CHAPTER ONE

1.0 INTRODUCTION
1.1 BACKGROUND OF STUDY
Due to rapid development and industrialization in many countries, the levels of industrial
pollution have been steadily rising. So the pollution problem of industrial wastewater is becoming
more and more serious in the world. Consequently, the treatment of polluted industrial wastewater
remain a topic of global concern since wastewater collected from municipalities, communities and
industries must ultimately be returned to receiving waters or to the land. Moreover, contamination
of ground water is today a major concern in the management of water resources (Weber et al.,
1991). Contaminants as pesticides (El-Geundi et al., 2005), heavy metals (Adesola et al, 2006)
and organic substances (Khouider et al., 2004) are characterised by a wide variety of processes
occurring in the soil including diffusion: mechanical dispersion, chemical reaction, decay,
adsorption and biodegradation. The presence of copper, zinc, lead, iron, nickel and others metals,
has a potentially damaging effect on human physiology and other biological systems when the
tolerance levels are exceeded. Many methods of treatment for industrial wastewater have been
reported in literature (Periasany and Namasivayam, 1995; Dimitrova and Mehandgiev, 1998).
Amongst these methods are ultrafiltration, precipitation, ion exchange and adsorption. For low
concentrations of metal ions in wastewater, the adsorption process is recommended for their
removal. The process of adsorption implies the presence of an “adsorbent” solid that binds
molecules by physical attractive forces, ion exchange, and chemical binding. It is advisable that
the adsorbent is available in large quantities, easily regenerable, and cheap. Activated carbon
(A.C.) is widely used as an effective adsorbent in many applications. It is the most commonly
used adsorbent in the adsorption process for the treatment of wastewater (Mckay et al., 2000) but
metal ion removal by adsorption with activated carbon is relatively expensive. Water pollution
due to heavy metal contaminants is a serious issue because of acute toxicities and carcinogenic
nature of the pollutants. Among various water treatment methods, adsorption is supposed as the
best one due to its inexpensiveness, universal nature and ease of operation. Many waste materials
used include fruit wastes, groundnut shell, coconut shell, scrap tyres, bark and other tannin-rich
materials, sawdust and other wood type materials, rice husk, petroleum wastes, fertilizer wastes,
fly ash, sugar industry wastes blast furnace slag, chitosan and seafood processing wastes, seaweed
and algae, peat moss, clays, red mud, zeolites, sediment and soil, ore minerals etc. These

1
adsorbents have been found to remove various organic pollutants ranging from about 80 to
99.9%.
The process for removing metal ions from aqueous solutions by different activated carbon
obtained from agricultural by-products has been published Orhan and Buyungor (1993) and
Mckay (1984). Due to the high cost of activated carbon and 10 – 15% loss during regeneration,
alternative low cost adsorbents have attracted the attention of several investigators to provide an
alternate for the high cost activated carbon. Though several studies were available explaining the
utilization of several low cost adsorbents, most of these work stand at the laboratory level and
only a very few cases have been directly implemented in practical applications at industrial level
(Abia et al., 2003). Agricultural by-products could be heavy metal adsorbents which could be
selective for some metal ions (Duri, 1995). Agricultural products such as banana and orange
peels. (Annadurai et al., 2002) bagasse pith, sawdust wastes (Asfour et al., 1995; Zarraa, 1995),
maize cob, coconut husk fibres (Tan et al., 1993; Babarinde, 2002), groundnut shells (Demirbas,
2003); soybeans and cotton seed hulls have been evaluated for their adsorptive properties. These
materials have been reported to adsorb different pollutants such as heavy metal ions, dyestuff and
other toxic pollutants (El-Geundi, 1997). Refined corn hulls, ground nut husks (Okiemen et al.,
1991), and rice hulls (Roy et al., 1993), and have been also evaluated for the adsorption of heavy
metal ions from wastewater. Research in the use of agricultural by-products (Abia and Asuquo,
2006) has included metal binding studies with Datura innoxia, dyed cellulosic materials, wheat
and rice bran, oat fiber, sugarcane bagasse, maize cob (El-Geundi, 1997; Al-Duri, 1995; Magdy,
1992; Nassar and El-Geundi, 1994) and sawdust to mention a few (Drake et al., 1996; Shukla and
Sakhardane, 1992; Weber et al., 1991; Weber and Morris, 1964).
In this study lead has been chosen because of its environmental importance related to its well
known toxicity (Hepple, 1972) and intensive use in industries such as storage-battery
manufacture, printing, pigment manufacturing, petrochemicals, fuel combustion and photographic
materials (Carson et al., 1986). Assimilation in the human body of relatively small amounts of
lead over a long period of time can lead to malfunctioning of certain organs and chronic toxicity
(Khurshid and Qureshi, 1984). Lead pollution in water has been increasing progressively in
Nigeria. This gives rise to concern health problems in man and animals. Therefore it is of great
relevance to develop a new method for its removal from water, and this is the aim of the present
work. This study may generate useful information for the utilization of native agricultural by-

2
products for the removal of Pb2+ from wastewater. Groundnut wastes, as agricultural byproducts
from groundnut, oil or peanut producing industries, could be heavy metal adsorbents which could
be selective for some metal ions. In this study the capabilities of groundnut shell wastes for lead
ion adsorption was tested. The effect of pH and adsorbent dose, on the rate of removal of lead was
investigated.
The equilibrium data is described by Freundlich and Lamgnuir adsorption isotherms.
Response surface methodology (RSM) could be employed as a statistical tool to optimize and
study interactions (Ariffin et al., 2008). RSM, a fractional factorial design involves a set of
designed experiment to obtain optimal response. In addition the relative significance of various
factors involved in complex interactions can be evaluated (Saha et al., 2009). Nowadays, these
techniques are widely employed for optimization of number of processes including adsorption
studies (Ozdemer et al., 2011). In this research, the influence of operating parameters such as pH,
contact time, and adsorbent dosage for the removal of lead onto activated groundnut shell was
investigated in batch mode. Also, groundnut shell was modified by activation with nitric acid
HNO3, to produce activated groundnut shell.

1.2 PROBLEM STATEMENT

The environmental issues due to globalization and rapid industrialization are becoming more and
more nuisance for human being. Therefore efficient and effective methods are needed especially
for chemical industries. Heavy metals such as lead present in wastewater and industrial effluent is
major concern of environmental pollution. This project focuses on industrial waste water
produced in industries evolving or utilizing lead as either raw material or finished goods. Lead's
toxicity has been a reason why lead was or is being phased out for some uses. If ingested or
inhaled, lead and its compounds are poisonous to animals and humans. Lead is a neurotoxin
which accumulates in soft tissues and bones, damaging the nervous system and causing brain
disorders. Excessive lead also causes blood disorders in mammals. With this adverse effect the
need of removing or adsorbing lead is necessary so as to save life (promoting healthy living) and
ensure better eco system. Also when adsorbing lead from waste water cost of adsorption should
be minimal and studying most adsorption processes such as ion exchange, chemical precipitation,
coagulation and flocculation, membrane filtration ultra filtration are quite expensive processes

3
this calls for the use of low cost adsorbent such activated carbon which can be obtained from
waste such as groundnut shell, rice husk, coconut shell, etc.

1.3 AIM

The aim of this study is to evaluate the treatment of lead in an aqueous solution using modified
groundnut shell.

1.4 OBJECTIVES
The general objective of the project study is to investigate the effectiveness of locally available
And low-cost groundnut shell (activated) for the removal of lead ions from aqueous solution
containing lead.
Specific objectives are:
1. To investigate the effect of adsorbent dose, contact time, and initial PH concentration of
the solution on the adsorption of lead ions using ground nut shell as adsorbent and Box-Behnken
design approach.
2. To find out if groundnut husk could be used to remove lead ions from its aqueous solutions.
3. To prepare the modified adsorbent

1.5 SCOPE OF WORK

This studies centers on the following:
1. Adsorption of lead using waste ground nut shell which is a low cost adsorbent.
2. Effect of process parameters on rate of adsorption.
The atomic adsorption spectrophotometer was used to determine the amount of metals removed.
The effect of adsorbent dosage, pH, and contact time on heavy metal removal from aqueous
medium using groundnut shell was investigated using Box-Behnken design in response surface
methodology (RSM) by design expert version 7.0.0 (Stat Ease, USA). The experimental data were
analyzed by fitting to a quadratic model, which was statistically validated by performing Analysis
of Variance (ANOVA) and lack-of-fit test to evaluate the significance of the model.

4
1.6 RELEVANCE OF STUDY
The findings of this study will help reduce the industrial waste water pollution with lead ions to
be minimal thereby enhancing and allowing a comfortable ecosystem, this study will help the
industries producing pollutant to optimize cost of lead adsorption since cost adsorbent(ground nut
shell) is used as a case study. This study also helps in understanding the significance of Response
Surface Methodology (RSM) in the optimization of lead adsorption.
1.7 LIMITATION OF STUDY
Only lead ion is considered in this study other toxic heavy metals such as chromium, selenium,
cobalt etc where not considered. Also groundnut shell is the only adsorbent used for the study,
other works might include the combination of adsorbent from different sources in lead ion
adsorption.
Isotherms as well as kinetics studies were not performed in this work.

5
 CHAPTER TWO

2.0 LITERATURE REVIEW

2.1 HEAVY METALS

Over the past two decades, the term “heavy metals” has been widely used. It is often used as a
group name for metals and semimetals (metalloids) that have been associated with contamination
and potential toxicity or ecotoxicity. At the same time, legal regulations often specify a list of
“heavy metals” to which they apply. Such lists differ from one set of regulations to another and
the term is sometimes used without even specifying which “heavy metals” are covered.
However, there is no authoritative definition to be found in the relevant literature.
There is a tendency, unsupported by the facts, to assume that all so-called “heavy metals” and
their compounds have highly toxic or ecotoxic properties. This has no basis in chemical or
toxicological data. Thus, the term “heavy metals” is both meaningless and misleading. Even the
term “metal” is commonly misused in both toxicological literature and in legislation to mean
the pure metal and all the chemical species in which it may exist. This usage implies that the pure
metal and all its compounds have the same physicochemical, biological, and toxicological
properties, which is untrue. In order to avoid the use of the term “heavy metal”, a new
classification based on the periodic table is needed. Such a classification should reflect our
understanding of the chemical basis of toxicity and allow toxic effects. In the fundamental review
paper written by Duffus (2002), 13 different works were cited that used lower limits on the
density of a “heavy” metal ranging from 3.5 to 7 g cm−3. The author stated that the threshold
varied depending on the author, and that “it is impossible to come up with a consensus”.
Moreover, he concluded that “any idea of defining “heavy metals” on the basis of density must be
abandoned as yielding nothing but confusion”. However, this is beside the point; although half of
the works cited suggested similar lower limits of 4.5 or 5 g cm−3, plants do not have the ability to
detect the density of a metal. Thus, “heavy metal” remains an obscure term in the life sciences. It
should also be noted that the review paper of Duffus (2002) was commissioned by the
International Union of Pure and Applied Chemistry, and certainly represents a chemical point of
view that is often neglected by biologists. Apart from the specific weight, the atomic weight, the

6
atomic number, specific chemical properties, and the toxicity were all mentioned as a possible
basis for classification – and then rejected for good reasons.

With the rapid development of industries such as metal plating facilities, mining operations,
fertilizer industries, tanneries, batteries, paper industries and pesticides, etc., heavy metals
wastewaters are directly or indirectly discharged into the environment increasingly, especially in
developing countries. Unlike organic contaminants, heavy metals are not biodegradable and tend
to accumulate in living organisms and many heavy metal ions are known to be toxic or
carcinogenic. Toxic heavy metals of particular concern in treatment of industrial wastewaters
include zinc, copper, nickel, mercury, cadmium, lead and chromium. Zinc is a trace element that
is essential for human health. It is important for the physiological functions of living tissue and
regulates many biochemical processes. However, too much zinc can cause eminent health
problems, such as stomach cramps, skin irritations, vomiting, nausea and anemia (Oyaro et al.,
2007). Copper does essential work in animal metabolism. But the excessive ingestion of copper
brings about serious toxicological concerns, such as vomiting, cramps, convulsions, or even death
(Paulino et al., 2006). Nickel exceeding its critical level might bring about serious lung and
kidney problems aside from gastrointestinal distress, pulmonary fibrosis and skin dermatitis
(Borba et al., 2006). And it is known that nickel is human carcinogen. Mercury is a neurotoxin
that can cause damage to the central nervous system. High concentrations of mercury cause
impairment of pulmonary and kidney function, chest pain and dyspnoea (Namasivayam and
Kadirvelu, 1999). The classic example of mercury poisoning is Minamata Bay. Cadmium has
been classified by U.S. Environmental Protection Agency as a probable human carcinogen.
Cadmium exposes human health to severe risks. Chronic exposure of cadmium results in kidney
dysfunction and high levels of exposure will result in death. Lead can cause central nervous
system damage. Lead can also damage the kidney, liver and reproductive system, basic cellular
processes and brain functions. The toxic symptoms are anemia, insomnia, headache, dizziness,
irritability, weakness of muscles, hallucination and renal damages (Naseem and Tahir, 2001).
Chromium exits in the aquatic environment mainly in two states: Cr (III) and Cr (VI). In general,
Cr (VI) is more toxic than Cr (III). Cr (VI) affects human physiology, accumulates in the food
chain and causes severe health problems ranging from simple skin irritation to lung carcinoma
(Khezami and Capart, 2005). Faced with more and more stringent regulations, nowadays heavy

7
metals are the environmental priority pollutants and are becoming one of the most serious
environmental problems. So these toxic heavy metals should be removed from the wastewater or
aqueous solution in which they are contained to protect the people and the environment. Many
methods that are being used to remove heavy metal ions include chemical methods such as
(chemical precipitation, ion-exchange, adsorption, electrochemical treatment technologies, etc)
and physical methods such as (membrane filtration, ultra filtration, nanofiltration, reverse osmosis
etc).

