REMOVAL OF TOXIC CHROMIUM (VI) AND LEAD (II) FROM

SYNTHETIC WASTEWATER USING PRICKLY PEAR PEEL

ACTIVATED CARBON

MSc Thesis

BY

ZEWDU TESFAYE

ADVISOR: TAJU SANI (PhD)

DEPARTMENT OF INDUSTRIAL CHEMISTRY

COLLEGE OF APPLIED SCIENCES
ADDIS ABABA SCIENCE AND TECHNOLOGY UNIVERSITY

JANUARY 2020
 Declaration

I hereby declare that this thesis entitled “Removal of Toxic Chromium (VI)

and Lead (II) from synthetic wastewater Using Prickly Pear Peel Activated

Carbon” was prepared by me, with the guidance of my advisor. The work

contained herein is my own except where explicitly stated otherwise in the text,

and that this work has not been submitted, in whole or in part, for any other

degree or professional qualification.

ii
 Certification

This is to certify that the thesis prepared by Mr. Zewdu Tesfaye entitled

“Removal of Toxic Chromium (VI) and Lead (II) from Synthetic

Wastewater Using Prickly Pear Peel Activated Carbon” and submitted as a

partial fulfillment for the Degree of Master of Science complies with the

regulations of the University and meets the accepted standards with respect to

originality, content and quality.

iii
 Abstract

In the current work a highly efficient prickly pear peel activated carbon, PPPAC, adsorbent
has been prepared from locally available prickly pear peel for the removal of toxic hexavalent
chromium and divalent lead ions from synthetic wastewater. In order to evaluate the optimum
conditions for the adsorption the effect of carbonization temperature, carbonization time,
solution pH, contact time and adsorbent dosage are carefully studied based on AAS, FTIR,
SEM, PZC and adsorption efficiency. The results from batch adsorption studies were showed
that the adsorption efficiency of both chromium and lead onto PPPAC adsorbent was
influenced by carbonization time, temperature, solution pH, contact time and adsorbent
dosage. The PPPAC adsorbent, which was found to have significantly higher efficiency in
chromium and lead removal was synthesized using carbonization time and carbonization
temperature of 1 hour and 600 C, respectively. The highest Cr (VI) and Pb (II) uptake were
obtained at adsorbent dose of 15 mg/50mL with removal efficiency of 99.8 % and 88.92 %,
respectively and achieved at pH 3 and contact time of 30 min for Cr (VI), and at pH 5 and a
contact time of 40 min for Pb (II), both from 0.5 mg/L of the respective metal solutions.

Key words; Prickly Pear peel, Activated carbon, Adsorption isotherm, Point of zero charge

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 Acknowledgment

First of all, I thank JESUS and his mother for giving me the stamina and tolerance all through
the way. I also would like to extend my sincere appreciation to my advisor, Taju Sani (PhD)
for the opportunity to work with him, and for his help, support and guidance throughout the
course of this research.

I also express my gratitude to the Addis Ababa University for undertaking FI-IR and AAS of

my samples analysis

I am also indebted to Addis Ababa Science and Technology University, Industrial Chemistry

department, for giving me the chance accomplishes my study.

I also would like to extend my sincere appreciation to my friends and colleagues for their
guidance and support during my research processes. Thanks also go to my family for their
encouragement and help in every aspect.

THANKS TO LORD

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Table of Contents
A
APPROVAL PAGE ................................................................................... ERROR! BOOKMARK NOT DEFINED.

DECLARATION ........................................................................................................................................... II
CERTIFICATION ....................................................................................................................................... III
ABSTRACT.................................................................................................................................................. IV
ACKNOWLEDGMENT ............................................................................................................................... V

LIST OF FIGURES.................................................................................................................................... VIII

LIST OF TABLES........................................................................................................................................ IX
LIST OF ABBREVIATION .......................................................................................................................... X
1. INTRODUCTION................................................................................................................................. 1
1.1. BACKGROUND OF THE STUDY .......................................................................................................... 1
1.1.1. Chromium (Cr)....................................................................................................................... 2
1.1.2. Lead (Pb) ............................................................................................................................... 2
1.2. METHODS FOR HEAVY METAL REMOVAL ......................................................................................... 3
1.2.1. Chemical Precipitation ........................................................................................................... 3
1.2.2. ION EXCHANGE ........................................................................................................................... 4
1.2.3. REVERSE OSMOSIS ...................................................................................................................... 4
1.2.4. Ultra Filtration ...................................................................................................................... 4
Figure 1. Ultra filtration system for removal of heavy metals from wastewater ......................................... 5
1.2.5. Adsorption ............................................................................................................................. 5
1.3. ACTIVATED CARBON PREPARED FROM AGRICULTURAL BIOMASSES .................................................. 5
1.4. STATEMENT OF THE PROBLEM ......................................................................................................... 7
1.5. SIGNIFICANCE OF THE STUDY ........................................................................................................... 7

1.6. OBJECTIVE ..................................................................................................................................... 9

1.6.1. GENERAL OBJECTIVE .................................................................................................................. 9
1.6.2. SPECIFIC OBJECTIVES .................................................................................................................. 9
2. LITERATURE REVIEW ....................................................................................................................10
2.1. ACTIVATED CARBON ......................................................................................................................10
2.2. PREPARATION OF ACTIVATED CARBONS FROM AGRICULTURAL WASTE MATERIAL ............................11
2.3. AGRICULTURAL BASED ACTIVATED CARBON IN THE REMOVAL OF HEAVY METALS .........................13
3. EXPERIMENTAL ...............................................................................................................................17

3.1. CHEMICALS AND INSTRUMENTS ......................................................................................................17

3.2. PREPARATION OF PPPAC ...............................................................................................................17
3.3. CHARACTERIZATION OF PPPAC......................................................................................................18
3.4. DETERMINATION OF POINT OF ZERO CHARGE (PZC) OF PPPAC ......................................................19
3.5. ADSORPTION STUDIES ....................................................................................................................19
4. RESULT AND DISCUSSION..............................................................................................................21

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 4.1. CHARACTERIZATION OF PPPAC......................................................................................................21
4.1.2. Point of Zero Charge ....................................................................................................................22
4.1.3. FT-IR Analysis results ...........................................................................................................22
4.1.4. SEM Analysis results .............................................................................................................24
4.2. ADSORPTION STUDIES ....................................................................................................................26
4.2.1. Effect of Adsorbent Dosage....................................................................................................26
4.2.2. Effect of pH ...........................................................................................................................27
4.3. REMOVAL EFFICIENCY OF PPPAC PREPARED AT DIFFERENT CARBONIZED TEMPERATURE ...............29

5. CONCLUSIONS ..................................................................................................................................31
6. REFERENCES ....................................................................................................................................32

7. APPENDICES .........................................................................................................................................39

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 List of figures

Figure 1. Ultra filtration system for removal of heavy metals from wastewater................................... 5
Figure 2. A picture of Prickly Pear ..................................................................................................... 6
Figure 3. Point of PZC of PPPAC .................................................................................................... 22
Figure 4 . FT-IR Spectra of PPPAC adsorbent before adsorption...................................................... 23
Figure 5. FT-IR Spectra of PPPAC adsorbent(a) Before adsorption, (b) and (c) after Cr (VI) and Pb
(II) adsorption, respectively ............................................................................................................. 24
Figure 6. SEM micrographs of the synthesized PPPAC samples: (a)before and (b) after adsorption of
Cr(VI) ions ...................................................................................................................................... 25
Figure 7. SEM micrographs of the synthesized PPPAC samples:(a)before (b) after adsorption of
Pb(II) ion......................................................................................................................................... 25
Figure 8. PPPAC adsorbent dosage effects on Cr (VI) and Pb (II) removal....................................... 27
Figure 9. pH effect on PPPAC adsorption of Cr (VI) and Pb (II) ...................................................... 28

viii
 List of Tables

Table 1: Summary of some agricultural based activated adsorbents used for removal of Cr (VI) ion
from aqueous solution .................................................................................................................... 15
Table 2: Summary of selected agricultural based activated adsorbents used for removal of Pb (II) ions
from aqueous solution ..................................................................................................................... 16
Table 3: Physico-chemical properties of PPP activated carbon ......................................................... 21
Table 4: removal efficiency of PPPAC at different carbonized temperature ..................................... 29

