FINAL YEAR PROJECT PROPOSAL

BIOSORPTION OF HEAVY METALS FROM AQUEOUS

SOLUTION USING ‘COMBO’ BIOSORBENT
(ORANGE PEELS AND TEA WASTE)

By

NURUL NAJWA BINTI NOORDIN

171200478

Supervised By:
DR. AIN NIHLA BINTI KAMARUDZAMAN

FACULTY OF CIVIL ENGINEERING TECHNOLOGY

 TABLE OF CONTENT
CONTENT PAGE

1.0 INTRODUCTION
1.1 Research Background 1
1.2 Problem Statement 3
1.3 Research Objectives 4
1.4 Scope of Research 4

2.0 LITERATURE REVIEW

2.1 Effects of Heavy Metal 5
2.1.1 Copper as Heavy Metal 6
2.1.2 Conventional Method for Heavy Metal Removal 7

2.2 Biosorption of Heavy Metal Removal 9

2.2.1 Biosorbents 11

2.3 Factors Influencing Biosorption Process

2.3.1 Biosorbent Dosage 14
2.3.2 pH 14
2.3.3 Contact Time 14
2.3.4 Initial Concentration 15

2.4 Biosorption Modelling of Isotherm and Kinetic 16

2.4.1 Isotherms Model
2.4.1.1 Langmuir Isotherm Model 16
2.4.1.2 Freundlich Isotherm Model 17
2.4.2 Kinetics Model
2.4.2.1 Pseudo-First-Order Kinetic Model 18
2.4.2.2 Pseudo-Second-Order Kinetic Model 19

3.0 RESEARCH METHODOLOGY

3.1 Research flow 20
3.2 Preparation of heavy metal solution. 21
3.3 Preparation of Biosorbent 21
3.4 Preparation of Batch Biosorption Experiment 21
3.5 Biosorption Performance 23
3.6 Heavy Metals Analysis 23
3.7 Evaluation of Existing Mathematical Models 24

4.0 SIGNIFICANCE OF PROJECT 25

5.0 REFERENCES 26
6.0 APPENDIX 28
1.0 INTRODUCTION

1.1 Research Background

Water pollution is a common form of pollution that environment is currently dealing

with. Many different sources such as agriculture, sewage wastewater and oil pollution that
can be related to water pollution. Wastewater may contain a wide range of heavy metals
especially waste that is discarded by industries.

Heavy metals are considered as one of the common causes of water contaminates.
Heavy metals are non- degradable and accumulate in the environment. Heavy metals in
streams, lakes and seas contaminate water in which marine organisms live. Not only the
aquatic life becomes threated, but the human health also becomes in danger as those heavy
metal bio-accumulate through the food chain. It can damage and alter the functioning of
organs such as the brain, kidney, lungs, liver, and blood. Long-term exposure of the body
to heavy metal can progressively lead to muscular, physical and neurological degenerative
processes that are similar to diseases such as Parkinson’s disease, multiple sclerosis,
muscular dystrophy and Alzheimer’s disease. The major water contaminants are nickel,
copper, zinc, cadmium, chromium, lead, and mercury (Jaishankar, Tseten, Anbalagan,
Mathew & Beeregowda, 2014).

Biosorption is one of biological-chemical treatment processes, it is desired for the

removal of toxic metals from wastewater since it is based on the metal binding capacity of
different biological materials. Biosorption may be simply defined as the ability of
biological materials to accumulate heavy metals from wastewater through metabolically
mediated or physio-chemical pathways of uptake (Fourest and Roux, 1992). The advantages
of this treatment over conventional include its low cost in term of materials and processes, high
efficiency, possible for regeneration of biosorbent and also no increase in the chemical
oxygen demand (COD) of water, which are otherwise the major limitations for most of the
conventional techniques (Burakov et al,2018).

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 The use of biosorption is one of the alternative options when conventional
wastewater treatment methods such as biological treatment or chemical precipitation,
cannot be used because of the high costs, low removal efficiency and large amount of
chemicals used or sludge produced (Ahluwalia, 2005). Thus, the use of food wastes
material and by-products of fruits and vegetables such as peel, pomace and seeds as a
biosorbents for the eradication of toxic metals is an emerging and potentially alternative
method and in the recent years this method has gained much attention (Burakov et al,2018).

Various types of food waste materials such as sugarcane bagasse, wheat bran, rice
bran, rice husk, orange peels, coffee beans, hazelnut shells, groundnut shells, wheat husk,
waste tea leaves, maize corn cob, apple peels, banana peels, coconut shells, soybean hulls,
cotton stalks etc have been tried by several researchers for the eradication of heavy metals
(Annadural, Juang, Lee, Alalwan, Kadhom, Alminshid, Farajzadeh & Boveiri Monji,
2003). The food waste materials, especially those containing cellulose show a high
biosorption capacity. Their components such as lignin, hemicellulose, starch, lipids,
proteins, hydrocarbons and other functional groups expedite metal complexation that helps
in the removal of heavy metals (Krishna, Chintalpudi and Muddada, 2018). Because of the
several advantages that are associated with the agricultural waste as mentioned it seems to
be a viable option for the removal of heavy metals.