2.2 TYPES OF HEAVY METALS

2.2.1 Iron

This is a chemical element with symbol Fe (from Latin: ferrum) and atomic number 26. It is a
metal in the first transition series. It is by mass the most common element on Earth, forming much
of Earth's outer and inner core. It is the fourth most common element in the Earth's crust. Its
abundance in rocky planets like Earth is due to its abundant production by fusion in high-mass
stars, where it is the last element to be produced with release of energy before the violent collapse
of a supernova, which scatters the iron into space(Fong,2011). Iron exists in a wide range of
oxidation states, −2 to +6, although +2 and +3 are the most common. Elemental iron occurs in
meteoroids and other low oxygen environments, but is reactive to oxygen and water. Fresh iron
surfaces appear lustrous silvery-gray, but oxidize in normal air to give hydrated iron oxides,
commonly known as rust. Unlike the metals that form passivating oxide layers, iron oxides
occupy more volume than the metal and thus flake off, exposing fresh surfaces for corrosion. Iron
metal has been used since ancient times, although copper alloys, which have lower melting
temperatures, were used even earlier in human history. Pure iron is relatively soft, but is
unobtainable by smelting because it is significantly hardened and strengthened by impurities, in
particular carbon, from the smelting process. A certain proportion of carbon (between 0.002% and
2.1%) produces steel, which may be up to 1000 times harder than pure iron. Crude iron metal is
produced in blast furnaces, where ore is reduced by coke to pig iron, which has high carbon
content. Further refinement with oxygen reduces the carbon content to the correct proportion to
make steel. Steels and iron alloys formed with other metals (alloy steels) are by far the most
common industrial metals because they have a great range of desirable properties and iron-

8
bearing rock is abundant (Fong, 2011). Iron chemical compounds have many uses. Iron oxide
mixed with aluminium powder can be ignited to create a thermite reaction, used in welding and
purifying ores. Iron forms binary compounds with the halogens and the chalcogens. Among its
organometallic compounds is ferrocene, the first sandwich compound discovered. Iron plays an
important role in biology, forming complexes with molecular oxygen in hemoglobin and
myoglobin; these two compounds are common oxygen transport proteins in vertebrates. Iron is
also the metal at the active site of many important redox enzymes dealing with cellular respiration
and oxidation and reduction in plants and animals. A human male of average height has about 4
grams of iron in his body, a female about 3.5 grams. This iron is distributed throughout the body
in hemoglobin, tissues, muscles, bone marrow, blood proteins, enzymes, ferritin, hemosiderin,
and transport in plasma.

2.2.2 Lead

This is the most prevalent heavy metal contaminant. Levels in the aquatic environments of
industrialised societies have been estimated to be two to three times those of pre-industrial levels.
As a component of tetraethyl lead, (CH3CH2)4Pb, it was used extensively in gasoline during the
(1930s–1970s). This chemical element has an atomic number 82 and symbol Pb (from Latin:
plumbum). It is a soft, malleable, and heavy metal. Freshly cut solid lead has a bluish-white color
that soon tarnishes to a dull grayish color when exposed to air; the liquid metal has shiny chrome-
silver luster. Lead's density of 11.34 g/cm3 exceeds that of most common materials. Lead has the
second highest atomic number of all practically stable elements. As such, lead is located at the
end of some decay chains of heavier elements, which in part accounts for the relative abundance
of lead: it exceeds those of other similarly-numbered elements. Lead is a post transition metal,
and is relatively inert unless powdered. Its weakened metallic character is illustrated by its general
amphoteric nature: it and its oxides react with both acids and bases. It also displays a marked
tendency toward covalent bonding. Its compounds are most commonly found in the +2 oxidation
state, rather than +4, unlike the lighter group 14 elements. Exceptions are mostly limited to
organolead compounds, where the positive charge on lead is dispersed and stabilized. Like the
lighter group 14 elements, lead shows a tendency to bond to itself, forming complicated chain,
ring, or polyhedral structures.

9
Lead is relatively easy to extract, and the metal was known to prehistoric people in Western Asia.
While its softness and dullness prevented it from high demand, galena, a principle ore of lead
often bore silver in it, which helped initiate production of lead. Lead production peaked in ancient
Rome, and lead became easily available to common people. After the fall of Rome, levels of lead
production fell, and those of Rome were not surpassed anywhere until as late as the Industrial
Revolution. The metal was established as poisonous as late as in the late nineteenth century,
which led to its eventual displacement from many uses, and it has been or is being phased out
from those which include immediate contact to people.

Lead has several properties that make it advantageous to use, alongside its commonness: high
density, low melting point, ductility, and relative inertness against oxygen attack. Lead minerals
are easier to mine and lead is easier to extract from its ores than many other metals, which makes
the resulting metal relatively inexpensive. For example, lead is used in building construction,
lead–acid batteries, bullets and shot, weights, as part of solders, pewters, fusible alloys, and as a
radiation shield. Currently, lead is produced in quantities of around ten thousand tonnes annually;
secondary production from recycling is gaining ground, accounting for around half of that figure.
Lead's toxicity has been a reason why lead was or is being phased out for some uses. If ingested
or inhaled, lead and its compounds are poisonous to animals and humans. Lead is a neurotoxin
which accumulates in soft tissues and bones, damaging the nervous system and causing brain
disorders. Excessive lead also causes blood disorders in mammals.

2.2.3 Cadmium

This is a chemical element with symbol Cd and atomic number 48. This soft, bluish-white metal
is chemically similar to the two other stable metals in group 12, zinc and mercury. Like zinc, it
demonstrates oxidation state +2 in most of its compounds, and like mercury, it has a lower
melting point than other transition metals. Cadmium and its congeners are not always considered
transition metals, in that they do not have partly filled d or f electron shells in the elemental or
common oxidation states. The average concentration of cadmium in Earth's crust is between 0.1
and 0.5 parts per million (ppm). It was discovered in 1817 simultaneously by (Stromeyer and
Hermann); both in Germany, as an impurity in zinc carbonate (Taylor, 2011).

10
Cadmium occurs as a minor component in most zinc ores and is a byproduct of zinc production.
Cadmium was used for a long time as corrosion-resistant plating on steel, and cadmium
compounds are used as red, orange and yellow pigments, to colour glass, and to stabilize plastic.
Cadmium use is generally decreasing because it is toxic (it is specifically listed in the European
Restriction of Hazardous Substances) and nickel-cadmium batteries have been replaced with
nickel-metal hydride and lithium-ion batteries. One of its few new uses is cadmium telluride solar
panels. Although cadmium has no known biological function in higher organisms, a cadmium-
dependent carbonic anhydrase has been found in marine diatoms.

2.2.4 Vanadium

This is a chemical element with symbol V and atomic number 23. It is a hard, silvery grey,
ductile, and malleable transition metal. The elemental metal is rarely found in nature, but once
isolated artificially, the formation of an oxide layer (passivation) stabilizes the free metal
somewhat against further oxidation.

Andrés Manuel del Río discovered compounds of vanadium in 1801 in Mexico by analyzing a
new lead-bearing mineral he called "brown lead", and presumed its qualities were due to the
presence of a new element, which he named erythronium (derived from Greek for "red") since,
upon heating, most of the salts turned red. Four years later, however, he was (erroneously)
convinced by other scientists that erythronium was identical to chromium. Chlorides of vanadium
were generated in 1830 ( Nils Gabriel Sefström) who thereby proved that a new element was
involved, which he named "vanadium" after the Scandinavian goddess of beauty and fertility,
Vanadís (Freyja). Both names were attributed to the wide range of colors found in vanadium
compounds. Del Rio's lead mineral was later renamed vanadinite for its vanadium content. In
1867 Henry Enfield Roscoe obtained the pure element.

Vanadium occurs naturally in about 65 different minerals and in fossil fuel deposits. It is
produced in China and Russia from steel smelter slag; other countries produce it either from the
flue dust of heavy oil, or as a byproduct of uranium mining. It is mainly used to produce specialty
steel alloys such as high-speed tool steels. The most important industrial vanadium compound,
vanadium pentoxide, is used as a catalyst for the production of sulfuric acid.

11
Large amounts of vanadium ions are found in a few organisms, possibly as a toxin. The oxide and
some other salts of vanadium have moderate toxicity. Particularly in the ocean, vanadium is used
by some life forms as an active center of enzymes, such as the vanadium bromoperoxidase of
some ocean algae.

2.2.5 Nickel

This is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous
metal with a slight golden tinge. Nickel belongs to the transition metals and is hard and ductile.
Pure nickel, powdered to maximize the reactive surface area, shows a significant chemical
activity, but larger pieces are slow to react with air under standard conditions because an oxide
layer forms on the surface and prevents further corrosion (passivation). Even so, pure native
nickel is found in Earth's crust only in tiny amounts, usually in ultramafic rocks, and in the
interiors of larger nickel–iron meteorites that were not exposed to oxygen when outside Earth's
atmosphere.

Meteoric nickel is found in combination with iron, a reflection of the origin of those elements as
major end products of supernova nucleosynthesis. An iron–nickel mixture is thought to compose
Earth's inner core.

Use of nickel (as a natural meteoric nickel–iron alloy) has been traced as far back as 3500 BCE.
Nickel was first isolated and classified as a chemical element in 1751 by Axel Fredrik Cronstedt,
who initially mistook the ore for a copper mineral. The element's name comes from a mischievous
sprite of German miner mythology, Nickel (similar to Old Nick), that personified the fact that
copper-nickel ores resisted refinement into copper. An economically important source of nickel is
the iron ore limonite, which often contains 1–2% nickel. Nickel's other important ore minerals
include garnierite, and pentlandite. Major production sites include the Sudbury region in Canada
(which is thought to be of meteoric origin), New Caledonia in the Pacific, and Norilsk in Russia.

Nickel oxidizes slowly at room temperature and is considered corrosion-resistant. Historically, it

has been used for plating iron and brass, coating chemistry equipment, and manufacturing certain
alloys that retain a high silvery polish, such as German silver. About 6% of world nickel
production is still used for corrosion-resistant pure-nickel plating. Nickel-plated objects

12
sometimes provoke nickel allergy. Nickel has been widely used in coins, though its rising price
has led to some replacement with cheaper metals in recent years.

Nickel is one of four elements (iron, cobalt, nickel, and gadolinium) that are ferromagnetic around
room temperature. Alnico permanent magnets based partly on nickel are of intermediate strength
between iron-based permanent magnets and rare-earth magnets. The metal is valuable in modern
times chiefly in alloys; about 60% of world production is used in nickel-steels (particularly
stainless steel). Other common alloys and some new superalloys comprise most of the remainder
of world nickel use, with chemical uses for nickel compounds consuming less than 3% of
production. As a compound, nickel has a number of niche chemical manufacturing uses, such as a
catalyst for hydrogenation. Nickel is an essential nutrient for some microorganisms and plants
that have enzymes with nickel as an active site.

2.2.6 Selenium

Selenium is found in metal sulfide ores, where it partially replaces the sulfur. Commercially,
selenium is produced as a byproduct in the refining of these ores, most often during production.
Minerals that are pure selenide or selenate compounds are known but rare. The chief commercial
uses for selenium today are glassmaking and pigments. Selenium is a semiconductor and is used
in photocells. Applications in electronics, once important, have been mostly supplanted by silicon
semiconductor devices. Selenium is still used in a few types of DC power surge protectors and
one type of fluorescent quantum dot.

Selenium salts are toxic in large amounts, but trace amounts are necessary for cellular function in
many organisms, including all animals. Selenium is an ingredient in many multivitamins and
other dietary supplements, including infant formula. It is a component of the antioxidant enzymes
glutathione peroxidase and thioredoxin reductase (which indirectly reduce certain oxidized
molecules in animals and some plants). It is also found in three deiodinase enzymes, which
convert one thyroid hormone to another. Selenium requirements in plants differ by species, with
some plants requiring relatively large amounts and others apparently requiring none.

13
2.2.7 Zinc

Zinc is an essential mineral perceived by the public today as being of "exceptional biologic and
public health importance", especially regarding prenatal and postnatal development. Zinc
deficiency affects about two billion people in the developing world and is associated with many
diseases. In children, deficiency causes growth retardation, delayed sexual maturation, infection
susceptibility, and diarrhea. Enzymes with a zinc atom in the reactive center are widespread in
biochemistry, such as alcohol dehydrogenase in humans. Consumption of excess zinc can cause
ataxia, lethargy and copper deficiency. Zinc is a chemical element with the symbol Zn and
atomic number 30. It is the first element in group 12 of the periodic table. In some respects zinc is
chemically similar to magnesium: both elements exhibit only one normal oxidation state (+2), and
the Zn2+ and Mg2+ ions are of similar size. Zinc is the 24th most abundant element in Earth's crust
and has five stable isotopes. The most common zinc ore is sphalerite (zinc blende), a zinc sulfide
mineral. The largest workable lodes are in Australia, Asia, and the United States. Zinc is refined
by froth flotation of the ore, roasting, and final extraction using electricity (electrowinning).

2.2.8 Copper

Copper is one of the few metals that occur in nature in directly usable metallic form as opposed to
needing extraction from an ore. This led to very early human use, from c. 8000 BC. It was the
first metal to be smelted from its ore, c. 5000 BC, the first metal to be cast into a shape in a mold,
c. 4000 BC and the first metal to be purposefully alloyed with another metal, tin, to create bronze,
c. 3500 BC. Copper is a chemical element with symbol Cu (from Latin: cuprum) and atomic
number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical
conductivity. A freshly exposed surface of pure copper has a reddish-orange color. Copper is used
as a conductor of heat and electricity, as a building material, and as a constituent of various metal
alloys, such as sterling silver used in jewelry, cupronickel used to make marine hardware and
coins, and constantan used in strain gauges and thermocouples for temperature measurement.

