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Table of Contents

COVER PAGE ..................................................................................................................i


CERTIFICATION ii
CHAPTER ONE ................................................................................................................ 2
INTRODUCTION ............................................................................................................. 3
BACKGROUND OF STUDY ....................................................................................... 3
PROBLEM STATEMENT ........................................................................................... 5
OBJECTIVE OF STUDY ............................................................................................. 5
IMPORTANCE OF THE STUDY ............................................................................... 6
CHAPTER TWO ............................................................................................................... 7
LITERATURE REVIEW ................................................................................................. 7
PRODUCED WATER .................................................................................................. 7
DISCUSSION ON SOME HEAVY METALS ........................................................... 8
Lead (Pb) .................................................................................................................... 8
Copper (Cu).............................................................................................................. 10
Mercury (Hg) ........................................................................................................... 11
Cadmium (Cd) ......................................................................................................... 12
Arsenic (As) .............................................................................................................. 13
METHODS ON REMOVAL OF HEAVY METALS .............................................. 15
Chemical precipitation ............................................................................................ 15
Solvent extraction .................................................................................................... 16
Reverse osmosis........................................................................................................ 16
Evaporation .............................................................................................................. 17
Electrodialysis .......................................................................................................... 17
Ion exchange ............................................................................................................. 17
Adsorption ................................................................................................................ 18
Bioadsorption ........................................................................................................... 19
Lagenaria siceraria ...................................................................................................... 19
Description ............................................................................................................... 19
Distribution .............................................................................................................. 20
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Adsorption models ....................................................................................................... 21


CHAPTER THREE ......................................................................................................... 25
MATERIAL AND METHODS ...................................................................................... 25
MATERIALS ............................................................................................................... 25
METHODS ................................................................................................................... 25
EQUIPMENTS ............................................................................................................ 25
EXPERIMENTS TO BE CONDUCTED .................................................................. 25
WORK PROGRAMME ............................................................................................. 26
REFERENCES ................................................................................................................ 27

CHAPTER ONE
INTRODUCTION
BACKGROUND OF STUDY
Environmental impact of industrial activities and reprisal activities of stakeholders
and public institutions has giving rise to a state of crises or near crisis in several regions
where projections are not made to monitor, prevent or reduce effect of industrial effluents
on the host environment and communities. Environmental impact assessment and
sustainable development are now keywords in all industrial project aim at creating a
balance between risks, socioeconomic and environmental considerations in the design,
construction, installation and operation of technological facilities.
The Niger Delta region of Nigeria is a region of high petroleum production activity.
The region is currently laden with incessant interference on economic activity due to issues
of sustainable development with stakeholders. One of the visible impacts pointed at is the
effect of the effluent discharge from oil production platforms into rivers and estuaries
(Gberesu, 1989). These affect host communities of these production activities when eat
fish from the rivers or drink contaminated water. International Occupational Safety and
Health Information Centre in her journal (1999) stated that heavy metal toxicity can result
in damaged or reduced mental and central nervous function, lower energy levels, and
damage to blood composition, lungs, kidneys, liver, and other vital organs. Formation
water is natural occurring water which in some cases and found in association with oil and
gas bearing rocks in oil formations or reservoir (Kobranova 1989).
Natural gas and formation water are the major byproducts of the crude oil
production industry. Crude oil, a mixture of oil, gas and water flows from the reservoir
through pipelines to the platform where the mixture is separated. The natural gas is flared
until the resent government program to stop flaring. The water from the separation process
which is known as process water is usually discharge after biological treatment in an
oxidation pond.
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The Federal Ministry of Environment, Nigeria Conservation Foundation noted that