The application of biosorption in batch processes has received increasing attention

from researchers because of its potential industrial roles. Batch process refers to a process
that involves a sequence of steps followed in a specific order. In fact, the decision to use
batch is a function of hydraulic flow, physical characters of the biosorbent, the types of
target pollutant, space availability and invested capital. If the flow rate is low, a simple
manual batch process is the most economical (Atkinson, Bux and Kasan,1998). In this case,
the batch of biosorption processes for removing heavy metal which is copper from aqueous
solution will be used. The important factors include solution pH, dosage, contact time and
initial concentration (Greene, Darnall and Zouboulis,1990).

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 1.2 Problem Statement

Heavy metals like nickel, copper, zinc, cadmium, chromium, lead, and mercury are
major pollutants that affect the fresh water reservoirs due to the discharge of large amounts
of metal-contaminated wastewater from industries. Because of their persistent, non-
biodegradable and toxic nature accumulate in the environment such as in the food chain
and cause serious health disorders (Gunatilake, 2015). Over the last few decades, many
conventional treatment methods have been used for the removal of heavy metals from
contaminated wastewaters. The commonly used methods include chemical precipitation,
ultra-filtration, ion exchange, reverse osmosis, electro winning and phytoremediation
(Joshi, 2017; Lakherwal, 2014; Gunatilake,2015; Barakat,2011; Azimi,2016).

However, all the mentioned technologies are associated with various disadvantages
like incomplete metal removal, generation of sludge, high reagent and energy requirements,
aggregation of metal precipitates, expensive and fouling of the membranes (Berefeld et al,
1982; Henze, 2001; Ghate, 2004 and Chen, 2004).

Biosorption is not only a method for the eradication of heavy metals but it is also
an example of the potential use of bio waste (food waste). Formation of biosorbent by using
food waste is cheap, economic, environment friendly and simple to design method and
moreover it does not produce any toxic and dangerous material (Sabino, 2016). The use of
orange peel as a biosorbent material presents strong potential due to its high content of
cellulose, pectin (galacturonic acid), hemicellulose and lignin (Ajmal et al, 2000). Tea
waste is gaining a much attention by researcher because it is very suitable biosorbent in
removing heavy metals like Iron (II), Cu (II), Lead and Nickel (Aikpokpodion, 2010). As
a low cost, orange peel and tea waste are an attractive and inexpensive option for the
biosorption removal of dissolved metals.

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 1.3 Research Objectives

The main aim of this research is to improve fundamental understanding on the role
of biosorbent in the biosorption process of heavy metals from aqueous solution. To achieve
of the following, objectives of the study are:

i. To assess the performance of ‘combo’ biosorbent which are orange peels and
tea waste to treat heavy metal (copper) from aqueous solution.

ii. To analysed the biosorption of copper onto ‘combo’ biosorbents using

existing sorption isotherms (Langmuir and Freundlich) and kinetics (pseudo
first-order and pseudo-second order) models.

1.4 Scope of Research

An experiment will be conducted for the biosorption process. For the first phase of
the experiment, the ability of ‘combo’ biosorbent (orange peel and tea waste) for
biosorption of heavy metals (copper) from aqueous solutions will be investigated. This
study consists of two parts which is laboratory work and modelling. The laboratory work
include preparation of biosorbent, optimisation operating conditions and evaluation of
heavy metal biosorption performance. The study will be conducted in batch experiment
under varying operating conditions such as dosage, pH, contact time and initial
concentration. The biosorption performance will be evaluated based on percentage removal
of heavy metals and uptake capacity of biosorbent. At the end of the study, results from
laboratory activities will be analysed using existing sorption isotherms (Langmuir and
Freundlich model) and kinetics (pseudo-first order and pseudo-second order) models.
Heavy metal analysis will be determined using Atomic Absorption Spectroscopy (AAS).

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2.0 LITERATURE REVIEW

2.1 EFFECTS OF HEAVY METAL

Presence of heavy metal in water as the contaminants is an indication of global

industrialisation attributed to large scale of inappropriate disposal and untreated of
wastewater containing heavy metal from anthropogenic sources (United Nations
Commission on Sustainable Development, 2010). Water functions as a medium of transport
for pollutants and they can be damaging to both living organisms and the environment
(Harrison, 2001). Heavy metal can bio-accumulate over a period of time and the
concentrations become apparent and measurable. Through food chains and trophic levels,
heavy metal bio-accumulation within target organ or tissue of organisms can ultimately
threaten human health (Malik and Maurya, 2014). However, the heavy metals are being
released at a higher concentration than the prescribed limits especially through
anthropogenic point source, thus leading to the health hazard and water pollution. Table
2.1 summarises the health hazard of heavy metal toxicity.

Table 2.1 Health effects of heavy metal

Metal Health Hazards

Arsenic Carcinogenic, producing liver tumors, skin and

gastrointestinal effects.
Cadmium Carcinogenic, cause lung fibrosis, dyspnea and weight loss.

