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determination-of-the-concentration-of-heavy-metals-in-water-sediment-and-fish-from-ufam-river (1)
determination-of-the-concentration-of-heavy-metals-in-water-sediment-and-fish-from-ufam-river (1)
determination-of-the-concentration-of-heavy-metals-in-water-sediment-and-fish-from-ufam-river (1)
1
ABSTRACT
The fish, sediments and water samples were collected from ozalla in nkaniu west, Enugu State
and analyzed using the standard analytical procedure. The physicochemical parameters were
determined such as pH, conductivity, total dissolved solids, total suspended solids, total solid,
dissolved oxygen, sulphate, nitrate, and chloride. The heavy metal concentration was determined
by using the AAS, and the results were compared with the standards prescribed by the WHO. The
results obtained in the physicochemical analysis revealed that water parameters were found
below limits except in dissolved oxygen which was above the WHO limit with a value of
87.56±13.90 and 67.90±13.90 in location 1 and 2 respectively. The metal ion concentration in
water sample (iron, Cr, Cu and Cd) where detected in the sample location 1. Same in location 2
except Cu which was found to be below detectable limit (0.00±0.011). In sediment sample, Cu
was also below detectable limit in location 2, Fe was found to have the highest concentration of
1.209±0.011 and 1.193±0.011 in location 1 and 2 respectively. Cd, Cu and Cr were observed in
the fish sample, Cu was also below detectable limit. The obtained results reveal that Ufam River
were polluted.
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TABLE OF CONTENT
Title Page i
Approval Page ii
Acknowledgment iii
Table of Content iv
Abstract x
CHAPTER ONE
1.1 Aim 3
1.2 Objectives 3
CHAPTER TWO
2.2 Cadmium 7
3
2.2.2 Chemical property of cadmium 8
2.3 Copper 11
2.4 Chromium 14
2.5 Iron 16
4
2.5.5 Health effect of iron in the body 18
2.6 pH of water 19
CHAPTER THREE
3.1 Equipment 24
3.3 Method 25
3.3.1 Determination of pH 26
5
3.3.10 Determination of heavy metal concentration 29
CHAPTER FOUR
4.0 Result 30
CHAPTER FIVE
5.0 Discussion 32
5.1 Conclusion 32
Reference 40
6
List of Table
7
List of Plate
8
CHAPTER ONE
1.0 Introduction
Over the last few decades, there has been growing interest in determining heavy metal levels in
the marine environment and attention was drawn to the measurement of contamination levels in
public food supplied, particularly fish (Kalay et al., 2019). Though heavy metal is a loosely
defined term, it is widely recognized and usually applied to the wide spread contaminants of
terrestrial and fresh water ecosystems. Some examples of heavy metal include lead, zinc,
cadmium, copper and manganese. Many of these heavy metals are toxic to organisms at low
concentration (Rose et al., 2019). The concentration of metals in bio-available form is not
necessarily proportional to the total concentration of the metal. The concentration of various
elements in the air, water and land may be increased beyond their natural level due to the
agricultural, domestic and industrial effluents (Collison and Shrimp, 2012). Metals and other
fluvial contaminants in suspension or solution, do simply flow down the stream, they form
complexes with other compounds settle to the bottom and ingested by plants and animals or
adsorbed to sediments (Schwarz, 2010). Consequently, aquatic organisms may acquire heavy
metals in body directly from the water via gills or food chain mechanisms (Tariq et al., 2013).
Heavy metals enter rivers and lakes from a variety of sources such as rock and soil directly
exposed to surface water, in addition to the discharge of treated and untreated liquid wastes into
water bodies. These harmful wastes and other dangerous industrial by-products constitute major
sources of environmental pollutants. Most industrial pollutants discharged into the environment
contain organic and inorganic pollutants in dissolved, suspended and insoluble forms (Grant and
Sheppard, 2008). Effluents discharged into the water bodies may affect fish and other aquatic
organisms, either directly or indirectly. Most rivers and freshwater streams are seriously polluted
9
by industrial waste water discharged from factories. A large amount of water used in industry
turns into wastewater that pollutes surface and groundwater, posing health hazards. Heavy metal
ions do not degrade into harmless end products and are toxic to humans and the surrounding
environment (Hirose and Tateno, 2010). Water and sediments are commonly used as indicators
for the state of pollution of aquatic ecosystem. Ufam river runs through the centre of the town
and the water from this stream serves domestic purposes as well as irrigation farming and aquatic
organisms (fish) from this water body is one the major sources of protein for the populace of this
location. However, the stream also serves as points of discharge for domestic wastes in some
areas along the length of the stream and runoffs from agricultural lands always flow into the
stream at different points. Aquatic animals (including fish) bio-accumulate heavy metals in
considerable amount in tissues over a long time and the dependence of the populace in this area
on this water body for domestic water supply and its aquatic organisms (fish) as source of protein
makes it imperative to assess the level of heavy metals in this aquatic ecosystem in view of the
The aim of the study was to determine the level of Cd, Cu, Cr and Fe in fish, sediments and
(i). To determine the level of (Cd, Cu, Cr and Fe) in Ufam River
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CHAPTER TWO
Heavy metals (HMs) are defined as those elements having an atomic number greater than 20 and
atomic density above 5 g cm− 3 and must exhibit the properties of metal (Galloway et al., 2010).
The HMs can be broadly classified into two categories: essential and nonessential heavy metals.