the damage from oil and gas operations is chronic and cumulative, and has acted
synergistically with other sources of environmental stress to result in a severely impaired
coastal ecosystem and compromised livelihoods and health of the regions impoverished
residents. The 70,000 square kilometers Niger Delta contains 7,400 of West Africas
20,000 square kilometers of mangroves, and is considered one of the 10 most important
wetlands and marine ecosystems in the world. Millions of people depend upon the deltas
natural resources for survival, including the poor in many other West African countries
who rely on the migratory fish from the delta. The region contains many threatened species
found nowhere else in the world, including several primates, ungulates and birds.
Information on the volume and characteristics of the effluent discharge is difficult
to assess due to the nontransparent nature of the multi nationals working in the oil
industries.
Several studies including that by Muhammad et al, (2005) and Lenntech (2006)
revealed that drive for proactive attention on effective treatment of waste before discharge
from petroleum has been on the increase to encourage the reduction of its impact on the
economy of such operation and on the environment.
Since heavy metal ions are not biodegradable in nature, effective removal of heavy
metal ions from aqueous solutions through other technologies (physical or chemical) is
important in the protection of environmental quality and public health. Various chemical
and physical methods have been used to remove heavy metal ions in the last few decades.
These methods include chemical precipitation, solvent extraction, ion exchange,
evaporation, reverse osmosis, electrolysis and adsorption. Among these methods, chemical
precipitation, solvent extraction, ion exchange and adsorption are more commonly used.
Chemical precipitation has traditionally been used to remove heavy metal ions from
wastewater with relatively high concentrations. The operation of chemical precipitation is
simple but generates large quantity of sludge that is often difficult for further disposal. In
addition, chemical precipitation is usually not effective to remove trace levels of metal ions
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from aqueous solutions. Solvent extraction has widely been used in organometal removal.
Although the process may have fast kinetics and high capacity, solvent extraction is often
costly due to the quantity and specific type of solvents needed. Ion exchange method has
commonly been used to remove metal ions from water or wastewater, but the process has
slow kinetics, consumes additional chemicals, generates hazardous streams, and is not well
applied to heavy metal ions due to possible problem of resin pollution. Adsorption has been
considered as, possibly, the most cost-effective method for heavy metal ion removal,
especially at medium to low concentrations, because the process is simple, and chemical
consumption or waste generation is not a significant issue. However, traditional adsorbents,
such as activated carbon, are often not effective to adsorb heavy metal ions from water or
wastewater.
The most important parameter for determining the efficiency and cost of adsorbents
is the adsorption capacity. Adsorption isotherm is a graphical; representation of the
relationship between the amounts of adsorbate adsorb per unit mass of adsorbent and the
equilibrium concentration of the solution at constant temperature (Kenedy et al, 1993).
PROBLEM STATEMENT
Most waters have been contaminated by toxic metals through the discharge of
industrial effluent. The contamination of these waters with industrial effluent is becoming
a serious environmental problem in Nigeria. Reports abound that these waters contain
heavy metal ions. The presence of these heavy metal ions in these waters has been
responsible for several health problems with plants, animals and human beings. Industries
in Nigeria pay huge amount of money as surcharges to public treatment plant.
OBJECTIVE OF STUDY
This study deals with the possibility of using lagenaria siceria biomass as an
adsorbent for removal of toxic ions, such as Pb2+, Cd2+, Zn2+,etc from produced water. To
achieve these, a study will carried out with the following specific objectives:

1. To prepare adsorbent from lagenaria siceria shell and seeds both as


carbonized and dried.
2. To evaluate the application of locally produced activated carbon in produced
water treatment by the removal of heavy metals.
3. To investigate the influence of batch sorption parameters, such as adsorbent
dosage, particle size, pH, initial metal ion concentration, temperature and
contact time.
4. To study the adsorption isotherms using model equations, such as Langmuir
and Freundlich isotherm models.
IMPORTANCE OF THE STUDY
The amount and variety of chemicals discharged into wastewaters has been
increasing considerably. This increase is as a result of rapid development of chemical,
petroleum processing and allied industries in Nigeria. Wastewaters from these industries
are discharged into ground and surface water, making it unfit for human and animal
consumption due to the presence of some chemical and biological pollutants. These
pollutants can cause severe ailments in human and animals, are carcinogenic, toxic and
mutagenic. The increase in the variety and amount of hazardous chemical in bodies of
water has made conventional methods of wastewater treatment ineffective and inefficient
as a result, a new method of treatment through the use of activated carbon has becomes
imperative.

CHAPTER TWO
LITERATURE REVIEW
PRODUCED WATER
Produced water is an inextricable part of the hydrocarbon recovery processes, yet it
is by far the largest volume waste stream associated with hydrocarbon recovery. Water
production estimates are in the order of 250 million B/D in 2007, for a water-to-oil ratio
around 3:1, and are expected to increase to more than 300 million B/D between 2010 and
2012 (Dal Ferro and Smith 2007). Increasingly stringent environmental regulations require
extensive treatment of produced water from oil and gas productions before discharge;
hence the treatment and disposal of such volumes costs the industry annually more than
USD 40 billion. Consequently, for oil and gas production wells located in water-scarce
regions, limited freshwater resources in conjunction with the high treatment cost for
produced water discharge makes beneficial reuse of produced water an attractive
opportunity.
Water consumption worldwide is roughly split, with 70% agricultural use, 22%
industrial use, and 8% domestic use (UNESCO 2003). A fifth of the population lives in
areas of water scarcity, and one in eight lacks access to clean water. Currently, properly
treated produced water can be recycled and used for waterflooding [produced water reinjection (PWRI)] and other applications, such as crop irrigation, wildlife and livestock
consumption, aquaculture and hydroponic vegetable culture, industrial processes, dust
control, vehicle and equipment washing, power generation, and fire control (Veil et al.
2004). These beneficial reuses directly decrease the withdrawal of potable water, a highly
valuable commodity in many regions of the world. Although produced water can
potentially be treated to drinking water quality (Tao et al. 1993; Doran et al. 1997; Kharaka
et al. 1998; Funston et al. 2002; Xu et al. 2008), little research has been done on the
feasibility and cost-effectiveness of direct or indirect potable reuse of produced water from
oil and gas production.
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Produced water is the aqueous liquid phase that is co-produced from a producing well along
with the oil and/or gas phases during normal production operations. This includes water
naturally occurring alongside hydrocarbon deposits, as well as water injected into the
ground. The following are the main contaminants of concern in produced water:

High level of total dissolved solids (TDS)

Oil and grease

Suspended solids

Dispersed oil

Dissolved and volatile organic compounds

Heavy metals

Radionuclides

Dissolved gases and bacteria.