Copper Long term exposure causes irritation of nose, mouth, eyes,

headache, stomach-ache, dizziness, and diarrhea.
Lead Suspected carcinogen, loss of appetite, anemia, muscle and
joint pains, diminishing IQ, cause sterility, kidney problem
and high blood pressure.
Mercury Corrosive to skin, eyes and muscle membrane, dermatitis,
anorexia, kidney damage and muscle pain
Nickel Carsinogenic, dermatitis, allergic sensitization, lung and
nervous system damages
(Malkoc and Nuhoglu, 2005; Sud et al., 2008)

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 Different route of heavy metal exposure to humans include food and water
consumption, inhalation of polluted air, skin contact and most importantly, occupational
exposure in the workplace. Although for some biochemical and physiological activities in
the body, certain heavy metals such as iron and manganese are important to elevated bone
health in the body and strong antioxidant may reduce disease risk (Amy Goodson, 2018).
The majority of other heavy metals at very low levels are typically harmful to the body.
Some of the heavy metal toxicity could be acute while others could be chronic after long-
term exposure which may lead to the damage of several organs in the body such as the
brain, lungs, liver, and kidney causing diseases in the body (Lesmana et al., 2009).

2.1.1 COPPER AS HEAVY METAL

Copper is mainly used in the manufacturing of electric cables and equipment which
contributes about half of the world’s production. It is both directly and indirectly utilised
for plumbing, alloys, wood preservative, leather and fabrics, pharmaceutical products and
agricultural fungicides (John Emsley, 2014). The anthropogenic sources of copper
contamination come from smelting industries, copper wire mills, iron and steel producing
industries, coal burning industries, metallurgical processes and mining operations
(Davenport, 1999). Department of Environment (1998) reported that a high concentration
of copper of 5.96 to 21.20 mg/L had been reported in Malaysian rivers.

Copper is an important essential element when in a low concentration, particularly

to higher plants and animals. In human, copper is a component of metalloenzymes which
can function as electron donor or acceptor (Hart, Steenbock and Waddell,1928). Copper is
also present in normal human serum at concentration of 120 to 140 µg/g via binding to
ceruloplasmin, albumin and other molecules (Pfeiffer and Caldwell, 2013). Conversely,
high levels of copper can cause adverse health effects such as liver and kidney damage,
anaemia and gastrointestine irritation. Furthermore, copper is also associated indirectly
with neurological disorders including Alzheimer’s disease, Wilson’s disease and prion
disease (Desai and Kaler, 2008; Huster, 2010).

However, bio-accumulation and bio-magnification of copper can bring its

concentration up to toxic amounts, thus cause apparent impact to living organisms and the
environment. Copper in the soil is could be as bad as its presence in the water as it also can
enter the food chain. This can be found when Badri (1988) had found that the grass has
uptake the copper that leached from power lines through contaminated the soil and

6
subsequently caused high levels of copper found in milk of livestock. While for aquatic
ecosystem, the dissolved copper which was generated from a non-point source, the cation
was not only progressively influenced the water chemistry and bio-accumulate in aquatic,
but also resulted in bio-magnification through food chain (Lemus and Chung, 1999;
McIntyre et al., 2008).

2.1.2 CONVENTIONAL METHOD FOR HEAVY METAL REMOVAL

Heavy metal are well-known as toxic agents and heavy metal contamination that
caused global deterioration of human health and environmental quality. Heavy metals like
nickel, copper, zinc, cadmium, chromium, lead, and mercury are major pollutants that
affect the fresh water reservoirs due to the discharge of large amounts of metal-
contaminated wastewater from industries (Tchounwou, Yedjou, Patlolla and Sutton, 2012).
Because of their persistent, non-biodegradable and toxic nature accumulate in the
environment such as in the food chain and cause serious health disorders (Azimi, Azari,
Rezakazemi and Ansarpour, 2016). Many conventional treatment methods have been used
for the removal of heavy metals from contaminated wastewaters. The commonly used
methods include ultra-filtration, reverse osmosis, ion exchange and chemical precipitation
and they are introduced briefly in the Table 2.2.

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 Table 2.2 Conventional Method of Heavy Metal Removal.

Conventional Process Description Benefits Limitations References

Method

Ultrafiltration Pressure driven membrane operations that use Produces a high-quality Generation of sludge and expensive Aliane et al., 2001;
porous membranes for the removal of heavy treated effluent Yurlova et al., 2002
metal.

Reverse osmosis Heavy metals are separated by a semi- Simple and Expensive Qdais and Moussa,
permeable membrane at a pressure greater than efficient even at high 2004
osmotic pressure caused by the dissolved solids concentrations
in wastewater.

Ion-exchange Metal ions from dilute solutions are exchanged Wide range of Expensive and partial removal of certain Lee et al., 2006
with ions held by electrostatic forces on the commercial products ions.
exchange resin available from several
manufacturers

Chemical Precipitation of metal ions was achieved by the Technologically simple High sludge production Dang et al., 2009;
precipitation addition of coagulants such as alum, lime, iron (simple equipment) Matlock et al., 2001
salts and other organic polymers.

