adsorbent is made of. Some

adsorbents can effectively adsorb materials in acidic solutions, while others need a basic

environment for adsorption to happen (Majeed, 2017).

Despite this, results of several adsorption studies indicate that aqueous solutions

with pH 3 to 7 are ideal ranges for effective adsorption of heavy metals to happen (Igwe,

Nwokennaya & Abia, 2005). Low pH level would result to a competition between

hydronium (H+) ions and adsorbates for the adsorption sites of any adsorbent. As a

result, low amounts of the target adsorbates would be removed from aqueous solutions
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 10

(Bernard & Jimoh, 2016). On the other hand, Bernard & Jimoh (2016) stated that high

pH level could make it difficult for adsorbents to bind with target adsorbates due to the

presence of excessive hydroxide ions. It is therefore needed to determine the optimum

pH of the aqueous solution that the activated carbon from pomelo albedo can effectively

adsorb Zn2+ ions.

Agricultural Waste Adsorbents

Adsorbent products from citrus fruits, like pomelo, are effective adsorbents of

heavy metals contaminating water sources and are potential alternatives of

commercialized activated carbon. In the study conducted by Jayarajan, Arunachalam

and Annadurai (2011), they revealed that the agricultural waste products of pomelo,

specifically the peel, are an efficient, low-cost alternative to activated carbon in

wastewater treatment. This research was supported by the study of Zhang et al. (2018),

in which they indicated that pomelo has a high adsorption capacity for heavy metals,

particularly Zn2+.

According to Tripathi and Ranjan (2015), low cost adsorbents originating from

agricultural waste and biological materials have high capabilities for the removal of

heavy metals, such as Zn, from wastewater. Examples are orange peel for nickel (Ni)

adsorption, hazel nut for chromium (Cr) adsorption, and citrus peels and watermelon

rinds for Zn adsorption (Jain, 2015). This is made possible by the presence of functional

groups such as phenolic groups, hydroxyl groups, and carboxylic acids in agricultural

waste adsorbents. These functional groups are able to chelate or bind with the heavy

metal ions to remove them from the water (Hao, Anbin & Shaohong, 2018).

The adoption of adsorption technique using agricultural wastes, such as fruit

peelings, manure and bagasse, to wastewater is a promising process in the removal of

heavy metals in contaminants (Zwain, Vaikili & Dahlan, 2014).


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 11

Pomelo and its Adsorptive Ability

One type of agricultural waste is the pomelo peeling. Aside from being rich in

vitamin C, pomelo has the highest pectin content among all citrus fruits. Quantitative

chemical analysis of pomelo indicated that the water-soluble pectin content of pomelo

peel is 68%-79%, with 63% of it coming from the pomelo albedo (Chaidedgumjorn &

Sotanaphun, 2009). In addition, the average pectin content of pomelo is about 60-85%,

in which most of it was extracted from its albedo, the spongy white part (Methacanon,

Krongsin & Gamonpilas, 2013). Pectin has been identified as an efficient adsorbent of

heavy metal contaminants in water (Zauro & Vishalakshi, 2015). Further studies

revealed that the ability of pectin to adsorb heavy metal, such as Zn 2+, is due to the

presence of functional groups in it.

Functional groups, according to Frank (2017), are groups of atoms joined in a

specific manner that has unique characteristics regardless of the molecules that bond

with them. Ogata, Kanagawa, Tominaga, Tanaka, Ueda, Iwata, and Kawasaki (2013)

stated that pectin is capable of adsorbing heavy metal ions due to the presence of

functional groups. These functional groups allow pomelo albedo to adsorb heavy metal

ions (Soiklom, Sirichort, Lampetch & Klinchan, 2013). A carboxyl group is a common

functional group having a carbonyl and hydroxyl group both linked to a carbon atom. A

carbonyl group is a functional group made of carbon double-bonded to oxygen, and a

hydroxyl group is an -OH group. In addition, a study by Hastuti, Siswanta, Mudasir and

Triyono (2015), identified hydroxyl group as the best functional group in adsorbing and

binding heavy metals to the surface of pectin-based adsorbents. Amide and methoxyl

are other main functional groups present in pectin which also contribute to the

adsorption of heavy metals by pectin-based adsorbents (Hastuti, et. al, 2015).


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 12

Citric acid is another compound which helps pectin in adsorbing heavy metals

and qualitative phytochemical analysis of pomelo confirms the presence of this

compound (Khan, Quian & Perveen, 2018). With regards to heavy metal adsorption,

carboxyl groups are present in citric acid. According to Wartelle and Marshall (2000), this

functional group is mainly responsible for the ability of citric acid to bind with heavy

metals in aqueous solutions.

Another reason why pomelo peeling is a great adsorbent has something to do

with its physical characteristics. Citrus peels have large surface areas, high swelling

capacities, and excellent mechanical strength (Zwain, Vakili & Dahlan, 2014). Being in

the same genus, pomelos also possess these similar characteristics. Having a large

surface area would give more available sites for adsorption to occur. Meanwhile, high

swelling capacities can enable the peeling to adsorb more heavy metals (Zwain et al.,

2014).

With all these, the study researched on the use of activated carbon from pomelo

albedo (ACPA) in adsorbing Zn2+ from aqueous solution. Despite the presence of

functional groups capable of heavy metal adsorption, no previous studies were

conducted yet on the ability of ACPA to adsorb Zn2+ ions from aqueous solutions.

Hence, this study focused on the use of ACPA in adsorbing Zn2+ ions from aqueous

solutions. The capability of ACPA in adsorbing Zn2+ was tested in various pH levels,

different initial Zn2+ concentrations, varying adsorbent dose, and increasing contact time.

In addition, the study compared its adsorptive ability to that of the commercially available

activated carbon from coconut husk (ACCH). This is the most commonly used heavy

metal adsorbent in small-scale mining sites and other metal industries.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 13

Research Questions

The study aimed to determine the feasibility of activated carbon from pomelo

albedo in adsorbing Zn2+ from aqueous solutions. Specifically, the study aimed to answer

the following questions:

1. What is the pre-assessment and post assessment Zn2+ concentration of the

aqueous solution before and after the intervention of the activated carbon from

pomelo albedo?