ix
 List of Abbreviation

UF Ultrafiltration

AC Activated carbon

PPP Prickly pear Peel

PPPAC Prickly pear Peel Activated Carbon

SEM Scanning Electron Microscopy

FT-IR Fourier Transform Infrared Spectroscopy

CPAC Cassava Peel Activated Carbon

CT Carbonized Temperature

CIP Common intersection point

PZC Point of zero charge

RE Removal Efficiency

x
 1. Introduction
1.1. Background of the Study

Heavy metals are naturally occurring elements that have a high atomic weight and density,
have densities greater than 5g/cm3 [1,2]. These are lead (Pb), cadmium (Cd), zinc (Zn),
mercury (Hg), arsenic (As), silver (Ag), and chromium (Cr), copper (Cu), iron (Fe) and
platinum (Pt) group of metals. They cannot be degraded or destroyed [3]. They also
considered as trace elements because of their presence in trace concentrations (ppb range to
less than 10ppm) in various environmental matrices [4]. Heavy metals are toxic even at very
low concentration as they tend to bio-accumulate, which is an increase in the concentration of
a chemical in a biological organism over time, and cause poisoning, destroy liver, cancer and
brain damage when found above the tolerance level set by World Health Organization
(WHO) [2,5]. Their toxicity depends on several factors including the dose, route of exposure,
and chemical species, as well as the age, gender, genetics, and nutritional status of exposed
individuals. Because of their high degree of toxicity, arsenic, cadmium, chromium, lead, and
mercury rank among the priority metals that are of public health significance [5,6].

Heavy metals have wider scope in applications in various synthetic sectors including
domestic, agricultural, medical and technological sectors. The effluents of these factories,
refineries, and waste treatment plants are the main sources of heavy metal contaminations to
the ecosystem (water bodies). Because of the possession of wide scope of distribution, they
raise serious concerns on human health and the environment [6,7]. For instance, Chromium
and lead are commonly present in higher concentration in wastewater effluents of leather
industry, electroplating, metallurgy, paints and pigments, pharmaceuticals and horticulture,
and thus have a high likely hood of contaminating of water sources used for human
consumption. Studies showed that Cr and Pb metals are usually found in drinking water
above their permissible level, 0.05 mg/l and 0.01 mg/l, respectively [2,8]. Therefore, it is of
great relevance to remove these particular heavy metal ions from aquatic environment, which
this study, off course deals with using low cost adsorbents.

1
 1.1.1. Chromium (Cr)
Chromium is a naturally occurring element found in rock, soil, and groundwater. It is an
essential element that is required in small amounts for carbohydrate metabolism, but becomes
toxic at higher concentrations. Two stable oxidation states of chromium persist in the
environment, trivalent chromium, Cr (III) and hexavalent chromium, Cr (VI), which have
contrasting toxicities, mobility and bioavailability. While Cr (III) is relatively innocuous and
immobile, Cr (VI) moves readily through soils and aquatic environments and is a strong
oxidizing agent capable of being absorbed through the skin. Cr (VI) is more hazardous,
carcinogenic, and mutagenic. Due to its high solubility in water, it can easily enter to living
cells [9].

Chromate and dichromate ions are oxoanions of chromium (VI). All hexavalent oxanoions of
chromium are toxic due to their strong oxidizing property. In an aqueous solution, chromate
and dichromate ions can be inter convertible. The chromate ion is the predominant species in
alkaline solutions, but dichromate can become the predominant ion in acidic solutions.

2CrO2-4 + 2H+ Cr2O2-7 + H2O (1)

1.1.2. Lead (Pb)

Lead is found at low levels in Earth's crust, mainly as sulfide. However, the widespread
occurrence of lead in the environment is largely the result of human activities, such as
mining, smelting, refining and informal recycling of lead; use of leaded petrol (gasoline);
production of lead-acid batteries and paints; jewellery making, soldering, ceramics, lead glass
manufacture and cottage (home-based) industries; electronic waste and use in water pipes and
solder [10].

Metallic Lead is present in drinking water to some extent as a result of its dissolution from
natural sources, but primarily from household plumbing systems in which the pipes, solder,
fittings or service connections to homes contain lead. The amount of lead from the plumbing
system that may be dissolved depends on several factors, including acidity (pH), water
softness, and standing time of the water. On contact with oxygenated water, metallic lead can

2
be oxidized and solubilized: The key aspect of lead in the body is that Pb2+ can be absorbed
through the intestine and is stored in bones [11].

2Pb + O2 + 4H+ 2Pb2+ +2H2O (2)

However, lead has no essential function in man, and rather is known to cause brain damage,
major organs failure, and even death [9,12,13]. Lead ions can be absorbed by the body
through inhalation, ingestion, dermal contact (mainly as a result of occupational exposure), or
transfer via the placenta. Once is absorbed, it enters either a “rapid turnover” biological pool
with distribution to the soft tissues (blood, liver, lung, spleen, kidney, and bone marrow) or a
“slow turnover” pool with distribution mainly to the skeleton [1]. Lead is a cumulative
general poison, with fetuses, infants, children up to six years of age, and pregnant women
(because of their fetuses) being most susceptible to adverse health effects [14]. Lead can
severely affect the central nervous system. Overt signs of acute intoxication include dullness,
restlessness, irritability, poor attention span, headaches, muscle tremor, hallucinations, and
loss of memory [15].

To prevent or at least minimize the hazardous effect of heavy metals to the aquatic
environment and thus to our health, their removal from wastewater before discharging into
water bodies is of great important. In this respect, many researchers have been devoted to
their removal, and off course this study as well deals with using low cost adsorbents.

1.2. Methods for Heavy Metal Removal

For many years, various methods have been used for removal of heavy metals from
wastewater. The most commonly used methods are chemical precipitation, ion exchange,
reverse osmosis, ultra filtration and adsorption [8,16].

1.2.1. Chemical Precipitation

Chemical precipitation processes involve the addition of chemical reagents and the separation
of the precipitated solids from the cleaned water. Precipitation of metals is achieved by the
addition of coagulants such as alum, lime, iron salts and other organic polymers. Precipitation
is used as the treatment method to extract metals ions from solutions by almost 75 percent of
plating companies. Cost of the coagulant and large amount of sludge containing toxic
compounds produced during the process is the main disadvantage [8,16].

3
 1.2.2. Ion Exchange
In this process, metal ions from dilute solutions are exchanged with ions held by electrostatic
forces on the exchange resin. It is widely used in the industry for the removal of heavy metals
from effluents. An ion exchanger is a solid capable of exchanging either cations or anions
from the surrounding materials. Synthetic organic ion exchange resins are used as matrices
for ion exchange. The main disadvantage of this method is that it cannot handle concentrated
metal solution as organics, and other solids in wastewater easily foul the matrix. Moreover, it
is non-selective, high cost and highly sensitive to pH of the solution [16,17].

1.2.3. Reverse Osmosis

In the reverse osmosis process cellophane-like membranes separates purified water from
contaminated water. It is usually used in desalination of the water. In this process heavy
metal ions are separated by a semi-permeable membrane at a pressure greater than osmotic
pressure caused by the dissolved solids in the wastewater. The disadvantage of this method is
that it is highly expensive [16,17].

1.2.4. Ultra Filtration

Ultra filtration is a separation process using porous membranes for the removal of heavy
metals. It is a pressure-driven membrane operation process and has size exclusion removal
mechanism. A noticeable improvement of ultrafiltration was brought by adding complexing
water soluble polymers that binds with the cations to be removed, forming complexes of
large size. Typically, ultrafiltration will remove high molecular-weight substances, colloidal
materials and organic and inorganic polymeric molecules. The main disadvantage of this
process is the generation of sludge [7,16,17]

4
 Figure 1. Ultra filtration system for removal of heavy metals from wastewater

1.2.5. Adsorption
Adsorption is a process that occurs when a gas or liquid solute accumulates on the surface of
a solid or a liquid (adsorbent), forming a molecular or atomic film (the adsorbate). This is a
commonly used technique for the removal of metal ions from various synthetic effluents.
Widely used natural adsorbents for adsorption of metal ions include activated carbon, clay
minerals [18], biomaterials [19] and zeolite [20] .