Essential HMs are those required by living organisms for carrying out the fundamental processes
like growth, metabolism, and development of different organs. There are numerous essential
heavy metals like Cu, Fe, Mn, Co, Zn, and Ni required by plants as they form cofactors that are
structurally and functionally vital for enzymes and other proteins (Collison and Shrimp, 2012).
Essential elements are often required in trace amounts in the level of 10–15 ppm and are known
as micronutrients. Nonessential heavy metals like Cd, Pb, Hg, Cr, and Al are not required by
Heavy metals can be hammered into thin sheets. Heavy metals are ductile. Heavy metals are a
good conductor of heat and electricity. Heavy metals are lustrous which means they have a shiny
appearance. Heavy metals have high tensile strength. Metals are sonorous. Heavy metals are hard
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2.1.2 Chemical property
The density of heavy metals is usually high. Heavy metals are malleable and ductile. Heavy
metals form an alloy with other metals or non metals. Some heavy metals react with air and
corrode. Heavy metals are good conductors of heat and electricity. Generally, heavy metals are
Heavy metal sources are magmatic, sedimentary, and metamorphic rocks, weathering and soil
formation, the rock cycle, the origin of heavy metals in surface and groundwater as well as in the
atmosphere, and anthropogenic sources stemming from human activities such as industrial
production and agriculture (Umar and Opaluwa, 2010). There are different sources for heavy
metals in the environment. These sources can be both of natural or anthropogenic origin. General
classification of sediments and sedimentary rocks, soil horizons that develop in a temperate
humid climate, layer structures of two-layer minerals, and heavy metals in water and
groundwater. Heavy metals are mainly introduced into groundwater by agricultural and industrial
activities, landfilling, mining, and transportation. There are various possibilities for the fate and
Some heavy metals are essential to human biological process, but depending upon their dosage
intake leads some unexpected hazardous effects on health and the physiological system.
According to (Hutton and Symon, 2016). Studies shows that despite of its beneficiary health
effects, heavy metals are acting as carcinogenic agents. Dissolved forms of these metals through
different forms as soil pollutants, water pollutant and air pollutant entering into food chain and
12
finally ending in humans, these are leading to severe damage to the cellular system and leading
to exposure towards cancer. According to the reports of the international agency for rearch on
cancer non-essential heavy metals (As, Cd, and CR) are major cancer causing agents
Heavy metal poisoning is caused by the accumulation of certain metals in the body due to
exposure through food, water, industrial chemicals, or other sources. While your body needs
small amounts of some heavy metals to function normally such as zinc, copper, chromium, iron,
and manganese toxic amounts are harmful. Some heavy metals such as lead, cadmium,
manganese, arsenic can enter the body through the gastrointestinal route; that is, through the
mouth when eating food, fruits, vegetables or drinking water or other beverages. Others can enter
the body by inhalation while others such as lead can be absorbed through the skin (Oluyemi et
al., 2008)
Environmental pollution of heavy metals is increasingly becoming a problem and has become of
great concern due to the adverse effects it is causing around the world. These inorganic
pollutants are being discarded in our waters, soils and into the atmosphere due to the rapidly
growing agriculture and metal industries, improper waste disposal, fertilizers and pesticides. This
review shows how pollutants enter the environment together with their fate (Kemdrin, 2017).
Some metals affect biological functions and growth, while other metals accumulate in one or
more different organs causing many serious diseases such as cancer. The pharmacokinetics and
toxicological processes in humans for each metal is described. In summary, the review shows the
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physiological and biochemical effects of each heavy metal bioaccumulation in humans and the
level of gravity and disquieting factor of the disease. The persistent pollutants such as heavy
metals can then enter the food chain through marine life such as fish which can then affect
predators such as bigger fish, birds and mammals, including humans, which migrate and
transport the pollutant to different ecosystems (Environmental Protection Agency EPA, 2016).
2.2 Cadmium Cd
Cadmium is a chemical element with the symbol Cd and atomic number 48. This soft, silvery-
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 the transition metals in groups 3 through 11. Cadmium and
its congeners in group 12 are often not 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
in zinc carbonate. 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 a corrosion-resistant plating on steel, and
cadmium compounds are used as red, orange and yellow pigments, to color 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 Directive) (Opaluwa and Umar, 2010)
and nickel-cadmium batteries have been replaced with nickel-metal hydride and lithium-
ion batteries. One of its few new uses is in cadmium telluride solar panels.
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2.2.1 Physical property of cadmium
Cadmium is a soft, malleable, ductile, silvery-white divalent metal. It is similar in many respects
to zinc but forms complex compounds. Unlike most other metals, cadmium is resistant
to corrosion and is used as a protective plate on other metals. As a bulk metal, cadmium
is insoluble in water and is not flammable; however, in its powdered form it may burn and
Although cadmium usually has an oxidation state of +2, it also exists in the +1 state. 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. Cadmium burns in air to
form brown amorphous cadmium oxide (CdO); the crystalline form of this compound is a dark
red which changes color when heated, similar to zinc oxide. Hydrochloric acid, sulfuric acid,
and nitric acid dissolve cadmium by forming cadmium chloride (CdCl2), cadmium
sulfate (CdSO4), or cadmium nitrate (Cd(NO3)2). The oxidation state +1 can be produced by
dissolving cadmium in a mixture of cadmium chloride and aluminium chloride, forming the
Cd22+ cation, which is similar to the Hg 22+ cation in mercury(I) chloride (Fthenakis et al., 2004).