2. What is the point of saturation in the adsorption of Zn 2+ by the activated carbon

from pomelo albedo?

3. What is the optimum pH level of the aqueous solution for the effective adsorption

of Zn2+ by the activated carbon from pomelo albedo?

4. What is the effect of pH level, initial concentration of Zn 2+, and adsorbent dose on

the adsorptive ability of activated carbon from pomelo albedo?

5. Is there a significant difference between the pre-assessed Zn2+ content of the

aqueous solution and the post-assessed Zn2+ content of the aqueous solution in

terms of Zn2+ concentration in the different treatments?

Ho: There is no significant difference between the pre and post assessed Zn 2+

content of the aqueous solution of the different treatments in terms of Zn 2+

concentration.

Significance of the Study

The researchers’ study will greatly help the environment by reducing the amount

of Zn2+ contaminants present in water bodies. As a result, aquatic ecosystems will be

spared from the toxic effects of this heavy metal. It will also prevent the bioaccumulation

of Zn2+ in aquatic food sources, such as fishes and crustaceans. In addition, industries

will be able to save resources when treating their wastewater contaminated by Zn 2+ with
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 14

activated carbon from pomelo albedo. It is because the common wastewater treatment

systems used today are expensive and inefficient in removing trace quantities of heavy

metal pollutants. The Zn2+ adsorbed from the pomelo peeling can also be recovered and

reused by these industries. Most importantly, the method of removing Zn 2+ using

activated carbon from pomelo albedo can be applied by people to clean their water

source if they are situated nearby industries that utilize Zn compounds.

Chapter 2

METHODOLOGY

Research Design

Since the study is experimental, randomized control-group pretest-posttest

design under completely-randomized design was applied in this research. This design

was used to determine if the activated carbon from pomelo albedo (ACPA) and activated

carbon from coconut husk (ACCH) were able to reduce the Zn 2+ concentration of the

aqueous solutions. Additionally, the performance of ACPA in adsorbing Zn 2+ in aqueous

solution under different conditions can be compared to that of ACCH (Salkind, 2010).

In this design, the initial and final concentration of Zn 2+ in the aqueous solution of

each treatment would be measured to determine if the intervention had an effect on

every treatment. Furthermore, each Zn2+ aqueous solutions will be randomly assigned to

the different treatments belonging to the experimental group and control group. This is to

avoid any bias in the results during experimentation due to extraneous variables

(Shalabh, 2017). It is because completely-randomized design assumes that on average,

extraneous factors will affect treatment conditions equally; so any significant differences

between treatments can fairly be attributed to the independent variable.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 15

Figure 1: Research design diagram of the treatments involved in the study.

In this diagram, the Zn²+ aqueous solutions made were randomly allocated to

each of the treatments of the experimental group and control group. The adsorptive

ability of the activated carbon from pomelo albedo was tested with varying pH level,

initial concentration of Zn 2+, various adsorbent dose, and contact time.

Data Gathering Procedure

Preparation of Adsorbents

Four kilograms of pomelo were gathered in Purok 14, Irisan, Baguio City.

Afterwards, the pomelos were peeled and the albedo was sliced from the pomelo

flavedo or pomelo rind. All of the pomelo albedos were washed 3 times with tap water to

remove any surface impurities.

The pomelo albedos were then sun dried for 5 days. Then, they were chemically

activated by soaking the pomelo albedos to 1 L of 20% ZnCl 2 solution for 24 hours. The

pomelo albedos were removed from the ZnCl2 solution and they were sun dried again for

3 days. Next, the dried pomelo albedos were carbonized using an electric torch. The

lumps of carbonized pomelo albedos were then ground using mortar and pestle.

Afterwards, the ACPA was soaked in 250 mL of 29% HCl solution for 24 hours to

remove any Zn and other organic materials that could have contaminated the product.

The ACPA was then filtered from the HCl solution and was washed with distilled water
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 16

until the pH of the adsorbent is neutral. Finally, the ACPA was sun dried for 3 days. The

ACPA particles were then transferred to a plastic container.

Preparation of Aqueous Zn2+ Solutions

Following the standard procedures of DENR (2016) in diluting solutions to create

an aqueous solution of Zn2+, 5 mL from the 20% ZnCl2 stock solution was diluted to 995

mL of water to create a liter of Zn 2+ standard solution at 1000 ppm. Afterwards, 1.5 mL

from the standard Zn2+ solution (1000 ppm) was diluted in 498.5 mL of water to create

500 mL of Zn2+ solution at 3 ppm.

In order to create 500 mL Zn 2+ solution at 1 ppm, 0.5 mL from the 1000 ppm

standard solution was diluted to 499.5 mL of distilled water.

One milliliter of the 1000 ppm standard solution was added to 499 mL of distilled

water to create 500 mL Zn2+ solution at 2 ppm.

To create the 500 mL Zn2+ solution at 4 ppm, 2 mL from the standard Zn 2+

solution was diluted to 498 mL of distilled water.

The researchers obtained 2.5 mL from the 1000 ppm standard solution of Zn 2+

and added it to 497.5 mL of distilled water to create 500 mL solution of Zn 2+ at 5 ppm.

The dissociation of ZnCl2 into its constituent compounds in water is demonstrated

by the following chemical equation.

ZnCl2(aq) + H2O(l)  Zn2+(aq) + 2Cl2(aq)

When ZnCl2 was dissolved in water, it dissociated into Zn 2+ and 2 Cl2 ions. The

(aq) symbol showed that the products were now aqueous.

Experimentation
A. Effect of Varying Contact Time
There were 22 treatments to be used in the experimentation. The contact time

intervals were based on the study of Majeed (2017) but with some modifications. The
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 17

treatments under the experimental ACPA group were; 0 minutes, 30 minutes, 60

minutes, 90 minutes, 120 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes,

270 minutes, and 300 minutes.