Chemicals (additives) used in production such as biocides, scale and corrosion


inhibitors, and emulsion and reverse-emulsion breakers

The amount of produced water, and the contaminants and their concentrations present
in produced water usually vary significantly over the lifetime of a field. Early on, the water
generation rate can be a very small fraction of the oil production rate, but it can increase
with time to tens of times the rate of oil produced. In terms of composition, the changes
are complex and site-specific because they are a function of the geological formation, the
oil and water (both in-situ and injected) chemistry, rock/fluid interactions, the type of
production, and required additives for oil-production-related activities.
DISCUSSION ON SOME HEAVY METALS
Lead (Pb)
Lead is one of the IV-A group elements (atomic number of 82) whose electron
configuration consists of filled shells plus four electrons in the 6s26p2 states. Lead has two
stable positive oxidation states: +2 and +4, and it is generally found in complexes with a
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coordination number of 6. The most common one and the one with the most complex
hydrolysis behavior is Pb2+ (Harrison and Laxen, 1981). Because of its low melting point
and durability, lead has been an important metal in human societies over many thousands
of years. During the period of Roman Empire, lead pipes were widely used in water supply.
Lead was also used early as a construction material. Since the early days of the industrial
revolution, the use of lead has increased dramatically (Harrison and Laxen, 1981).
Nowadays, lead is normally used as a radiation shield around X-ray equipment and nuclear
reactor and is extensively used in paints and, in lead arsenate, as insecticides in agriculture
(Schneegurt et al., 2001). The major reason for lead pollution in environment is due to
anthropogenic factor of industrial applications, such as in electroplating industries, metal
finishing industries, burning of leaded gasoline, mining and metallurgic industries, and
trash incineration. According to a report, the anthropogenic inputs of lead (direct deposition
from air and runoffs) to the environment were one or two orders of magnitudes greater than
that from natural sources (Hutchinson and Meema, 1987). For example, the storage battery
industry has been the largest user of lead. Lead from burning leaded gasoline used to be a
major source of atmospheric and terrestrial lead, much of which eventually entered natural
water systems.
Lead is a cumulative poison and concentrates primarily in the bones. The effects on
human include hypertension and brain damage. Acute lead poisoning in humans causes
severe dysfunction in the kidneys, reproductive system, liver, brain and central nervous
system. Lead poisoning from environmental exposure is known to cause mental
retardation, especially in children. Mild lead poisoning causes anemia. The victim may
have headaches and sore muscles and may feel generally fatigued and irritable (Harrison
and Laxen, 1981). Hence, lead has been classified as priority pollutant by the US
Environmental Protection Agency (EPA) and the Maximum Contaminant Level (MCL) of
lead ions in drinking water has been set at a very low level of 0.015 mg/L by the EPA.