14
2.3 EFFECTS OF HEAVY METALS
The environmental issues due to globalization and rapid industrialization are becoming more and
more nuisance for human being. Therefore efficient and effective methods are needed especially
for chemical industries. Heavy metals present in wastewater and industrial effluent is major
concern of environmental pollution. Heavy metals are generally considered as those whose
density exceeds 5 g per cubic centimeter. Most of the elements that fall into these categories are
highly soluble in water, well-known toxics and carcinogenic agents. Heavy metals are considered
to be the following elements: Copper, Silver, Zinc, Cadmium, Gold, Mercury, Lead, Chromium,
Iron, Nickel, Tin, Arsenic, Selenium, Molybdenum, Cobalt, Manganese, and Aluminum
(Gunatilake, 2015). They represent serious threats to the human population and the fauna and
flora of the receiving water bodies. They can be absorbed and accumulated in human body and
caused serious health effects like cancer, organ damage, nervous system damage, and in extreme
cases, death. Also it reduces growth and development. Industrial wastewater streams containing
heavy metals are produced from different industries. Heavy metals such as cadmium, zinc, lead,
chromium, nickel, copper, vanadium, platinum, silver, and titanium are generated in
electroplating, electrolysis depositions, conversion-coating, and anodizing-cleaning, milling, and
etching industries. Significant amount of heavy metals wastes like Tin, lead, and nickel result
from printed circuit board (PCB) manufacturing. Wood processing industries where a chromated
copper-arsenate wood treatment produces arsenic containing wastes; inorganic pigment
manufacturing producing pigments contain chromium compounds and cadmium sulfide;
petroleum refining generates conversion catalysts contaminated with nickel, vanadium, and
chromium; and photographic operations producing film with high concentrations of silver and
ferrocyanide (Dhokpande,2009). All of these generators produce a large quantity of wastewaters,
residues, and sludge that can be categorized as hazardous wastes requiring extensive waste
treatment. As the low amounts of these metals are highly toxic, removal of heavy metals from
wastewater has recently become the subject of considerable interest owing to strict legislations.
Wastewater regulations were established to minimize human and environmental exposure to
hazardous chemicals. These include limits on the types and concentration of heavy metals that
may be present in the discharged wastewater. The Maximum Contaminated Level (MCL)
standards, for those heavy metals, established by USEPA are summarized in Table 2.1. Therefore
it is necessary to treat metal contaminated wastewater prior to its discharge to the environment.

15
Heavy metal removal from inorganic effluent can be achieved by conventional treatment
processes. Removal of heavy metals from industrial wastewaters can be accomplished through
various treatment options, including such unit operations as chemical precipitation, coagulation,
complexation, activated carbon adsorption, ion exchange, solvent extraction, foam flotation,
electro-deposition, cementation, and membrane operations.
Table 2.1 (metals and their effects in concentration)
Heavy Metals Toxicities MCL(mg/L)
Arsenic Skin manifestations, visceral 0.05
cancers, vascular disease
Cadmium Kidney damage, renal disorder, 0.01
human carcinogen
Chromium Head ache, diarrhea, nausea, 0.05
vomiting, carcinogen
Copper Liver damage, Wilson disease, 0.25
insomnia
Nickel Dermatitis, nausea, chronic 0.2
asthma, coughing, human
carcinogen
Zinc Depression, lethargy, 0.8
neurological signs and nervous
system
Lead Demand the fetal brain, 0.006
diseases of the kidneys,
circulatory system and nervous
system.
Mercury Rheumatoid arthritis, and 0.00003
diseases of the kidneys
circulatory system and nervous
system.

16
Chemical precipitations, conventional adsorption, ion exchange, membrane separation methods
and electro-remediation methods are used more commonly to treat industrial wastewater. Among
these methods precipitation is most economical and hence widely used, but many industries still
use chemical procedures for treatment of effluents due to economic factors. However due to
complexing agents in wastewater, efficiency of the precipitation process can drastically be
decreased and this creates incomplete processing and production of toxic sludge. Therefore
numerous novel approaches have been studied to develop cost effective and more efficient heavy
metal adsorption techniques.
Biosorption is considered as a user-friendly, effective purification and separation method for the
removal of heavy metals from industrial wastewater with the advantages of specific affinity, low
cost and simple design. Therefore it has been widely used for treatment of wastewater. Sorption
with sorbents made of agricultural or industrial by-products are used widely to remove heavy
metals from aqueous solution due to their abundant availability, low cost, and favorable physical,
chemical and surface characteristics.
2.3.1 FACTORS AFFECTING ADSORPTION OF HEAVY METALS
The factors affecting the adsorption processes are: surface area, nature and initial concentration of
adsorbate, solution pH, temperature, interfering substances, and nature and dose of adsorbent.
2.3.1.1 SURFACE AREA
Since adsorption is a surface phenomenon the extent of the adsorption is proportional to the
specific surface area which is defined as that portion of the total surface area that is available for
adsorption (Eckhard., 2012). The major contribution to surface area is located in the pores of
molecular dimensions. For example, surface area of several activated carbon used for wastewater
treatment is about 1,000m2/g with a mean particle diameter of bout 1.6mm and density of
1.4g/cm3. Assuming spherical particles, only about 0.0003% of the total surface is the external
surface of the carbon particle (Culp et al., 1978).
2.3.1.2 NATURE OF ADSORBATE
The physiological nature of the adsorbent drastically affects both rate and capacity of adsorption.
The solubility of the solute greatly influences the adsorption equilibrium. In general, an inverse
relationship can be expected between the extent of a solute and its solubility in the solvent where
the adsorption takes place. Molecular size is also relevant as it relates to the rate of uptake of
organic solutes through the porous of the adsorbent materials if the rate is controlled by

17
intraparticle transport. In this case, the reaction will generally proceed more rapidly with decrease
in adsorbate molecule (Yoon et al., 2003).
2.3.1.3 SOLUTION pH
The pH of the solution affects the extent of adsorption because the distribution of surface charge
of the adsorbent can change, because of the composition of raw materials and the technique of
activation, thus, varying the extent of adsorption according to the adsorbate functional groups.
2.3.1.4 TEMPERATURE
Another important parameter is the temperature. Adsorption reactions are normally exothermic;
thus the extent of adsorption generally increases with decreasing temperature. Temperature can
change the adsorption equilibrium depending n the exothermic or endothermic nature o a process
(Siti et al., 2013).

2.4 HEAVY METAL REMOVAL METHODS

2.4.1 Chemical methods
The conventional chemical processes for removing heavy metals from wastewater include many
processes such as chemical precipitation, flotation, adsorption, ion exchange, and electrochemical
deposition. Factors that may limit the applicability and effectiveness of the chemical process are
high content of clay/silt, humic, calcite, Fe & Ca, heavy metals, anions, or high buffering
capacity.
2.4.1.1 Chemical Precipitation
Chemical precipitation is one of the most widely used for heavy metal removal from inorganic
effluent in industry due to its simple operation (Rao, 2010). These conventional chemical
precipitation processes produce insoluble precipitates of heavy metals as hydroxide, sulfide,
carbonate and phosphate. The mechanism of this process is based on to produce insoluble metal
precipitation by reacting dissolved metals in the solution and precipitant. In the precipitation
process very fine particles are generated and chemical precipitants, coagulants, and flocculation
processes are used to increase their particle size to remove them as sludge. Once the metals
precipitate and form solids, they can easily be removed, and low metal concentrations, can be
discharged (Tangahu, 2011). Removal percentage of metal ions in the solution may be improved
to optimum by changing major parameters such as pH, temperature initial concentration, charge

18
of the ions etc. The most commonly used precipitation technique is hydroxide treatment due to its
relative simplicity, low cost of precipitant (lime), and ease of automatic pH control. The
solubilities of the various metal hydroxides are minimized for pH in the range of 8.0 to 11.0
2.4.1.2 Coagulation and Flocculation
The coagulation-flocculation mechanism is based on zeta potential (ζ) measurement as the criteria
to define the electrostatic interaction between pollutants and coagulant-flocculant agents.

Coagulation process is reduced the net surface charge of the colloidal particles to stabilize by
electrostatic repulsion process. Flocculation process continually increases the particle size to
discrete particles through additional collisions and interaction with inorganic polymers formed by
the organic polymers added. Once discrete particles are flocculated into larger particles, they can
be removed or separated by filtration, straining or floatation. Production of sludge, application of
chemicals and transfer of toxic compounds into solid phase are main drawbacks of this process.
2.4.1.3 Electrochemical Treatments
Electrolysis: Electrolytic recovery is one technology used to remove metals from wastewater
streams. This process uses electricity to pass a current through an aqueous metal-bearing solution
containing a cathode plate and an insoluble anode. Electricity can be generated by movements of
electrons from one element to another (Maldonado, 2014). Electrochemical process to treat
wastewater containing heavy metals is to precipitate the heavy metals in a weak acidic or
neutralized catholyte as hydroxides. Electrochemical treatments of wastewater involve electro-
deposition, electro-coagulation, electro-flotation and electro-oxidation.
Electrodestabilization of colloids is called coagulation and precipitation by hydroxide formation
to acceptable levels. It is the most common heavy metal precipitation method forming coagulants
by electrolytic oxidation and destabilizing contaminants to form folc. The electro-coagulation
process the coagulant is generated in situ by electrolytic oxidation of an appropriate anode
material. In this process, charged ionic metal species are removed from wastewater by allowing it
to react with anion in the effluent. This process is characterized by reduced sludge production, no
requirement for chemical use, and ease of operation (Gunatilake, 2015).

19
However, chemical precipitation requires a large amount of chemicals to reduce metals to an
acceptable level for discharge. Other drawbacks are huge sludge production, slow metal
precipitation, poor settling, the aggregation of metal precipitates, and the long-term environmental
impacts of sludge disposal. It changes the aqueous pollution problem to a solid waste disposal
problem without recovering the metal.

2.4.1.4 Ion Exchange

Ion exchange can attract soluble ions from the liquid phase to the solid phase, which is the most
widely used method in water treatment industry. As a cost-effective method, ion exchange
process normally involves low-cost materials and convenient operations, and it has been proved
to be very effective for removing heavy metals from aqueous solutions, particular for treating
water with low concentration of heavy metals. In this process cations or anions containing special
ion exchange is used to remove metal ions in the solution (Parmar,2013). Commonly used ion
exchangers are synthetic organic ion exchange resins. It can be used only low concentrated metal
solution and this method is highly sensitive with the pH of the aqueous phase.
Ion exchange resins are water-insoluble solid substances which can absorb positively or
negatively charged ions from an electrolyte solution and release other ions with the same charges
into the solution in an equivalent amount. The positively charged ions in cationic resins such as
hydrogen and sodium ions are exchanged with positively charged ions, such as nickel, copper and
zinc ions, in the solutions. Similarly, the negative ions in the resins such as hydroxyl and chloride
ions can be replaced by the negatively charged ions such as chromate, sulfate, nitrate, cyanide and
dissolved organic carbon (DOC).
2.4.1.5 Electrodialysis
Electrodialysis (ED) is a membrane separation in which ionized species in the solution are passed
through an ion exchange membrane by applying an electric potential. The membranes are thin
sheets of plastic materials with either anionic or cationic characteristics (Barakat,2011). When a
solution containing ionic species passes through the cell compartments, the anions migrate toward
the anode and the cations toward the cathode, crossing the anion exchange and cation-exchange
membranes. A noticeable disadvantage is membranes replacement and the corrosion process.
Using membranes with higher ion exchange capacity resulted in better cell performance. Effects

20
of flow rate, temperature and voltage at different concentrations using two types of commercial
membranes, using a laboratory ED cell, on lead removal were studied

Fig. 2.1 (Electrodialysis principles (Chen, 2004) CM – cation exchange membrane, D-dialute
chamber, e1 and e2-electrode chambers,AM-anion exchange membrane and K-concentrate
chamber)
Results show that increasing voltage and temperature improved cell performance and separation
percentage decreased with an increasing flow rate. This offers advantages for the treatment of
highly concentrated wastewater laden with heavy metals to recovery undesirable impurities from
water.
2.4.2 Physical methods
Following methods have been used by various researchers for removal of heavy metals. Physical
separation techniques are primarily applicable to particulate forms of metals, discrete particles or
metal-bearing particles. Physical separation consists of mechanical screening, hydrodynamic
classification, gravity concentration, flotation, magnetic separation, electrostatic separation, and
attrition scrubbing (Guntatilake, 2015). The efficiency of physical separation depends on various
soil characteristics such as particle size distribution, particulate shape, clay content, moisture
content, humic content, heterogeneity of soil matrix, density between soil matrix and metal
contaminants, magnetic properties, and hydrophobic properties of particle surface.

2.4.2.1 Membrane Filtration

Membrane filtration has received considerable attention for the treatment of inorganic effluent. It
is capable of removing suspended solid, organic compounds and inorganic contaminants such as

21
heavy metals. Depending on the size of the particle that can be retained, various types of
membrane filtration such as ultrafiltration, nanofiltration and reverse osmosis can be employed
for heavy metal removal from wastewater (Barakat, 2011).
2.4.2.2 Ultra filtration (UF)
This utilizes permeable membrane to separate heavy metals, macromolecules and suspended
solids from inorganic solution on the basis of the pore size (5–20 nm) and molecular weight of the
separating compounds (1000– 100,000 Da). Depending on the membrane characteristics, UF can
achieve more than 90% of removal efficiency with a metal concentration ranging from 10 to 112
mg/L at pH ranging from 5 to 9.5 and at 2–5 bar of pressure. UF presents some advantages such
as lower driving force and a smaller space requirement due to its high packing density. Another
similar technique, complexation– ultrafiltration, proves to be a promising alternative to
technologies based on precipitation and ion exchange. The use of water-soluble metal-binding
polymers in combination with ultrafiltration (UF) is a hybrid approach to concentrate selectively
and to recover heavy metals in the solution. In the complexation – UF process cationic forms of
heavy metals are first complexed by a macro-ligand in order to increase their molecular weight
with a size larger than the pores of the selected membrane. The advantages of complexation–
filtration process are the high separation selectivity due to the use of a selective binding and low-
energy requirements involved in these processes. Water-soluble polymeric ligands have shown to
be powerful substances to remove trace metals from aqueous solutions and industrial wastewater
through membrane processes.
2.4.2.3 Polymer-supported ultrafiltration (PSU)
This technique adds water soluble polymeric ligands to bind metal ions and form macromolecular
complexes by producing a free targeted metal ions effluent. Advantages of the PSU technology
are the low-energy requirements involved in ultrafiltration, the very fast reaction kinetics and
higher selectivity of separation of selective bonding agents in aqueous solution (Ahmed, 2016).
2.4.2.4 Reverse osmosis (RO)
This separation process that uses pressure to force a solution through a membrane that retains the
solute on one side and allows the pure solvent to pass to the other side. The membrane here is
semipermeable, meaning it allows the passage of solvent but not for metals. The membranes used
for reverse osmosis have a dense barrier layer in the polymer matrix where most separation
occurs. Reverse osmosis can remove many types of molecules and ions from solutions, including