Cadmium is a common impurity in zinc ores, and it is most often isolated during the production
of zinc. Some zinc ores concentrates from zinc sulfate ores contain up to 1.4% of cadmium. [34] In
the 1970s, the output of cadmium was 6.5 pounds per ton of zinc. Zinc sulfide ores are roasted in
the presence of oxygen, converting the zinc sulfide to the oxide. Zinc metal is produced either
15
by smelting the oxide with carbon or by electrolysis in sulfuric acid. Cadmium is isolated from
the zinc metal by vacuum distillation if the zinc is smelted, or cadmium sulfate
Cadmium has no known function in higher organisms and is considered toxic. Cadmium is
considered an environmental pollutant that causes health hazard to living organismsn (Grant and
Sheppard, 2008). Administration of cadmium to cells causes oxidative stress and increases the
levels of antioxidants produced by cells to protect against macro molecular damage. However a
cadmium-dependent carbonic anhydrase has been found in some marine diatoms. The diatoms
live in environments with very low zinc concentrations and cadmium performs the function
normally carried out by zinc in other anhydrases. This was discovered with X-ray absorption
near edge structure (XANES) spectroscopy. Cadmium is preferentially absorbed in the kidneys
and adolescence. Cadmium is under research regarding its toxicity in humans, potentially
elevating risks of cancer, cardiovascular disease, and osteoporosis (Jiao et al., 2018).
Cadmium taken up from lung and gastrointestinal tract is transported via blood to liver and
kidney. On long-term exposure to cadmium, renal tubular dysfunction develops in humans and
experimental animals. Data from animal experiments demonstrate that initially after exposure
cadmium in blood is bound to albumin and proteins with higher molecular weight. Such
cadmium is mainly taken up in liver. For a few days after exposure cadmium exists as
metallothionein in plasma and blood cells (Hem and John, 2012). After both single and long-
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term administration of cadmium bound to metallothionein, cadmium is taken up by the kidney.
renal clearance. Cadmium from metallothionein is taken up in renal tubules by pinocytosis and
rebinding are continuous and prevent excretion of cadmium. Because of differences in transport,
renal metabolic handling forms of cadmium are also different for different forms of cadmium
intravenously is almost immediately and completely taken up in the renal tubule. Under such
conditions, resynthesis and rebinding processes are insufficient to sequester cadmium from
sensitive tissue receptors, and renal damage occurs at total tissue concentrations much lower than
when renal cadmium concentrations rise slowly (Rickett and Payer, 2015). This explains the
wide range (10-200 micrograms Cd/g wet weight) of cadmium in the renal cortex that associated
2.3 Copper
Copper is a chemical element with the symbol Cu 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 pinkish-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. Copper is one of the few metals that
can occur in nature in a directly usable metallic form (native metals). This led to very early
human use in several regions, from c. 8000 BC. Thousands of years later, it was the first metal to
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be smelted from sulfide ores, c. 5000 BC; the first metal to be cast into a shape in a mold, c.
4000 BC; and the first metal to be purposely alloyed with another metal, tin, to create bronze, c.
Copper, silver, and gold are in group 11 of the periodic table; these three metals have one s-
orbital electron on top of a filled d-electron shell and are characterized by high ductility, and
electrical and thermal conductivity. The filled d-shells in these elements contribute little to
interatomic interactions, which are dominated by the s-electrons through metallic bonds. Unlike
metals with incomplete d-shells, metallic bonds in copper are lacking a covalent character and
are relatively weak. This observation explains the low hardness and high ductility of single
crystals of copper (Romano et al., 2007). At the macroscopic scale, introduction of extended
defects to the crystal lattice, such as grain boundaries, hinders flow of the material under applied
stress, thereby increasing its hardness. For this reason, copper is usually supplied in a fine
grained polycrystalline form, which has greater strength than monocrystalline forms. The
softness of copper partly explains its high electrical conductivity (59.6×10 6 S/m) and high
thermal conductivity, second highest (second only to silver) among pure metals at room
temperature. This is because the resistivity to electron transport in metals at room temperature
originates primarily from scattering of electrons on thermal vibrations of the lattice, which are
relatively weak in a soft metal (Schwarz, 2010). The maximum permissible current density of
copper in open air is approximately 3.1×106 A/m2 of cross-sectional area, above which it begins
to heat excessively.
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2.3.2 Chemical properties
Copper does not react with water, but it does slowly react with atmospheric oxygen to form a
layer of brown-black copper oxide which, unlike the rust that forms on iron in moist air, protects
the underlying metal from further corrosion (passivation) ((Lu et al., 2016). A green layer
of verdigris (copper carbonate) can often be seen on old copper structures, such as the roofing of
many older buildings and the Statue of Liberty. Copper tarnishes when exposed to
some sulfur compounds, with which it reacts to form various copper sulfides (Wallwork, 2016).