Copper (Cu)
Copper, the 29th element in the Periodic Table, has the electronic configuration of
1s22s22p63s23p63d104s1. It is the least reactive element in the first row of the transition
metals and it forms some compounds in which there is an incomplete d-subshell. Being a
transition metal, copper occurs in metallic form or in compounds as Cu (I) or Cu (II)
(Merian, 1991). Copper is a reddish metal that occurs naturally in rock, soil, water,
sediment, and air. The primary use of copper, accounting for approximately half of its
production is in electrical equipment. Copper is also a component of many alloys where it
may occur together with other metals, such as silver, cadmium, tin and zinc. Other
important uses of copper are in plating, plumbing and heating. Copper salts may also serve
as pesticides (Friberg et al., 1986). Copper pollution is mainly caused by anthropogenic
factor of industrial applications. Corrosion of plumbing, metal cleaning operations, plating
baths and rinses are by far the greatest cause of concern. For example, copper levels in
plating baths can be as high as 50,000 mg/L, while its concentration in the rinse waters
may be as high as 0.02 to 1% of the process bath concentration (Golomb, 1972). Copper is
rarely found in source water directly, but copper mining and smelting operations and
municipal incineration of wastes may be the major sources of copper contamination to
source water. For example, the concentrations of copper in the sewage to Winnipegs three
wastewater treatment facilities were reported to be 157, 271, 201 g/L, respectively. The
presence of copper in the sewage was attributed mainly to the industrial effluents received
in one of the facilities and was due to the use of copper piping in the districts served by the
other two plants (Carroll and Lee, 1977). It was estimated that the annual industrial
discharges of copper into freshwater environments was at 1.4 x 1010 g/year, and the
amounts of copper in industrial wastes and sewage sludge that have been dumped into the
ocean was 1.7 x 1010 g/year worldwide (Nriagu, 1979).
Copper is an essential element for living organisms, including humans, and
necessary in small amounts in our diet to ensure good health. However, too much copper
can cause adverse health effects, including vomiting, diarrhea, stomach cramps, and nausea
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(Ng et al., 2002). Copper is stored mainly in liver, brain, heart, kidney and muscles. There
are evidences to suggest that copper may be carcinogenic and large acute doses and intake
could accumulate in the liver or kidney and be extremely harmful, even fatal (Tseng et al.,
1999). Marine and aquatic organisms can also be at great risk because copper is highly
toxic to them, even at low concentrations. Although it is an essential element to plants,
exceptionally high copper concentrations may be toxic to plants by affecting mainly the
growth of the roots (Massey et al., 1973).
Mercury (Hg)
Mercury has an atomic number of 80 and exists in ionic form as Hg2+ (mercuric
salts) and Hg+ (mercurous salts). Organic mercury compounds consist of diverse chemical
structures in which mercury forms a covalent bond with carbon. Occurring as elemental
mercury, and as inorganic and organic compounds, all forms of mercury have different
toxicological properties (ONeill, 1985). Elemental and inorganic mercury compounds are
used in the manufacture of scientific instruments (thermometers, barometers), electrical
equipment (switches, rectifiers, oscillators, electrodes, batteries, coulometers, mercury
vapor lamps, X-ray tubes, lead and tin solders), dental amalgams, synthetic silk. Mercury
has also been used in the plating, tanning and dyeing, textile, photographic and
pharmaceutical industries (Watras and Huckabee, 1994). Human activities have resulted in
the release of a wide variety of inorganic and organic forms of mercury. Elemental mercury
was released into the atmosphere through the electrical industry, chloralkali industry, and
the burning of fossil fuels (coal, petroleum, etc.). Metallic mercury has also been released
directly into fresh water by chloralkali plants, and both phenylmercury and methylmercury
compounds have been released into fresh and sea water by wood paper-pulp industry and
chemical manufacturers. One of the major sources of mercury waste comes from the use
of mercury cells in the chloralkali industry. Water contains mercury mainly in the form of
Hg2+. The acute and long-term action of Hg2+ can be gastrointestinal disturbance and renal
damage appearing as a tubular dysfunction with tubular necrosis in severe cases (Liu et
al., 2003).
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Methylmercury is formed naturally in the aquatic and terrestrial environment from


elemental mercury and mercuric mercury. The methylmercury is rapidly taken up by living
organisms in aquatic environment and enters the food chain. The hazards involved in longterm intake of food containing methylmercury are from the efficient absorption (90%) of
methylmercury in man and methylmercury accumulation in the brain. Chronic poisoning
can cause degeneration and atrophy of the sensory cerebral cortex, as well as parenthesis,
ataxia, hearing and visual impairment. Methylmercury exposure to pregnant females may
result in inhibited brain development of the fetus with psychomotor retardation of the child
as a consequence (Watras and Huckabee, 1994). Hence, one of the ways to reduce the effect
of methylmercury can be to minimize the presence of Hg2+.
Cadmium (Cd)
Cadmium (Cd) is a soft, malleable, bluish white metal found in zinc ores, and to a
much lesser extent, in the cadmium mineral greenockite. In 2011, US production of
cadmium was estimated at 600 metric tons, down approximately 40% from the production
levels 20 years ago (1992). Most of the cadmium produced today is obtained from zinc
byproducts and recovered from spent nickel-cadmium batteries. First discovered in
Germany in 1817, cadmium found early use as a pigment because of its ability to produce
brilliant yellow, orange, and red colors. Cadmium became an important metal in the
production of nickel-cadmium (Ni-Cd) rechargeable batteries and as a sacrificial corrosionprotection coating for iron and steel. Common industrial uses for cadmium today are in
batteries, alloys, coatings (electroplating), solar cells, plastic stabilizers, and pigments.
Cadmium is also used in nuclear reactors where it acts as a neutron absorber. While lithium
ion batteries have made significant gains in popularity for lightweight electronic devices,
new market opportunities for industrial applications of Ni-Cd batteries will continue to fuel
cadmium use. Increased investment in solar power will also drive cadmium use in the
future. China, South Korea, and Japan are the leading producers of cadmium in the world,
followed by North America.