8
Generally, the use of conventional treatment process entails high cost in order to
achieve desirable removal percentages or to meet the compliance level. In fact, these
methods are infeasible because they are not very effective or not economically
affordable (Chong and Volesky, 1995). Among these methods, biosorption is the most
efficient than other techniques. Conventional techniques have limitations such as the
generation of a large amount of sludge, low efficiency, sensitive operating conditions
and expensive. Hence, an ideal progressing treatment technology should be in between
the cost considerations as well as sustainability of the materials used and amount of
waste produced from the treatment technologies.

2.2 BIOSORPTION OF HEAVY METAL REMOVAL

Biosorption is the process in which a microorganism is used to remove and recover

heavy metals from aqueous solutions. Biosorption has been known for a few decades
but has emerged a low-cost promising technology in the last decades. Biosorption can
be defined as the ability of biological materials to accumulate heavy metals from
wastewater through metabolically mediated or physio-chemical pathways of uptake
(Fourest and Roux, 1992). The ability of certain microbial biomaterials to bind and
concentrate heavy metals from even the most dilute aqueous solutions, offers a
technically feasible and economically attractive alternative (Petersen, Aldrich and Esau,
2005). The potential of biosorption of a metal ion by a biosorbent is evaluated by the
biosorption capacity value and equilibrium time for the biosorption process.
Biosorption capacity is calculated according to the following formula:

(𝐶𝑜 − 𝐶𝑒)𝑉
𝑞𝑒 =
𝑊

where qe is the biosorption capacity (in mg of metal/g of biosorbent), C0 and Ce are the
initial and equilibrium concentration of metal ion solution (in mg/L) respectively, V is
the volume of metal ion solution (in L), and W is the amount of biosorbent material
dose used (in g). The higher the biosorption capacity, the higher the amount of heavy
metal ion(s) of biosorbent can biosorb (Wei et al.,2016).

9
 Furthermore, biosorption offers the advantages of low cost, effectiveness for
dilute effluents, minimum chemicals usage and reduced toxic sludge generation (Gupta
et al., 2000). Table 2.3 lists the advantages of biosorption and its limitation.

Table 2.3 Benefits and Limitations of Biosorption.

Benefits Limitations References

High efficiency, the minimization Early saturation. Volesky and

of chemical or biological sludges, Ahluwalia,
the ability to regenerate (2007)
biosorbents, and the possibility of
metal recovery following
adsorption.

Low cost, high efficiency, Limited potential for biological Alhaya,

minimisation of chemical and process improvement because Ramachandra,
biological sludge, no additional cells are not metabolizing and Kanamadi,
nutrient requirement, regeneration there is no potential for (2003);
of biosorbent and possibility of biologically altering the metal Goyal, (2007)
metal recovery valency state.

Cheaper production, multiple Saturation of active sites of Aksu, Sag &

heavy metals uptake at a time and metal binding ligands. Kutsal,
treatment of large volumes of (1992)
wastewater.

No need for chemical additions as Reversible sorption of metals Abbas,

highly selective for uptake and on biomass. Ismail,
removal of specific metals and Mostafa,
reduced volume of waste or toxic Sulaymon &
materials production. Kazemi,
(2014)

Hence, the development of new alternative cost-effective procedure to remove

toxic heavy metals has been directed toward biosorption. The biosorption method is a
relatively new process and is emerging as a potentially preferred alternative for the
removal of heavy metals because it provides flexibility in design, high-quality treated
effluent and is reversible and the adsorbent can be regenerated (Fu & Wang 2011).

10
 2.2.1 BIOSORBENTS

Identification of biosorbents for the process of biosorption is a major challenge.

Biosorbent can be defined as any kind of biological material that has an affinity for
inorganic and organic pollutants meaning there is enormous biosorption potential
within countless types of biomaterials (Gadd, 2009; Dhankhar and Hooda, 2011). A
wide variety of materials available in nature can be used as biosorbents for the removal
of metals from contaminated water resources. Any kind of plant, animal, and microbial
biomass and their derivatives such as plant, industrial and agriculture wastes and by-
products discharged from various industries can be employed as biosorbents. It is
important to select a biosorbent from the large spectrum of available materials. The
desired characteristics of an ideal biosorbent are high affinity for metals (biosorption
capacity), low economic values (low cost), availability in large quantities and easy to
desorption of the adsorbed metal ions and possible multiple reuses of the biosorbent.
(Macek and Mackova, 2011)

Agricultural waste, pulp, peels and seeds of fruits and vegetables are the
discarded waste material and due to its several properties. It may have a wide range of
application in the removal of heavy metal ions. Generally, the agricultural waste having
cellulose shows a high metal biosorption capacity. The ingredients of agricultural waste
such as proteins, lipids, lignin, hemicelluloses, starch, hydrocarbons and functional
groups facilitate metal complexation which helps in the removal of heavy metals
(Demirbaş, 2000). In the past several years, a research has been carried out for the
eradication of toxic metal ions using several biosorbents that come from agricultural
and food waste such as wheat bran, rice bran, coconut shells, wheat husk, rice husk,
sugar cane bagasse, coffee beans, apple peels, banana peels, orange peels, sugar beet
pulp, and tea waste etc (Ahluwalia & Goyal D 2005; Annadural, Juang & Lee, 2003).
They have been used either in their natural form or after some modification (may be
physical or chemical). The use of different materials from agriculture and food waste
as biosorbents are explained in details in Table 2.4.