Copper forms coordination complexes with ligands. In aqueous solution, copper(II) exists
as [Cu(H2O)6]2+. This complex exhibits the fastest water exchange rate (speed of water ligands
attaching and detaching) for any transition metal aquo complex. Adding aqueous sodium
hydroxide causes the precipitation of light blue solid copper (II) hydroxide. A simplified
Most copper is mined or extracted as copper sulfides from large open pit mines in porphyry
copper deposits that contain 0.4 to 1.0% copper. Copper can also be recovered through the in-situ
leach process (Birck et al., 2009). An alternative source of copper for collection currently being
researched are polymetallic nodules, which are located at the depths of the Pacific
Ocean approximately 3000–6500 meters below sea level (Frei et al., 2009). These nodules
Gram quantities of various copper salts have been taken in suicide attempts and produced acute
copper toxicity in humans, possibly due to redox cycling and the generation of reactive oxygen
19
species that damage DNA (Kotaś and Stasicka, 2000). Chronic copper toxicity does not normally
occur in humans because of transport systems that regulate absorption and excretion. Autosomal
recessive mutations in copper transport proteins can disable these systems, leading to Wilson's
disease with copper accumulation and cirrhosis of the liver in persons who have inherited two
defective genes. Elevated copper levels have also been linked to worsening symptoms
Copper is absorbed in the gut, then transported to the liver bound to albumin. After processing in
the liver, copper is distributed to other tissues in a second phase, which involves the
protein ceruloplasmin, carrying the majority of copper in blood. Ceruloplasmin also carries the
copper that is excreted in milk, and is particularly well-absorbed as a copper source (Lu et al.,
2016). Copper in the body normally undergoes enterohepatic circulation (about 5 mg a day, vs.
about 1 mg per day absorbed in the diet and excreted from the body), and the body is able to
excrete some excess copper, if needed, via bile, which carries some copper out of the liver that is
2.4 Chromium
Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first
element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal. Chromium is
the main additive in stainless steel, to which it adds anti-corrosive properties. Chromium is also
highly valued as a metal that is able to be highly polished while resisting tarnishing. Polished
chromium reflects almost 70% of the visible spectrum, and almost 90% of infrared light (Hirose
and Tateno, 2010). Chromium metal is valued for its high corrosion resistance and hardness. A
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major development in steel production was the discovery that steel could be made highly
resistant to corrosion and discoloration by adding metallic chromium to form stainless steel
Chromium is extremely hard, and is the third hardest element behind carbon (diamond)
and boron. Its Mohs hardness is 8.5, which means that it can scratch samples of quartz and topaz,
but can be scratched by corundum. Chromium is highly resistant to tarnishing, which makes it
useful as a metal that preserves its outermost layer from corroding, unlike other metals such
as copper, magnesium, and aluminium (Stixrude et al., 2007). Chromium has a melting point of
1907 °C (3465 °F), which is relatively low compared to the majority of transition metals.
However, it still has the second highest melting point out of all the Period 4 elements, being
topped by vanadium by 3 °C (5 °F) at 1910 °C (3470 °F). The boiling point of 2671 °C
(4840 °F), however, is comparatively lower, having the third lowest boiling point out of
the Period 4 transition metals alone behind manganese and zinc (Boehler and Reinhard, 2000).
high specular reflection in comparison to other transition metals. In infrared, at 425 μm,
chromium has a maximum reflectance of about 72%, reducing to a minimum of 62% at 750 μm
Chromium metal left standing in air is passivated - it forms a thin, protective, surface layer of
oxide. This layer has a spinel structure a few atomic layers thick; it is very dense and inhibits the
diffusion of oxygen into the underlying metal. In contrast, iron forms a more porous oxide
21
through which oxygen can migrate, causing continued rusting (Galloway et al., 2010).
Passivation can be enhanced by short contact with oxidizing acids like nitric acid. Passivated
chromium is stable against acids. Passivation can be removed with a strong reducing agent that
destroys the protective oxide layer on the metal. Chromium metal treated in this way readily
dissolves in weak acids. Chromium, unlike iron and nickel, does not suffer from hydrogen
embrittlement. However, it does suffer from nitrogen embrittlement, reacting with nitrogen from
air and forming brittle nitrides at the high temperatures necessary to work the metal parts (Pate et
al., 2011). Chromium(VI) compounds are oxidants at low or neutral pH. Chromate anions
(CrO2−4) and dichromate (Cr2O72−) anions are the principal ions at this oxidation state. They exist
The two main products of chromium ore refining are ferrochromium and metallic chromium. For
those products the ore smelter process differs considerably. For the production of
ferrochromium, the chromite ore (FeCr2O4) is reduced in large scale in electric arc furnace or in
2004). For the production of pure chromium, the iron must be separated from the chromium in a
two step roasting and leaching process. The chromite ore is heated with a mixture of calcium
carbonate and sodium carbonate in the presence of air. The chromium is oxidized to the
hexavalent form, while the iron forms the stable Fe 2O3. The subsequent leaching at higher
elevated temperatures dissolves the chromates and leaves the insoluble iron oxide. The chromate
is converted by sulfuric acid into the dichromate (Ram and Bernath, 2003).
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2.4.4 Health effect of chromium
The biologically beneficial effects of chromium (III) are debated. Chromium is accepted by the
U.S. National Institutes of Health as a trace element for its roles in the action of insulin, a
hormone that mediates the metabolism and storage of carbohydrate, fat, and protein. The
mechanism of its actions in the body, however, have not been defined, leaving in question the
and mutagenic. Ingestion of chromium(VI) in water has been linked to stomach tumors, and it
may also cause allergic contact dermatitis (ACD) (Opaluwa and Umar, 2010). "Chromium
deficiency", involving a lack of Cr(III) in the body, or perhaps some complex of it, such
as glucose tolerance factor, is controversial. Some studies suggest that the biologically active
form of chromium (III) is transported in the body via an oligopeptide called low-molecular-
weight chromium-binding substance (LMWCr), which might play a role in the insulin signaling
pathway. The chromium content of common foods is generally low (1-13 micrograms per
serving). The chromium content of food varies widely, due to differences in soil mineral content,
growing season, plant cultivar, and contamination during processing. Chromium (and nickel)
leach into food cooked in stainless steel, with the effect being largest when the cookware is new.