Meanwhile, the treatments for the control ACCH group were: 0 minutes, 30

minutes, 60 minutes, 90 minutes, 120 minutes, 150 minutes, 180 minutes, 210 minutes,

240 minutes, 270 minutes, and 300 minutes. The 500 mL plastic beakers were equally

divided to each treatment and were labeled. Afterwards, each of the 500 mL plastic

beakers belonging to the 22 treatments was filled with 500 mL of Zn 2+ aqueous solution

at 3 ppm.

At the same time, the adsorbents were weighed using an analytic balance to

obtain 33 1 g of ACPA and 33 1 g of ACCH which were used in the experimentation.

For the experimental group, 1 g of ACPA was added in each of the plastic

beakers containing the 3 ppm Zn 2+ aqueous solution while 1 g of ACCH was added to

the plastic beakers under the control group. Afterwards, the aqueous solutions in these

beakers were stirred for 5 minutes. After stirring, each of the beakers was sealed with

clear wrap and was placed in a separate tray to begin the experimentation. The 500 mL

Zn2+ solution in each beaker was left untouched for the time prescribed in the treatment

they belong. Each treatment had three replicates.

When the contact time has lapsed for each of the sealed beakers under the

different treatments, the plastic covering was removed. Then, the ACPA and ACCH were

filtered from their respective aqueous solutions. The filtered Zn2+ aqueous solutions in

the beakers were then transferred to the sample bottles for the post assessment test

using FAAS machine. Each of the sample bottles were labeled according to their contact

time.
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 18

After the experimentation was finished, the ACPA and ACCH used were stored in

a tightly sealed container and it was labeled as hazardous materials. Likewise, the Zn2+

aqueous solutions used in the laboratory experiment were transferred to closed

containers and they were labeled as toxic substances. The containers of the adsorbents

and Zn2+ aqueous solutions were given to the Environment Management Bureau of

Department of Natural Resources - Region 1 for proper disposal.

B. Effect of pH Level of the Aqueous Solution


There were 10 treatments used in the experimentation to study the effect of pH

level in the adsorption capacity of the adsorbents. The pH ranges used in this research

were based on the study of Bernard and Jimoh (2016) with some modifications. Each of

the 10 500 mL plastic beakers was filled with 500 mL of 3 ppm Zn 2+ solution. The initial

pH level of the aqueous solutions was initially measured before adjusting their pH level

to the desired value. In order to lower the pH level of the aqueous solution, 1 mL of HCl

solution was poured on selected beakers until the desired pH level was reached. On the

other hand, 1 mL of 20% baking soda solution was poured on the beakers to increase

the pH level to the desired value. The treatments used for both ACPA and ACCH were

the following: pH level of 3, pH level of 4, pH level of 5 w, pH level of 6, and pH level of

7. All of the treatments had three replicates.

At the same time, ACPA and ACCH were weighed using an analytic balance to

obtain 15 1 g of ACPA and 15 1 g of ACCH which were used in the experimentation.

For the experimental group, 1 g of ACPA was added to each of the plastic

beakers containing the 3 ppm Zn2+ aqueous solution under the experimental group.

Similarly, 1 g of ACCH was added to the beakers under the control group. The aqueous

solutions of all the beakers belonging to the experimental and control group were stirred

for 5 minutes. After stirring, each of the beakers was sealed with clear wrap to begin the
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 19

experimentation. The contact time for the experimental group and control group is 180

minutes.

When the time of exposure has lapsed for each of the sealed beakers under the

different treatments, the clear wrap covering was removed. The ACPA and ACCH were

filtered from their respective aqueous solutions. The filtered Zn2+ aqueous solutions in

the beakers were then transferred to the sample bottles for the post assessment test

using FAAS machine. Each of the sample bottles were labeled according to their pH

value.

C. Effect of Varying Adsorbent Dose

Ten treatments were used to determine the effect of varying adsorbent dose to

the concentration of Zn2+ in the aqueous solution after the intervention has been applied.

The mass of adsorbents were based from the study of Hasar, Cuci, Obek and Dilekoglu

(2003) with some medications. The treatments for both ACPA and ACCH were; 1 g, 2 g,

3 g, 4 g, and 5 g. The mass of ACPA and ACCH were measured using an analytic

balance. Each of the treatments for both the experimental and control group had 3

replicates.

The 500 mL plastic beakers were equally divided to each treatment and they

were labeled. Afterwards, each of the plastic beakers belonging to the 10 treatments

was filled with 500 mL of Zn2+ aqueous solution at 3 ppm.

The ACPA was added to the beakers under the experimental group while ACCH

was added to the beakers under the control group. All of the aqueous solutions in these

treatments were stirred for 5 minutes. After stirring, each of the beakers was sealed with

clear. All of the treatments had a contact time of 180 minutes.

When the time of exposure has lapsed for each of the sealed beakers under the

different treatments, the plastic covering was removed. The ACPA and ACCH were
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 20

filtered from their respective aqueous solutions. Afterwards, the filtered Zn2+ aqueous

solutions in the beakers were transferred to the sample bottles for the post assessment

test using FAAS machine. Each of the sample bottles were labeled according to their

adsorbent dose.

D. Effect of Varying Initial Concentration of Zn2+


To study the effect of varying concentration of Zn 2+ in the aqueous solution to the

adsorptive ability of the adsorbents, 10 treatments were used in the experimentation.

With some modifications, the initial Zn2+ concentration values were based from the study

of Hasar et al. (2003). The treatments for both ACPA and ACCH were; 1 ppm, 2 ppm, 3

ppm, 4 ppm, and 5 ppm. Each of the treatments for both the experimental and control

group had 3 replicates.

The 500 mL plastic beakers were equally divided to each treatment and they

were labeled. Afterwards, each of the plastic beakers belonging to the 10 treatments

was filled with 500 mL of Zn2+ aqueous solution with the prescribed Zn 2+ concentration

per beaker.

At the same time, the ACPA and ACCH were weighed using an analytic balance

to obtain 15 1 g of ACPA and 15 1 g of ACCH which were used in the experimentation.

The ACPA was added to the beakers under the experimental group while ACCH

was added to the beakers under the control group. All of the aqueous solutions in these

treatments were stirred for 5 minutes. After stirring, each of the beakers was sealed with

clear. All of the treatments had a contact time of 180 minutes.