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 Table 2.4 Biosorption capacities of different agriculture waste and food waste.

Heavy Metal Biosorbent Uptake Capacity Combination of References

(mg/g) Biosorbents
Wheat bran 8.34 No Basci, Kocadagistan &
Kocadagistan, 2004
Rice husk (acid treated) 29.00 No Wong et al., 2003
Orange peel 77.60 Yes Abbas Parvez Kazi, 2016;
76.57 Aparna Vashist, 2016;
50.94 Liang et al., 2009
Cu (II)
Orange peel 70.67 Yes Liang et al., 2009
(chemically modified)
Potato peel 74.00 No Moreno-Piraján & Giraldo,
(ZnCl2 treated) 2011
Tea Waste 48.00 Yes Amarasinghe, 2006;
65.00 Williams, 2006;
31.00 Tee,1988
Mango peel 46.09 Yes Iqbal, Saeed & Kalim, 2009
Chestnut shell 12.56 No Yao, Qi & Wang, 2010

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 The use of agricultural and food wastes as biosorbent are recommended because
of their sustainability, easy availability, low cost, and high affinity towards the removal
of heavy metals. Numerous studies have recommended the use of several agriculture
and food wastes. It solves the problems of the health and environmental hazards of
heavy metals in our ecosystem and the utilization of huge quantities of agriculture and
food waste. This method has proven itself to be efficient and environment friendly.

The use of combination biosorbents will simultaneously exert two kinds of

materials perform on the biosorption (Arıca et al., 2001). Combo biosorbent means
there are two biosorbent that will use in this research. Orange peel and tea waste are
suitable combo biosorbent because of their own characteristic. The use of orange peel
as a biosorbent material presents strong potential due to its high content of cellulose,
pectin (galacturonic acid), hemicellulose and lignin (Ajmal et al., 1998).

Tea (Camellia sinensis) is the most widely consumed beverage in the world. Tea
waste has been utilized in agricultural field to enhance the production under heavy
metal stress (Azmat and Akhter, 2010). Tea waste is a cheap material so it’s utilizing
in industrial wastewater plants would be convenient. Meanwhile it is possible to
increase the treatment efficiency by pre-treatment with some chemical such as acids,
bases and detergents (Ajmal et al., 1998). Tea waste represents an unused resource and
pose increasing disposal problem (Arvanitoyannis and Varzakas, 2008). The cell wall
of waste tea consists of cellulose, lignin, carbohydrate which have hydroxyl groups in
their structures. One third of total dry matter in tea leaves should have good potential
as metal scavengers from solution and waste water because they contain functional
groups (Aikpokpodian et al., 2010).

As the good characteristic, orange peel and tea waste are an attractive and
inexpensive option for the biosorption removal of dissolved metals.

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 2.3 FACTORS INFLUENCING BIOSORPTION PROCESS

2.3.1 Biosorbent dosage

The biosorbent dosage strongly influences the extent of biosorption. Lower

biosorbent dosages yield higher uptake due to high surface area and availability for
more sorption sites (Vijayaraghavan, 2006). Conversely, with increase in biosorbent
dosage, the decrease in adsorption capacity may be observed due to unsaturated binding
sites and reduction in the effectiveness surface area (Esposito, 2001; Aksu& Cagatey,
2006).

2.3.2 pH

pH affects the solution chemistry of pollutants and the activity of the functional
groups of the biomass surface (Galun et al., 1987; Esposito et al.,2002). The range pH
between 3 to 6 has been found favorable for biosorption, because of the presence of
negatively charged carboxyl groups on cell wall which are responsible for the
extracellular binding of metal cations (Gadd & Rome, 1988). However, higher solution
pH complicates the sorption process due to the decrease in solubility of metal
complexes.

2.3.3 Contact Time

Contact time usually refers to the time allocated for biosorption process to take
place. Biosorption capacity is not directly affected by contact time of the biosorbent
and sorbate, however it can act as a limiting factor. Under experimental conditions,
increasing contact time would allow the biosorbent material to unveil the maximum
biosorption capacity. When the biosorbent reaches its maximum biosorption capacity
at defined conditions its binding sites become fully saturated, increasing contact time
would not have any further effect (Hajahmadi, Younesi, Bahramifar, Khakpour, &
Pirzadeh, 2015).

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 2.3.4 Initial Concentration

The initial concentrations have an impact on biosorption. Higher concentration

(initial) resulting in a high solute uptake (final), due to the elevated surface area of the
biosorbent which in turn increases the number of binding sites (Ho & McKay, 1999).
However, at higher concentrations, the sites available for sorption become fewer
compared to the moles of solute present and hence, the removal of solute is strongly
dependent upon the initial solute concentration (Vijayaraghavan & Yun, 2008). Rate of
the biosorption decrease with an increase in metal ion concentration of copper (Oves,
2013).

Table 2.5 shows the range for the factors influencing biosorption process by using
orange peel and tea waste as biosorbent based on the experiment done by another
researcher.

Table 2.5 Range for the factors influencing biosorption process.