Acidic foods that are cooked for many hours also exacerbate this effect (Ibok et al., 2009).
Water-insoluble chromium(III) compounds and chromium metal are not considered a health
hazard, while the toxicity and carcinogenic properties nhof chromium(VI) have been known for a
long time (Pate et al., 2011). Because of the specific transport mechanisms, only limited amounts
of chromium(III) enter the cells. Acute oral toxicity ranges between 50 and 150 mg/kg.[135] A
2008 review suggested that moderate uptake of chromium(III) through dietary supplements
23
poses no genetic-toxic risk. In the US, the Occupational Safety and Health
Administration (OSHA) has designated an air permissible exposure limit (PEL) in the workplace
as a time-weighted average (TWA) of 1 mg/m3. The National Institute for Occupational Safety
and Health (NIOSH) has set a recommended exposure limit (REL) of 0.5 mg/m3, time-weighted
average. The IDLH (immediately dangerous to life and health) value is 250 mg/m3 (Hutton and
Symon, 2016).
2.5 Iron
Iron is a chemical element with symbol Fe and atomic number 26. It is a metal that belongs to
the first transition series and group 8 of the periodic table. It is, by mass, the most common
element on Earth, right in front of oxygen (32.1% and 30.1%, respectively), forming much of
Earth's outer and inner core. It is the fourth most common element in the Earth's crust. In
the modern world, iron alloys, such as steel, stainless steel, cast iron and special steels are by far
the most common industrial metals, because of their mechanical properties and low cost.
The iron and steel industry is thus very important economically. However, iron reacts readily
with oxygen and water to give brown to black hydrated iron oxides, commonly known as rust.
Unlike the oxides of some other metals, that form passivating layers, rust occupies more volume
than the metal and thus flakes off, exposing fresh surfaces for corrosion. Although iron readily
reacts, high purity iron, called electrolytic iron, has better corrosion resistance (Grant and
Sheppard, 2008).
The physical properties of iron at very high pressures and temperatures have also been studied
extensively, because of their relevance to theories about the cores of the Earth and other planets
(Romano et al., 2007). Iron, like other metals, conducts heat and electricity, has a luster, and
24
forms positive ions in its chemical reactions. Pure iron is fairly soft and can easily be shaped and
formed when hot. Its color is silvery white. Iron is easily magnetized. When combined with
Important iron compounds are of two types ferrous, in which the iron ions that form the
compound have a valence (a measurement of combining power) of +2, and ferric, in which the
ions have a valence of +3. The element has four stable isotopes, or forms. The crystal structure
and magnetism of iron undergo changes when it is heated. If an iron magnet is heated red hot, it
loses its magnetism but regains it when it is cooled (Wallwork, 2016). In the presence of
moisture, iron rusts quickly because it combines easily with oxygen in the air. Iron can be
protected against rusting by coating it with a phosphate solution. Coating iron with zinc to make
galvanized iron also prevents rusting. The melting and boiling points of iron, along with
its enthalpy of atomization, are lower than those of the earlier 3d elements
from scandium to chromium, showing the lessened contribution of the 3d electrons to metallic
bonding as they are attracted more and more into the inert core by the nucleus; however, they are
higher than the values for the previous element manganese because that element has a half-filled
3d sub-shell and consequently its d-electrons are not easily delocalized (Stixrude et al., 2007).
The binary ferrous and ferric halides are well-known. The ferrous halides typically arise from
treating iron metal with the corresponding hydrohalic acid to give the corresponding hydrated
Prehistoric societies used laterite as a source of iron ore. Historically, much of the iron ore
utilized by industrialized societies has been mined from predominantly hematite deposits with
25
grades of around 70% Fe. These deposits are commonly referred to as "direct shipping ores" or
Iron is required for life. The iron–sulfur clusters are pervasive and include nitrogenase, the
transport, storage and used of oxygen. Iron proteins are involved in electron transfer. Examples
valent iron), and catalase. The average adult human contains about 0.005% body weight of iron,
or about four grams, of which three quarters is in hemoglobin a level that remains constant
despite only about one milligram of iron being absorbed each day, because the human body
recycles its hemoglobin for the iron content (Birck et al., 2009).
Iron uptake is tightly regulated by the human body, which has no regulated physiological means
of excreting iron. Only small amounts of iron are lost daily due to mucosal and skin epithelial
cell sloughing, so control of iron levels is primarily accomplished by regulating uptake (Jiao et
al., 2018). Regulation of iron uptake is impaired in some people as a result of a genetic
defect that maps to the HLA-H gene region on chromosome 6 and leads to abnormally low levels
of hepcidin, a key regulator of the entry of iron into the circulatory system in mammals. In these
people, excessive iron intake can result in iron overload disorders, known medically
as hemochromatosis (Rickett and Payer, 2015). Overdoses of ingested iron can cause excessive
levels of free iron in the blood. High blood levels of free ferrous iron react with peroxides to
produce highly reactive free radicals that can damage DNA, proteins, lipids, and other cellular
26
components. Iron toxicity occurs when the cell contains free iron, which generally occurs when
iron levels exceed the availability of transferrin to bind the iron. Damage to the cells of
the gastrointestinal tract can also prevent them from regulating iron absorption, leading to further
increases in blood levels. Iron typically damages cells in the heart, liver and elsewhere, causing
adverse effects that include coma, metabolic acidosis, shock, liver failure, coagulopathy, adult
respiratory distress syndrome, long-term organ damage, and even death (Okazawad et al., 2014).