When the time of exposure has lapsed for each of the sealed beakers under the

different treatments, the plastic covering was removed. Filtration of the ACPA and ACCH

from their respective aqueous solutions was initiated. Afterwards, the filtered Zn2+

aqueous solutions in the beakers were transferred to the sample bottles for the post
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 21

assessment test using FAAS machine. Each of the sample bottles were labeled

according to their initial Zn2+ concentration.

Flame Absorption Spectroscopy Machine

For the determination of the Zn 2+ ion concentration of each of the treatments, a

flame absorption spectroscopy (FAAS) machine was used. Analytik Jena contrAA FAAS

from the laboratory of the Environment Management Bureau was utilized to analyze the

amount of Zn2+ present in the water of each treatment after the application of the ACPA

and ACCH has been done. FAAS works by atomizing the water samples through the

creation of mist dispersions (Thermal Fisher Scientific, n. d.). Afterwards, the mist was

fed into a flame to break up molecular bonds in the sample. The sample was then

exposed to light waves to energize and excite any metal ions present in the sample.

When absorption of light occurs, the Zn 2+ ions were energized and release a light

spectrum that was unique only for Zn. The machine then detects the wavelength

intensity of the light being emitted by Zn 2+ to determine its concentration (Aberdeen,

2017). The samples were fed into the machine and results were expected to be obtained

after an hour.

Data Analysis

Concentration of Zn2+ Ions

For each treatment, the mean concentration of Zn 2+ present in the aqueous

solution before and after the application of ACPA and ACCH were computed for

descriptive analysis after the results from the FAAS were released. In here, the mean

was the basis to pre-determine which treatment has the most adsorbed Zn 2+ and which

treatment has the least adsorbed Zn 2+ present in the aqueous solution.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 22

Calculation of Adsorption Capacity and Removal Efficiency

To compute for the adsorption capacity of the adsorbents at a particular time

interval, the mass balance equation (Horsfal et al., 2006) was used. The formula to

obtain this is:

Where: Co is the initial metal ion concentration, Cf is the final ion concentration,

V is the volume of the aqueous solution, and M is the mass of the adsorbent. The same

equation can also be used to determine the adsorptive capacity at equilibrium after the

data for adsorption capacity has been plotted.

The following equation was used for computing the removal efficiency of the

adsorbents to the Zn2+ ions (Fahad, 1994):

Where: Co is the initial adsorbate concentration and Cf is the final adsorbate

concentration.

Statistical Analysis

Independent sample t-test was used to determine if there is a significant

difference between the pre-assessed and post assessed Zn 2+ concentration of the

aqueous solutions for both the ACPA and ACCH group. This type of t-test was used

since the two groups being compared, ACPA and ACCH, are unrelated to each other in

terms of point of saturation in adsorption.

Pearson r correlation analysis was used to determine if there is a relationship

between pH value of the aqueous solution and adsorption capability of ACPA and

ACCH.
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 23

Adsorption Kinetics

The kinetics of adsorption was determined by analyzing the adsorptive capacity

of ACPA and ACCH in the different time intervals. According to Hu, Lu, Bing-cai, Qing-

jian, Wei-ming and Quan-xing (2009), the pseudo-first model and pseudo-second model

are used to model the kinetics of Zn2+ adsorption by ACPA and ACCH. The R2 value of

the graph of these models would indicate whether the kinetics model being analyzed

would suitably describe the adsorption process or not. The adsorption kinetics model

with an R2 value nearest to one would be the suitable model to describe the adsorption

process done by the adsorbents (Qiu, 2009). Adsorption kinetics provide an ideal model

on how the adsorbents bind with adsorbates (Hu et al., 2009).

The equation for the pseudo-first order is:

Where: qe is the adsorption capacity at equilibrium, qt is the adsorption capacity

at a given time interval, t is the time interval, and k is the rate constant of pseudo-first

order adsorption.

If the adsorption data fits the pseudo-first model, this means that the adsorption

process is physisorption (Hu et al., 2009).

On the other hand, the equation for the pseudo-second order model is (Yuh,

2006):

Where: qe is the adsorption capacity at equilibrium, qt is the adsorption capacity

at a given time interval, t is the time interval, and k2 is the rate constant of pseudo-

second order adsorption.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 24

If the adsorption data fits the pseudo-second model, the adsorption process is

chemisorption (Yuh, 2006).

Adsorption Isotherm

Langmuir isotherm was used to determine the saturation point of the ACPA and

ACCH in adsorbing Zn2+ from aqueous solution, the maximum adsorption capacity of the

adsorbents, and also to describe the behavior of Zn2+ and the adsorbents during

adsorption process. This isotherm model assumes that the uptake of metal ions occurs

via monolayer adsorption on a homogeneous surface (Chen, 2015). In addition,

adsorption happens without any interaction between the adsorbed ions. It was fitted to

the data from the treatments under contact time in which the amount of Zn2+ present in

the aqueous solution approached an equilibrium amount.

The equation for the linear model of Langmuir isotherm is (Chen, 2015):

Where: qe is the equilibrium adsorption capacity, Ce is the equilibrium adsorbate

concentration, qm is the maximum adsorption capacity, and K L is the Langmuir constant.

Chapter 3

Results and Discussion

Effect of Contact Time and Adsorption Efficiency

The post-assessed concentration of Zn2+ in the aqueous solutions for both the

ACPA and ACCH treatments were tested using FAAS machine. The effect of contact

time on the removal of Zn2+ ions was studied at a period of 300 minutes.
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 25

Table 1: Comparison of Concentrations of Zn2+ in the Aqueous Solutions during

the Contact Time Experiment for Adsorption

Mean Concentration of Time (minutes) Mean Concentration of

Zn2+ for ACPA (ppm) Zn2+ for ACCH (ppm)

2.8500 0 2.8500

1.8396 30 1.5588

1.2238 60 1.0862

0.9217 90 1.0297

0.7315 120 0.7199

0.5044 150 0.7131

0.4187 180 0.7127

0.4184 210 0.7125

0.4183 240 0.7124

0.4181 270 0.7121

0.4180 300 0.7121

At the equilibrium point of 180 minutes, 0.4187 mg/L of Zn 2+ was left on the

aqueous solutions after undergoing ACPA treatment. In addition, this has been identified

as the equilibrium concentration for the ACPA treatment since there was no significant

reduction in the amount of Zn 2+ of the aqueous solutions in the succeeding treatments.