Among these methods, adsorption is currently considered to be suitable for wastewater

treatment because of its simplicity, easy availability and cost. In this study the activated
carbon prepared from prickly pear peel has been tested in the removal of toxic Pb (II) and Cr
(VI) from synthetic wastewater and synthetic (tanning and paint factories) wastewater.

1.3. Activated Carbon Prepared From Agricultural biomasses

Activated carbon is a highly porous, amorphous solid used as effective adsorbent. It can
remove a wide variety of toxic metals such as cadmium, lead and zinc from sewage sludge
and wastewater. It can reduce the concentration of metal ions to environmentally acceptable
levels at an affordable cost [2,8].

Agricultural biomasses are widely available and wide range of locally existing biomaterials
can be employed for removal of heavy metals. Adsorption by agricultural waste has many

5
attractive features compared to the conventional method. They are a rapid, eco-friend,
economically feasible, possibility of regeneration of biosorbents and metal, no additional
nutrient requirement, absence of toxic sludge generation and they are fairly effective [21].

Prickly pear is one of the most abundant biomass of the Cactaceae family, grown throughout
the Americas as well as the central area of the Mediterranean, Europe, Asia, Africa that
include Ethiopia and Eritrea. It is belonging to the genus Opuntia spp. According to some
legends prickly pear locally known as “beles” was introduced between 1848 and 1870 by
Catholic Missionaries to eastern zone of Tigray by a priest called “Abune Yakob” who
visited Erob, northern part of Tigray, introduced cactus with the realization of unsuitability of
the area for cropping and other agricultural activities due to recurrent drought, erratic rainfall,
rocky and mountainous topography. Prickly pear is one of the drought tolerant species and
has a number of applications. It uses for food, livestock feed, cash income, environmental
protection, fence, firewood, cochineal production and bee forage. After removing the thin
thorns and peeling the thick skin of the fruit, the flesh of the prickly pear can be eaten raw.
There are increased interests in the cactus from the recognition of its potential contribution to
agricultural diversification, their application to the exploitation of marginal lands and
changing environments, and their utility as additional income sources for farmers [22].

Figure 2. A picture of Prickly Pear

The cactus pear fruit also called prickly pear fruit is an oval elongated berry, with a thick
pericarp, a juicy pulp with a considerable number of seeds and a semi-hard rind with thorns.

6
It is an edible and nutritious cactus and has antioxidant and anticlastogenic property [23]. In
Ethiopia the fruit is commonly eaten, but the peels are thrown out, as witnessed by the street
of Addis Ababa, our big city.

The focus of this study is to evaluate and assess the adsorption efficiency of PPP based
activated carbon for removal of hexavalent chromium and divalent lead. Various
experimental parameters that influence the removal efficiency of adsorbent materials such as
pH of the solution, adsorbent dosage and contact time are to be studied and optimized. The
adsorption isotherms of Cr (VI) and Pb (II) ions onto Prickly Pear Peel activated carbon
(PPPAC) also studied using two common adsorption isotherms: Langmuir and Freundlich
isotherm models. The adsorption kinetics also studied.

1.4. Statement of the Problem

In many cases the sources of water have been rendered unsafe for the human consumption as
well as for other activities such as synthetic needs and irrigation. The degraded water quality
can contribute to water scarcity as it limits its availability for both human use and ecosystem.
water contamination by heavy metals increased from time to time due to syntheticization and
other activities, which impose serious concerns because of their toxicity as well as bio-
accumulating tendency. The quantity of heavy metals that exists in effluents released into the
natural environment is often higher than the acceptable level and cause adverse health effects,
such as gastrointestinal disorders, diarrhea, stomatitis, tremors, hemoglobinuria, ataxia,
paralysis, vomiting and cancer. As Cr (VI) and Pb (II) are two of these toxic metals and is
present in high concentration in wastewater of various industries as well as due to the strict
environmental regulation on the discharge of heavy metals, it is necessary to develop low
cost adsorbents for the removal of heavy metal ions.

1.5. Significance of the Study

Recently, the population growth of Ethiopia has been accompanied by an increase in the
number of industries to meet the faster growing demands of the population. Along with the
useful products produced by the industries, a large amount of toxic materials are generated
and released to the environment as contaminants. Therefore, it is highly important to
minimize the toxic effect of these contaminants using low cost, environmentally friendly,
easily accessible and effective adsorbents.

7
So, this study intends to develop an effective adsorbent based on the widely available,
renewable and potentially less expensive raw material of PPP for the removal of hexavalent
chromium and divalent lead from synthetic wastewater and thrown to the environment, and
become the sources of environmental pollution. Thus, this study can contribute to solve
environmental problems as well.

8
 1.6. Objective
1.6.1. General Objective
Synthesis of activated carbon from prickly pear peel for the removal of toxic heavy metal
ions from synthetic wastewater

1.6.2. Specific Objectives

 Synthesis of activated carbon from prickly pear peel (PPP)
 Characterization of the synthesized PPPAC
 PPPAC adsorbent efficiency test in the removal of Chromium (VI) and Lead (II) ions
 Optimization of adsorption parameters (dose of PPPAC, pH, contact time and
temperature) for maximum adsorption efficiency

9
 2. Literature Review
2.1. Activated Carbon
Activated carbon (AC) defined as a group of materials with highly developed internal surface
area and porosity, and hence a large capacity for adsorbing various compounds and elements
from different media. The use of carbon extends so far back in time that its origin is
impossible to determine exactly. However, in 1773 Scheele discovered the gas adsorption
powers of AC and in 19th century, the synthetic production of activated carbon was well
established and used in sugar refining processes. In 20 th century, the decolorizing capacity
and sorption phenomena were interpreted and documented [24].

Currently, AC is used as an excellent and versatile adsorbent and its main applications
include the adsorptive removal of color, odor, taste, and other undesirable organic and
inorganic impurities from drinking waters; in the treatment of synthetic waste water; air
purification in food processing and chemical industries [25]. It is one of the effective
adsorbent for the removal of toxic heavy metal ions and organic pollutants from synthetic and
municipal wastewaters. It can remove a wide variety of toxic ions such as cadmium, lead,
chromium and zinc from sewage sludge and wastewater. This can reduce the concentration of
metal ions to environmentally acceptable levels at an affordable cost [16,26].

The high adsorptive capacities of activated carbons are highly related to porous
characteristics such as surface area, pore volume, and pore size distribution. All activated
carbons have a porous structure, containing up to 15 % of mineral matter in the form of ash
content. The porous structure of AC formed during the carbonization and activation
processes. The structure of pores and pore size distribution largely depends on the nature of
the raw material and activation process route. The activation process removes disorganized
carbon by exposing the crystallites to the action of activating agent, which leads to the
development of porous structure. The AC pores can be classified as Micropores (<2nm),
Mesopores (2-50nm) and macrospore (>50nm) according to their width [25].

Besides the porous structure, activated carbons have chemical structure and crystalline
structure as well. Activated carbon is associated with heteroatoms like oxygen, sulfur,
hydrogen, nitrogen, halogen and other elements in the forms of functional groups and/or

10
atoms which bonded chemically to the structure. Oxygen is one of the predominant atoms
which exist in the form of functional groups such as carboxyl, carbonyl, phenols and lactone.
The precursor and the activation treatment will determine the nature and amount of oxygen
surface group that will be contained in any activated carbon. These carbon–oxygen groups of
acidic (carboxylic, lactonic) evolve as CO2 where as that of non-acidic (carbonyl, ether,
quinone) are given out as CO, upon thermal decomposition. Generally, the heteroatoms
derived from the raw material involve in the structure of AC during carbonization process, or
they may be chemically bonded to the surface during activation. The microcrystalline
structure of ACs starts to develop during the carbonization process [26-29].

2.2. Preparation of activated carbons from Agricultural waste Material

Coal and wood are the most widely used carbonaceous materials for the synthetic production
of activated carbons. This commercially available activated carbons are quite expensive due
to the use of non-renewable and relatively high-cost starting materials. Besides, it is not
reliable in pollution control applications. Therefore, in recent years, many researchers have
tried to produce activated carbons for removal of various pollutants using renewable and
cheaper precursors, which are mainly synthetic and agricultural by products [16,26,30].