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Cadmium and its compounds are highly toxic and exposure to this metal is known
to cause cancer and targets the body's cardiovascular, renal, gastrointestinal, neurological,
reproductive, and respiratory systems.
Workers may be exposed during smelting and refining of metals, and manufacturing
batteries, plastics, coatings, and solar panels. The expanding Ni-Cd battery recycling
industry is a concern for cadmium exposure. Electroplating, metal machining, welding and
painting are operations associated with cadmium exposure. Workers involved in landfill
operations, the recycling of electronic parts, or the recycling of plastics may be exposed to
cadmium. Compost workers and waste collectors are also potentially exposed to dust which
may contain cadmium. The incineration of municipal waste is another source of cadmium
exposure.
Cadmium is an important metal for many types of businesses and industrial
processes. Cadmium is most often used in the manufacturing sector but worker exposure
can also occur in other industry sectors including construction, wholesale trade, and
transportation.
Arsenic (As)
Arsenic is a widely distributed metalloid, occurring in rock, soil, water and air.
Inorganic arsenic is present in groundwater used for drinking in several countries all over
the world (e.g. Bangladesh, Chile and China), whereas organic arsenic compounds (such
as arsenobetaine) are primarily found in fish, which thus may give rise to human exposure
(WHO, 2001). Smelting of non-ferrous metals and the production of energy from fossil
fuel are the two major industrial processes that lead to arsenic contamination of air, water
and soil, smelting activities being the largest single anthropogenic source of atmospheric
pollution (Chilvers et al., 1987).
Concentrations in air in rural areas range from <1 to 4 ng/m3, whereas
concentrations in cities may be as high as 200 ng/m3. Much higher concentrations (>1000
ng/m3) have been measured near industrial sources. Water concentrations are usually <10
g/l, although higher concentrations may occur near anthropogenic sources. Levels in soils
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usually range from 1 to 40 mg/kg, but pesticide application and waste disposal can result
in much higher concentrations (WHO, 2001). General population exposure to arsenic is
mainly through intake of food and drinking water. Food is the most important source, but
in some areas, arsenic in drinking water is a significant source of exposure to inorganic
arsenic. Contaminated soils such as mine-tailings are also a potential source of arsenic
exposure (WHO, 2001).
Absorption of arsenic in inhaled airborne particles is highly dependent on the
solubility and the size of particles. Soluble arsenic compounds are easily absorbed from
the gastrointestinal tract. However, inorganic arsenic is extensively methylated in humans
and the metabolites are excreted in the urine. Arsenic (or metabolites) concentrations in
blood, hair, nails and urine have been used as biomarkers of exposure. Arsenic in hair and
nails can be useful indicators of past arsenic exposure, if care is taken to avoid external
arsenic contamination of the samples.
Inorganic arsenic is acutely toxic and intake of large quantities leads to
gastrointestinal symptoms, severe disturbances of the cardiovascular and central nervous
systems, and eventually death. In survivors, bone marrow depression, haemolysis,
hepatomegaly, melanosis, polyneuropathy and encephalopathy may be observed. Ingestion
of inorganic arsenic may induce peripheral vascular disease, which in its extreme form
leads to gangrenous changes (black foot disease, only reported in Taiwan). Populations
exposed to arsenic through drinking water show excess risk of mortality from lung, bladder
and kidney cancer, the risk increasing with increasing exposure. There is also an increased
risk of skin cancer and other skin lesions, such as hyperkeratosis and pigmentation changes.
Studies on various populations exposed to arsenic by inhalation, such as smelter
workers, pesticide manufacturers and miners in many different countries consistently
demonstrate an excess lung cancer. Although all these groups are exposed to other
chemicals in addition to arsenic, there is no other common factor that could explain the
findings. The lung cancer risk increases with increasing arsenic exposure in all relevant
studies, and confounding by smoking does not explain the findings. The latest WHO
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evaluation concludes that arsenic exposure through drinking water is causally related to
cancer in the lungs, kidney, bladder and skin, the last of which is preceded by directly
observable precancerous lesions. Uncertainties in the estimation of past exposures are
important when assessing the exposureresponse relationships, but it would seem that
drinking water arsenic concentrations of approximately 100 g/l have led to cancer at these
sites, and that precursors of skin cancer have been associated with levels of 50100 g/l.
The relationships between arsenic exposure and other health effects are less clear. There is
relatively strong evidence for hypertension and cardiovascular disease, but the evidence is
only suggestive for diabetes and reproductive effects and weak for cerebrovascular disease,
long-term neurological effects, and cancer at sites other than lung, bladder, kidney and
skin.
METHODS ON REMOVAL OF HEAVY METALS
The separation of heavy metal ions presented as contaminants in water is
complicated by the number of variables that must be considered, including the solution
composition, the pH, and the presence of organic substances. Also a challenge encountered
in the removal of heavy metal ions is that the target species are usually in low
concentrations and exist in complex mixtures. Various methods have been used in the
removal of heavy metal ions, including chemical precipitation, solvent extraction, ion
exchange, evaporation, reverse osmosis, electrolysis and adsorption (Harrison, 1990).
Chemical precipitation
This is the most traditional, common and simple method. The conventional way to
separate heavy metals from the wastewaters they are dissolved in is to adjust pH to cause
metal precipitation by the addition of lime or other anionic polyelectrolyte. For example,
Janson et al. (1982) used hydroxide precipitation method to remove Zn2+, Pb2+, Cr3+ by
adjusting the pH of the solution to a value greater than 10. Cu2+ can be removed by forming
heavy metal sulfide precipitation. However, Hg2+ cannot be effectively removed by
chemical precipitation. The precipitation method produces a large amount of sludge, which
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transforms an aquatic pollution problem to a solid waste pollution problem. In addition,