On the other hand, 0.72 mg/L of Zn 2+ was left on the aqueous solutions after the

equilibrium time of 120 minutes in the ACCH treatment. There has been no significant

increase in the uptake of Zn2+ by ACCH from this point. Therefore, this period is the

equilibrium time for the adsorption of Zn2+ by ACCH.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 26

Furthermore, the adsorption capacity of ACPA at equilibrium is 1.22 mg/g. This

means that 1 g of ACPA can adsorb 1.22 mg of Zn 2+ ions after 180 minutes. Meanwhile,

the adsorption capacity of ACCH at equilibrium is at 1.07 mg/g. One gram of ACCH can

adsorb 1.02 mg of Zn2+ ions after 120 minutes.

The percentage removal of Zn 2+ for ACPA and ACCH treatments were calculated

to determine the point of saturation of adsorption in terms of contact time.

Effect of Contact Time


90%
80%
Zn2+ Ion Removal (%)

70%
60%
50%
40%
30%
20%
10%
0%
0 30 60 90 120 150 180 210 240 270 300
Time (minutes)

Activated Carbon from Pomelo Albedo Activated Carbon from Coconut Husk (Control)

Figure 2: Linear graph data for the effect of contact time on the percentage removal of

Zn2+ in the aqueous solution.

For ACPA treatment, the adsorption rate of Zn 2+ increased rapidly by 35% after

30 minutes of contact time until the point of saturation was attained at 180 minutes. At

this period, 85% of the Zn 2+ content of the aqueous solutions were adsorbed by ACPA.

Further increase in time after 180 minutes did not bring about any improvement in the

amount of Zn2+ adsorbed by ACPA.

On the other hand, ACCH attained an earlier saturation point, at 120 minutes.

However, it was only able to adsorb 75% of the Zn2+ content of the aqueous solution.
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 27

Similar to ACPA, there was no significant increase in the amount of Zn 2+ ions adsorbed

by ACCH after 120 minutes.

The attainment of equilibrium contact time for adsorption is due to the fact that

adsorption is a surface phenomenon (Helmenstine, 2018). The surfaces of ACPA and

ACCH have been fully occupied by the initially adsorbed Zn 2+ ions, leaving no area for

other Zn2+ ions to bind with.

Table 2: Comparison of Pre-assessed Zn2+ Concentration and Post Assessed Zn2+

Concentration of Aqueous Solutions and Test of Significant Difference

Treatments Pre-assessed Post Mean p- value Decision

Zn2+ assessed Zn2+ Difference

Concentration Concentration

ACPA 2.85 0.4185 -2.4313 <0.001 Reject Ho

0.4195

0.4181

0.4187

ACCH 2.85 0.7146 -2.1301 <0.001 Reject Ho

0.7289

0.7163

=0.7199

The mean difference between the pre-assessed Zn2+ content of ACPA and post

assessed Zn2+ content of ACPA is -2.4313. This indicates that 2.4313 ppm of Zn 2+ was

removed by ACPA after the equilibrium contact time of 180 minutes. Meanwhile, the

mean difference between the pre and post assessed Zn 2+ content of ACCH is -2.1301.
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 28

The concentration of Zn2+ removed by ACCH after the equilibrium time of 120 minutes is

2.1301 ppm.

In relation to this, Kurniawan et al. (2003) stated that the contact time required by

all types of adsorbents to efficiently adsorb metals in wastewaters ranges from 2 to 6

hours. This suggests that for ACPA, there was a rapid transport and binding of Zn 2+ ions

from the aqueous solutions to the surface of the adsorbent during the 180-minute period.

Similarly, the same phenomenon happened to ACCH during the 120-minute period.

Since the p-computed value of <0.001 for both ACPA and ACCH is less than the

p-critical value of 0.05, the null hypothesis is rejected. There is a significant difference

between the pre and post assessed Zn 2+ content of the aqueous solution of the different

treatments in terms of Zn2+ concentration. It means that both ACPA and ACCH can

effectively remove significant concentrations of Zn2+ from aqueous solutions.

With the data gathered, ACPA has an advantage to ACCH. Even though ACCH

could adsorb Zn2+ ions at a faster rate than ACPA, ACPA has a higher adsorption

capacity. This means that ACPA can be used by small-scale mining companies and

other metal industries to decontaminate their wastewater of Zn 2+.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 29

Effect of pH of the Aqueous Solution

The effect of pH level in the adsorptive capability of ACPA and ACCH was

studied in varying pH levels, ranging from pH 1 to pH 7.

Effect of pH Level
90.00%

80.00%

70.00%
Zn2+ Ion Removal (%)

60.00%

50.00%

40.00%

30.00%

20.00%

10.00%

0.00%
1 2 3 4 5 6 7
pH Level

Activated Carbon from Pomelo Albedo Activated Carbon from Coconut Husk (Control)

Figure 3: Line graph showing the percentage removal of Zn 2+ ions with respect to the pH

level of the aqueous solution.

The adsorption capacity of ACPA was at efficient levels when the pH level of the

aqueous solutions was in the range of pH 3 to pH 7. At pH 5, maximum adsorption of

Zn2+ ions amounting to 85.41% was observed. The adsorption capacity of ACPA started

decreasing when the pH level of the aqueous solutions was higher than pH 5. As a

result, pH 5 is the optimum pH level for the effective adsorption of Zn 2+ by ACPA. This

result coincides with the study of Kumar (2013) wherein maximum adsorption of their

pectin-based adsorbent was attained at pH 5. Afterwards, it was also observed in their


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 30

study that adsorption capacity started to decline after the pH of the aqueous solution

increased from pH 5 (Kumar, 2003).