Activated Carbon obtained from agricultural waste and by product has the advantage of
offering an effective low cost replacement for non-renewable coal-based granular activated
carbons provided that they have similar or better adsorption efficiency. Agricultural waste is
a rich source for activated carbon production due to its abundance and availability at a cheap
price; make them good sources of raw materials for natural sorbents. The basic components
of the agricultural waste materials include hemicelluloses, lignin, lipids, proteins, simple
sugars, water, hydrocarbons and starch, containing a variety of functional groups [30,31]. In
particular agricultural materials containing cellulose show a potential sorption capacity for
various pollutants [31].

So far a significant number of AC have been developed and studied for the effective removal
of heavy metals, like chromium, cadmium, zinc, iron and copper and lead from aqueous
solution and synthetic waste water from agricultural waste materials. Agricultural waste
materials such as sugarcane bagassess [31,32], soya bean hulls, walnut hulls, cotton seed
hulls and corn cobs, orange peel, linseed deoiled cake, banana and avocado peels, rice husk

11
[33], tea-waste [34], peanut hulls, coconut shells, pineapple waste, Olive waste cake, citrus
peel, cassava peel [35], mango kernel, peanut shell, cactus, ground nut shell, coconut tree
[36], sawdust [37], orange peel [38], bamboo[34], oil palm, peach stones, grape seeds, oat
hulls, corn Stover, apricot stones, cotton stalk, cherry stones[34], coconut shell and seed shell
of palm tree [39], hazelnut shell [40], coconut husk [27], corncob and wheat straw [34,41]
have been used for the production of activated carbons, to mention some. The production of
activated carbons from agricultural waste materials has significantly reduced the problems of
disposal and management of the wastes as well as by products.

There is two commonly used basic activation processes in the production of activated
carbons: physical and chemical activation method. The choice of activation method is
depending upon the nature of the starting material and whether a low or high density,
powdered or granular carbon is desire. AC from the carbonaceous raw material can be
prepared and manufactured by carbonization (pyrolysis) followed by activation processes.
Carbonization of the carbonaceous raw material takes place at elevated temperature in an
inert atmosphere and mainly volatile materials are removed. The resulting carbonized product
has activated by either physical or chemical activation processes [25].

Physical activation involves carbonization of a carbonaceous material followed by the

activation of the resulting char at elevated temperature in the presence of suitable oxidizing
gases such as carbon dioxide, air or their mixtures. The activating agents, like CO 2, react
with the carbon structure to evolve CO, CO2, H2 or CH4 gases, which are responsible for the
formation of pores [25,29]. Carbon is oxidized by atmospheric oxygen and oxidized to CO 2,
so the air should be excluded or very controlled during carbonizing and activating. Steam and

CO2 act as mild oxidizing agents at 800-1000 oC as described by the following equations
(Eq. 3 - Eq. 5).

Cx + (H2O)y C (s) + yH2O -------------------- Carbonization (3)

C(s) + 2H2O CO2 + 2H2 --------------- Steam activation ( H = +75 KJ) (4)
C(s) + CO2 2CO ----------------- Activation by CO2 ( H = +159 KJ) (5)

As shown from the above equations, the activation of charcoal by this method yields
incomplete combustion products, burn up and volatilize. As the result, the surface of the

12
carbon is tremendously increased by the removal of hydrocarbon or tars. The Poor
absorbability of normal charcoal can be due to its small and very limited surface area due to
the filling of its pores largely with resins and products of incomplete combustion, which are
formed during preparation of charcoal. Activation process sweeps the tarry materials, opens
the pores, develop porosity, and increase surface area significantly [28].

Chemical activation is a single-step process including the impregnation of the carbonaceous

material with dehydrating agent prior to carbonization. The raw material generally used is
mixed with activating inorganic reagents such as ZnCl2, FeCl3, Na2CO3 and K2CO3,
inorganic acids (H3PO4, H2SO4 and HNO3) and alkali metal hydroxide (KOH and NaOH) in

proper ratio, and then dried, and subjected to carbonization at temperatures between 400oC to

800oC [25,28,34]. Among the above listed chemicals used in the chemical activation
processes, H3PO4 acid is the most commonly used chemical agent for the synthesis of
activated carbon due to the pyrolytic decomposition of the raw precursor and the formation of
the cross-linked structure and easily removed by washing with water after activation, where
as the use of ZnCl2 has declined due to environmental issues with zinc disposal [25,34].The
most important characteristic of an activated carbon is its adsorption capacity or uptake,
which is highly influenced by the activated carbon preparation conditions. This is because
activated carbon preparation variables such as activation temperature, activation time and
chemical impregnation ratio will influence the pore development and surface characteristics
of the activated carbon produced. Therefore, the challenge in activated carbon production is
to produce very specific carbons which are suitable for certain applications [26].

2.3. Agricultural Based Activated Carbon in the Removal of Heavy Metals

In recent years, researchers give due attention on the use of natural adsorbents obtained from
natural materials as an alternative to replace commercial activated carbon in the removal of
toxic heavy metals effluent from different sources of wastewater due to their environmental
and the economic advantages [26]. For instance, agricultural based activated carbon has been
used as adsorbents for removing heavy metals from wastewater. Mokhlesur M. Rahman etal
removed Ni(II) Pb(II) and Cr(VI) from wastewater using activated carbons prepared from
oil palm and coconut shells, using low temperature activation with phosphoric acid, suitable
for removing heavy metal ions and reported maximum adsorption capacity of 19.6 mg/g, 74.6

13
mg/g, 46.30 mg/g at optimum conditions, respectively. In case of Cr (VI), Maximum
adsorption capacity in their work was lower as compared to commercially available powder
activated carbon [42] M.K.Rai e tal prepared activated carbon with good potential from
mango kernel for removal of Cr(VI) from aqueous solution, and reported the maximum
adsorption capacity of 7.8 mg/g at pH 2 and temperature of 35°C [43]. In another study, Lo
etal prepared an activated carbon adsorbent from moso and maa bamboo for removal of
Cr(VI), and reported 100 % removal using once activated maa bamboo and 91.7 % removal
using twice activated maa bamboo [44]. In another similar study, Udeh, N. U and
Agunwamba, J. C evaluate the adsorption potential of bamboo based activated carbon, but in
this case for the removal of lead and cadmium metal ions and found removal efficiency of
83.44 % at pH 9 for Cd(II) and 96.09% at pH 11 for Pb (II) [45]. Similar study was
conducted by Mohamed H. H. Ali etal for removal of Pb (II) using orange peel activated
carbon adsorbent for the removal of Pb+2 and Cr+3 metals ions from their aqueous solution
[46] and reported the maximum adsorption efficiency of 99 and 85.2% for lead and
chromium at optimum reaction conditions, respectively. This study also revealed that the
adsorption process was affected by pH, time and adsorbent dosage.
However, in adsorption study by M. Chaudhuri & S. N. B. Saminal reported different result,
which was only about 33.2 % removal efficiency of Pb(II) by Coconut coir derived activated
carbon at pH 5 [47].
Cassava peel activated carbon (CPAC) by chemical activation method has been used for
removal of heavy metals from synthetic wastewater. Olayiwola oo reported that the
decontamination efficiency of the CPAC was found to be 100% for Cr [35]. Cr (III) removal
from the aqueous solutions with the orange peel activated modified by potassium carbonate
(OPAPC) were reported by Yasin Arslan and et al [38]. They reported that the adsorption
efficiency was increased as the adsorbent amount increased but no significant increase was
observed after the adsorbent amount of 8 g/L. Activated carbon derived from waste coconut
buttons were used to remove Pb (II), Hg (II) and Cu (II) ions from synthetic waste water by
using batch adsorption techniques and the results indicated that the produced activated carbon
was proper to remove for these metals [48]. Rice husks and avocado seeds derived activated
carbon have been reported to be capable of removing substantial amounts of metal ion and
organic pollutants from aqueous solutions [49]. Reports by Mohan et al, investigated the use
of low-cost activated carbon derived from bagasse, an agricultural waste material has as a

14
replacement for the current expensive methods of removing heavy metals from wastewater.
These studies were carried out at the initial concentration of 200 mg/l for Pb2+ and adsorption
capacity of NaOH pretreated biomass found was 87.74 mg/g.

