CHAPTER 2

Literature Review

2.1 Introduction

Water contamination by heavy metal is a major concern for environmental

preservation and human health. The use of heavy metal has been increasing drastically
and so has the heavy metal pollution because of human activities such as the industrial
that commonly produces wastewater that contaminated with heavy metal. Nowadays,
a lot of heavy metal was used by human being and accidentally has caused
contamination to our environment. Whenever toxic heavy metals are exposed to the
natural eco-system, accumulation of metal ions such as lead, cadmium and mercury in
human body will be occurred through either direct intake or food chains (Yoo et al.,
2002). In addition, Heavy metal pollution can cause many diseases to our health
without our conscious. Furthermore, some of heavy metal can cause dangerous to
human health and also environment and some of them may cause corrosion or harmful
in other ways. Although adverse health effects of heavy metals have been known for
a long time, exposure to heavy metals continues and is even increasing in some areas
(Br Med Bull, 2003).
 Furthermore, water is among one of many things that can be considered as
crucial to human beings and other living things through the aspect of their importance
and variant usage. For the information, water is one of a kind chemical that can exist
naturally in three physical state (liquid, gas and solid) on earth which made it very
unique considering its simple chemical property and appearance. In the new
globalization era the improper management of heavy metal waste can be one of the
causes of the pollution to our earth. Many countries, especially in developing countries
need to manage heavy metal waste properly to prevent from any pollution that caused
by heavy metal. Lately, with the improvement of the researches about the ways to
control heavy metal pollution, human being slowly getting a solution way to save and
preserve our environment from any pollution for our next future generation. In order
to remove toxic heavy metals from water systems, several methods have been
suggested and investigated. Although chemical precipitation, coagulation, ion
exchange, solvent extraction, filtration, evaporation and membrane methods have been
applied in this purpose, most techniques have some limitations such as requirement of
several pre-treatments as well as additional treatments. In addition, some of them are
less effective and require high capital cost (Kam et al., 2002; Kim, 2002;
Volesky,1990).

2.2 Theory Of Pollution

Pollution is introduction of contaminants into the natural environment that can

cause adverse change. In addition, there are have two types of pollution which are
chemical substances or energy. Pollutants is the components of pollution that can be
either foreign substances or naturally occurring contaminants. As addition in
knowledge, pollution can be classified as point source pollution and non point source
pollution. A point source of pollution is a single identifiable source of air, water,
thermal, noise or light. For nonpoint source (NPS) pollution, it is refers to both water
and air pollution from diffuse sources. Nowadays, there are many types of pollution
on the world such as air pollution, water pollution, sound pollution and heavy metal
pollution.
 Furthermore, heavy metal can be defined as subset of elements that exhibit
metallic properties. Heavy metal mainly includes the transition metals, some
metalloids, and also actinides. After that, heavy metal can be defined based on their
density, some on atomic number or atomic weight and some on chemical properties or
toxicity. The term of heavy metal is an alternative term for toxic metal (Yoo et
al.,2002). Actually, heavy metals occur naturally in the ecosystem with large of
variation in concentration. Some of heavy metals are required by human being in
certain level such as iron, cobalt, copper, manganese and zinc. Excessive levels of
heavy metal can be damaging to the organism. The conclusion, heavy metal pollution
must be prevented because there may cause the human healthy decrease. However,
today many of people are use the automobile either car, lorry, motorcycle and so on.
This may cause the pollution of heavy metal and also it is a source of heavy metal
come from. Furthermore, the heavy metal that produced on the road travel such as
zinc, copper, and also lead. As the example, brakes will produces the copper while the
tire will produces zinc.

Figure 2.1:Heavy metal pollution

Figure 2.2:The infection disease from heavy metal pollution

2.2.1 Theory Of Biosorbent

Biosorbent is referring to a certain material or substances that have the ability

of binding and concentrating heavy metals from even very dilute aqueous solutions.
Actually, biosorbent comes from biomass or natural origin such as microorganism,
residuals of agricultural activities and also wastes of food industries that can be easily
found in abundance at a low cost. Therefore the adsorption process for removal of
toxic species from the aqueous effluents becomes very attractive from the economical
point of view (S. Babel, T.A. Kurniawan, 2003) .Those mentioned before are the main
criteria needed for any material to become biosorbent. But in order for materials to be
labelled in such name, it must also have high adsorption capability for it to adsorp even
at low concentration of contaminant.