22
bacteria, and is used in both industrial processes. Reverse osmosis involves a diffusive
mechanism, so that separation efficiency is dependent on solute concentration, pressure, and
water flux rate.
2.4.3 Biological Methods
Biological removal of heavy metals in wastewater involves the use of biological techniques for
the elimination of pollutants from wastewater. In this processes microorganisms play a role of
settling solids in the solution. Activated sludge, trickling filters, stabilization ponds are widely
used for treating wastewater. Activated sludge is the most common option uses microorganisms
in the treatment process to break down organic material with aeration and agitation, and then
allows solids to settle out (Gunatilake,2015). Bacteria-containing “activated sludge” is continually
re-circulated back to the aeration basin to increase the rate of organic decomposition. Most of the
research on heavy metals removal in biological systems has been directed towards the suspended
growth activated sludge process. Trickling Filters which consist beds of coarse media (often
stones or plastic) 3-10 ft. deep help to grow microorganisms. Wastewater is sprayed into the air
(aeration), then allowed to trickle through the media and microorganisms break down organic
materials in the wastewater. Trickling filters drain at the bottom and the wastewater is collected
and then undergoes sedimentation. Stabilization ponds or lagoons are slow, cheap, and relatively
inefficient, biological method that can be used for various types of wastewater. They rely on the
interaction of sunlight, algae, microorganisms, and oxygen.
Biosorption is another method that can use to remove heavy metals from wastewater. Sorption
process is transfer of ions from solution phase to the solid phase, actually describes a group of
processes, which includes adsorption and precipitation reactions. Adsorption has become one of
the alternative treatment techniques for wastewater. Basically, adsorption is a mass transfer
process and substances bound by physical and or chemical interactions to solid surface ( Hubbe,
2015). Various low-cost adsorbents, derived from agricultural waste, industrial by-product,
natural material, or modified biopolymers, have been recently developed and applied for the
removal of heavy metals from metal-contaminated water. Use of activated carbon in water and
wastewater treatment has been oriented towards organics removal. Research efforts on inorganic
removal by activated carbon, specifically metallic ions, have been markedly 1imited Selective
adsorption by red mud,coal,photocatalyst beads, nano-particles fertilizer industrial waste ,
biomass, activated sludge biomass, algae etc. has generated increasing excitement.

23
2.5 ADSORPTION A SEPARATION PROCESS

The word "adsorption" was coined in 1881 by German physicist Heinrich Kayser (1853-1940).
Adsorption (or sorption) is a process that involves the contact of a free aqueous phase with a rigid
particulate phase that has the ability to selectively remove or store one or more solutes (e.g.
metals species) present in the solution (waste streams). Usually, the sorbent has a fixed total
uptake, where by one solute is exchanged for another (as in ion exchange processes). The word
adsorb is important here, When a material adsorbs something, it attaches to it by chemical
attraction. The huge surface area of the activated charcoal gives it countless bonding sites. When
certain chemicals pass next to the carbon surface, they attach to the surface and are trapped.
The most common industrial adsorbents are activated carbon, silica gel, and alumina, because
they present enormous surface area per unit weight.

Adsorption is the adhesion of atoms, ions, or molecules from a gas, liquid, or dissolved solid to
a surface. This process creates a film of the adsorbate on the surface of the adsorbent. This
process differs from absorption, in which a fluid (the adsorbate) is dissolved by or permeates a
liquid or solid (the absorbent), respectively. Adsorption is a surface-based process while
absorption involves the whole volume of the material. The term sorption encompasses both
processes, while desorption is the reverse of it. Adsorption is a surface phenomenon.

Similar to surface tension, adsorption is a consequence of surface energy. In a bulk material, all
the bonding requirements (be they ionic, covalent, or metallic) of the constituent atoms of the
material are filled by other atoms in the material. However, atoms on the surface of the adsorbent
are not wholly surrounded by other adsorbent atoms and therefore can attract adsorbates. The
exact nature of the bonding depends on the details of the species involved, but the adsorption
process is generally classified as physiosorption (characteristic of weak van der Waals forces)
or chemisorption (characteristic of covalent bonding). It may also occur due to electrostatic
attraction.

Adsorption is a widely used technique for wastewater treatment. Adsorption is a process by which
certain components of a fluid phase are attracted to the surface of a solid adsorbent and form
attachments via physical or chemical bonds, thus removing the component from the fluid phase.
In general, adsorption processes maybe classified as physical or chemical depending on the nature
of the forces involved. Activated carbon is a commonly used adsorbent in water and wastewater

24
treatment. Low cost and non-conventional adsorbents include agricultural by products such as nut
shells, wood, bone, peat processed into activated carbon. In many parts of sub Saharan Africa,
groundnuts shells constitute a source of environmental pollution and its utilization is required so
as to keep the environment unpolluted.

Adsorption is present in many natural, physical, biological, and chemical systems, and is widely
used in industrial applications such as activated charcoal, capturing and using waste heat to
provide cold water for air conditioning and other process requirements (adsorption
chillers), synthetic resins, increase storage capacity of carbide-derived carbons, and water
purification. Adsorption, ion exchange, and chromatography are sorption processes in which
certain adsorbates are selectively transferred from the fluid phase to the surface of insoluble, rigid
particles suspended in a vessel or packed in a column. Pharmaceutical industry applications,
which use adsorption as a means to prolong neurological exposure to specific drugs or parts
thereof, are lesser known.
This necessitates the use of groundnut shell for adsorption of heavy metals. Groundnut shell is a
carbonaceous, fibrous solid waste which encounters disposal problem and is generally used for its
fuel value. Therefore, it was of interest to prepare a higher value product such as activated carbon
from groundnut shell (Idris, 2012).

2.6 TREATMENT PROCESSESS FOR LEAD REMOVAL

A number of treatments processes for the removal of heavy metals such as lead ion from aqueous
solutions or industrial wastewater have been reported, mainly ion-exchange, electrochemical
reduction, evaporation, solvent extraction, reverse osmosis, chemical precipitation, membrane
filtration, adsorption etc.(Demirba et al, 2002). Depending on the nature of the aqueous effluent,
flow rate and metal ion concentrations, the industrial application of the processes is restricted by
the operating cost or by the inefficiency of the technique (Curkovic, 2001). The most important
treatment processes for the removal of heavy metals such as lead using low cost adsorbent is
using activated groundnut shell.

25
2.7 ADSORBENTS

Adsorbents are used usually in the form of spherical pellets, rods, moldings, or monoliths with
a hydrodynamic radius between 0.25 and 5 mm. They must have high abrasion resistance,
high thermal stability and small pore diameters, which results in higher exposed surface area and
hence high capacity for adsorption. The adsorbents must also have a distinct pore structure that
enables fast transport of the gaseous vapors.

Most industrial adsorbents fall into one of three classes:

1. Oxygen-containing compounds – Are typically hydrophilic and polar, including materials

such as silica gel and zeolites.
2. Carbon-based compounds – Are typically hydrophobic and non-polar, including materials
such as activated carbon and graphite.
3. Polymer-based compounds – Are polar or non-polar functional groups in a porous
polymer matrix.

2.7.1 Silica gel

Silica gel is a chemically inert, nontoxic, polar and dimensionally stable (< 400 °C or 750 °F)
amorphous form of SiO2. It is prepared by the reaction between sodium silicate and acetic acid,
which is followed by a series of after-treatment processes such as aging, pickling, etc. These after-
treatment methods results in various pore size distributions.Silica is used for drying of process air
(e.g. oxygen, natural gas) and adsorption of heavy (polar) hydrocarbons from natural gas.

2.7.2 Zeolites

Zeolites are natural or synthetic crystalline aluminosilicates, which have a repeating pore network
and release water at high temperature. Zeolites are polar in nature. They are manufactured by
hydrothermal synthesis of sodium aluminosilicate or another silica source in an autoclave
followed by ion exchange with certain cations (Na+, Li+, Ca2+, K+, NH4+). The channel diameter
of zeolite cages usually ranges from 2 to 9 Å. The ion exchange process is followed by drying of
the crystals, which can be pelletized with a binder to form macroporous pellets. Zeolites are
applied in drying of process air, CO2 removal from natural gas, CO removal from reforming gas,
air separation, catalytic cracking, and catalytic synthesis and reforming. Non-polar (siliceous)

26
zeolites are synthesized from aluminum-free silica sources or by dealumination of aluminum-
containing zeolites. The dealumination process is done by treating the zeolite with steam at
elevated temperatures, typically greater than 500 °C (930 °F). This high temperature heat
treatment breaks the aluminum-oxygen bonds and the aluminum atom is expelled from the zeolite
framework.

2.7.3 Activated carbon

Activated carbon is a highly porous, amorphous solid consisting of microcrystallites with a

graphite lattice, usually prepared in small pellets or powder. It is non-polar and cheap. One of its
main drawbacks is that it reacts with oxygen at moderate temperatures (over 300 °C).

Activated carbon can be manufactured from carbonaceous material, including coal (bituminous,
subbituminous, and lignite), peat, wood, or nutshells (e.g., coconut). The manufacturing process
consists of two phases, carbonization and activation. The carbonization process includes drying
and then heating to separate by-products, including tars and other hydrocarbons from the raw
material, as well as to drive off any gases generated. The process is completed by heating the
material over 400 °C (750 °F) in an oxygen-free atmosphere that cannot support combustion. The
carbonized particles are then "activated" by exposing them to an oxidizing agent, usually steam or
carbon dioxide at high temperature. This agent burns off the pore blocking structures created
during the carbonization phase and so, they develop a porous, three-dimensional graphite lattice
structure. The size of the pores developed during activation is a function of the time that they
spend in this stage. Longer exposure times result in larger pore sizes. The most popular aqueous
phase carbons are bituminous based because of their hardness, abrasion resistance, pore size
distribution, and low cost, but their effectiveness needs to be tested in each application to
determine the optimal product.

Activated carbon is used for adsorption of organic substances and non-polar adsorbates and it is
also usually used for waste gas (and waste water) treatment. It is the most widely used adsorbent
since most of its chemical (e.g. surface groups) and physical properties (e.g. pore size distribution
and surface area) can be tuned according to what is needed. Its usefulness also derives from its
large micropore (and sometimes mesopore) volume and the resulting high surface area. Activated
carbon includes a wide range of amorphous carbon-based materials prepared to exhibit a high
degree of porosity and an extended interparticulate surface area. It is also a common term used for

27
a group of adsorbing substances of crystalline form, having large developed internal pore
structures that make the carbon more adsorbent.

2.8 Advantages of low-cost adsorbents over conventional adsorbents

The efficiencies of removal of lead ions of various nonconventional adsorbents vary between
50% to 90% depending on the characteristics and particle size of absorbance. A combination of
adsorbents can also be used effectively in lead treatment. Nonconventional adsorbents are
relatively cheaper compared to conventional ones and are easily available resulting in savings in
cost. Nonconventional adsorbents require simple alkali or/and acid treatment for the removal of
lignin before their application and to increase efficiency. Since the cost of these adsorbents is
relatively low they can be used once and discarded .Nonconventional adsorbents require less
maintenance and supervision. Separation is possible to segregate the nonconventional adsorbents
from the effluents before their disposal.
These nonconventional adsorbents can be disposed off easily and safely. Used adsorbents can be
reused as a filler material in low-lying areas and hence their disposal does not cause any serious
problem. Results show that these low-cost bioadsorbents could be fruitfully used for the removal
of lead over a wide range of concentrations. Lead removal for a given adsorbent size increased
with time attaining equilibrium within 1.5 h. the percentage of lead removal could be found to be
a function of adsorbent dose and time at a given initia2l solute concentration. It increased with
time and adsorbent dose, but with higher initial solute concentration decreased with time and
adsorbent dose. The process of adsorption by treated adsorbents follows Langmuir isotherm,
which comprises statistical and empirical data estimated from Isotherm equation.
2.8.1 Ground nut shell as low cost adsorbents
For agricultural byproduct, the mode of sorption can be attributed to two main factors; these are
the nature of adsorbent and the columbic interaction between active site and the fluoride ion to be
sorbet. Beside charge on both substrates, the hardness and that of charge on both sides are
responsible for the intensity of interaction between the active site and the fluoride ion in the
solution. Cationic species on the adsorbent can absorb anionic ion from the solution through
columbic interaction (Gang and Weixing, 1998).The nature of adsorbent like surface area,
porosity and availability of sorbing site on the surface of adsorbent can affect the adsorption
capacity (Igwe and Abia, 2003).The obvious advantages of this method compared to other are
28
lower cost involved when organic waste materials are used. Activated carbon adsorption appears
to be a particularly competitive and effective process for the removal of fluoride ion at trace
quantities (Huang and Blankenship, 1984). However, the use of activated carbon is not suitable
for developing countries because of its high cost (Panda et al., 1985). For that reason, the uses of
low cost materials as possible media for fluoride removal from wastewater have been highlighted.
These materials range from industrial products such rubber tyres (Knocke and 22 Hempill, 1981),
industrial wastes and some natural material including agricultural product and by-product as
mentioned earlier. The native exchange capacity and general sorption characteristics of these
materials derive from their constituent polymers (in approximately decreasing order of
abundance): cellulose, hemicelluloses, pectin, lignin, and protein. Kou et al. (2001);Shang et.al.
(2003) have proposed the utilization of biomaterials or abandoned biomaterials (BIOM), new
name for agricultural wastes of which the major component is cellulose (C6H10O5) n. Cellulosic
surface becomes partially negatively charged when immersed in water and, therefore, possess
columbic interaction with cationic species in water (Laszlo,1994; McKay et al., 1987).
Groundnut botanically known as Arachishypogeae belongs to Leguminosae family. A complete
seed of Groundnut is called as pod and outer layer of groundnut is called shell or husk Brian
(George et.al., 2004) investigated the groundnut shell fiber characterization. Average length of the
groundnut shell fibers was found to be 38 mm and 0.25 mm diameter. Average tenacity of
groundnut shell fiber is of 1.06 g Also, average strain of the fibers was 7.45 % and average
modulus 25.3g. Lignocelluloses fibers are constituted by three main components: hemicelluloses,
cellulose and lignin, which are known to present very complex structure. Cellulose, which is the
main fraction of the fibers, is a semi crystalline polysaccharide made up of D-glucosidic bonds.
A large amount of hydroxyl groups in cellulose gives hydrophilic properties to the natural fibers.
Hemi-cellulose is strongly bound to the cellulose fibres, presumably by hydrogen bonds.