Meanwhile for ACCH, it was observed that there was an increase in the

adsorption capacity of ACCH as the pH level of the aqueous solutions increase.

However, efficient levels of adsorption were observed when the pH level of the aqueous

solutions was in the range of pH 4 to pH 7. At pH 7, the maximum uptake of Zn 2+

amounting to 75.14% was observed. As a result, pH 7 is the optimum pH level for the

most efficient adsorption of Zn 2+ by ACCH. Similarly, the study of Hasar et al. (2003)

determined the optimum pH range of 4.5 to 7 of the aqueous solution for the efficient

adsorption of Zn2+ by AC from husk materials.

pH vs Adsorption Capacity for ACPA


1.6
1.4
1.2
q of ACPA (mg/g)

1
0.8 R² = 0.7251
0.6
0.4
0.2
0
0 1 2 3 4 5 6 7 8
pH Level

Figure 4: Scatter plot of the relationship between pH level of the aqueous solution and

adsorbency of ACPA.

The scatter plot shows an uphill trend in the adsorbency of ACPA with respect to

the pH level of the aqueous solution. It means there is a positive relationship between

pH level of the aqueous solution and adsorptive capability of ACPA.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 31

Table 3: Test of Correlation Between pH of Aqueous Solution and Adsorbency of

ACPA to Zn2+

r-value p-value Interpretation

pH vs. Adsorbency 0.7251 0.015 Strong Correlation

To determine the relationship between pH level and the adsorptive capability of

ACPA, a Pearson correlation study was conducted. An r-value of 0.7251 was computed.

This indicates a strong positive correlation between pH level of the aqueous solution and

adsorbency of ACPA to Zn2+ions. It means that an increase in the pH level of the

aqueous solution allows for the increase in the adsorptive capacity of ACPA in removing

Zn2+ ions. Additionally, since the p-computed value of 0.015 is less than the p-critical

value of 0.05, the correlation is statistically significant. This implies that pH level

generally dictates the amount of Zn 2+ ions that would be adsorbed by ACPA. According

to Annadurai, Juang and Lee (2003), the adsorption capability of citrus-based

adsorbents increase with the pH level of the aqueous solution.

pH vs Adsorption Capacity for ACCH


1.4
q of ACCH (mg/g)

1.2
1
0.8
0.6
0.4
0.2
0
0 1 2 3 4 5 6 7 8
pH Level

Figure 5: Scatter plot showing the relationship between pH level of the aqueous solution

and adsorbency of ACCH to Zn2+ ions.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 32

Similar to ACPA, a positive relationship between pH and adsorptive capability of

ACCH can be seen in the scatter plot due to the uphill trend of the plots.

Table 4: Test of Correlation Between pH of Aqueous Solution and Adsorbency of

ACCH to Zn2+

r-value p-value Interpretation

pH vs. Adsorbency 0.920 0.003 Strong Correlation

A Pearson correlation study was also conducted to determine the relationship

between pH level of the aqueous solution and the adsorbency of ACCH to Zn2+. Since

the r-computed value is equal to 0.920, a strong positive correlation exists between the

pH level of the aqueous solution and adsorbency of ACCH to Zn 2+ .This means that the

increase in the pH value of the aqueous solution allows for the increase in the adsorptive

capacity of ACCH to Zn2+ as well. In addition, the p-computed value of 0.03 is less than

the p-critical value of 0.05. This means the pH level of the aqueous solution indeed has

an effect on the adsorbency of Zn 2+ ions by ACCH. This was confirmed by the study of

Hasar et al. (2016) where the adsorption capability of activated carbon derived from

husk materials tend to increase with the pH level of the aqueous solution.

For ACPA and ACCH, pH 2 and pH 3 respectively yielded low percentages of

Zn2+ removed by the adsorbents. Low pH level of the aqueous solution resulted to a low

percentage of Zn2+ adsorbed because hydronium ions compete with Zn 2+ ions to the

adsorption sites of both adsorbents (Bernard & Jimoh, 2016). In addition, the decline in

the adsorption capacity of ACPA at pH levels higher than pH 5 was due to the formation

of insoluble OH- ions which makes the adsorption of Zn 2+ more difficult (Bernard &

Jimoh, 2016). The pH value of the aqueous solution influenced the binding of Zn 2+ at the

surface of ACPA. As a result, water treatment systems should adjust the pH of Zn2+
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 33

contaminated water to pH 5 to enable ACPA to uptake the greatest amount of Zn 2+ from

the wastewater.

Effect of Adsorbent Dose

The effect of the dose of ACPA and ACCH added to the aqueous solutions to the

amount of Zn2+ concentration left after intervention was studied in varying adsorbent

dose ranging from 1 g to 5 g.

Effect of Adsorbent Dose


100.00%
90.00%
80.00%
Zn2+ Ion Removal (%)

70.00%
60.00%
50.00%
40.00%
30.00%
20.00%
10.00%
0.00%
1 2 3 4 5
Adsorbent Dose (g)

Activated Carbon from Pomelo Albedo Activated Carbon from Coconut Husk (Control)

Figure 6: Line graph showing the trend in the percentage removal of Zn 2+ by ACPA and

ACCH with respect to the mass of the adsorbent.

For the effect of adsorbent dose on the removal of Zn2+ ions by ACPA, there was

a gradual increase in the amount of Zn 2+ removed by ACPA up until 3 g of the adsorbent

was added to the aqueous solutions. Using 1 g of ACPA resulted to the removal of

85.72% of the Zn2+ content of the aqueous solutions. Furthermore, 89% of the Zn 2+

content of the aqueous solution was adsorbed using 3 g of ACPA. From this point, there

was no more significant increase in the amount of Zn 2+ adsorbed by ACPA. This


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 34

indicates that up to 3 g of ACPA can be used to efficiently adsorb Zn2+ in aqueous

solutions. In the study of Annadurai et al. (2003), the adsorption density of pectin based

adsorbents tend to reach an equilibrium percentage regardless of the adsorbent dose.