Biosorbent Biosorbent pH Contact Initial References

Dosage (g) Time (hr) Concentration
(mg/L)
1.0 g 5.5 1 hr 50 mg/L Cay et al (2004)
Tea Waste
0.1 g 5-6 1.5 hr 100 mg/L Amarasinghe
(2007)
Orange 0.25g 3-6 1hr 50 mg/L Srinivas
Peel Tadepalli (2016)

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 2.4 Biosorption Modelling of Isotherm and Kinetic

Modelling of biosorption process usually used the initial heavy metal

concentration, time and temperature as the experimental parameters, which were
evaluated with a few existing models. Most of the study carried out the biosorption
curve being fitted to existing isotherm and kinetic models. For isotherm models, include
two basic equations of Langmuir and Freundlich. Both contain two parameters equation.
Other than the isotherm-based modelling, biosorption parameters also can be derived
from Pseudo first-order and Pseudo second-order models are commonly employed
existing kinetic models.

2.4.1 Isotherms Model

2.4.1.1 Langmuir Isotherm Model
The Langmuir Isotherm Model is represented by the following equation:
qmKLCe
qe =
1 + KLCe

Where: qe is the amount of metal adsorbed per specific amount of adsorbent (mg/g), Ce
is the equilibrium concentration of the solution (mg/L) and qm is the maximum amount
of metal ions required to form a monolayer (mg/g). The Langmuir equation can be
rearranged to a linear form for the convenience of plotting and determination of the
Langmuir constant (KL) as below. The values of qm and KL can be determined from the
linear plot of Ce/qe versus Ce:

Ce 1 1
= + Ce
qe KLqe qm

The essential characteristics of the Langmuir isotherm parameters can be used to predict
the affinity between the sorbate and the sorbent using the separation factor or
dimensionless equilibrium parameter ‘RL’, expressed as in the following equation:

1
RL =
1 + KLCo

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Where: KL is the Langmuir constant and C0 is the initial concentration of the metal ion.
The value of the separation factor RL provides important information about the nature
of adsorption. The value of RL is between 0 and 1 for favourable adsorption, while
RL >1 represents unfavourable adsorption and RL = 1 represents linear adsorption. The
adsorption process is irreversible if RL = 0.

2.4.1.2 Freundlich Isotherm Model

It is described by the following equation:

1
𝑞𝑒 = 𝐾𝐹 𝐶𝑒 𝑛

In its linear form, this equation assumes the following form:

1
𝑙𝑜𝑔𝑞𝑒 = 𝑙𝑜𝑔𝐾𝐹 + ( ) 𝑙𝑜𝑔𝐶𝑒
𝑛

Where: qe is the metal uptake (mg/g) at equilibrium, KF is the measure of the sorption
capacity, 1/n is the sorption intensity, and Ce is the final ion concentration in solution,
or equilibrium concentration (mg/L). The Freundlich isotherm constants KF and 1/n are

evaluated from the intercept and the slope respectively, of the linear plot of log qe
versus log Ce.

Table 2.6 summarize the trend of existing isotherm models evaluation for heavy
metal biosorption using raw agricultural and food waste based biosorbents. The trend
of using existing isotherm models to evaluate biosorption effectiveness was initially
simple and only focused on two parameters equations of Langmuir and Freundlich
models.

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 Existing Biosorbent Heavy Metal References
Isotherms Model
Langmuir, Modified coconut Cu Baes et al., 2011
Freundlich coir
Langmuir Sugar beet pulp Ni, Cu Reddad et al., 2002
Langmuir, Tea waste Cu Padma and Richard,
Freundlich 2007
Langmuir, Rice husk Ni Bansal, Singh, Garg &
Freundlich Rose, 2009
Langmuir Banana pith Cu Low et al., 2015
Langmuir Orange peel Cu Ahsan, 2007
Table 2.6 Isotherm models used for the evaluation of heavy metal biosorption
using various types of biosorbent.

2.4.2 Kinetics Models

2.4.2.1 Pseudo-First-Order Kinetic Model

It is given by equation is below:

k1
log( qe − qt ) = log( qe) − t
2.3030

Where: qt and qe are the amount of solute sorbed per mass of sorbent (mg/g) at any
time and equilibrium, respectively, and k1 is the rate constant of first-order sorption
(min−1). The straight-line plot of log (qe − qt) against t gives log (qe) as slope and
intercept equal to k1 /2.303. Hence the amount of solute sorbed per gram of sorbent at

equilibrium (qe) and the first-order sorption rate constant (k1) can be evaluated from
the slope and the intercept.

18
 2.4.2.2 Pseudo-Second-Order Kinetic Model
The model is represented by:
𝑡 1 1
= 2
+ ( )𝑡
𝑞𝑡 𝑘2 𝑞𝑒 𝑞𝑒

where k2 is the rate constant of pseudo-second-order biosorption (𝑔𝑚𝑔−1 𝑚𝑖𝑛−1 ).

The pseudo-second-order rate constant k2 and qe values were calculated from the
slope and intercept of the plots t/q vs t.

Existing kinetic models used are principally applied to suggest the rate limiting
factors involved in heavy metal biosorption process. Table 2.7 shows the existing
kinetic models’ evaluation for heavy metal biosorption using raw agricultural waste and
food waste derived biosorbents. The pseudo first-order and second-order kinetic models
are the two major components used to gain insight into biosorption process.