A compilation of the results of some studies that was used various agricultural based
activated carbons for the removal of chromium (VI) and lead (II) is presented in Table 1 and
Table 2, as shown below.

Table 1: Summary of some agricultural based activated adsorbents used for removal of
Cr (VI) ions from aqueous solution.
AC derived Adsorbent Adsorbent Adsorbent References
Dose (g/L) Capacity (mg/g) Removal (%)
Sugarcane bagasse 20 3.8 99.0 [50]
Rice husk 4 8.9 94 [51]
Prawn shell 1.6 100 98 [52]
Jatropha wood 0.6-2 106.4-140.8 97 [53]
Medlar seed 3 200 99.9 [54]
Hazelnut shell 2.5 170 92 [55]
Juniperus procera Leaves 10 23 96 [56]
Palm Kernel Shell 0.5 125 92 [57]
Cassava peel 1.6 43.9 95-100 [58]

15
Table 2: Summary of selected agricultural based activated adsorbents used for removal of Pb
(II) ions from aqueous solution
AC derived Adsorbent Adsorbent Adsorbent References
Dose (g/L) Capacity (mg/g) Removal (%)
Banana peel 66.67 0.16 98 [59]
Hazelnut husk 12 13.05 97.2 [60]
Pineaple peele 10 0.952 96.46 [61]
coffee residue 10-90 89.29 63.29 [62]
Cassava peel 1.6 42.5 45% [58]
Juniperus procera Leaves 8 30.3 98 [56]

16
 3. Experimental
3.1. Chemicals and Instruments
PPP from local market of Addis Ababa and its modified version was prepared in the
laboratory of synthetic chemistry here in AASTU. Industrial wastewater samples were
donated by the Mojo Tannery factory and Galan paint factory. The following chemicals:
K2Cr2O7 (99%,FINKEM, England), Pb(NO3)2(Sigma-Aldrich), H3PO4 (85%,Sigma-Aldrich),
NaOH (pellet), HCl (37%,Sigma-Aldrich), HNO3(India), NaOH( India), N2 gas (Ethiopia and
distilled water were used in this study. All chemicals used were of analytical grade.
Apparatus used were volumetric flask, beakers, measuring cylinders, plastic sample holder,
mortar and pestle, sieve (150-250µm) and crucible. Instruments flame atomic absorption
spectrophotometer (AAS, MY15110003), UV-Vis spectrometer (HACH 6000), Fourier-
transform infrared spectroscopy (Spectrum 65 FT-IR (PerkinElmer)), Scanning electron
microscopy (JSM-IT300), Oven, furnace, digital pH meter (Jenway, 3510), electronic
balance (JD210-4CE), Shaker (Wise Shake, SHQ2D) were used in this study.

3.2. Preparation of PPPAC

PPP was collected from local market, Addis Ababa. The Peels of prickly pear were washed
several times with tape water to remove impurities and then rinsed with distilled water. The
resulting cleaned peels were dried in an oven over night at a temperature of 110 oC.
Preparation of PPPAC was initially followed the procedure reported by Carolyn Palm et al
for the preparation of AC from avocado peel [63] which then some modifications were
introduced through optimization. Accordingly, 130 gm of dried PPP was crushed to small
size and then the crushed PPP was impregnated with 30% H3PO4. The contents of beaker
were thoroughly mixed (15 rpm) and heated with autoscience (AM5250A) for 25 min at 300
o
C, until all the activating liquor is absorbed by the sample. This was placed in a furnace and
subjected at 400,500,600 and 700 oC for 1h each. Then the samples were allowed to cool at
room temperature. It was then washed with 0.5 M NaOH followed by distilled water to a
neutral pH [49], and the resulting product, PPPAC was allowed to dry at 110 oC. The yield
of the dried weight of PPPAC was calculated using Equation 6.

Wf
CY = × 100 (6)
Wo

17
Where: Wf = mass of PPPAC after carbonization, Wo = mass of PPP AC before
carbonization

Scheme 1. Preparation process of PPPAC

3.3. Characterization of PPPAC

Adsorption activity is largely dependent on the nature and particle size of adsorbent
materials. Thus, combinations of different characterization techniques have been used to
analyze the chemical composition and structural properties of PPPAC adsorbent material in
order to understand them in depth. Characterization of PPPAC samples were began with the
analysis of physico-chemical properties in terms of carbon yield, ash content, and pH.
Following, the surface morphology was analyzed using Scanning Electron Microscopy
(SEM), model JSM-IT300, here at Addis Ababa Science and Technology University,
Department of Industrial chemistry. In order to investigate the functional groups present in
PPPAC and to understand the shift after adsorption, Fourier-Transform Infra-Red (FT-IR)
spectrophotometer, Spectrum 65 FT-IR (PerkinElmer), in the range 4000-400 cm-1 using KBr
pellets technique, FT-IR spectra of the AC was measured before and after the adsorption
process of chromium and lead ions in order to determine the functional groups in frequency
ranged between 4000 to 400 cm-1, using KBr technique at room temperature (AAU). The
residual concentrations of the chromium ions before and after adsorption were measured by
UV-Vis Spectrometry and the concentration of lead ions was measured by AAS.

18
 3.4. Determination of Point of Zero Charge (PZC) of PPPAC

It is well known that the study of adsorption from solution strongly demands the knowledge
of the PZC, because the ability of the adsorbent materials to adsorb, either anions or cations,
is defined by the charge on the adsorbent surface. The PZC of PPPAC was measured by
potentiometric mass titrations technique [66]. It was identified as the CIP of the
potentiometric titration curve of the blank solution with the corresponding curves of the
impregnating suspensions containing 0.5, 1.0, and 1.5 g of the adsorbent in electrolytic
solution (0.02 N NaNO3 in 50 mL of deionized water). The experiment was performed, under
N2 atmosphere and the aqueous suspensions were equilibrated for 1 h to reach an equilibrium
pH value. Small amount of 1 M NaOH was added to make the pH around 10 and recorded as
initial pH after 15–20 min. Then the solid suspensions were titrated by 0.1 N HNO3, using
665 Dosimat (Metrohm, Switzerland). The pH of each suspension was then measured with 2
min time interval using a digital pH meter standardized by buffers (WTW Inolab pH/ION
Level 2, Germany).

3.5. Adsorption Studies

Adsorption studies started with the preparation Cr (VI) and Pb (II) stock and standard of
solutions. Stock solution (1000 mg/L) of Cr (VI) was prepared by dissolving 2.827 gm
K2Cr2O7 in distilled water, from which the samples of initial concentration of 0.5 mg/L have
been prepared by appropriate dilution in accordance with the real polluted water
compositions obtained in Ethiopia for experimental purpose. Similarly, the stock solution
(1000 mg/L) of Pb (II) was prepared by dissolving 1.599 gm Pb (NO3)2 with distilled water,
from which 0 .5 mg/ L working solution of Pb (II) were prepared. The pH of the solution was
adjusted using either 0.1 M NaOH or 0.1 M HCl solutions. The pH was measured with digital
pH meter (Jenway, 3510). Then, the adsorption studies were performed following the
procedures as previously described by N.U.Udeh et al [45] and S. Leta [61] with slight
modification. The optimum condition for adsorption of Cr (VI) and Pb (II) ions from aqueous
solution was investigated by batch method. The effect of adsorbent dose was investigated by
adding 50 ml of 0.5 mg/L initial adsorbate concentration to Erlenmeyer volumetric flask
containing different adsorbent doses (PPPAC), between 2.5 - 30 mg. The mixtures were
attached to shaker (Wise Shake, SHQ2D) and then agitated for 1 h at 150 rpm and room
temperature. Then the mixtures were filtered by Whatman filter paper (0.45 µm) and

19
analyzed for residual concentrations of Cr (VI) and Pb (II). The optimum adsorbent dosage
for the adsorption of Cr (VI) and Pb (II) was noted and adopted for the next experiment. The
effect of adsorbate pH was studied by adjusting the pH to 3-8 by adding 0.1M (NaOH) or
HCl solutions. The optimum adsorbent dosage for Cr (VI) and Pb (II) were adopted while
other test conditions and experimental procedure remained same. Their optimum adsorbate
pH was noted. The effect of contact time on the adsorption of Cr (VI) and Pb (II) was
conducted by varying the time form 5 min to 60 min, but adopting the optimum adsorbent
dose and optimum pH. The residual concentration of Cr (VI) and Pb (II) was analyzed and
their optimum contact time was noted.
The concentration of Cr (VI) & Pb (II) ions was measured using UV-Vis spectrometer
(HACH 6000) and flame atomic absorption spectrophotometer (AAS, MY15110003),
respectively. The concentration was calibrated prior to each experiment over a concentration
range of interest by using Cr (VI) and Pb (II) standard solutions. All experiments were
performed in triplicate and mean values are reported. All measurements were made at room
o
temperature (23 ± 2 C).
The adsorption efficency of PPPAC for removal of chromium and lead ions was calculated
using the following equation 7:

The % adsorption efficeincy = Co-Cf *100 (7)

Co

Where: Co and Cf are the initial and equilibrium concentration (ppm) of metal ions ,
respectively.