2.9 History of Activated Carbon

The use of carbon extends so far back into history that its origin is impossible to document. The
first known use of activated carbon dates back to the Ancient Egyptians as early as 1500 B.C.
who utilized its adsorbent properties for purifying oils and medicinal purposes. Charcoal was used
for drinking water filtration by ancient Hindus in India.

29
Centuries later, the early ocean-going vessels stored drinking water in wooden barrels, the inside
of which had been charred. However, by modern definition the carbon used in these applications
could not truly be described as “activated”. By the early 19th century both wood and bone
charcoal was in large-scale use for the decolourization and purification of cane sugar. The first
documented use of activated carbon in a large scale water treatment application was in 19th-
century England, where it was used to remove undesirable odours and tastes from drinking water.
In recent years, the use of activated carbon for the removal of priority organic pollutants has
become very common. Today, hundreds of brands of activated carbon are manufactured for a
large variety of purposes.
The largest market for activated carbon is currently in the municipal water purification industry,
where charcoal beds have been used for the dual purpose of physical filtration and sorption. In
fact, activated carbon filters are used today in drinking water treatment to remove the natural
organic compounds (i.e. tannins) that produce carcinogenic chlorinated by-products during
chlorine disinfection of water. In wastewater treatment, activated carbon is usually used as a filter
medium in tertiary (later) treatment processes. In these applications, carbon filters are usually
quite effective in removing low concentrations of organic compounds, as well as some inorganic
metals. In addition to its drinking water and wastewater treatment applications, activated carbon is
used today for many other purposes
Some other common uses are: corn and cane sugar refining, gas adsorption, dry cleaning
recovery processes, pharmaceuticals, fat and oil removal, electroplating, alcoholic beverage
production, and as nuclear power plant containment systems.
2.10 Structure of Activated Carbon
In order to explain the capabilities of activated carbon, an appreciation of its structure is most
useful. Much of the literature quotes a modified graphite-like structure; the modification resulting
from the presence of micro crystallites, formed during the carbonization process, which during
activation, have their regular bonding disrupted causing free valences which are very reactive. In
addition, the presence of impurities and process conditions influence the formation of interior
vacancies, in the microcrystalline structures. Such theory generally explains pores as the result of
faults in crystalline structures. However, more recent research studies provide a more feasible
explanation of the carbon structure.

30
The generally accepted graphite-like structure theory falls down since the hardness of activated
carbon is not in keeping with the layered structure of graphite. Furthermore, the manufacturing
conditions are different; in particular the temperature range utilized for activated carbon
production is lower than that required for graphitization (Supunnee, 2006). Supporters of the
graphite-like structure generally only explain the modified microcrystalline structure and ignore
photographic and other methods of examining the residual macro structure. High magnification
electron scanning microscopy, at 20,000x magnification, has revealed the presence of residual
cellular structures. These were previously unseen and unsuspected, except in the case of wood-
based activates which have sufficiently open structures visible to the naked eye. Cellular units are
built from sugars, the most important being glucose (Wolf, 2012). Sugars ultimately will build to
cellulose (the most important single unit in cellular construction) and cellulose polymers cross-
link to form the wall of individual plant cells. Glucose units are wound into very tight helical
spirals and under polarized light, these exhibit anisotropy-demonstrating the presence of
crystalline structures. Although not as yet proven, it has been postulated that in the areas of
maximum strain in cellulose chains it is conceivable that smaller crystalline units could be
produced. In addition to cellulose, other materials also exist in cell wall structure. Hemi-cellulose,
which undergoes degradation more easily than cellulose and Lignin (the structure of which is still
unproven) also exists and this is the most resistant to oxidation(Li, 2014).
Most theories attribute the structure of activated carbon to be aromatic in origin, thus, allowing
the carbon structure itself to be described as aromatic in order to explain active centres, etc.
Structures of the size of cell dimensions obviously do not influence physical adsorption but
illustrate that the only material available for oxidation lies within the cell walls themselves.
Final activates consist almost entirely of elemental carbon together with residual ash which, in the
case of wood and coconut, originate from minerals within the vessels of living tissues; silica
being the only constituent actually incorporated within the cell wall tissue matrix(Jemma
Rowlandson, 2014). The ash content of coal is of different composition and due to intrusion of
inorganic materials during coalification. Thus, the overall structure consists of a modified
cellular-like configuration with varying ash components depending on the particular raw material.
The cellular-like structure theory offers a logical explanation for the differences in apparent
density between activates of wood, coal and coconut. Wood activates have a very open structure
with thin wall cells whereas coconut activates show very thick walls with many pits. It is known

31
that the carbonization and activation processes destroy, to varying degrees, intercellular walls and
sieve plates between cells. The end result on wood is a very open, sponge-like macrostructure
seriously reducing the probability of adsorbate contact with cell walls. Activation of coconut
produces a composition of rod-like cells in very close contact and large surface cavities are
formed by destruction of dividing walls but these are shallow and do not extend through the
activates granule. The coconut activates thus differ significantly from wood activates in
mechanical strength and density. Coconut activates exhibit extensive micro pore volume, whereas
wood activates have a definite trend to Mesopores/macro pores and a corresponding change in
their basic properties. In the case of coal based carbons, pre-treatment of the raw coal is necessary
in order for it to be processed, since raw coal swells during heating to produce coke-like
structures. Control of this is achieved by first grinding the raw coal and mixing it with various
additives, such as pitch, before it is introduced to the activation furnace. However, the grinding
process destroys the mechanical strength of coal - therefore, ground coal is reconstituted into
briquettes prior to processing. Despite such pre-treatment, mercury penetration data for coal
activates support the presence of structures similar to those identified in activates of wood and
coconut, but to date no detection of residual plant structures has been found in coal activates.
Activated carbon is an effective fettering material, highly porous with immense surface area. The
most common described activated carbon is that it acts like a sponge, sucking contaminates from
liquids and gases. Activated carbon removes many organic and some specific inorganic
substances such as chlorine, cadmium, nicked, lead and chromium from common industrial
pollutants. Wastewaters from textile, brewery and tannery effluents attract attention of
environmental protection agencies all over the world. They not only deface the look of natural
waters, but are also highly toxic (Chu, 2001). Some are reported to harm mammalian cells by
causing kidney tumors and reproductive difficulties (Fernendes et al., 1997; Henderson et al.,
1997). Dyes for example are potentially carcinogenic, genotoxic, mutagenic in many animal
species (Nimrat et al., 2004). Adsorption process is considered very effective in industrial
wastewater treatment. It proves superior to the other processes by being sludge free and can
completely remove even very minute amounts of contaminants in wastewater (Nigarn et al.,
1996). Adsorption process using commercial activated carbons is very effective for removal of
lead from wastewater but its high cost has provided the search for alternatives and low-cost
adsorptions. Lead is widely used and extremely toxic in relatively low dosages, the main pathway

32
through which Lead and chromium enters the water bodies via wastes from industrial processes.
Heavy metals of concern in this work cause different ailment like cancer (Alluri, 2007). The idea
of using various agricultural products for the removal of heavy metals from wastewater has been
investigated by number of authors.( Henderson et al. 1997) have investigated the efficiency of
number of different organic waste materials as adsorbents for
heavy metals. Such adsorbents including coconut shell, peanut shell, rice husk and groundnut
shell have been considered for the adsorption on lead. The use of activated carbons however, has
been widely considered because of their high adsorption rate on lead.
Heavy metal pollution has become one of the most serious environmental problems today.
Wastewaters containing heavy metals are produced each year by textile industries and other
processing industries. Most of the chemical methods used in cleaning up of these heavy metals
are not effective. Microorganisms have been used extensively in cleaning of heavy metals in the
environment but plant has not been used extensively in removing heavy metals from wastewater.
Isotherm determinations reveal extensive micro pore structures, although coal activates’ pore
spectra are different to those of coconut activates with a tendency toward Meso pores at lower
activation. The most reliable carbon structure model suggested to date is similar to that of
polyamantane (C66H59) which allows for a large degree of non-aromaticity, electron transfer and
resonance. Progressive activation would tend to increase the number of active sites, and in turn
the surface activity, similar to observed reactions with higher activate.
.
2.11 MODELLING OF ADSORPTION PROCESSESS
Modeling (M) refers to using models – physical, mathematical, or otherwise logical
representation of a system, entity, phenomenon, or process as a basis for simulation. Methods for
implementing a model (either statically or) over time – to develop data as a basis for managerial
or technical decision making.
Adsorption modeling combines both the isotherms and kinetics models together. The adsorption
isotherm is a relationship between the amount of a substance removed from liquid phase by unit
mass of adsorbent, and its concentration at a constant temperature. The adsorption isotherm is the
basic requirement for designing any adsorption system. They include Langmuir, Freundlich, BET
theory etc.

33
2.11.1 Freundlich
Freundlich equation

The first mathematical fit to an isotherm was published by Freundlich and Küster (1906) and is a
purely empirical formula for gaseous adsorbates,
x 1/n
= KCe (2.1)
m

Where x is the quantity of adsorbate adsorbed in moles, m is the mass of the adsorbent, P is the
pressure of adsorbate (this can be changed to concentration if investigating solution rather than
gas) and K and n are empirical constants for each adsorbent-adsorbate pair at a given temperature.
The function is not adequate at very high pressure because in reality x/m has an asymptotic
maximum as pressure increases without bound. As the temperature increases, the
constants K and n change to reflect the empirical observation that the quantity adsorbed rises
more slowly and higher pressures are required to saturate the surface.

2.11.2 Langmuir

Langmuir equation

Irving Langmuir was the first to derive a scientifically based adsorption isotherm in 1918. The
model applies to gases adsorbed on solid surfaces. It is a semi-empirical isotherm with a kinetic
basis and was derived based on statistical thermodynamics. It is the most common isotherm
equation to use due to its simplicity and its ability to fit a variety of adsorption data. It is based on
four assumptions:

1. All of the adsorption sites are equivalent and each site can only accommodate one
molecule.
2. The surface is energetically homogeneous and adsorbed molecules do not interact.
3. There are no phase transitions.
4. At the maximum adsorption, only a monolayer is formed. Adsorption only occurs on
localized sites on the surface, not with other adsorbates.

These four assumptions are seldom all true: there are always imperfections on the surface,
adsorbed molecules are not necessarily inert, and the mechanism is clearly not the same for the
very first molecules to adsorb to a surface as for the last. The fourth condition is the most
troublesome, as frequently more molecules will adsorb to the monolayer; this problem is

34
addressed by the BET isotherm for relatively flat (non-microporous) surfaces. The Langmuir
isotherm is nonetheless the first choice for most models of adsorption, and has many applications
in surface kinetics (usually called Langmuir–Hinshelwood kinetics) and thermodynamics.

Langmuir suggested that adsorption takes place through this mechanism: Ag + S ⇌ AS where
A is a gas molecule and S is an adsorption site. The direct and inverse rate constants are k and k−1.
If we define surface coverage,ᶿ as the fraction of the adsorption sites occupied, in the equilibrium
we have:

𝐾 𝜃
𝐾= = (2.2)
𝐾−1 (1−𝜃)𝑃
or
𝐾𝑃
𝜃= (2.3)
1+𝐾𝑃

KadsC
𝜃= (2.4)
1+KabsC
where p is the partial pressure of the gas or the molar concentration of the solution. For very low

pressures 𝜃 = KP and for high pressures 𝜃 = 1 is difficult to measure experimentally; usually, the
adsorbate is a gas and the quantity adsorbed is given in moles, grams, or gas volumes at standard
temperature and pressure (STP) per gram of adsorbent. If we call vmon the STP volume of
adsorbate required to form a monolayer on the adsorbent (per gram of adsorbent), we obtain an
expression for a straight line:
1 1 1 1
= + (2.5)
𝑣 𝐾𝑣𝑚𝑜𝑛 𝑃 𝑣𝑚𝑜𝑛

Through its slope and y-intercept we can obtain vmon and K, which are constants for each
adsorbent/adsorbate pair at a given temperature. vmon is related to the number of adsorption sites
through the ideal gas law. If we assume that the number of sites is just the whole area of the solid
divided into the cross section of the adsorbate molecules, we can easily calculate the surface area
of the adsorbent. The surface area of an adsorbent depends on its structure; the more pores it has,
the greater the area, which has a big influence on reactions on surfaces.

35
2.11.3 BET

BET Theory

Often molecules do form multilayers that are, some are adsorbed on already adsorbed molecules
and the Langmuir isotherm is not valid. In 1938 Stephen Brunauer, Paul Emmett, and Edward
Teller developed a model isotherm that takes that possibility into account. Their theory is
called BET theory, after the initials in their last names. They modified Langmuir's mechanism as
follows:
A(g) + S ⇌ AS
A(g) + AS ⇌ A2S
A(g) + A2S ⇌ A3S and so on

The derivation of the formula is more complicated than Langmuir's (see links for complete
derivation). We obtain:
𝑥 1 𝑥(𝑐−1)
=𝑣 + (2.6)
𝑣(1−𝑥) 𝑚𝑜𝑛 𝑐 𝑣𝑚𝑜𝑛 𝑐

x is the pressure divided by the vapor pressure for the adsorbate at that temperature (usually
denoted ), v is the STP volume of adsorbed adsorbate, vmon is the STP volume of the amount of
adsorbate required to form a monolayer and c is the equilibrium constant Kwe used in Langmuir
isotherm multiplied by the vapor pressure of the adsorbate. The key assumption used in deriving
the BET equation that the successive heats of adsorption for all layers except the first are equal to
the heat of condensation of the adsorbate.