chemical precipitation is usually inefficient to deal with low concentration of heavy metals.
Solvent extraction
It is extensively utilized in organometal removal from wastewater. The extractant is
capable of ion exchanging or forming chelates with the metal ions to be removed. Upon
mixing, the metal ions are transported to the organic phase. The phases are allowed to
separate, and the metal ions are stripped from the loaded organic phase. The concentrated
metal ion solution can then be purified or disposed. Solvent extraction offers the
advantages of fast kinetics, high capacities and selectivity for target metal ions. The finite
aqueous solubility of the extractant, solvents and modifiers is, however, a significant
disadvantage (Ritcey and Ashbrook, 1979). It not only adds to the cost of the process
through loss of reagents, but also contaminates the water with potentially toxic organics.
There is also loss of the organics through evaporation and entrainment. In addition, solvent
extraction is not recommended for diluted metal ion solution due to the large volumes of
extractants needed (Beauvais and Alxandratos, 1998). Solvent extraction may not be
effective to inorganic species of heavy metal ions.
Reverse osmosis
It is employed for the recovery of precious and common metals in the metal
finishing industry. Reverse osmosis can show excellent performance in treating
wastewaters containing a single metal or a mixture of metal ions. However, there are certain
drawbacks which have limited its wide applications in industrial effluents. In particular,
the process requires high pressures (up to 100 atmospheres) and is thus fairly costly in
terms of energy. The delicacy of the membranes is also restrictive with regard to the solid
content to be handled and the pH of the liquids to be treated. Nevertheless, the process has
been used for the effluents from electroplating in the electronic components industry. With
the continuous development of the process and improved mechanical strength of
membranes, the range of applications can be expected to increase (Harrison, 1990),
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especially if other removal methods cannot effectively reduce the concentrations of heavy
metals to the desired or required levels.
Evaporation
This is one of the most common methods used in industry for the concentration of
aqueous solutions. Nevertheless, the use of this process as a means for effluent treatment
is rare and occurs only under special circumstances where the effluent contains a high
concentration of static rinses from electroplating operations, particularly chromium
plating. In this application the rinse liquor is evaporated to a metal concentration which
makes the concentration suitable for direct re-use in the plating bath (Harrison, 1990).
Electrodialysis
Electrodialysis separates an aqueous flow under the influence of an electric field
into an enriched stream and a depleted stream. Among the applications of electrodialysis
are the production of potable water from brackish waters, deminerization of cheese whey,
treatment of acid mine drainage, desalting of cooling tower waters, and removal of metals
from plating wastes (Nriagu, 1979). The cost of electrodialysis is very dependent on
dissolved solids concentration. It does not find common use in effluent treatment but may
be appropriate in certain circumstances where the concentrate is of value.
Ion exchange
In recent years, ion exchange resins have been applied in heavy metal ion
adsorption. Ion exchange is one of the most effective techniques for removing heavy metals
from wastewaters. The resins contain functional groups capable of complexing or ion
exchanging with metal ions. The process is employed extensively for metal finishing bath
purification, effluent polishing after primary treatment, and recovering precious metals.
The resin is contacted with the contaminated solution, loaded with metal ions, and stripped
with an appropriate elute (Beauvais and Alexandratos, 1998). Beker and co-workers (1999)
synthesized ion exchange resin based on hydroxethyl cellulose and applied the ion
exchange resin in Fe3+, Co2+, Cu2+, Zn2+ ions removal. However, ion exchange has
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problems in treating aqueous wastes containing mixtures of metal ions due to low
selectivity of metal ions. Another disadvantage of ion exchange resins is the slow kinetics,
as compared to solvent extraction, although increasing the porosity of the resin or
decreasing the size of the beads can improve the kinetics. In addition, although heavy metal
ions can be removed effectively, in many cases, from wastewaters by means of ion
exchange, most ion exchange resins are too expensive to be discarded once they have been
loaded with heavy metals. The resins must therefore be regenerated and regeneration again
yields a solution of heavy metals which is hard to be disposed of. Regeneration with very
concentrated acids or bases has been recommended to reduce the volume of the
regeneration liquid that must be disposed of, but the concentration technique is not
effective for recovery of ion exchanger. Most important of all, synthetic resins have a poor
contact with aqueous solutions and their modification and/or pretreatment by activation
solvents are necessary for enhanced water wettablility.
Adsorption
In addition to other conventional methods, adsorption is another effective and
widely used method to remove heavy metal ions. Adsorption technology has good potential
to treat waster and industrial residues because it is cost-effective, easy for application and
efficient in various kinds of heavy metal removal. Various adsorption materials have been
studied, such as activated carbons, clays, polymeric synthetic resins, metal oxides, and
some natural materials. Among them, activated carbon is one of the oldest and most
commonly used adsorbents. Adsorption by activated carbon is an established treatment
method for organic contaminants but has been rarely used in an actual treatment setting for
inorganic adsorbates, despite the fact that the ability of activated carbons to remove heavy
metal ions has been established by numerous researchers. For example, adsorption with
activated carbon has been reported for Cu2+, Cd2+, Zn2+, Pb2+, Hg2+, CO2+, Mn2+, Ca2+, Ni2+,
Cr3+ (Dastgheib and Rockstraw, 2002). However activated carbon has some disadvantages
in heavy metals removal. Firstly, the adsorption capacity and kinetics for many metals,
such as Mn2+, Pb2+, CO2+, Zn2+ ions are rather poor. Secondly, activated carbon is
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expensive (activated carbon adsorbents are sold at market price about US$20-22/kg, and
the higher the quality, the greater the cost). Thirdly, the regeneration of activated carbon is
another challenge, which usually requires thermal chemical process that is expensive, and
causes loss of the adsorbent. Hence, the search for alternative and more effective
adsorbents has attracted great interests in heavy metal removal.
Bioadsorption
As a sub branch of adsorption, biosorption aims to use cheaper materials of
biological origins as adsorbents and has developed rapidly in the last one or two decades.
Biosorption, a passive non-metabolically mediated process, removes metals or metalloid
species, compounds and particulates from solution, by materials of living or dead biomass
(Gadd, 2001) and has served as an important means for purifying industrial wastewaters
containing toxic heavy metal ions. Bioadsorption has the following advantages (Volesky,
2003):
Using cheap raw materials (usually naturally abundant or a waste from other
industries), bioadsorption allows significant cost savings in comparison with
existing competing technology, i.e. ion exchange, its close rival.
Biosorption is more effective than its closest rival, ion exchange in performance,
due to its low sensitivity to environmental and impurity factors.
Additional value may come from the possible recovery of heavy metals as the
sorbed metal ions can be easily desorbed.
Lagenaria siceraria
The bottle gourd is one of humankind's first domesticated plants, providing food,
medicine and a wide variety of utensils and musical instruments.
Description
Vigorous annual herb. Stems prostrate or climbing, angular, ribbed, thick, brittle, softly
hairy, up to 5 m long, cut stems exude no sap. Leaves simple, up to 400 mm long and 400
19