20
 4. Result and Discussion

4.1. Characterization of PPPAC

The prepared PPP activated carbon adsorbent was characterized in terms of carbon yield, ash
content, pH, PZC, functional groups and morphology.

4.1.1. Physico-chemical Analysis of PPPAC results

Characterization of PPPAC samples were first began with the analysis of its physico-
chemical properties in terms of carbon yield, ash content, and pH. The carbon yield, ash
content, volatile matter, moisture content and pH value of PPPAC, prepared at 600 oC for 1h,
was found to be 60.9%, 25.7%, 2.3%,11.1% and 7.27, respectively. The content of ash,
another characteristics parameter, depends on the raw material used. The low ash content,
volatile matter and high carbon yield may indicate the activated carbon is suitable for
adsorption process [64]. The physical-chemical properties of PPPAC at operating condition
600 oC are near normal and comparable with the values reported earlier [61].

Table 3: Physico-chemical properties of PPP activated carbon

Types of AC T(o) t(hour) Moisture Ash Volatile Carbon pH Reference

content content mater yield

Pine Apple AC 800 2 10.8% 21.8% 3.9% 63.5% 7.44 [61]

400 1 13.27 % 20.45% 18.14% 48.14% 7.32

PPPAC 500 1 12.40% 23.10% 5.4% 59.1% 7.28

600 1 11.1% 25.7% 2.3% 60.9% 7.27

700 1 10.74% 29.82% 1.93% 57.51 7.01

21
 4.1.2. Point of Zero Charge

PZC is the pH at which a surface has a net charge of zero. If the measured pH of a colloid is
lower than the PZC, the surface is positively charged; if the pH>PZC, the surface is net
negatively charged. The experimental curves (plots of pH vs Volume of HNO3) based on the
data as indicated on appendix (B); obtained following the mass potentiometric titration
technique is presented in Fig. 3. The intersection point fig 3 appears at the same pH value
irrespective of the amount of the adsorbent contained in the suspension. The blank, 0.5
gm,1.5 and 1gm of PPPAC intersects around pH value of 2.3. It has been reported that PZC
of orange peel activated carbons is 6.33 [67]. The point of zero charge of PPPAC was 2.3
lower than this report. The surface of PPPAC is negatively charged above the pH value of 2.3
and it will have high adsorption capacity for cations, metal ions (in this case which is Pb (II)
and Cr (VI)).

11

10
0.5gm
9 1gm
8
1.5gm
blank
7
pH

1
0 5 10 15 20 25
Volume(ml) of HNO3

Figure 3. Point of PZC of PPPAC

4.1.3. FT-IR Analysis results

Structural studies on PPPAC adsorbent sample by FT-IR provide important information
concerning the functional groups present on adsorbent surface. Figure 4 shows FT-IR spectra
of the synthesized PPPAC before adsorption
In the synthesized PPPAC before adsorption (Figure 4), the two short and broad
transmittance peaks that appear at about 3397 and 3174 cm-1 are associated with the presence

22
O–H stretching vibration of hydroxyl functional groups (or intermolecular hydrogen bonded).
The other two low intense peaks observed at about 2921 and 2722 cm-1 may corresponds to
asymmetric and symmetric C-H stretching vibrations of aliphatic functional groups (-CH3 or
–CH2 groups), respectively. The weak peaks observed at 1575 cm-1 might correspond to C–
H, stretching in –C=C– and aromatic C=C, and the band at 1452 cm–1 is possibly due to the
O-H bending band. The bands 1029-1256 cm−1 corresponds to the presence of aromatic and
hydro-carbons on the surface. Finally, the band in the range of 400 to 700 cm-1 indicates C-C
stretching.

40

38 a

1575
Transmitance(%)

36
3397 3176
1452
2921 2722
770
34

1256 494

32

30
1029

4000 3500 3000 2500 2000 1500 1000 500

-1
Wave length(cm )

Figure 4 . FT-IR Spectra of PPPAC adsorbent before adsorption

After adsorption (Figure 5b and c), the main bands due to the PPPAC framework remained.
However, both the FT-IR spectra of Cr (VI) and Pb (II) show the decrease in transmittance
intensity and the slight location shifts of some peaks. Figure 5b and c indicates such shifting
of peaks that occurs in the range between 1578 to 503 cm-1, whereas even the disappearance
of the peaks observed in the rage between 3399 to 2851 cm-1 after adsorption of the metal
ions onto PPPAC. Moreover, the broad peak observed in the range of 1578 to 771 cm-1
before adsorption (Figure 5a) changed to narrow peak after adsorption in both case of metal

23
ions (Figure 5b and c). Thus, the shifted peak locations at different frequencies confirms the
adsorption or binding of Cr (VI ) and Pb (II) takes place on the surface of PPP activated
carbon.

Before
Cr(VI)
50 Pb(II)

45
3174 b 1578 771
503
2921 1400
40 1275
1029
1575
35 a
Transimitance(%)

2921 770
1256 494
30 1029

25

20

1577 770 494

15
c 1275
1031
10

5
4000 3500 3000 2500 2000 1500 1000 500
-1
Wave Number(cm )

Figure 5. FT-IR Spectra of PPPAC adsorbent(a) Before adsorption, (b)

and (c) after Cr (VI) and Pb (II) adsorption, respectively

4.1.4. SEM Analysis results

The morphology of raw PPPAC adsorbent, before and after adsorption of chromium and lead
ions was studied by SEM microscopic technique. The SEM micrographs in Figure 6(a) show
small crystals of different sizes (at micron size) and shapes with rough surface in irregular
manner for PPP activated carbon before adsorption. Interestingly, it can be clearly seen from
the SEM micrograph that the surface morphology of the PPPAC was stable under synthesis
conditions, in which chemical treatments using phosphoric acid have involved during the
synthesis. With careful observation at the SEM micrograph after adsorption process of Cr
(VI) (fig 6(b)) and Pb (II) (fig 7(b)) showed the reduction in pores of PPPAC and in the small
particles of activated carbon crystals, as well as the disappearance of several white spot on
the surface, which possibly due to the adsorption of the Cr (VI) and Pb (II) metal ions onto
the surface of PPPAC.

24
 a b
Figure 6. SEM micrographs of the synthesized PPPAC samples: (a)before and (b) after
adsorption of Cr(VI) ions

a b

Figure 7: SEM micrographs of the synthesized PPPAC samples:(a)before (b) after

adsorption of Pb(II) ion

Still, based on SEM images, it was difficult to generalize the clear relationship that may exist
between the PPPAC crystal before adsorption and the corresponding crystal nature after
metal ions adsorption.

25
 4.2. Adsorption Studies

4.2.1. Effect of Adsorbent Dosage

The effect of activated carbon dose (quantity in weight) on the extent of solute adsorbed was
investigated by varying the dose of activated carbon under the selected initial solute mass
concentration. The specific uptake of adsorbate (e.g metal) is influenced by the concentration of
activated carbon in the solution. Dose of adsorbent also one of the main points to determine the
capacity uptake of adsorbate by adsorbents. Usually, an increase in adsorbent dose increases the
number of active sites available to the solute for adsorption, thus increasing the rate of adsorption.
If further increase the dose, the adsorption capacity will be constant. Conversely, the quantity of
solute adsorbed per unit weight of adsorbent decrease with increasing adsorbent dosage, which
may due to the complex interaction of several factors [48].