Similarly, there is an increase in the amount of Zn2+ adsorbed by ACCH with an

increase in the dose of the adsorbent used. From 74.43% of Zn 2+ removed from the

aqueous solution using 1 g of ACCH, 88.74% of the adsorbate content of the aqueous

solution was removed using 5 g of ACCH. However, the increase in the percentage of

Zn2+ removed from the aqueous solution slowly increased in the subsequent treatments

from 3 g. Hasar et al. (2016) stated that the equilibrium adsorption density for activated

carbon derived from husk materials can be attained by using adsorbent doses in the

range of 3-8 g.

The equilibrium adsorption density of adsorbents is connected to the saturation

of the adsorbent sites of ACPA and ACCH. According to Kolon, Mitko and Bok-Badura

(2017), at high dose of the adsorbent, the majority of metal ions were already adsorbed,

but some active sites of the adsorbents remained unsaturated. This explains the

decrease of the adsorption capacity of metal ions per unit mass of adsorbent and

increase of percentage of zinc removal by both ACPA and ACCH. At most 3 g of ACPA

should be used by water treatment systems to attain an effective uptake of Zn 2+ from

contaminated water.

Effect of Initial Concentration of Zn2+

Varying initial concentrations of Zn 2+ in the aqueous solutions were created to

determine if it has an effect on the adsorptive capacity of a constant amount of ACPA

and ACCH.
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 35

Effect of Initial Zn2+ Concentration


100.00%
90.00%
80.00%
Zn2+ Ion Removal (%)

70.00%
60.00%
50.00%
40.00%
30.00%
20.00%
10.00%
0.00%
1 2 3 4 5
Initial Zn2+ Concentration (ppm)

Activated Carbon from Pomelo Albedo Activated Carbon from Coconut Husk (Control)

Figure 7: Line graph showing the trend in the percentage removal of Zn 2+ by ACPA and

ACCH with respect to the initial concentration of Zn2+ in the aqueous solutions.

Increasing the initial concentration of Zn 2+ resulted to the decline in the

percentage of Zn2+ ions adsorbed by both ACPA and ACCH. From 90.76% of Zn2+ ions

removed by ACPA in 1 ppm concentration, it decreased to 73.23% of Zn 2+ adsorbed by

ACPA in 5 ppm concentration. However, the adsorptive capacity of ACPA increased with

increasing Zn2+ concentration. From 0.45 mg/g at 1 ppm of Zn 2+, the adsorption capacity

of ACPA became 1.8307 mg/g at 5 ppm Zn 2+ concentration.

At 1 ppm concentration of the adsorbate, 85.60% of Zn 2+ was removed by ACCH.

However, the amount of Zn2+ adsorbed by ACCH decreased to 43.86% at 5 ppm

concentration. Similar to ACPA, the adsorptive capacity of ACCH also increased with

increasing Zn2+ concentration up until 4 ppm concentration of the adsorbate was

reached. From 0.43 mg/g at 1 ppm of Zn 2+, the adsorption capacity of ACCH increased
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 36

to 1.37 mg/g at 4 ppm Zn2+ concentration. However, the adsorptive capacity of ACCH

decreased at 1.1 mg/g upon reaching 5 ppm of adsorbate concentration.

The decrease in the percentage removal of Zn 2+ by the adsorbents is due to the

increasing amount of Zn2+ ions present in the aqueous solution (Padmavathy et al.,

2015). The Zn2+ ions compete with the limited binding sites of the adsorbents, leading to

an excess amount of Zn2+ left in the aqueous solution as its initial concentration

increases. In the study of Kolon et al. (2017), the low concentration of Zn 2+ ions enabled

them to fill all the active sites of the adsorbents. This explains the high percentage

removal of Zn2+ by ACPA at low initial concentrations of the adsorbates.

Adsorption Kinetics

To determine if the adsorption process for ACPA and ACCH falls under

physisorption or chemisorption, adsorption kinetic studies were conducted. The data

obtained from ACPA and ACCH were plotted in pseudo-first models and pseudo-second

models.

Pseudo-first Model for ACPA


0.5

0
0 50 100 150 200 250 300 350
-0.5
log (qE-qT)

-1

-1.5 y = -0.0099x + 0.1081


R² = 0.9037
-2

-2.5

-3
Time (minutes)

Figure 8: Scatter plot diagram for the pseudo-first kinetics model of ACPA.
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 37

For ACPA, a correlation value of 0.9037 was computed. In addition, the data

plotted in pseudo-first model does not follow a straight line. This signifies that adsorption

process for ACPA does not fall under physisorption (Hu et al., 2009).

Pseudo-first Model for ACCH


0.5
0
0 50 100 150 200 250 300 350
-0.5
-1
log (qe-qt)

-1.5
-2
-2.5
-3 y = -0.0112x - 0.2913
R² = 0.8275
-3.5
-4
Time (minutes)

Figure 9: Scatter plot diagram for the pseudo-first kinetics model of ACPA.

The correlation value for ACCH under the pseudo-first model is 0.8275. Likewise,

the data plotted for ACCH in this model does not follow a straight line. Adsorption

process done by ACCH does not fall under physisorption (Hu et al., 2009).
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 38

Pseudo-second Model for ACPA


300

250

t/qt (min/ mg/g)


200

150

100 y = 0.6955x + 30.716


R² = 0.9928
50

0
0 50 100 150 200 250 300 350
Time (minutes)

Figure 10: Scatter plot diagram for the pseudo-second kinetics model of ACPA.

Since the correlation value of ACPA under pseudo-second model is 0.9928,

higher than the correlation value obtained in the pseudo-first model, this adsorption

kinetic model fits the adsorption process that occurred under this treatment.

Furthermore, the plotted data follows a linear pattern. This indicates that chemisorption

occurred during the adsorption of Zn 2+ by ACPA (Yuh, 2006).

In relation to this, the study of Kolon et al. (2017) found out that pseudo-second

model of adsorption fitted their data for pectin-based adsorbents. Pectin-based

adsorbents used chemisorption to remove adsorbates from aqueous solutions (Kolon et

al., 2017). Due to the presence of functional groups in pectin, the adsorbate Zn 2+ ions

were chemically bonded to the surface of ACPA.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 39

Pseudo-second Model for ACCH


300

250 y = 0.8701x + 15.341


R² = 0.997

t/qt (min/ mg/g)


200

150

100

50

0
0 50 100 150 200 250 300 350
Time (minutes)

Figure 11: Scatter plot diagram for the pseudo-first kinetics model of ACPA.