mm broad, shortly and softly hairy, broadly egg-, kidney- or heart-shaped in outline,
undivided, angular or faintly 3-7-lobed, lobes rounded, margins shallowly toothed, crushed
leaves non-aromatic. Leaf stalks up to 300 mm long, thick, often hollow, densely hairy,
with two small, lateral glands inserted at the leaf base. Fruit large, variable, up to 800 x
200 mm, subglobose to cylindrical, flask-shaped or globose with a constriction above the
middle; fleshy, densely hairy to ultimately glabrous, indehiscent, green, maturing
yellowish or pale brown, pulp drying out completely on ripening, leaving a thick, hard,
hollow shell with almost nothing inside except the seeds. The fruit often is an indehiscent
berry (soft-shelled) or gourd (hard-shelled) with one to many, often flattened seeds. Seeds
many, embedded in a spongy pulp, 7-20 mm long, compressed, with two flat facial ridges,
in some variants rather irregular and rugose.
Distribution
It is generally accepted that lagenaria siceraria (previously known as lagenaria
vulgaris) is indigenous to Africa and that it reached temperate and tropical areas in Asia
and the Americas about 10 000 years ago, with human help or probably as a wild species
whose fruits had floated across the seas. Fruits are known to float in the sea for many
months without the seeds losing their viability. Independent domestications from wild
populations are believed to have occurred in both the Old and New Worlds. African and
American land races (subsp. siceraria) are morphologically distinct from Asian land races
(subsp. asiatica). It is uncertain if the seemingly spontaneous populations in Africa are truly
wild.
In southern Africa the calabash flowers mainly in April and May and fruits mainly
from April to July. In this region it grows from about 245-1 265 m above sea level, in areas
with a rainfall of about 400-600 mm annually. Heiser (1997) observed that the bottle gourd
flowers are pollinated at night by hawk-moths and other moth species; by day bumble bees,
cucumber beetles and other insects are active. In the Americas hummingbirds are also

20

attracted by the nectar that only the male flowers produce. He also observed that about 40
male and about 3 to 4 female flowers occur on a single plant.
According to Watt & Breyer-Brandwijk (1962), human poisoning has been reported
from eating the fruit, presumably of the bitter form. (As with other members of the
Cucurbitaceae, e.g. Cucumis africanus, some plants of L. siceraria produce bitter,
poisonous fruits and others non-bitter, edible fruits). Various medicinal uses of the leaves,
fruit and seeds have been recorded from various countries, e.g. as a pectoral, an
anthelmintic, a purgative and even as a headache remedy.
In rural southern Africa and elsewhere in developing countries, the calabash fruit is
still widely used for various kinds of household containers and utensils. Non-bitter types
are used to store water, milk and beer. These calabashes and products made from them are
commonly sold as ornaments at roadside stalls and curio markets.
The calabash can be grown from seed in frost-free areas. It prefers sandy or loamy
soil, some shade, good rainfall or enough water. It can be treated either as a prostrate
ground cover or as a climber, in which case the maturing fruit might need some support.
Adsorption models