Table 2.7 Kinetic models used for the evaluation of heavy metal biosorption using
various types of biosorbent.
Kinetic Model Biosorbent Heavy Metal Reference
Pseudo first-order Chestnut shell Cu Yao et al., 2010
and second-order
Pseudo first-order Peanut shell Cr, Cu Witek-Krowiak et
and second-order al., 2011
Pseudo first-order Sugarcane bagasse Ni Alomá et al., 2012
and second-order
Pseudo first-order Orange peel Pb, Cd, Ni, Cu N. Feng et al.,
and second-order 2011
Pseudo first-order Tea waste Cu, Pb, Zn Amarasinghe and
and second-order Williams, 2007;
Wasewar et al.,
2008

19
3.0 RESEARCH METHODOLOGY

3.1 Research Flow

Figure 3.1 show the flowchart of research work implementation in this study.
The study included preparation of biosorbent from food waste which is ‘combo’
biosorbent (orange peels and tea waste). By using batch experiment four factors will be
determined which is dosage, pH, contact time and initial concentration. This study
involved two scopes of work which is laboratory work and mathematical analysis
including modelling. The flowchart below shows activities involved in laboratory work
and modelling of this study which correspond to the objectives. Each experimental
design and procedure are described in the following sections.

Preparation of Biosorbent

Batch Experiment

⚫ Dosage
⚫ pH
Ob Objective 1
⚫ Contact time
⚫ Initial concentration

Modelling

Equilibrium Sorption Sorption Kinetics

Models
⚫ Pseudo-First-Order
⚫ Langmuir Isotherm Kinetic Model Objective 2
Model ⚫ Pseudo-Second-Order

⚫ Freundlich Kinetic Model

Isotherm Model

Figure 3.1: Flowchart of research work.

20
 3.2 Preparation of Heavy Metals solution

1000mg/L of Cu(II) stock solution will be prepared by dissolving an appropriate

amount of CuSO4 salt in distilled water. By using distilled water, the stock solution will
be diluted in order to achieve the required concentrations. The pH of the Cu(II) solution
will be adjusted using 0.10 M HCl or 0.10 M NaOH.

3.3 Preparation of Biosorbent

In this study, orange peel and tea waste will be used as biosorbents. There are a
few steps of preparation orange peel and tea waste as a biosorbents. Orange peel and
tea waste will be collected from local market. These wastes will be washed with tap
water several times to remove soluble lighter materials before being wash with double
distilled water. Orange peel will be cut into small pieces. After that, orange peels and
tea waste will be dried in open sun for two days and keep inside a hot oven at
temperature 80°C for 24 hours to ensure all the moisture is being eliminated The dried
orange peel and tea waste will be grinded and sieve using 0.5mm sieve and keep in
storage for further use (Kamsonlian, Suresh, Ramanaiah, Majumder, Chand, Kumar,
2012; Rifat Mamun et al, 2019).

3.4 Preparation of Batch Biosorption Experiment.

Batch mode biosorption studies will be carried out to investigate the effect of
different parameters such as dosage, pH, contact time and initial concentration of
copper. The biosorbent will be weighted in the range 0.25g-1.0g and 100 ml of stock
solution of Copper (II) Sulphate will be prepared using distilled water in a 250mL
conical flask. 10-60 mg/L of Copper (II) Sulphate will be selected and pH will be varied
in range 3 to 6. For the first step, the weighted biosorbent t will be added into the Copper
(II) Sulphate solution. Next, the solution will be incubated on the orbital shaker with
the rotational at 120 rpm for 15-60 minutes at 25±1°C. After the biosorption process is
done, filter through qualitative filter paper and the filtrate will be analysed using Atomic
Absorption Spectrometer (AAS). Figure 3.2 show the schematic diagram for the

21
biosorption procedure and Table 3.1 show the operating biosorption parameters of
heavy metal removal.

Figure 3.2 The schematic diagram for the biosorption procedure.

Table 3.1 Summary of operating parameters heavy metal biosorption

Initial
Parameters Dosage (g) pH Concentration Contact Time
(mg/L) (minutes)
Dosage(g) 0.25-1.00 5.5 50 15
pH Optimize 3-6 50 15
Initial Optimize Optimize 10-60 15
Concentration
(mg/L)
Contact Time Optimize Optimize Optimize 15-60
(minutes)

22
 3.5 Biosorption Performance

The biosorption performance will be evaluated based on percentage

removal of heavy metals and uptake capacity of biosorbent. The potential of biosorption
of a metal ion by a biosorbent is evaluated by the biosorption capacity value and
equilibrium time for the biosorption process. Biosorption capacity is calculate
according to the following formula:

(𝐶𝑜 − 𝐶𝑒)𝑉
𝑞𝑒 =
𝑊

where qe is the biosorption capacity (in mg of metal/g of biosorbent), C0 and Ce are the
initial and equilibrium concentration of metal ion solution (in mg/L) respectively, V is
the volume of metal ion solution (in L), and W is the amount of biosorbent material
dose used (in g). The higher the biosorption capacity, the higher the amount of heavy
metal ion(s) of biosorbent can biosorb (Wei et al.,2016). The percentage of heavy metal
is calculate using the formula below:

𝐶𝑜 − 𝐶𝑒
𝑞%= 𝑥100%
𝐶𝑜

Where q % is the percentage of biosorption (%), Co is the initial heavy metal

concentration (mg/L) and Ce is the equilibrium concentration of heavy metal in solution
(mg/L).