The effect of PPPAC dosage on the removal of chromium (VI) at room temperature was
investigated by varying the amount of PPPAC from 2.5 to 30 mg and agitated at 150 rpm for 30
min using initial Cr (VI) ion concentration of 0.5ppm and at pH value of 3.0. Similarly the effect
of PPPAC dosage on the removal of Pb (II) was studied for 40 min at pH value of 5. The adsorbent
efficiency for the adsorption of Cr (VI) and Pb (II) is presented in fig 8.

The percent removal of chromium (VI) increased with the increase in the amount of adsorbent, 2.5
to 15 mg and decreased at adsorbent dose of 30 mg. The removal of Cr (VI) attains high removal,
even at lower PPPAC dosage with 50%, 78% and 91% removal for 2.5 mg/50 mL and 5 mg/50 mL
and 10 mg/50 mL PPPAC, respectively. The highest Cr (VI) uptake was obtained at adsorbent
dose of 15 mg/50 mL with removal efficiency of 99.8 %. The lowest Cr (VI) uptake was observed
at high PPPAC dosage (of 30 mg/50 mL). Thus, the increase in percent removal of adsorbate ions
with increase in the adsorbent dose could be attributed to greater availability of adsorption sites at
optimum adsorbent dose. Several authors have also reported the same trend of adsorbent
concentration effect on lead adsorption. Further increase in adsorbent mass has no effect because
all the Cr ions are maximally adsorbed on the available sites. In agreement with our study, Leta
Shifera et al revealed that the percentage removal increases from 97.44% to 98.26% with
increasing dosage from 0.1 to 0.25g of pineapple activated carbon for adsorption of Cr (VI) [61].

26
On the other hand, removal efficiency of Pb2+ show narrow variation with increasing of PPPAC
dosage up to 15mg and show a slight decrement at maximum adsorbent dosage. The highest
removal efficiency of 88.92% was attained at15mg/50ml PPPAC dosage (Fig. 8). 66.8%, 72.6%,
79.48% and 72.6% removal was achieved at 2.5mg, 5mg, 10mg and 30mg/50m1 addition of
PPPAC, respectively.

Thus, 15mg/50ml (0.3g/L) was obtained as optimum dosage of PPPAC for adsorption of both
metal ions Cr (VI) and Pb (II) the percent removal became Constant at equilibrium probably
because of the saturation of the available active site of PPPAC and used for further investigation.
The adsorption for Cr (VI) and Pb (II) data is indicated on appendix, Table 1C & 2C respectively.

Cr(VI)
100 Pb(II)

90

80
Adsorption(%)

70

60

50

40

0 5 10 15 20 25 30
Dose(mg)

Figure 8. PPPAC adsorbent dosage effects on Cr (VI) and Pb (II) removal

4.2.2. Effect of pH

pH is an important factor controlling the adsorption process, affects the protonation of the
functional groups on adsorbents and the solubility of the metal ions. The effect of pH on the
adsorption efficiency of PPPAC, in pH range of 3-7, is presented in Fig. 9 and applying at an

27
initial Cr (VI) and Pb (II) concentration of 0.5ppm, PPPAC dose of 15mg, at room temperature,
agitating speed of 150rpm and contact time of 30 min for Chromium and 40 min for lead ions.

As illustrated in fig.9 removal of Cr (VI) from aqueous solution highly dependent on the pH values
of the solution and the percent removal of decreased with an increase in pH values. The maximum
adsorption of Cr (VI) ions was observed at pH 3 with removal efficiency reached to 99.8%, and
then the efficiency gradually decreased by increasing pH values. At pH 5, 68% of removal was
obtained for Cr (VI) ions. While low adsorption (32%) removal efficiency was achieved at pH of
7, and chromium uptake was not observed above pH value of 7, chromium complexes form/
precipitates and hence was not considered. Cr (VI) exists in various Oxo anionic and /or
complexes forms in aqueous solution depending upon the solution pH and thus Oxo
anionic/complexes may compute for the adsorption site which retards the approach of Cr ions
towards the adsorbent surface [65]. Similar observations were reported by several authors for
adsorption of Cr (VI) using different agricultural based activated carbons .The results obtained in
this study were agreed with those obtained by Mohamed H.H. Ali et al who found that the
maximum removal efficiency of greater than 80% Cr ions occurred at a lower pH value by orange
peel activated carbon [46].

Cr
110 Pb

100

90

80

70
Adsorbed(%)

60

50

40

30

20

10

3 4 5 6 7
pH

Figure 9. pH effect of PPPAC adsorption of Cr (VI) and Pb (II)

28
In case of Pb (II), it is observed that adsorption increased at acidic pH value of up to pH 5 and a
sharp decreased in adsorption was observed above pH 5, up to pH value of 7, as shown in figure 9
(red plot). High removal efficiency 88.92% and 47.36% was found at pH 5 and 3, respectively,
which is acidic medium tend to support the adsorption of Pb (II). Low removal efficiency of 5.34%
Pb ions was observed at pH values of 7. In similar to this study, Mohamed H. H. Ali et al used
orange peel activated carbon for removal of lead from natural waste water and obtained
maximum adsorption of 80% Pb+2 ions at acidic pH range between 5.5 to 6, then the efficiency
gradually decrease by increasing pH values [46]. In contrary to Mohamed H. H. Ali et al and our
study, Udeh, N. U and Agunwamba, J. C used Bamboo Based Activated Carbon for Pb2+ ions
removal from aqueous solution and obtained maximum adsorption of 94.49% at alkaline pH (at
pH of 11) [45]. This is may be due to the nature of source of activated carbon prepared.

As described above, maximum adsorption of Cr (VI) and Pb (II) occurred at pH 3 and 5,

respectively, by using our prepared prickly peel activated carbon (PPPAC). The maximum
removal at both pH values, pH 3 and 5, may be explained in terms of point of zero charge (pHpzc)
of the PPPAC in the solution. At pH 3 and 5 (pH > pHpzc), the PPPAC is negatively charged and
the adsorbate species are positively charged. Such a situation enhanced the electrostatic attraction
between the positive sorbate species (Cr (VI) and Pb (II)) and the negatively charged adsorbent
(PPPAC) surface, which ultimately resulted in the increased adsorption of metal ion. Thus, the
effects of pH on Cr (VI) and Pb (II) removal onto PPPAC tend towards acidic medium. The
adsorption for Cr (VI) and Pb (II) data is indicated on appendix, Table 1C & 2C respectively.

4.3. Removal Efficiency of PPPAC Prepared at Different Carbonized

Temperature
Carbonized temperature affects the morphology and adsorption property of agricultural based
activated carbon. The PPPAC prepared at 600oC for 1hr was studied and optimized for adsorption
of both metal ions. The maximum removal efficiency was recorded with the addition of 15 mg
PPPAC for both metal ions at pH of 3, contact time of 30 min for Cr (VI) and PH 5 and 40 min for
Pb (II) was obtained. PPPAC was prepared at different carbonized temperature, 700 0C, 600 0C,
500 0C and 400 oC at time interval of 1h and subjected to chromium and lead adsorption at
optimized condition. The results obtained tabulated below (Table 4).

29
 Table 4: removal efficiency of PPPAC at different carbonized temperature
CT Initial Cr(VI) Residual Cr Cr(VI) Residual Pb Pb(II)
o
( C) and Pb (II)(ppm) (ppm) RE (%) Ppm RE (%)
700 0.5 0.1775 64.5 0.235 53
600 0.5 0.001 99.8 0.0535 88.92
500 0.5 0.0895 82.1 0.145 71
400 0.5 0.103 79.4 0.187 62.6

The result indicates that improvements of adsorption efficiency were observed for carbonized
temperature of 600 oC. Based on the result, activated carbon from prickly peel that prepared at
temperature of 600 oC have best removal efficiency as compared to that of at lower and above
temperature of PPPAC and thus, the optimum carbonized temperature for preparation of AC of
PPP is 600 oC

30
 5. Conclusions

Activated carbon from prickly pear peel is successfully prepared at 600 oC for 1 hr and used for
removal of chromium (VI) and lead (II). Batch adsorption experiments were conducted and
showed that the adsorption of chromium (VI) and lead (II) are time dependent, adsorbent dosage
dependent and pH dependent. The batch adsorption studies revealed a high removal efficiency of
99.8% at pH-3 within 30mins for 0.5mg/l initial Cr concentration upon the addition of 15mg
PPPAC. In the case of lead, high removal efficiency of 88.92% at pH-5 was achieved within
40mins. Consequently, PPPAC was effective when it applied to real samples, tannery and paint
waste water.