The Langmuir isotherm is usually better for chemisorption and the BET isotherm works better for
physisorption for non-microporous surfaces.
2.12 RESPONSE SURFACE METHOD
Response surface methodology (RSM) is a collection of mathematical and statistical approach for
experimental design useful for analyzing and evaluating the effects of variable as well as
searching optimum conditions of variable to predict targeted responses. RSM has been proven to
be successfully implemented in some researches, such as engineering, food processing,
biotechnology and adsorption processes for optimization. Response surface methodology (RSM)
can avoid the limitations of conventional methods and is commonly used in many fields. The
main purpose of RSM is to check the optimum operational conditions for a given system or to

36
determine a region that satisfies the operational specifications (Montgomery 2001). It might then
be possible to obtain a second-order polynomial prediction equation or some other mathematical
equations to describe the experimental data obtained at some particular combination of input
variables. In optimizing the adsorption parameters of lead using RSM, in other to ensure high
removal efficiency and determine the interactive effects of the initial lead concentration, the pH
and temperature on the adsorption process, Its anticipated that such data could give guidance for
the process optimization of lead removal by adsorption.

Response surface methodology uses statistical models, and therefore practitioners need to be
aware that even the best statistical model is an approximation to reality. In practice, both the
models and the parameter values are unknown, and subject to uncertainty on top of ignorance. Of
course, an estimated optimum point need not be optimum in reality, because of the errors of the
estimates and of the inadequacies of the model.

Nonetheless, response surface methodology has an effective track-record of helping researchers

improve products and services: For example, Box's original response-surface modeling enabled
chemical engineers to improve a process that had been stuck at a saddle-point for years. The
engineers had not been able to afford to fit a cubic three-level design to estimate a quadratic
model, and their biased linear-models estimated the gradient to be zero. Box's design reduced the
costs of experimentation so that a quadratic model could be fit, which led to a (long-sought)
ascent direction.

There are different types of RSM such as central composite design (CCD), two level factorial
designs, and Box-Behnken Design. Since Box-Behnken design is to be used we now discuss more
on it.

2.12.1 DESIGN OF EXPERIMENTS (DOE)

Products/process design is typically complex due to varying customer demands and technology
advancements. Several responses must generally be considered in complex product/process
designs. Therefore, simultaneously optimizing multiple responses is of priority concern among
manufacturers. Design of experiment (DOE) is extensively adopted in industry to improve
processes, product design or obtain an optimal parameter-setting for process parameters
(Montgomery, 2001). The concept of a design space is introduced as the set of all possible
37
experiments or simulation that interest the analyst. This is the set that consist of all controllable
variables sets at all possible levels and associated dependent features of interest. Because the total
design space is often prohibitively large, methods have been developed in the literature to
efficiently explore it. In the case of response surface metamodels, design of experiments methods
(often called response surface modelling) are employed.

Design of experiment relies on analysis of variance, or ANOVA, to choose a few points out of the
full factorial set that efficiently provide information about the full response space. Metamodels
may then be fit to these intelligently chosen data points using standard multiple regression
methods resulting in a polynomial model that relates input parameters to output features.

2.12.2 BOX-BEHNKEN DESIGN

This design was developed by Box and Behnken (Box and Behnken, 1960). It provides three
levels for each factor and consists of a particular subset of the factorial combinations from the 3k
factorial design. The use of the Box-Behnken design is popular in industrial research because it is
an economical design and requires only three levels for each factors where the settings are -
1, 0, +1 and therefore many runs, as a result, the confounding in blocks can be used. Some Box-
Behnken designs are rotatable, but, in general, this design is not always rotatable. Box and
Behnken list a number of design arrangements for k=3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 16 factors.

The three-level fractional factorial design partitions the full 3q runs into blocks, but its only runs
one of the blocks, but its only runs one of the blocks. This design is more efficient, it allows
collecting information on the main effects and on the lo-order interactions. The one problem with
three-level fractional factorial design is that when number of factors is large, it becomes very
complicated o separate the aliased effects and to interpret their significance. For this reason, when
q is large, most of the time this kind of design is used for screening designs. After an appropriate
design is conducted, the response surface analysis can be done by any statistical computer
software and then statistical analysis can be applied to draw the appropriate conclusions (Myers et
al., 1995).

38
2.13 LEAD EFFECTS
Dust exposure than to outdoor soil exposure. Lead exposure can also occur during remodeling of
a home built prior to 1978, when lead-based paints were still in commerce. In a population-based
study, children who lived in a home that had undergone some type of renovation, repair, or
remodeling work in the prior year were at 1.3 times greater risk of having an elevated blood lead
level than children not exposed to such activities. The risk was even higher among children living
in homes where practices, such as the removal of paint with heat guns, had been used. Drinking
water is also a major source of lead exposure, estimated to be responsible for approximately 20
percent of the total daily exposure experienced by the majority of the U.S. population.
The 1986 amendments to the federal Safe Drinking Water Act banned the use of lead solder and
leaded pipes from public water supply systems and plumbing, and limited faucets and other brass
plumbing components to no more than eight-percent lead. Leaded plumbing components continue
to be used in schools and daycare centers, however, and pose a significant contribution to lead in
drinking water in these buildings. Even valves currently used in drinking water supply lines may
contain 5-7 percent leaded brass (“lead-free” brass fixtures), have been shown to discharge lead
into drinking water, and constitute a significant source of lead in the water supply. Drinking water
in public schools in Seattle, Washington, in August 2005 still contained elevated levels of lead,
after 2004 testing revealed more than 20 ppb. After replacing 387 fountains and fixtures, 46
percent of tests failed a self-imposed limit of 10 ppb. The water quality testing facility believed
that leaded brass fixtures in the new systems may have contributed to lead contamination in the
water. A recent episode of lead contamination in the District of Columbia water supply illustrates
other problems inherent in urban water supplies. The U.S. Environmental Protection Agency
(EPA) reported in January 2004 that the majority of 23,000 homes known to have lead service
pipes had lead levels that exceeded the EPA’s action level of 15 ppb.
A water decontamination chemical added to the city water supply resulted in the corrosion of lead
inside the lead service pipes. One hundred sixty-three homes had lead levels over 300 ppb, 20
times higher than the EPA action level. As a result, the EPA has taken legal action against the
District of Columbia Water and Sewer Authority. Lead contamination of municipal water supplies
may be an under-reported problem. Ellen Silbergeld, PhD, EPA Science Advisory Board
Committee Member and lead toxicologist, stated in testimony before the Oversight Committee on
Government Reform in the U. S. House of Representatives: “[lead contamination of the water

39
supply is unlikely to be limited to the District of Columbia. There are likely to be many public
water supplies in this country where water is not being tested, or if it is tested where the
information is not promptly or fully communicated to consumers, and where appropriate actions
are not being taken.”Since 2000, the EPA has received elevated lead-level reporting information
from 274 water utility services serving a total of 11.5 million people. The EPA Inspector General
issued a finding in 2004 that the EPA’s national drinking water database is incomplete and out of
date, and that the EPA has not communicated accurately to the public about drinking water
quality and compliance because violations are seriously under-reported

40
 CHAPTER THREE

3.0 MATERIALS AND METHODOLOGY

3.1 Materials and Apparatus
3.1.1 Apparatus and Instruments
Table 3.1 ( Apparatus and instrument)
S/N EQUIPMENT/APPARATUS FORMATION USES
1 Atomic Absorption Buck Scientific To measure the
Spectrophotometer model 210 VGP concentration of
the metals after adsorption

2 Muffle Furnace Gallenkamp muffle To carbonate the

furnace size 2. Item groundnut shells.
model: GH2000.
Made in Japan.
3 Mesh sieve Tyler series To sieve the grounded
carbonized groundnut
shells to a size between
0.22-0.425mm.
4 Digital weighing Balance. Adventurer, OHAUS To measure the samples of
corporation activated carbon.
5 Orbital shaker Stuart SSLIS To obtain uniform stirring
Rotating at 250rpm. when mixing the aqueous
solution and during
adsorption.
6 Oven Gellenkamp DHG- To dry the groundnut
9023A shells after washing.
7 pH meter To measure the pH of the
sample to verify
neutrality.

41
8 Beaker To prepare the
synthesized waste.
9 500ml and 100ml measuring Pyrex To measure the required
cylinders volumes of liquid when
preparing the aqueous
solution.
10 Tight lid plastic containers To store the prepared
aqueous solution and
activated carbon to avoid
contamination.
11 Filter paper Whatt man (No.1) To filter each sample after
adsorption experiment.
12 Spatula To carry the solids into
their respective
containers.
13 Stirrer Technico Stir solutions when
preparing stock solutions
14 500ml volumetric flask Pyrex Preparing the concentrates
of the metals from their
stock solutions.
15 Clay pot Made from clay Placing the groundnut
shells for carbonizing.
16 Calibrated piette Pyrex BS 604 made To measure the required
in England. volume from the stock
solutions.
17 Plastic bucket To wash the groundnut
shells before carbonizing
and to carry all samples
from analysis.
18 Deionizer To deionize water

42
19 Vacuum pump To aid filtration process
20 120ml sample bottles To carry out the
adsorption experiment.
21 Plastic funnel To contain the filtrate
ready for AAS analysis.
22 Wash bottle To add liquid to
containers in minute
proportions.
23 Masking tape To label all containers.
24 Mortar and pestle To grind the carbonized
groundnut shell.
25 Test sample bottles To contain the filtrate
ready for AAS analysis.
Materials used for sample preparation were thoroughly washed with liquid soap and deionized
water. Then the containers were dried at ambient temperature till they we completely dry.
3.1.2 Chemicals and Materials used
All solutions were prepared from analytical-reagent grade chemicals and distilled/deionized
water. These includes Lead (ii) Nitrate (Pb(NO3)2), this is the solute for the stock solution of lead.
Nitric acid (HNO3) to activate the Carbonized shells.
The groundnut shell (waste from groundnut) was collected from Uselu market, Benin City which
was used in preparing the activated carbon i.e. the adsorbent.
3.2 METHODS
3.2.1 PREPARATION OF ACTIVATED CARBON
The main type of materials used in this study was groundnut shells which was bought from one of
the famous markets in Benin City called Uselu market.
The groundnut shells was ripped off to remove dusts and washed with water to remove adhered
particles before sun drying for 8 hours for easy burning. The dried samples were weighed on an
electrical balance in the Chemical Engineering Laboratory at University of Benin. Nitric acid was
used as activating agents. After weight measurements, nitric acid solution was used in activating
the groundnut shell. The ratio used for the activation was 1:4 by weight; 1g of groundnut shells
with 4g for activating agent. The measured groundnut shell was placed in the muffle furnace at

43
500oC for 1 hour, after which the carbonated groundnut shell was sieved to attain 0.425mm before
activation. The activation was done by soaking the sieved carbonated groundnut shell in the
solution of nitric acid following the above ratio for 24 hours for activation purposes. Then the
activated groundnut shells were removed from the solution and placed in the oven for 2 hours, at
600C (Samuel et al.,) then left to cool in a desiccator. After cooling, the groundnut shell was
washed with distilled water and placed in a container, ready to be dried in the oven for another 4.5
hours, at 1050C.
3.2.2 AQUEOUS SOLUTION PREPARATION.
The salt used for the preparation of the aqueous solution was analytical grade Lead (II) nitrate.
Other chemicals used were sodium hydroxide and trioxonitrate (V) acid. All reagents were of
analytical grade. Stock solution of 1000 mg/l of lead (ii) nitrate (Pb(NO3)2) was prepared by
dissolving reagent grade Pb(NO3)2 in an appropriate amount of distilled water. From this stock
solution a working solution of 100mg/l was prepared which was used for the batch adsorption
process.

3.3 ADSORPTION EXPERIMENT

The batch adsorption experiments were carried out on the removal of lead ion from aqueous
solution to study the effect of some specific process parameter.
In the kinetic experiments, the parametric effects of adsorbent dosage, contact time, and pH were
investigated for the adsorption onto groundnut shell. 100mg/l of concentration of lead solution
(Ci) with pH range of 2 to 6 was transferred into a conical flask with a range of amount of
adsorbent dosage (0.2g to 1g). Each solution was agitated at 250rpm in an orbital shaker at a room
temperature and contacted for a period of 10minutes to 120minutes. At the end of each contact
time, the solution was filtered using Whatmann No. 1 filter paper and the residual concentrations
were analyzed. The pH of the solution was adjusted using tri-oxo nitrate v acid and sodium
hydroxide.
The concentrations of the metal ion in the filtrate were analyzed using the atomic adsorption
spectrophotometer (AAS). Batch adsorption experiments were carried out at room temperature by
shaking a series of beakers containing the desired dose of adsorbent in a known concentration of
lead solution. Samples of lead solutions were withdrawn at different intervals, filtered and the
filtrate was analyzed for the trace of heavy metal content.

44
The design of this experiment was done using Box-Behnken Design method of response surface
analysis which specifically made each effect to require only three (3) levels given in table 3.3.
Then the concentrations of the samples were determined by using a calibrated curve.
The removal efficiency of Pb ion was defined as:
Ci−Cf
Re (%) = × 100 (3.1)
Ci

Where;
Re (%) was the ratio of difference in metal concentration before and after adsorption.
Ci was the concentration of heavy metals ions before adsorption (mg/L)
Cf as the concentration of heavy metals ions after adsorption (mg/L)
The amount of ach metal ion adsorbed at time t, (qt) was calculated using the formula (Badmus et
al., 2007):
Ci−Cf
qt = × V (3.2)
M

Where;
V was the volume (L) of the aqueous solution used for adsorption.
M was the mass (g) of the adsorbent used.
3.4 EXPERIMENTAL DESIGN
RSM is a collection of mathematical and statistical techniques employed to optimize the operating
parameters for the maximum removal of lead metal ions. Then, a three-level-three-factor Box-
Behnken factorial design (BBD) (Design Expert Software, Trial Version 7.1.6, Stat-Ease Inc.,
Minneapolis, MN, USA).was applied to determine the best combination of adsorption variables
for the yields of the metal ions. The main objective behind design of experiments is to optimize a
response and to determine the relationship between a response (output variable) and the
interactive effects of independent variable (input variables) (Montgomery., 1997). The main
advantage of using RSM is to understand and evaluate the effect of multiple parameters and their
interactions with each other in bringing out the response(s). Hence, it is considered as an
appropriate approach to optimize a process with one or more responses.
The variable input parameters were pH values in the range of 2-6, contact time of 10-120minutes,
and adsorbent dosage of 0.2-1gram. The three independent variables were designated as A-
Adsorbent dosage, B- contact time and C- pH for the statistical analysis. The low, center and high

45
levels of each variable are designated as -1, 0, and +1, respectively as illustrated in table 3.3
below:
Table 3.3 Independent variables and their levels used for Box-Behnken Design.
FACTORS VARIABLES LOW LEVEL CENTER HIGH LEVEL
LEVEL
Adsorbent A 0.2 0.6 1.0
Dosage, (gram)
Contact B 10 65 120
time,(minutes)
pH C 2 4 6

The experimental levels for each variable were selected based on results from preliminary
experiments. The response function was percent metal adsorption.
Coding of the variables was done according to the following equation:
(Xi−Xo)
xi = (3.3)
∆Xi

Where:
xi is the dimensionless value of an independent variable
Xi is the real value of an independent variable
Xo is the real value of an independent variable at the center point
∆Xi Is the step change of the real value of the variable, i, corresponding to the variation of a unit
dimensionless value of variable, i.
The number of experiments (N) needed for the development of Box-Behnken matrix is defined
as:
N = 2K (K-1) + r (3.4)
Where:
K is the factor number
r is the replicate number of the central point
A total of 17 trials were run in order to optimize the parameter at which the maximum removal
was obtained.