3.6 Heavy Metals Analysis

The AAS technique is ideal suitable for element analysis in agriculture, food
and beverages industries and as well for analysis of soil and water like performed by
environmental testing labs (Shimadzu, 1968). For this study, heavy metal analysis will
be determined using Atomic Absorption Spectroscopy (AAS) because of its low cost
and easy usage. AAS also a commonly used for separation enrichment techniques for
trace heavy metals from environmental samples such as biosorption, solvent extraction,
cloud point extraction and membrane filtration (Celik et al., 2010; Marahel et al., 2011;
Soylak, 2004; Soylak et al., 2005). The use of separation and preconcentration

23
procedure for the determination of trace heavy metals prior to AAS. The application is
very important because analysis is achieved at lower level of detection limit than when
the procedure in not applied. Also, the interference effects of the foreign ions in the
samples are minimal when separation–preconcentration procedure is applied (Tokman
et al., 2004; Yang et al., 2004).

3.7 Evaluation of Existing Mathematical Models

The results from laboratory activities will be analysed using existing sorption
isotherms model (Langmuir and Freundlich) and kinetics (pseudo-first order and
pseudo-second order) models that will be addressed in following sections.

Isotherm models are usually classified into the empirical equations and the
mechanistic models. The mechanistic models are based on mechanism of metal ion
biosorption, which are able not only to represent but also to explain and predict the
experimental behaviour (Pagnanelli et al., 2002; Volesky, 2003). The Langmuir model
(L type, based on monolayer adsorption of solute) and the Freundlich model (F type,
developed for heterogeneous surfaces) are the most widely accepted and used in
literatures. The model describes the multi-layer adsorption at the adsorbent surface and
assumes that the Langmuir isotherm applies to each layer. These models can provide
information of metal uptake capacity and difference in metal uptake between various
species (Kapoor and Viraraghavan 1995; Pagnanelli et al., 2002; Volesky and Holan
1995). Volesky and his colleagues carried out a series of work on modelling biosorption,
considering metal biosorption involving ion exchange and/or complexation. These
models considered the sorbate speciation in solution, pH and even electrostatic
attraction (Chong and Volesky, 1995; Figueira et al., 2000; Schiewer, 1999; Schiewer
and Volesky, 1996; Schiewer and Wong, 2000; Yang and Volesky, 1999).

Numerous kinetic models have been suggested to describe the reaction order of
adsorption systems based on solution concentration. Kinetic models based on the
capacity of the adsorbent have also been presented, such as the Lagergren's first-order
equation and Ho's second-order expression (Ho, 2006). The first-order equation of
Lagergren (Lagergren, 1898) and the pseudo second-order equation are the most widely
used kinetic models to describe the biosorption process. The pseudo second-order
equation fitted the data very well in a large quantity of literature for biosorption (Ho,

24
2006; Ho and McKay, 1999). Ho (2006) gave a review on the application of second-
order kinetic models to adsorption systems, including an earlier adsorption rate
equation based on the solid capacity for a system of liquids and solids, the Elovich
equation for adsorption of gases onto a solid, and applying a second-order rate equation
for gas/solid and solution/solid adsorption systems, a second-order rate expression for
ion exchange reactions, and a pseudo-second-order expression.

4.0 SIGNIFICANT OF PROJECT

Human and industrial activities produce and discharge wastes containing heavy
metals into the water resources making them unavailable and threatening human health
and the ecosystem. Heavy metals are reaching hazardous levels when compared with
the other toxic substances (Vieira, Volesky, 2000). Heavy metals are a unique group of
naturally occurring compounds. Their continuous release leads to overconsumption and
accumulation. As a result, people around the globe are exposed to health hazard of these
heavy metals. Many industries such as fertilizers, metallurgy, leather, iron and steel and
aerospace discharge waste containing heavy metals either directly or indirectly into the
water resources (Vimala and Karthika, 2008).

One advantage of biosorption is the removal of residual or minute

concentrations of contaminants. Conventional water treatments may not completely
remove contaminants. Hence, biosorption may be integrated downstream of other
conventional water treatments. This is especially relevant in the case of pollutants like
heavy metals. With the efficiency of the biosorption process for removal heavy metal,
the health hazard may be reduced. In this regard, biosorption may be applied to wastes
and effluents before it enters the sewage or natural discharge streams like rivers, seas
and so on.

However, with the aim of treating effluent, water resources of most

contaminants may be an advantage to have all pollutants (metal or contaminants)
removed simultaneously using a non-specific biosorbent and reducing the number of
operations. Multiple biosorbents of different specificities can also be used.

25
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6.0 APPENDIX

GANTT CHART

28
HIRARC FORM

29