The correlation value obtained in the pseudo-second model is 0.997, higher than

the value computed in the pseudo-first model for ACCH. As a result, pseudo-second

model describes the adsorption process that occurred under this treatment. The plotted

data gathered from ACCH treatment follows a linear pattern. This signifies that ACCH

adsorbed Zn2+ through chemisorption (Yuh, 2006). According to Tan, Ahmad and

Hameed (2008), chemisorption of Zn 2+ by ACCH is due to the presence of OH- functional

groups in it. These functional groups bind with the Zn 2+ ions that come in contact on the

surface of ACCH.

Adsorption Isotherm

The manner by which ACPA and ACCH uptakes Zn 2+ ions can be described by

several mathematical models, one of which is the Langmuir isotherm.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 40

Table 5: Langmuir Isotherm Model for the Adsorption of Zn2+ by ACPA and ACCH

Isotherm Model ACPA ACCH

Zinc (II) Zinc (II)

Langmuir Isotherm

qmax (mg/g) 1.22 1.07

R2 1 1

KL 0.35 0.70

Using Langmuir isotherm model, the maximum adsorptive capacity for Zn2+ of

ACPA was computed at 1.22 mg/g while 1.07 mg/g is the maximum capacity computed

for ACCH. Since the correlation value for both ACPA and ACCH is 1, the Langmuir

isotherm model fits them both. This coincides with the study of Hasar et al. (2016)

wherein Langmuir isotherm model fitted their data to describe the adsorption of metal

ions by husk-derived activated carbon.

Langmuir Isotherm Model for ACPA


2.5

1.5
C/qE

y = 0.8197x + 0.6248
1 R² = 1

0.5

0
0 0.5 1 1.5 2 2.5 3
Concentration (mg/L)

Figure 12: Scatter plot diagram for the Langmuir isotherm model of ACPA.
Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 41

The separation factor or RL for ACPA is equal to 0.35. This indicates that the

adsorption of Zn2+ by ACPA is favorable. It means that adsorption indeed caused the

decrease in the amount of Zn 2+ present in the aqueous solution. Furthermore, since the

RL value approaches 0, a fairly strong chemical bonding exists between the surface of

ACPA and Zn2+.

Langmuir Isotherm for ACCH


3

2.5

2
(C/qE)

1.5

1 y = 0.9346x + 0.1414
R² = 1
0.5

0
0 0.5 1 1.5 2 2.5 3
Concentration (mg/L)

Figure 13: Scatter plot diagram for the Langmuir isotherm model of ACPA.

Similar to ACPA, the RL for ACCH is 0.70. It means that the adsorption of Zn 2+

ions by ACCH is favorable as well. However, the force of attraction that holds Zn 2+ ions

on the surface of ACPA is stronger than that of ACCH.

Since the adsorption data fits for the adsorbents fit the Langmuir isotherm model,

both ACPA and ACCH adsorbs Zn 2+ ions on a monolayer fashion (Hare et al., 2016;

Kolon et al., 2017).


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 42

Chapter 4

Conclusions and Recommendations

Conclusions

Based on the findings of the study, the following conclusions were drawn:

1. The pre-assessed content of Zn2+ aqueous solution before the intervention of the

activated carbon from pomelo albedo is at 2.8500 mg/L.

1a. The average post assessed content of the Zn2+ aqueous solution for the 180

minutes equilibrium contact time is 0.4187 ppm.

1b. The average post assessed content of the Zn2+ aqueous solution for pH 5 is

0.4158 ppm.

1c. The average post assessed content of the Zn2+ aqueous solution for the

absorbent dose of 3g of activated carbon is 0.3138 ppm.

1d. The average post assessed content of the Zn 2+ aqueous solution for the initial

concentration of activated carbon is 0.7630 ppm.

2. The point of saturation in the adsorption of Zn2+ by the activated carbon from

pomelo albedo is at 180 minutes or 3 hours since there was no significant

reduction in the amount of Zn 2+ of the aqueous solutions in the succeeding

treatments.

3. The optimum pH level of the aqueous solution for the effective adsorption of Zn 2+

by the activated carbon from pomelo albedo is at pH 5.

4. The effects of the following parameter on the adsorptive ability of activated

carbon is as follow :

a) Effects of pH level

- The adsorption capacity of ACPA was at efficient levels when the pH

level of the aqueous solutions was in the range of pH 3 to pH 7.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 43

b) Initial concentration of Zn2

- Increasing the Zn2+ concentration also increases the adsorptive

capacity of the activated carbon from pomelo albedo.

c) Effect of adsorbent dose

- Increasing the amount of the adsorbent dose up to 3g indicates that

the adsorptive ability of activated carbon from pomelo albedo was

efficient in this level and from this point there was no more

significant increase in the amount of Zn 2+ adsorbed by ACPA.

5. There is a significant difference between the pre-assessed Zn2+ content of the

aqueous solution and the post-assessed Zn2+ content of the aqueous solution in

terms of Zn2+ concentration in the different treatments.

Recommendations

Based on the results of the study, the following recommendations were made:

1. Activated carbon from pomelo albedo can be used as a bio-remedy by small-scale

mining industries and other manufacturing industries which still use Zn in their major

activities

2. Activated carbon from pomelo albedo can be used to remove Zn2+ from polluted

water within 3 hours.

3. The pH of Zn2+ contaminated water should be adjusted to pH 5 for the effective

adsorption of Zn2+ by activated carbon from pomelo albedo to happen.

4. Adsorbent dose, initial concentration of Zn 2+, and pH of the contaminated water

should be considered when applying activated carbon from pomelo albedo to

decontaminate water of Zn2+.

5. Activated carbon from pomelo albedo can be an alternative to commercial activated

carbon in removing Zn2+ in contaminated water.


Running Head: Activated Carbon from Pomelo as Adsorbent to Zn 2+ 44

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