46
Three basic steps involved in optimization process are to perform statistically designed
experiment, to determine the coefficient estimate, to analyze the response and to check the
adequate model (Wang et al., 2010; Arulkumar et al., 2012).
Investigations over different tests such as sequential model sum of squares, lack of fit tests, model
summary statistics helps in selecting the best model for describing the relationship between the
response and other influencing independent variable. Regression analysis n Analysis of Variance
response was also employed to analyze the result. In order to fit the generated experimental data
and to identify the relevant model terms, the most widely used second order polynomial equation
can be represented as equation;
Y = βo + ∑ βiXi + ∑ βiiXii2+ ∑ βijXiXj + ϵ (3.5)
Where:
Y is the predicted response (the percentage removal of Pb ions),
βo is the constant coefficient,
βi is the linear coefficient of the input factor Xi
βii is the ith quadratic coefficient of the input factor Xi
βij is the different interaction coefficient between the input factor Xi and Xj.
ϵ is the error of the model (Box-Behnken, 1960), assumed to have a zero mean.
For this study, the independent variables were coded as A, B, and C. Thus, the equation can be
represented as equation (3.4):
Y= β0 + βiA + βiC + βiC + βiiA2 +βiiB2 + βiiC2 + βijAB + βijAC + βijBC (3.6)

47
 Table 3.4 EXPERIMENTAL BOX-BEHNKEN DESIGN WITHOUT RESPONSES
STD RUN BLOCK FACTOR 1 FACTOR 2 FACTOR 3 RESPONSE 1
A:ADSORBENT B: CONTACT C: pH % REMOVAL
DOSAGE(grams) TIME (%)
(minutes)
16 1 Block1 0.6 65.0 4.0
4 2 Block1 0.6 120.0 6.0
9 3 Block1 0.2 10.0 4.0
2 4 Block1 0.6 10.0 6.0
11 5 Block1 1 10.0 4.0
15 6 Block1 0.6 65.0 4.0
14 7 Block1 0.6 65.0 4.0
17 8 Block1 0.6 65.0 4.0
1 9 Block1 0.6 10.0 2.0
8 10 Block1 1.0 65.0 6.0
7 11 Block1 1.0 65.0 2.0
12 12 Block1 1.0 120.0 4.0
13 13 Block1 0.6 65.0 4.0
10 14 Block1 0.2 120.0 4.0
6 15 Block1 0.2 65.0 6.0
5 16 Block1 0.2 65.0 2.0
3 17 Block1 0.6 120.0 2.0

100ml of 100mg/L of lead solution was used for the adsorption studies at the various conditions
stated on the table.
3.5 DESIRABILITY FUNCTION
The desirability function approach is a technique for the simultaneous determination of optimum
settings of input variables that can determine optimum performance levels for one or more
responses. The desirability procedure involves two steps:
1) Finding the levels of the independent variables that simultaneously produce the most
desirable predicted responses on the dependent variables and
48
2) Maximize the overall desirability with respect to the controllable factors.
The desirability function approach was originally introduced by Harrington, 1965. Then another
version was developed by Derringer and Suich (1980). The general approach is to first convert
each response (Yi) into an individual desirability function (di) varying over the range (Mourabet
et al., 2014).
0 ≤ di ≤ 1
Where if response Yi is at its goal or target, then di = 1, if the response is outside an acceptable
region, di = 0. Then the design variables are chosen to maximize the overall desirability.
D = (d1 × d2 × …..× dn ) 1/n (3.7)
Where n is the number of response in the mixture.
3.6 CHARACTERISZATION STUDIES
3.6.1 MOISTURE CONTENT DETERMINATION
2g of the fresh biosolids were weighed in clean dried and preweighed Petri dishes. These samples
were thinly spread in the dishes. They were dried in air- circulated oven t 1050C for 24 hours. The
dried samples were cooled in a desiccator for 30minutes and then weighed (Itodo et al., 2010). To
ascertain constant weight, the process was repeated in one hour interval. The percentage moisture
content (% loss in weight) was calculated in triplicate and the average, recorded as mean.
Loss in weight in drying (g)
Moisture (%) = × 100 (3.8)
initial sample weight (g)

3.6.2 BULK DENSITY DETERMINATION

Density was measured on activated sample of 0.425mm. this was determined by measuring the
volume of water displaced when a known weight (2g) of sample of activated carbon were dropped
into a graduated measuring cylinder with tapping until the carbon occupies and initial volume,
(Bhatia, 2006). A 100cm3 calibrated measuring cylinder was washed and dried. Then, 50cm3 of
the waste water was added to the measuring cylinder and was noted. 2g of the sample was
transferred into the measuring cylinder and volume of the increased water level was recorded.
Care was taken to ensure there were no air bubbles before taking volume measurements. The
mass and volume were recorded and density calculated as equation (Aziza et al., 2008).
Volume of water displaced (cm3) = final volume – initial volume
Mass of sample (adsorbent)
Bulk density (g/cm3) = Volume of water displaced
(3.9)

49
3.6.3 SURFACE AREA DETERMINATION
The specific surface area of the activated carbon (groundnut shell) will be estimated using sear
method by agitating 1.5g of activated carbon samples in 100ml of dilute nitric acid at pH of 3.
Then a 30g of sodium nitrate was added while stirring the suspension and then the volume was
made up to 150ml with deionised water. The solution was titrated with 0.1N sodium hydroxide
(NaOH) to raise the pH from 4 to 9 and the volume V recorded.
The surface area according to this method was calculated as:
S = 32V – 25 (3.9.1)
Where
S is the surface area of the activated carbon,
V is the volume of sodium hydroxide required to raise the pH sample from 4 to 9.

50
 CHAPTER FOUR
4.0 RESULTS AND DISCUSSION
4.1 CHARACTERIZATION OF ADSORBENT
4.1.1 PHYSIOCHEMICAL CHARACTERISTICS OF ADSORBENT
As shown in table 4.1, moisture content was 17%, bulk density was 430g/L and surface area was
980m2/g. The bulk density determines the mass of adsorbent in specific volume and it was
calculated as 0.43g/cm3. The sieving of the groundnut shell was also analyzed using mesh sieve of
0.425mm.
Table 4.1: PHYSIOCHEMICAL CHARACTERISTICS OF ADSORBENT
PARAMETER VALUE UNIT
Moisture content 7.25 %
Bulk density 0.43 g/cm3
Surface area 980 m2/g

4.2 APPLICATION OF BOX-BENHKEN DESIGN WITH RESPONSE

SURFACE METHODOLOGY
In general the application of a Box-Behnken design with RSM includes four main steps:
1. An experimental plan is provided based on the chosen conditions.
2. Statistically designed experiments are performed
3. The coefficients in the mathematical model are estimated and the accuracy of the model
is checked.
4. Response analysis is performed to predict the optimal conditions and these predictions
are confirmed experimentally.

51
4.2.1 BOX-BEHNKEN STATISTICAL ANALYSIS
The Box-Behnken responses were analyzed and the results for adsorption study of lead metal ions
is presented in table 4.2
TABLE 4.2 EXPERIMENTAL BOX-BENHKEN DESIGN WITH RESPONSES
STD RUN BLOCK FACTOR 1 FACTOR 2 FACTOR 3 RESPONSE 1
A:ADSORBENT B: CONTACT C: Ph % Removal
DOSAGE(grams) TIME (%)
(minutes)
16 1 Block1 0.6 65.0 4.0 90.00
4 2 Block1 0.6 120.0 6.0 99.10
9 3 Block1 0.2 10.0 4.0 98.00
2 4 Block1 0.6 10.0 6.0 98.80
11 5 Block1 1 10.0 4.0 96.65
15 6 Block1 0.6 65.0 4.0 91.50
14 7 Block1 0.6 65.0 4.0 92.00
17 8 Block1 0.6 65.0 4.0 92.50
1 9 Block1 0.6 10.0 2.0 97.75
8 10 Block1 1.0 65.0 6.0 99.80
7 11 Block1 1.0 65.0 2.0 98.40
12 12 Block1 1.0 120.0 4.0 99.02
13 13 Block1 0.6 65.0 4.0 92.30
10 14 Block1 0.2 120.0 4.0 96.79
6 15 Block1 0.2 65.0 6.0 99.00
5 16 Block1 0.2 65.0 2.0 98.80
3 17 Block1 0.6 120.0 2.0 98.90

As established earlier from the literature, the response of heavy metal removal via adsorption
depends on certain factors and this factor includes the parameters which act as conditions to the
process. In this study, the combined effect of these parameters on heavy metal removal (lead ions)
were investigated and optimized. Optimization by classical method involving one factor at a time
52
(OFAT) is time consuming and expensive. Besides this, number of trials required will be large,
making the full factorial design very complex.
4.2.2 LEAD METAL RESPONSE
In order to overcome such difficulties experimental Box-Behnken design was used for
optimization of the various parameters for lead metal ion recovery. Parameters and their
corresponding range considered are adsorbent dosage (0.2 to 1.0g), contact time (10 to 120mins),
and pH of (2 to 6). The experiments were conducted at different level of combination of these
parameters using statistically designed experimental procedure. The coded and actual values of
the independent variables A (adsorbent dosage ), B ( contact time), and C (pH) as designed by
design expert 7.0.0 with their corresponding response (predicted and actual) is showed in table 4.3
below:
Table 4.3: The Box-Behnken Design and the experimental Response of
Dependent Variable Ylead (Lead Metal Concentration, mg/L).
RUNS FACTORS RESPONSES
CODED LEVELS ACTUAL VALUES LEAD METAL
CONCENTRATION
A B C A B C ACTUAL PREDICTED
1 0 0 0 0.6 65 4 90.00 91.66
2 0 1 1 0.6 120 6 99.10 99.11
3 -1 -1 0 0.2 10 4 98.00 98.02
4 0 -1 1 0.6 10 6 98.80 98.88
5 1 -1 0 1.0- 10 4 96.65 96.55
6 0 0 0 0.6 65 4 91.50 91.66
7 0 0 0 0.6 65 4 92.00 91.66
8 0 0 0 0.6 65 4 92.50 91.66
9 0 -1 -1 0.6 10 2 97.75 97.74
10 1 0 1 1.0 65 6 99.80 99.82
11 1 0 -1 1.0 65 2 98.40 98.50
12 1 1 0 1.0 120 4 99.02 98.996
13 0 0 0 0.6 65 4 92.30 91.66

53
14 -1 1 0 0.2 120 4 96.79 96.89
15 -1 0 1 0.2 65 6 99.00 98.90
16 -1 0 -1 0.2 65 2 98.80 98.78
17 0 1 -1 0.6 120 2 98.90 98.82

4.2.3 REGRESSION MODEL EQUATION FOR LEAD ION CONCENTRATION

A system or process with several variables is likely to be influenced by several external as well as
internal parameters and low order interactions. Investigations on linear, cubic, two factor
interaction and quadratic model were done to select the statistically significant model for
determining the relationship between the response and input (independent variables). From the
sequential model sum of squares, it can be seen that p value is less than 0.0001 and F value
(94.84) for quadratic model (table 4.5). Lack of fit test for quadratic model was found to be
insignificant which indicate that the model fits the experiment and its p value was 0.9961.
From the model summary statistics (Table 4.4), it can be predicted that the quadratic model had
maximum predicted and adjusted R2 value. From the above results, it had been concluded that
quadratic model provides an excellent relationship between the response and the independent
variables.
TABLE 4.4: Model Summary for Lead Metal Response
Std. Adjusted Predicted
R- R-
Source Dev. R-Squared Squared Squared PRESS
Linear 3.65 0.0118 -0.2162 -0.4201 248.77
2FI 4.12 0.0332 -0.5469 -1.2719 397.98
Quadratic 0.76 0.9768 0.9469 0.9592 7.14 Suggested
Cubic 1.00 0.9771 0.9084 N/A N/A Aliased

From the table above, the coefficient of determination (R2) of the model was 0.9768 which
indicated a good fit between predicted values and the experimental data points (Fig 4.1). In
addition, this implies that 97.68% of the variations for percent lead ion adsorption are explained

54
by the independent variables, and this also means that model does not explain only about 2.32%
of variation. Predicted R2 is a measure of how good the model predicts a response value.
Experiments were performed using the BOX-Behnken experimental design. The experimental and
predicted lead metal concentrations are shown along with the experimental conditions in Table
4.2. Based on the model analysis, a quadratic model was chosen to fit the data. The second order
polynomial equation fitted between the responses represents metal removal efficiency (Ylead) and
the input variable of A-Adsorbent dosage, B-Contact time, and C-pH. The relationship between
the adsorption efficiency and the three chosen factors is shown in Eq.4.1
Ylead = 120.04394 − 27.43494A − 0.13092B − 8.28381C + 0.040682AB + 0.37500AC −
1.93182X10−3 BC + 19.7421A2 + 9.24380X10−4 B 2 + 1.04531C2 (4.1)