2.2.2 Theory of Biosorption kinetics

Biosorption kinetics is provided vital information for determining and selecting

optimum operational conditions for full-scale batch heavy metal removal process in
industry. In this work, the pseudo-first order (Lagergren, 1898) and the pseudo-second
order (Blanchard et al., 1984) kineticmodels were employed to correlate kinetic
experimental data. The pseudo-first order kineticmodel has the mathematic form as
follow:

qt = qe(1 − exp(−k1t)) (4)

where qt is the amounts of Cr-metal ions adsorbed per mass of durian shell used at
time t (mmol/g), k1 is the rate constant of pseudo-first-order reaction (min−1) and t is
time (min). The pseudo-second order kinetic model, on the other hand can be
expressed in the following mathematic form:

where k2 is the rate constant of pseudo-second order reaction (gmmol−1 min−1)

2.3 Type of process

2.3.1 Process of Cycle of water

In every day, water supplied to us from the natural and artificial reservoir and
runs through a cycle of mechanism which keep on repeating in order to sustain it
storage. The water cycle, it is started with water storage at the evaporation of the ocean
heated by the sun at the high temperature and this will cause the water raise up to the
atmosphere in form vapor then will make a cloud as a storage of water. In addition,
the water vapor will converted back into water in the condensation process and will
make the cloud’s density increase. Furthermore, when cloud become heavier, the water
will fall down to the land as rain. Then, the cycle will rotate and repeated until the end
of the world.

Figure 2.3: Cycle of water

2.3.2 Process of Removal of heavy metal

The removal of heavy metal ions from aqueous solutions is quite a complicated
process, consisting of ion exchange and adsorption and is likely to be accompanied by
precipitation of metal hydroxide complexes on active sites of the particle surface.
Some of the author said, removal of heavy metal of lead by shell of crab, Lee suggested
potential possibility of regenerated wastes as adsorbents (Lee, 1994). In addition, the
applicability of wastes such as scoria, fly ash, zeolite, chitosan, sawdust and coal has
been studied (Kwon et al., 2005; Nugteren et al., 2002; Inglezakis and Grigoropoulou,
2004; Cao et al.,2004; Kim and Ryu, 1995). Furthermore, the important issues in the
industrial process are minimization of waste, recovery of precious material, and
maximum regeneration of waste and energy. The eggshell, is widely produced from
house, restaurant, and bakery.

In additional knowledge, there are have many ways for remove heavy metal in
waste water or pollution of water either river water and tap water. The test of removal
heavy metal can depend on many type of manipulated variable or known as a
parameter such as temperature, dosage and so on. In addition, removal heavy metal
also can tested with acid and alkaline. So, in removal heavy metal there are can tested
on treated waste water and also untreated waste water. For remove heavy metal such
as lead, copper, zinc and any heavy metal there must be some waste product to tested,
it is call sorbent means that waste product that come from plant, vegetable, and also
fruit. Mostly, many scientist are used fruit as a sorbent to remove heavy metal such as
areca nut, durian shell, nut shell and banana skin. Furthermore, it might be use a sea
life such as shrimp and seashell. Finally, the removal heavy metal, completed when
the heavy metal waste water absorbed by sorbent while this method is a very cheaper
technology process.
2.3.3 The process of adsorption

When using the term’s biosorbent, it must be clearly understood that the word
itself is referring to the type of material used for the removal of heavy metal in waste
water treatment while the process behind these concept is known as the adsorption
process. From Kopecký F., Kaclík P., and Fazekaš T, 1996, the process of adsorption
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). It is different from
absorption, in which a substance diffuses into a liquid or solid to form a solution. The
term sorption encompasses both processes, while desorption is the reverse process.

Adsorption is operative in most natural physical, biological, and chemical

systems, and is widely used in industrial applications such as activated charcoal,
synthetic resins and water purification. The exact nature of the bonding depends on the
details of the species involved, but the adsorbed material is generally classified as
exhibiting physisorption which is a type of adsorption in which the adsorbate adheres
to the surface only through Van der Waals (weak intermolecular) interactions, which
are also responsible for the non-ideal behaviour of real gases. On the other hand,
chemisorption is a type of adsorption whereby a molecule adheres to a surface through
the formation of a chemical bond, as opposed to the Van der Waals forces which cause
physisorption (J. Oremusová, 2007).
2.4 Application Of Durian Fruit

The durian is the fruit of several tree species belonging to the genus Durio and
the family Malyaceae. Therefore, Durian is a fruit mostly have in Southeast Asia such
as Malaysia, Brunei, Indonesia and also Thailand. Durian or its scientific name, Durio
was regarded by many people in Southeast Asia as the “king of fruits” because durian
have distinctive for its large size, stomach-churning odor and also formidable thorn-
covered husk. As information, Some people regard the durian as pleasantly fragrant;
others find the aroma overpowering and revolting. In addition, Durian fruit can grow
as large as 30 centimeter or 12 inch long and also 15 centimeter or 6 inch in diameter
while The durian is grown in other areas with a similar climate; it is strictly tropical
and stops growing when mean daily temperatures drop below 22 °C (72 °F). Durians
weight can achieve from one to three kilograms and about 2 to 7 lb.

Table 2.1: Application of Part of Durian

Durian Application

shell  Moluccas islands used as fuel to smoke fish

 Methane production

Shoot and  Occasionally cooked as greens.

leaves  the ash of the burned rind is added to special cakes
 The petals of durian flowers are eaten in the North Sumatra
province of Indonesia
Durian flesh  eaten fresh with sweet sticky rice
 durian paste
 Unripe durians may be cooked as a vegetable
 both sugared and salted preserves from durian

Seed  can be eaten whether they are boiled, roasted or fried in
coconut oil
 In Java, the seeds are sliced thin and cooked with sugar as a
confection
 For this experiment, we want to use waste product as biosorbent so that it can
remove heavy metal to avoid from any pollution.