Water pollution occurs when harmful substances often chemicals or microorganisms contaminate
a stream, river, lake, ocean, aquifer, or other body of water, degrading water quality and
climate change, and expansion of urban areas produce a variety of water pollutants. In this work,
we discuss some of the most recent and relevant findings related to the release of heavy metals,
the possible risks for the environment and human health, the materials and technologies available
for their removal. Anthropogenic activities are identified as the main source of the increasing
amounts of heavy metals found in aquatic environments. Some of the health hazards derived
from repeated exposure to traces of heavy metals, including lead, cadmium, mercury, and
arsenic, are outlined. We also give some perspectives about several techniques used to detect
heavy metals, as well as about the factors that could affect the contaminant removal. The
advantages and drawbacks of conventional and non-conventional heavy metal removal methods
are critically discussed, given particular attention to those related to adsorption, nanostructured
materials and plant-mediated remediation. Some of the commercial products currently used to
eliminate heavy metals from water are also listed (Kotaś and Stasicka, 2000). Finally, we point
27
out some the requirements and opportunities linked to developing efficient methods for heavy
The release of substances into subsurface groundwater or into lakes, streams, rivers, estuaries,
and oceans to the point where the substances interfere with beneficial use of the water or with the
natural functioning of ecosystems (Romano et al., 2007). In addition to the release of substances,
such as chemicals or microorganisms, water pollution may also include the release of energy, in
the form of radioactivity or heat, into bodies of water. Water bodies can be polluted by a wide
waste, plant nutrients, toxic chemicals, sediments, heat, petroleum (oil), and radioactive
substances (Pate et al., 2011). Several types of water pollutants are considered below. (For a
discussion of the handling of sewage and other forms of waste produced by human activities
However, the predominant source resulting in measurable human exposure to heavy metals is the
consumption of contaminated drinking water and the resulting health issues may include
cardiovascular disorders, neuronal damage, renal injuries, and risk of cancer and diabetes. ven in
the current era of growing technology, the concentration of heavy metals present in drinking
water is still not within the recommended limits as set by the regulatory authorities in different
countries of the world (Ayejuyo et al., 2013). Drinking water contaminated with heavy metals
namely; arsenic, cadmium, nickel, mercury, chromium, zinc, and lead is becoming a major
health concern for public and health care professionals. Occupational exposure to heavy metals is
28
known to occur by the utilization of these metals in various industrial processes and/or contents
including color pigments and alloys. However, the predominant source resulting in measurable
human exposure to heavy metals is the consumption of contaminated drinking water and the
resulting health issues may include cardiovascular disorders, neuronal damage, renal injuries,
and risk of cancer and diabetes. The general mechanism involved in heavy metal-induced
toxicity is recognized to be the production of reactive oxygen species resulting oxidative damage
and health related adverse effects. Thus utilization of heavy metal-contaminated water is
resulting in high morbidity and mortality rates all over the world (Collison and Shrimp, 2012).
Thereby, feeling the need to raise the concerns about contribution of different heavy metals in
various health related issues, this article has discussed the global contamination of drinking water
with heavy metals to assess the health hazards associated with consumption of heavy metal-
2.7.1 Bioaccumulation
Bioaccumulation is the process of the building of chemicals in an organism that take place if the
rate rate of intake exceeds the rate of excretion (Kemdrin, 2017). Chemicals are introduced to the
organism through exposure to the abiotic environment or as dietary intake (Okazawad et al.,
2014). Bioaccumulation also refers to how pollutants enters the food chain and relates to the
2.7.2 Biomagnifications
the food chain. As contaminated smaller organisms are consumed, chemicals are accumulated
29
and magnified in the tissue and organs of larger animals. Animals at the top of food chain
2.7.3 Bioconcentration
Bioconcentration is the concentration of a chemical that is higher within the organism composed
from passage from one phase into another phase (Okazawad et al., 2014).
2.8.1Bioconcentration factor
This is ratio of equilibrium concentrations of specific chemical between two phases. It is also
define as the uptake of contaminants from the dissolved phase, it can be calculated by the
following equation:
BCF=C/Cw
calculation of BCF is that of equilibrium between the contaminant and organisms with growth
rate, but difficult for fish is as its large (Ibok et al., 2009).