The equation above has been used to visualize the effects of experimental factors on percentage
response (Lead metal concentration) as shown in Figs 4.2a to 4.2f. Positive coefficient values
indicate the positive interaction of factors and its impact on lead ion adsorption whereas the
negative coefficient values points to the detrimental and interfering effect of the parameters on
overall adsorption.
From equation, it can be said that none of the factors, adsorbent dosage, A, Contact time, B, and
PH, C have positive impact on the lead metal adsorption whereas the interaction between
adsorbent dosage, A and Contact time, B, adsorbent dosage, A and pH, C contact time, B and pH,
C, have an overall positive effect on the adsorption but the interaction between contact time, B,
and pH, C, have a negative impact on the adsorption concentration.
4.2.4 ANALYSIS OF VARIANCE (ANOVA)
Analysis of variance, ANOVA, is a statistical decision making tool used for detecting any
differences in average performances of tested parameters (Ross, 1996). It employs sum of squares
and F statistics to find out relative importance of the analyzed processing parameters,
measurement errors and uncontrolled parameters. Analysis of variance (ANOVA) was used to
check the adequacy of the model for the responses in the experimentation. It subdivides the total
variation of the results in two sources of variation, the model and the experimental error, showing
whether the variation from the model is significant when compared to the variation due to residual
error (Segurola et al., 1996). Fisher’s F-test value, which is the ratio between the mean square of

55
the model and the residual error, performs this comparison (Kasiri et al., 2013; Khataee et al.,
2010).
4.2.4.1 (ANOVA) FOR RESPONSE SURFACE QUADRATIC MODEL OF LEAD.
Table 4.5: (Analysis Of Variance for Lead Metal)
Sources Sum of Degree of Mean F value P value
squares freedom square prob>F
Model 171.11 9 19.01 32.73 <0.0001 significant
A- Adsorbent 0.2 1 0.20 0.35 0.5714
dosage
B- contact 0.85 1 0.85 1.47 0.2653
time
C- Ph 1.02 1 1.02 1.75 0.2277
AB 3.20 1 3.20 5.52 0.0512
AC 0.36 1 0.36 0.62 0.4570
BC 0.18 1 0.18 0.31 0.5945
A2 42.01 1 42.01 72.32 <0.0001
B2 32.92 1 32.92 56.67 0.0001
C2 73.61 1 73.61 126.71 <0.0001
Residual 4.07 7 0.58
Lack of fit 0.0055 3 0.018 0.018 0.9961 Not significant
Pure Error 4.01 4 1.00
Cor Total 175.18 16

ANOVA table suggest whether the equation is adequate to describe the relationship between
response and other independent variables. The model can be considered as statistically significant,
if the value of p is lower than 0.05 with a larger F value (Oehlert and Gray, 2000). From the
ANOVA table (table 4.4, it is observed that the quadratic model fitted well with the data
generated and can be considered as statistically significant, since the F value is large (239.51) and
p value is lesser than 0.0001. in this case AB,A2,B2,and C2 were considered to be the significant
model terms, whereas other terms are not listed as significant factors since their p values were
greater than 0.1.

56
Table 4.6: Statistical Information on Box-Behnken Design for Lead.
Std Dev. 0.76 R-Squared 0.9768
Mean 96.43 Adj R- Squared 0.9469
C.V% 0.79 Pred. R- Squared 0.9592
PRESS 7.14 Adequate precision 13.952

The coefficient of Variance (CV) is the ratio of standard error of estimation to the mean value and
considered reproducible once it is not greater than 10%. In my study, CV obtained was 0.79%.
Adequate precision value measures signal to noise ratio. A ratio greater than 4 is desirable. The
obtained ratio from my research was 13.952 which indicate and adequate signal.
4.2.5 DIAGOSNOSTIC PLOTS FOR LEAD RESPONSE
The generated data were analyzed to determine the correlation between the actual and predicted
values as shown in fig. 4.1 below.

Fig 4.1: Diagnostic plot of predicted against actual lead ion concentration.

57
From the plot, it is observed that the data points are distributed near the straight line indicating
that the quadratic model could be employed as the significant model for predicting Lead response
over the independent input variables.
4.2.6 RESPONSE SURFACE PLOTS OF LEAD METALS
Each contour plot gives the graphical representation of influence of interactive effects of
individual parameter over the response. The contour plot may be rising ridges, saddle point,
elliptical or circular plot. Circular or elliptical plot indicates that there exists a significant
interaction between the operating parameters.
4.2.7 ESTIMATION OF QUANTITATIVE EFFECTS OF THE FACTORS
4.2.7.1 INTERACTION BETWEEN ADSORBENT DOSAGE AND CONTACT TIME.

Figure 4.2a: surface plot of the predicted percent adsorption capacity as a function of
adsorbent dosage and contact time with pH fixed at 4.
From the fig 4.2a above, it was observed that as both contact time and adsorbent dosage increases,
lead ion concentration decreases leading to percent increase in adsorption capacity. This can be
traced back to effect of time on rate of adsorption since increasing time of contact between the
adsorbent and the adsorbate increases the rate of adsorption it implies that the active site are well
filled with lead ion if contacted for long. Also adsorbent dosage increase, increases the rate of

58
adsorption in the sense that when there is enough adsorbent dosage, the actives site increases
leading to large surface area and adsorption rate increases as well because there is enough space
for the adsorbate to bind.
4.2.7.2 INTERACTION BETWEEN pH and TIME

Fig. 4.2b: surface plot of the predicted percent adsorption capacity as a function of contact
time and pH with adsorbent dosage fixed at 0.6g.
From the above fig 4.2b, it can be deduced that as both contact time and pH increases,
adsorption capacity increases from 97.75% to 99.1%. This value is obtained from table 4.2
indicating low pH (2) and low time (10minutes) corresponding to 97.75% to higher pH (6) at
increased time (120minutes) corresponding to 99.1%. This is reasonable because research has
shown that increased pH increases the rate of adsorption for metal since metals are protons with
positive ions they tend not to be adsorbed when the solution is acidic with low pH since like
charges repels each other but easily absorbed in basic solution with high pH. Also Increase in
contact time from 10minutes to 120 minutes led to an increase in percentage adsorption capacity

59
from 96.65% to 99.1%. PH increment led to increase in percentage adsorption capacity from
97.75% to 99.10%. Therefore it can be concluded that the interaction between both factors have
an overall positive effects on lead ion adsorption process.
4.2.7.3 INTERACTION BETWEEN ADSORBENT DOSAGE AND pH

Fig 4.2c: surface plot of the predicted percentage adsorption capacity as a function of
adsorbent dosage and pH with contact time fixed at 65minutes.
From figure 4.2c it is observed that as both adsorbent dosage and pH increase, percentage
adsorption capacity increases from 98.8 %to 99.8% these corresponds to lower pH and adsorbent
dosage value(2,0.2g respectively) to a higher pH and adsorbent value (6,1g respectively) as
shown in table 4.2. An increase in adsorbent dosage (0.2-1) gram resulted to an increase in
percentage adsorption capacity from 96.79% to 99.80%. Also an increase in pH from (2-6)
resulted into an increase in percentage adsorption capacity from 97.75% to 99.1%. Therefore it
can be concluded that the interaction between adsorbent dosage and pH has an overall positive
effect in the adsorption process of lead ion.

60
 CHAPTER FIVE
5.0 CONCLUSIONS AND RECOMMENDATIONS

5.1 CONCLUSION
In this research, the adsorption study includes the characterization of the adsorbent using three
parameters: moisture content, bulk density and surface area and values ascertained were 7.25%,
0.43g/cm3 and 980m2/g respectively. Furthermore, the statistical methodology, Box-Behnken
Response Surface Design was demonstrated to be effective and reliable in finding the optimal
conditions for the adsorption of lead metal ion onto modified groundnut shell. The results showed
that the adsorption conditions have significant effects on the removal of lead metals. The response
surface plot was used for estimating the interacting effects of three independent variables
(adsorbent dosage, time and pH) on the responses (percent lead adsorption capacity). The
quadratic model was developed by regression analysis of the experimental data obtained from the
17 runs with coefficient of determination, R2 of 0.9768 applying the method of desirability
function, optimization of adsorbent dosage (0.94g), contact time (115.36minutes), and pH (5.42),
gave a maximum desirability of 0.933 of lead ion metal removal. Also the following conclusions
were drawn:
 Activated groundnut shell is a good adsorbent for the removal of lead ion metals from
aqueous solution
 The preparation of adsorbents is cheap and economically suitable for the treatment of
heavy metal pollutants from water and waste water.

61
5.2 RECOMMENDATIONS

In order to achieve more success in this research, the following recommendations are necessary:
 More studies should be carried out in order to promote large-scale of non-conventional
adsorbents in industries for waste water treatment due to their local availability, technical
feasibility, engineering applicability, and cost effectiveness.

 The effect of temperature and concentration on adsorption of lead metal ion on modified
groundnut shell can also be carried out other than the parameters considered in this study.

 The presence of other metals combined with lead ion in an aqueous solution can be
studied to see the effect of metal interaction if any, on rate of adsorption.

 Central composite design can be used to optimize the process other than Box- Behnken
design.

62
 5.3 REFERENCE
Adamson, Arthur W. (1979). “A Textbook of Physical Chemistry,” 2nd Ed. Academic Press,
New York.pp. 68-73.
Annadurai G., Lee J. F.; (2002) Equilibrium studies on the adsorption of acid dye into
chitin.,Environ Chem Lett 6, pp. 77–81.
Barakat, M., (2005) Adsorption behavior of copper and cyanide ions at TiO2–solution interface.
Journal of Colloid and Interface Science, Research gate Journal 291(2): pp. 345-352.
Bishnoi, N. R., Bajaj, M., Sharma, N., & Gupta, A. (2004). Adsorption of Cr (VI) on activated
rice husk carbon and activated alumina. Bio-resource Technology Research Journal 91(3),
pp.305-307.
Chu W,(1999) “Lead metal removal by recycled alum sludge”, Journal of Water Research, vol
33, No.13,pp. 3019-3025.
Deng, H., Li, G., Yang, H., Tang, J. and Tang, J. (2010). Preparation of activated carbons from
cotton stalk by microwave assisted KOH and K2CO3 activation. Chemical Engineering Journal,
163, 2010, pp.373-381.
Dhokpande (2009) Biological method for heavy metal removal .pp, 195-226

Duff, David G., Ross, Sheina M.C. and Vaughan, D. Huw (1988) “Adsorption from Solution: An
Experiment to Illustrate the Langmuir Isotherm” J. Chem. Ed. 65, pg.815.

Ho, Y.S., McKay, G., 2000. “The kinetics of sorption of divalent metal ions onto sphagnum
moss peat”. Water Research, 34(3):pp.735-742.

Idris, Isal and Ahmed (2012), ‘’Kinetics and equilibrium studies of the adsorption of phenol on
groundnut husk” research gate Journal (42) pp. 21-32.

Khezami and R. Capart (2005). ‘’Removal of chromium iv from aqueous solution by activated
carbon”, Research gate Journal 123 (1-3):pp.223-313.

M. K. Mondal, “Removal of Pb (II) from Aqueous Solution by Adsorption Using Activated Tea
Waste,” Korean Journal of Chemical Engineering, Vol. 27, No. 1, 2010, pp. 144-151.

63
Montgomery, D.C., (1997). Design and Analysis of Experiments: Chapter 13, 4th Edn., John
Wiley & Sons, USA.
Namasivayam, C., pariasary, D., (1995). Adsorption removal of 2,4-dichlorophenol from
aqueous solution by low-cost carbon from an agricultural solid waste: coconut coir pith.
Research gate journal 142(5) pp, 23.
Naseem and Tahir (2001) ‘’Equilibrium sorption isotherm for pb (ii) ions on saw dust’’.
Separation Science and Technology, 39(6):pp.1407-1425.

Ramakrishna Gottipati, and Susmita Mishra. (2012). Application of response surface

methodology for optimization of Cr(III) and Cr(VI) adsorption on commercial activated carbons,
Research Journal of Chemical Sciences, 2(2), pp.40-48.
Weber J Jr, (1991), ‘’physiochemical processes for water quality control” (Wiley Interscience,
New York),.Adsorption Science and Technology, Vol. 28, No. 10, , pp. 913- 921
Wu, F.C., Tseng, R.L. (2006). Preparation of highly porous carbon from fire wood by KOH
etching and CO2 gasification for adsorption of dyes and phenols from water. Journal of Colloid
and Interface Science, 294, pp.21–30.
Wong, K. K., Lee C. K., Low K. S. and Haron, M. J. (2003). Removal of Cu and Pb by tartaric
acid modified rice husk from aqueous solutions. The Open Environment Pollution and
Toxicology Journal , 50: pp.23.
Tan W. Tao and WI (1993). Copper (II) Adsorption by Waste Tea Leaves and Coffee Powder.
Pertanika Research journal 8(2):pp. 223-230.
Y.C. Sharma, B. Singh, Uma,( 2009), Fast removal of malachite green by adsorption on rice
husk activated carbon, The Open Environment Pollution and Toxicology Journal, 1,pp.74-78.

Y. LiuZheng and A. Wang, (2010) “Response Surface Method-ology for Optimizing Adsorption
Process Parameters for Methylene Blue by a Hydrogel Composite,” Research gate journal
pp.23-27.

64
 APPENDIX
Table 5.1: Sequential model sun of squares for lead metal.
source Sum of Df Mean F value P- value
squares square Prob>F
Mean vs 1.581 x 105 1 1.581 x 105
Total
Linear vs 2.07 3 0.69 0.052 0.9837
mean
2FI vs 3.74 3 1.25 0.074 0.9727
Linear
Quadratic vs 165.29 3 55.10 94.84 <0.0001 Suggested
2FI
Cubic vs 0.055 3 0.018 0.018 0.9961 Aliased
Quadratic
Residual 4.01 4 1.00
Total 1.583 x 105 17 9309.05

Table 5.2 Lack of fit Tests

Source Sum of Df Mean F Value p- value
squares square
linear 169.09 9 18.79 18.79 0.0063
2FI 165.35 6 27.56 27.56 0.0033
Quadratic 0.055 3 0.018 0.018 0.9961 Suggested
cubic 0.000 0 Aliased
PureError 4.01 4 1.00

65