Bio-adsorption is a process that occurs naturally in certain biomass which

allows it to passively concentrate and bind contaminants onto its cellular structure.
Adsorption process is differs from absorption which is a fluid permeates or is dissolved
by a liquid or solid. Biosorbent is a material that needs to be used to treated water by
using bio-adsorption process. Basically, biosorbent is kind of sorbent that made from
biological material. Durian stone is chosen as biosorbent for this experiment to remove
heavy metal that contain in waste water especially lead.

Actually, there are several ways to remove heavy metal to avoid from heavy
metal pollution. Usually, heavy metal can be removed by using conventional methods
such as ion exchange and also activated carbon. Unfortunately, the conventional
methods that are used to remove heavy metal need higher cost to be operated. So, one
of the purpose of this experiment is to try a new method that can replace the other
conventional methods. Bio absorbent from waste materials can be used to remove
heavy metal and at once can offer a better solution because it is cheaper and abundant
compared to the other conventional methods. That’s why we try to use durian stone
based on the observation of waste materials because it is potentially excellent
candidate as adsorbent in order to remove heavy metal.
2.5 Criteria Needed for Waste Materials to Become Biosorbent

In order for waste material which in this case; durian stone, can be selected in
becoming the next biosorbent, it must fulfill the basic requirement of having high
adsorption capacity. Several other criteria needed are namely;

(1) high adsorption capacity;

(2) high availability in large quantity within one location;

(3) low economical value (less advantage for other purpose);

(4) high reusability potential (attached metal can be easily removed).

Indeed, nearly all of the alternative adsorbents found through successful studies
already fulfilled 2 or 3 of these criterias (Alfin Kurniawana, Vincentius Ochie Arief
Sisnandya, Kiki Trilestari, 2010).
2.6 Past Study of Removal Heavy Metal

2.6.1 Using Banana Peels

Banana peel is rich with phenolic especially antioxidant. The total amount of phenolic
compound in banana peel ranges from 0.90 to 3.3 g/ 100 g DW (Nguyen & Ketsa,
2003) and other finding have been identified gallocatechin at concentration of 160 mg/
100 g DW (Someya, 2002). One of the main interest is phenolic compound are widely
distributed in fruit and plant. Phenolic compound have important sensory and
nutritional qualities that possible for the taste, colour and flavour of many fruits and
plants.As a result, the concentration of phenolic compound for cultivar ‘bluggoe’ and
cultivar ‘pisang awak’ is higher at fresh condition. There is because, extraction of
antioxidants is typically conducted at temperatures ranging from 20 to 50 ◦C (Kondo,
et. al., 2005).

2.6.2 Using Low Cost Adsorbent

In this study, the adsorption behavior of some low-cost adsorbents such as peanut
husk charcoal, fly ash, and natural zeolite, with respect to Cu2+, and Zn2+ ions, has
been studied in order to consider its application to the purification of metal finishing
wastewater. The batch method was employed: parameters such as pH, contact time,
and initial metal concentration were studied. The influence of the pH of the metal ion
solutions on the uptake levels of the metal ions by the different adsorbents used were
carried out between pH 4 and pH 11. The optimum pH for copper and zinc removal
was 6 in the case of peanut husk charcoal and natural zeolite, and it was 8 in case of
fly ash. An equilibrium time of 2 h was required for the adsorption of Cu(II) and Zn(II)
ions onto peanut husk charcoal and fly ash and an equilibrium time 3 h was required
for the adsorption of Cu(II) and Zn(II) ions onto natural zeolite. The results showed
that peanut husk charcoal, fly ash and natural zeolite all hold potential to remove
cationic heavy metal species from industrial wastewater in the order fly ash.
(Bioresource Technol, 99 (7) (2008), pp. 2516-2527)
2.7 Conclusion Of Removal Heavy Metal

Heavy metal can be thought as the major contributor which affects the quality
of water. Heavy metal such as Cadmium, zinc, copper, nickel, lead, mercury and
chromium are frequently spotted in industrial waste waters, causing an obvious or
potential threat to water quality especially on human health and biodiversity in the
ecosystems (Huidong et al., 2008). It potentially become toxic when they are not
metabolized by the body and pile up in the soft tissues. Such example referring to Lead
(Pb) which is one of the contaminant, is a toxic heavy metal that frequently
contaminates aquatic environments. Industrial activities, such as mining and metal
processing, can lead to heavy metal contamination in surface water, groundwater, and
oceans, causing toxic effects upon entering the food chain (S. Schiewer and S.B. Patil.
2008). Besides, highest or lower concentration of heavy metal also aided in buildup of
toxicity. In terms of health, lead poisoning in human beings causes severe damage to
the kidneys, liver, brain, nervous and reproductive systems (S.H. Hasan; P. Srivastava,
M. Talat. 2009). It impairs hemoglobin synthesis and causes several neurological
disorders. These contaminated should appropriately be treated and if unrecognized, it
can cause risky illness and diminish quality of life (Ferner, 2001)