Biomgnification factor have several ways for calculation. A method where the TLS are directly
taken into accounts in the calculation is the method used by () who calculates the trophic
30
magnification factors as the antilog of the empirical slope m from the log. Linear regression
between the concentration in brota and TLS for which specifically 15N, measurement are used
BMF= CB
CD ,
(Kemdrin, 2017)
This is important in toxicology because it provides data regarding the amount of pollutants in an
area and can give clues of distruption to pollution and ecological communities (Oluyemi et al.,
2008)
The ufam river is found in the Enugu State of Nigeria. The River originates from a town called
ozalla and flows through several others across the state. The river, which crisscrossed five
source of potable water for the communities. Although it is less than 10 minutes drive from
Enugu town, it has neither seen nor had pipe-borne water.It has an average depth and width
of 0.2m and 1.9m respectively. The river is about more than 15km long. The ufam river is a river
of outstanding beauty. It is one of the best River in Enugu state. It is home to a great biodiversity
of plants and animals. The river provides ecosystem services such as flood control, climate
change regulation, recreation, spiritual homage, water supply, food, research and education,
medicine, building materials etc to many communities through which it passes. However, the
ability of Ufam River to continue to provide these ecosystem services to man and other living
31
climate change driven by poverty, ignorance and corruption. . Its center of attraction is the
32
Plate 2: Location 2 of Ufam River
33
2.9.1 Description of sample collection area
The ufam river is covered by vegetations. The vegetation cover here includes Dryopteris spp. and
Bambusa vulgaris. The River currently acts as host to numerous tourist sites and is expected to
help with irrigation of the more than 10,000 hectares of land sited at nearby for the
community/town cassava bread and high quality Cassava Flour Development Initiative for a
34
CHAPTER THREE
3.1 Equipment
x. Refrigerator (Thermacool)
xi. Beakers
The chemical and reagents used in this study with their manufacturers in parenthesis are:
35
v. Colbalt standard solution (BDH, England)
3.3 Methology
Water and sediment samples was collected from the sampling location submerged at about 0.5m
below the water surface and was filtered in a pre cleared liter of bottle and kept for analysis.
Then the sediment was collected in a polythene bag while wearing protective gloves and was
The fish sample were collected using cast nets which were thrown by the fisherman and
withdrawn by the means of line attached to its opening. When it was caught, ity was washed,
36
3.4 Water parameters
3.4.1 Determination of pH
pH was measured by Electrometric Method using Laboratory pH Meter Hanna model H1991300
(APHA, 1998).The pH electrode was rinsed with distilled water and blotted dry.The pH
electrode was then rinsed in a small beaker with a portion of the sample.Sufficient amount of the
sample was poured into a small beaker to allow the tip of the pH electrode to be immersed to a
depth of about 2cm. The pH electrode was at least 1cm away from the sides and bottom of the
beaker.The temperature adjustment dial was adjusted accordingly.The pH meter was turned on
3.4.2 Conductivity
Conductivity is measured with a probe and a meter. Voltage is applied between two electrodes in
a probe immersed in the sample water. The drop in the voltage caused by the resistance of the
water is used to calculate the conductivity per centimeter. The meter converts the probe
measurement to microsiemens per centimeter and displays the result (APHA, 1998).
Total dissolved solids was determined by conventional method using filter paper and weighing
scale (SMARTLIST, 2020).The evapourating dish was weighed on an analytical balance. The
evapourating dish was completely dry and free from extraneous particulate matter and reading
was recorded in mg.The water sample was poured into a sterilized beaker and vigorously stirred
to ensure that particulate matters, if any, was distributed evenly.A volume of50ml of the sample
was collected using the pipette. The liquid was continuously stirred while the sample was
37
collected to ensure particulate matter did not settle at the bottom of the beaker.The sample was
poured through the filter paper into another beaker. The procedure was repeated at least three
times to ensure the collection of the entire particulate matter in the filter paper.The filtrate was
transferred from the beaker into the weighed evapourating dish and was allowed to dry using a
hot air oven at temperature 104 OC. To prevent splattering the oven temperature was initially
lowered to 0OC and was gradually raised to 104OC for one hour.The dried evapourating dish was
weighed along with the filtrate and reading was recorded in mg.
(Weight of evapourating dish and the filtrate - Weight of evapourating dish alone
Total Dissolved Solids(TDS) =
(ml of water sample)
500ml of the water sample was collected using a measuring cylinder and was added into a 500ml
beaker. 1g of potassium iodide was added into the beaker and was dissolved by agitating the
content of the beaker. 5ml of sulfuric acid (Sulfuric acid : Water = 1:5) was added. It was titrated
0.01mol/L-sodium thiosulfate solution until the end point (ml) F : Factor of 0.01mol/L-sodium
3.4.5 Sulphate
The sulphate was determined by the methods described by American public health association
(APHA, 1998). In the spectrophotometric method sulphate is measured by the addition of barium
38
chloranilate, which reacts with sulphate ions to librate chloralinic acid. Sulphate concentration is
3.4.6 Nitrate
The nitrate was determined by the methods described by American public health association
(APHA, 1998). The nitrate in the water and samples were determined using a nitrate electrode
(used with a meter) which is similar in function to a dissolved oxygen meter. It was made of a
probe with a sensor that measured the nitrate activity in the water, the activity affected the
electric potential of the solution in the probe. The change was then transmitted to the meter,
which converted the electric signal to a scale that was read in millivolts. The millivolts was then
The stopper was carefully removed from the sample bottle and 1cm 3 manganese sulphate
solution followed by 1cm3 of alkaline– iodide– azide solution was added consecutively into the
sample bottle. The tip of the pipettes was placed below the surface of the liquid to introduce
various reagents into the full bottle of the sample. The stopper was replaced carefully after each
addition to avoid the inclusion of air bubbles. The content was thoroughly mixed by inversion
and rotation until clear supernatant water is obtained. 1cm 3 of concentrated sulphuric acid was
added with the tip of the pipette below the level of the solution and again, replaced with the
stopper. The solution was mixed well by rotation until the precipitation was completely
dissolved. 100cm3 of the sample was pipette into a 250cm3 conical flask and was immediately
titrated against standard sodium thiosulphate (0.0125 mol dm 3) using freshly prepared starch
39
solution as the indicator which was added when the solution became pale yellow. The titration
Heavy metal concentration was determined by Atomic Absorption Spectroscopy using Varian
AA240 Atomic Absorption Spectrophotometer (APHA, 1995).The water sample was placed on a
bench. The atomic absorption spectrophotometer was switched on and set to required wavelength
which was determined by the heavy metal being assayed.The appropriate lamp which was
determined by the heavy metal was in the appropriate place in the machine.A tube from the
machine was inserted into the water sample on the bench and water sample was aspirated into the
instrument through the tube.The machine was then set to take the absorbance as well as the
concentration which was displayed on the screen at the front of the machine. Concentration of
Data obtained were presented as mean ± standard deviation (SD). The result of were analysed
using one way analysis of variance ANOVA) using statistical products and service solution
(SPSS) and where a significant (p< 0.05) difference was obtained, turkey (multiple comparison
40
CHAPTER FOUR
4.0 Result
The pH was slightly alkaline and are within the who standard limit. The conductivity, total
dissolved solid (TDS), chloride, sulphate and nitrate were detected in the samples at a low varied
concentration and are also within the WHO standard limit. Dissolved oxygen (DO) was detected
41
4.2 Concentration of Cadmium (Cd), Copper (Cu), Chromium (Cr) and Iron (Fe) in the
water samples.