Isotherm adsorption models have been used in waste stream treatment to predict the
ability of a certain adsorbent to remove a pollutant down to a specific discharge value.
When a mass of adsorbent and a waste stream are in contact for a sufficiently long time,
equilibrium between the amount of pollutant adsorbed and the amount remaining in
solution will develop. For any system under equilibrium conditions, the amount of material
adsorbed onto the media can be calculated using the mass balance of equation below:
=

21

where C0 and Ce (mg/L) are the initial and the final concentrations of adsorbates in flasks,
respectively, V is the volume of the solution (in Litres) and ms is the mass of dry adsorbent
used (in grammes).(Wang et al., 2010)
Adsorption isotherms are important criteria in optimizing the use of adsorbents as
they describe the nature of interaction between adsorbate and adsorbent. Thus, analysis of
experimentally obtained equilibrium data by either theoretical or empirical equations is
useful for practical design and operation of adsorption systems. The Langmuir and
Freundlich adsorption isotherms were applied to each metal under study.
Langmuir Isotherm
Langmuir equation relates the coverage of molecules on a solid surface to
concentration of a medium above the solid surface at a fixed temperature. This isotherm
based on three assumptions, namely adsorption is limited to monolayer coverage, all
surface sites are alike and only can accommodate one adsorbed atom and the ability of a
molecule to be adsorbed on a given site is independent of its neighbouring sites occupancy.
By applying these assumptions, and a kinetic principle (rate of adsorption and desorption
from the surface is equal), the Langmuir equation can be written in the following form:
=


1 +

Where:
Ce equilibrium concentration of metal ions in the liquid
Qe equilibrium concentration of metal ions in the solid phase
Qmax Langmuir constant for maximum metal uptake
b Langmuir sorption equilibrium constant
The above Langmuir equation is often written in the linear form as follows:

1
1
=
+


22

Qmax and b can be calculated from the slope and intercept of the linear plot, C e/qe versus
Ce. That is, Qmax = 1/slope and b = 1 / (intercept,Qmax).
Freundlich Isotherm
Freundlich isotherm is an empirical equation. This equation is one among the most
widely used isotherms for the description of adsorption equilibrium. Freundlich isotherm
is capable of describing the adsorption of organic and inorganic compounds on a wide
variety of adsorbents including biosorbent. This equation has the following form:
= 1/
Where:
Qe and Ce are the equilibrium concentrations of metal ions in the adsorbed and liquid
phases
Kf is the Freundlich constant characteristic of the system, indicating the capacity
n is the Freundlich constant characteristic of the system, indicating the adsorption
intensity
This equation can also be expressed in the linearized logarithmic form as follows:

= +

The plot of log Qe versus log Ce has a slope with the value of 1/n and an intercept magnitude
of log Kf. Thus, the Freundlich constants Kf and n can be calculated from the intercept and
slope of the linear plot of log qe versus log Ce. log Kf is equivalent to log Qe when Ce equals
unity. However, in other case when 1/n 1, the Kf value depends on the units upon which Qe
and Ce are expressed. On average, a favourable adsorption tends to have Freundlich
constant n between 1 and 10. Larger value of n (smaller value of 1/n) implies stronger
interaction between biosorbent and heavy metal while 1/n equal to 1 indicates linear
23

adsorption leading to identical adsorption energies for all sites. This isotherm attempts to
incorporate the role of substrate-substrate interactions on the surface. (Febrianto et al.,
2009; Reddy et al., 2010)

24

CHAPTER THREE
MATERIAL AND METHODS
MATERIALS
Lagenaria siceraria will be gotten from Ikot Ekpene, LGA, Akwa Ibom state or from
the Department of Crop Science, University of Uyo, Uyo, Akwa Ibom state. The produced
water will be gotten from a location field in the southern part of the country.
METHODS
Lagenaria siceraria dry shells will be collected in bulk, crushed and washed in cold
water to remove dust and dirt before drying them in an oven at 700C for 24 hours. The seed
and shell will be ground to powder using mortar and pestle. The grounded powder will be
sieved using a desired mesh size to aid in removal of larger particles and also to have a
certain diameter range. The powder gotten from the shell and the seed will be separated
and dried at room temperature in open air on a slab. A portion of the seed and shell will be
taken separately and slowly heated until it turns to charcoal over a Bunsen burner.
EQUIPMENTS
The following equipment will be used during the entire project:
a. pH meter
b. Atomic Adsorption Spectrophotometer
c. Acid and Alkaline solution
d. Oven
e. Water bath
f. Laboratory stirrer
g. Beaker
h. Whatman filter paper
EXPERIMENTS TO BE CONDUCTED

1. Determination of pH value
25

2. Effect of contact time


3. Effect of initial metal ion concentration
4. Effect of dosage
5. Effect of agitation
6. Adsorption isotherms
WORK PROGRAMME
S/N

Activities

Weeks

Material collection

Pre-treatment of material

2 to 3

Consultation with laboratory technologist

3 to 4

Laboratory experiments

5 to 9

Discussion of results

9 to 11

26

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