This study revealed that the PPPAC can remove Cr (VI) and Pb (II) ions from aqueous solution
and thus this finding recommends the use of PPPAC for removing metal ions from contaminated
water or effluents to replace commercial adsorbents.

31
 6. References

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 7. Appendices

Appendices A: Calibration curves for Cr (VI) and Pb (II)

0.4
0.35
0.3
0.25
Absorbance

0.2 y = 0.017x + 0.0002

0.15 R² = 0.9993
0.1
0.05
0
0 5 10 15 20 25
Concetration in mg/l Pb

2.5

2 y = 0.1358x - 0.0805
R² = 0.9951
1.5
Absorbance

0.5

0
0 5 10 15 20
-0.5
Concetration in mg/l Cr

39
Appendix B: PHpzc data for PPPAC

V PH ( 2min. interval
HN blank Mass of PPPAC(gm)
O3
0.5 1 1.5
0 10.15 9.7 10.3 10.5
1 8.78 7.93 9.55 10
2 5.54 6.55 8.23 9.86
3 3.79 5.12 7.13 8.06
4 3.35 4.45 6.12 7.23
5 3.06 3.76 4.58 5.86
6 2.86 3.24 4.52 4.62
7 2.72 2.94 4.19 3.91
8 2.62 2.71 3.68 2.78
9 2.53 2.57 3.33 2.68
10 2.46 2.48 3.13 2.67
11 2.40 2.41 2.97 2.61
12 2.35 2.36 2.77 2.54
13 2.30 2.31 2.64 2.50
14 2.25 2.27 2.56 2.45
15 2.22 2.23 2.46 2.40
16 2.18 2.16 2.39 2.36
17 2.15 2.12 2.33 2.33
18 2.12 2.09 2.24 2.30
19 2.07 2.03 2.20 2.27
20 2.05 2.00 2.17 2.24
21 2.03 1.98 2.14 2.22
22 2.01 1.96 2.07 2.19
23 1.99 1.95 2.06 2.01

40
Appendix C: Adsorption batch Experimental data

Table 1C: Adsorption data for optimization of adsorption parameters on Cr (VI)

dose pH contact initial conc Readind Removal Dose pH contact initial conc Reading Rmoval
(mg) time (mg/L) (mg/L) efficiency (mg) time (mg/L) (mg/L) Efficiency
2.5 3 15min 0.5 0.25 50 3 3 40min 0.5 0.2 60
5 3 15min 0.5 0.211 57.8 5 3 40 0.5 0.25 50
10 3 15 0.5 0.209 58.2 10 3 40 0.5 0.298 40.4
15 3 15 0.5 0.21 58 15 3 40 0.5 0.41 18
30 3 15 0.5 0.12 76 30 3 40 0.5 0.35 30
2.5 5 15 0.5 0.16 68 3 5 40 0.5 0.11 78
5 5 15 0.5 0.311 37.8 5 5 40 0.5 0.13 74
10 5 15 0.5 0.201 59.8 10 5 40 0.5 0.143 71.4
15 5 15 0.5 0.112 77.6 15 5 40 0.5 0.151 69.8
30 5 15 0.5 0.09 82 30 5 40 0.5 0.08 84
2.5 7 15 0.5 0.21 58 2.5 7 40 0.5 0.175 65
5 7 15 0.5 0.24 52 5 7 40 0.5 0.25 50
10 7 15 0.5 0.18 64 5 7 40 0.5 0.265 47
15 7 15 0.5 0.14 72 15 7 40 0.5 0.29 42
30 7 15 0.5 0.26 48 30 7 40 0.5 0.081 83.8
2.5 3 30min 0.5 0.25 50 2.5 3 1hr 0.5 0.15 70
5 3 30 0.5 0.11 78 5 3 1 0.5 0.11 78
10 3 30 0.5 0.045 91 5 3 1 0.5 0.104 79.2
15 3 30 0.5 0.001 99.8 15 3 1 0.5 0.12 76
30 3 30 0.5 0.22 56 30 3 1 0.5 0.16 68
2.5 5 30 0.5 0.12 76 2.5 5 1 0.5 0.12 76
5 5 30 0.5 0.26 48 5 5 1 0.5 0.256 48.8
10 5 30 0.5 0.14 72 10 5 1 0.5 0.296 40.8
15 5 30 0.5 0.16 68 15 5 1 0.5 0.36 28
30 5 30 0.5 0.26 48 30 5 1 0.5 0.16 68
2.5 7 30 0.5 0.21 58 2.5 7 1 0.5 0.32 36
5 7 30 0.5 0.051 89.8 5 7 1 0.5 0.351 29.8
10 7 30 0.5 0.291 41.8 10 7 1 0.5 0.252 49.6
15 7 30 0.5 0.34 32 15 7 1 0.5 0.24 52
30 7 30 0.5 0.231 53.8 30 7 1 0.5 0.261 47.8

Table 2C: Optimization data for Pb (II) adsorption

Dose pH contact initial conc Reading Removal Dose pH contact initial conc Reading Removal
(mg) time (mg/L) (mg/L) Efficiency (mg) time (mg/L) (mg/L) Efficiency
2.5 3 15min 0.5 0.4567 8.66 2.5 3 40min 0.5 0.4356 12.88
5 3 15min 0.5 0.421 15.8 5 3 40 0.5 0.49 2
10 3 15 0.5 0.41 18 10 3 40 0.5 0.413 17.4
15 3 15 0.5 0.4215 15.7 15 3 40 0.5 0.2632 47.36
30 3 15 0.5 0.318 36.4 30 3 40 0.5 0.48061 3.878
2.5 5 15 0.5 0.1663 66.74 2.5 5 40 0.5 0.1656 66.8
5 5 15 0.5 0.4261 14.80% 5 5 40 0.5 0.137 72.6
10 5 15 0.5 0.4298 14.04% 10 5 40 0.5 0.1026 79.48
15 5 15 0.5 0.4358 12.84 15 5 40 0.5 0.0554 88.92
30 5 15 0.5 0.4873 2.54 30 5 40 0.5 0.137 72.6
2.5 7 15 0.5 0.228 54.4 3 7 40 0.5 0.465 7
5 7 15 0.5 0.3836 23.28 5 7 40 0.5 0.3554 28.92
10 7 15 0.5 0.4512 19.52 10 7 40 0.5 0.4106 17.88
15 7 15 0.5 0.4799 4.02 15 7 40 0.5 0.4733 5.34
30 7 15 0.5 0.3076 38.48 30 7 40 0.5 0.267 46.6
2.5 3 30min 0.5 0.4843 3.14 2.5 3 1hr 0.5 0.4873 2.54
5 3 30 0.5 0.4501 9.98 5 3 1 0.5 0.329 34.2

42
10 3 30 0.5 0.4206 15.88 10 3 1 0.5 0.2703 45.94
15 3 30 0.5 0.2739 45.22 15 3 1 0.5 0.2401 51.98
30 3 30 0.5 0.4675 6.5 30 3 1 0.5 0.211 57.8
2.5 5 30 0.5 0.1656 66.88 2.5 5 1 0.5 0.3729 25.42
5 5 30 0.5 0.1364 72.72 5 5 1 0.5 0.3015 39.7
10 5 30 0.5 0.1062 78.76 10 5 1 0.5 0.2703 45.94
15 5 30 0.5 0.0909 81.82 15 5 1 0.5 0.2111 57.78
30 5 30 0.5 0.6758 35.16 30 5 1 0.5 0.2392 52.16
2.5 7 30 0.5 0.0639 88 2.5 7 1 0.5 0.3954 20.92
5 7 30 0.5 0.0751 84.98 5 7 1 0.5 0.4458 10.84
10 7 30 0.5 0.063 87.4 10 7 1 0.5 0.4376 12.48
15 7 30 0.5 0.1938 61.24 15 7 1 0.5 0.4243 15.14
30 7 30 0.5 0.4058 18.84 30 7 1 0.5 0.4655 6.9

43