All the heavy metals were detected in all the locations except Cu and Fe were not detected in
location 2.
Table 4.2- For Concentration in Cadmium (Cd), Copper (Cu), Chromium (Cr) and Iron
42
4.3 Concentration in Cadmium (Cd), Copper (Cu), Chromium (Cr) and Iron (Fe) in
sediment sample.
In the (Table 4.3) All the heavy metals in study were detected in sediment sample of Ufam
River. Fe was found to have the highest concentration in both location with a value of
Table 4.3- For Concentration in Cadmium (Cd), Copper (Cu), Chromium (Cr) and Iron
43
4.4 Concentration in Cadmium (Cd), Copper (Cu), Chromium (Cr) and Iron (Fe) in fish
sample.
In the (Table 4.4) All the heavy metals under review were detected in fish sample of Ufam River
Table 4.4- For Concentration in Cadmium (Cd), Copper (Cu), Chromium (Cr) and Iron
Metals
Cd 0.016±0.00
Cu 0.00±0.00
Cr 0.090±0.00
Fe 0.018±0.00
44
CHAPTER FIVE
5.1 Discussion
Water quality parameters such as total dissolved solid, conductivity and pH are usually evaluated
in water because of their health related consequences (Doisy et al., 2006). The results of water
quality parameters are as in Tables 4.1. Extreme pH in water is not usually healthy for
consumption especially when the acidity is high (Streeten et al., 2004). Water with an elevated
pH above 11 can cause skin, eye and mucous membrane irritation (Singh et al., 2009). On the
opposite end of the scale, pH values below 4 also cause irritation due to the corrosive effects of
low pH levels (Freiberg et al., 2009). World health organization warns that extreme pH levels
can worsen existing skin conditions (WHO, 2009). pH for water lies between 6.5 and 8.5 (WHO,
2005). Results from this study showed the pH of the location 1 and 2 of the water sample to be
slightly (acidic) with location 1 showing a value of 6.47±0.11 while the location 2 gives value of
6.32±0.11 and are within the WHO acceptable limit (Table 4.1). However, the result indicates
that the water in Ufam river is acidic in nature (Chen et al., 2007), but it is not of a major health
concern because the acid concentration (acidity) is low. However, minimum level of treatment is
required to increase the pH to a fairly neutral and acceptable range. In location 1 water sample
there is a low concentration in conductivity, total dissolved solids (TDS), chloride and sulphate
than in the location 2 that gives higher variable values of 74.89±12.96, 15.67±2.04, 92.70±2.26
and 119.43±9.12 respectively and did not exceed the WHO acceptable limits. Nitrate and
dissolved oxygen was found to have a higher concentration in upstream water sample with a
45
value of 9.56±0.83 and 87.5613.90 respectively, however dissolved oxygen exceeded the WHO
Heavy metal refers to any metallic chemical element that has a relatively high density and
is toxic or poisonous at low concentrations (Danyal et al., 2006). Heavy metals are dangerous
because they tend to bio-accumulate in living organism over time without been eliminated
(Wallace et al., 2015). Heavy metal toxicity can result to damaged or reduced mental and central
nervous function, lower energy levels, blood composition and damage of the lungs, kidneys,
liver, and other vital organs (Godt et al., 2006). Allergies are not uncommon and repeated long-
term contact with some metals or their compounds may even cause cancer (Rubio et al., 2006).
In this study, cadmium (Cd), copper (Cu), Chromium (Cr) and Iron (Fe) were detectable with
0.048±0.018 and 0.010±0.007mg/L respectively while Cu and Fe were not detected in location 2
(Table 4.2). The location 1 and 2 of sediment sample has a varied concentration of Cd), copper
(Cu), Chromium (Cr) and Iron (Fe), however Fe was detected in a very high concentration in
both samples with a given value of 1.209±0.011mg/L for location 1 and 1.193±0.011mg/L for
location 2. In fish sample Cu was below detectable limit while Cd, Cr and Fe have a
The results indicated that most of the parameters and heavy metals fell within the tolerable and
permissible levels recommended. From the results obtained on heavy metals, it was discernible
that the samples do not contain high concentration of heavy metals except in water sediment
46
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