CHAPTER ONE

1.0 INTRODUCTION

Improper management of solid waste areas has resulted in serious ecological,

environmental health problems and biocorrosion of metal such as mild steel,
iron and copper. Such practices contribute to widespread of environmental
pollution as well as spread of diseases (Susu and salami, 2011). Solid waste
disposal methods are a major public concern. Majority of the municipal solid
waste disposal sites in Nigeria are still open dumps. Solid waste disposal by
landfill poses a threat to many metals such as mild steel quality through the
formation of polluting liquids known as leachate (Mohd, et al 2011). Leachate
generally comes into existence during dissolution in the in the landfill. The
environments can be polluted by the Leachate, which occurs at the end of
decayed solid waste, mixed with precipitates of surface water. As a result,
surface water collection system (rivers, creeks, lakes) subsurface collection
system (groundwater reservoirs), metal (such as mild steel and iron) and solid
system (different soil layers) have been seriously polluted by this Leachate.

The activities of micro-organisms in corrosion process have been studied by

many scholars. Many micro-organisms are known to cause the corrosion of
metals associated with aquatic or terrestrial environments.(Krougman and
Ijsscling,1976) . The bio element of steel exposed to pathogenic solution (such
as leachate and flowing sea water) are severely attacked by various
aerobic,facultative and anaerobic species together with aggressive chemical
species such as sulphur and chlorine.(Obuekwe et al ,1983).

Landfills are one of the sources of groundwater and soil pollution due to the
production of Leachate and transportation of the contamination to farther points
in the ecosystem (susu and salami, 2011). The contaminations of soil, water and
air with heavy metals even at low concentrations are known to have potential

1
impact on material of construction quality and human health. These also pose a
long-term risk to groundwater and ecosystem in general (Hunachew and sandip,
2011). Leachate is any liquid that is passing through matter, extracts solutes,
suspended solids or any other component of the material through which it has
passed .Leachate is a widely used term in the environmental sciences where it
has the specific meaning of a liquid that has dissolved or entrained
environmentally harmful substances which may then enter the environment. It is
most commonly used in the context of land-filling of putrescible or industrial
waste. In the narrow environmental context, leachate is therefore any liquid
material that drains from land or stockpiled material and contains significantly
elevated concentrations of undesirable material derived from the material that it
has passed through a porous media. Leachate from a land fill varies widely in
composition depending on the age of the landfill and the type of waste that it
contains.( Henry and Heinke, 1996) .It can usually contain both dissolved and
suspended material. The generation of leachate is caused principally by
precipitation percolating through waste deposited in a landfill. Once in contact
with decomposing solid waste, the percolating water becomes contaminated and
if it then flows out of the waste material it is termed leachate. (Christensen and
Cossu,1992). Additional leachate volume is produced during this decomposition
of carbonaceous material producing a wide range of other materials including
methane,carbon dioxide and a complex mixture of organic acids, aldehydes
,alcohols and simple sugars. The risks of leachate generation can be mitigated
by properly designed and engineered landfill sites, such as sites that are
constructed on geologically impermeable materials or sites that use
impermeable liners made of geomembranes or engineered clay. The use of
linings is now mandatory within both the United States and the European Union
except where the waste is deemed inert. In addition, most toxic and difficult
materials are now specifically excluded from land filling. However despite
much stricter statutory controls leachate from modern sites are found to contain

2
a range of contaminants that may either be associated with some level of illegal
activity or may reflect the ubiquitous use of a range of difficult materials in
household and domestic products which enter the waste stream legally.
Leachate poses an interesting threat to many metals as a result of biogenic
bacterial present in it .Micro-organism such as bacteria primarily result in
microbiologically induced corrosion since they produce sulphuric acid and
hydrogen gas which are potential threat for mild steel near such environment.
Microbial corrosion of metal surface cause severe change in the ions
concentration, pH, conductivities, and dissolved oxygen altering the passive or
active behaviour of the metallic substratum and its corrosion products as well
the electrochemical variables. Micro-organisms influence corrosion by changing
the electrochemical conditions at the metal- solution interface. In a dumpsite
environment, a lot of factors are responsible for corrosion .These factors
include, but not limited to PH,conductivity, total dissolved solids and dissolved
oxygen. .These changes may have different effects, ranging from induction of
localized corrosion to corrosion inhibition through a change in the rate of
general corrosion. (Beech and Sunner 2004). A proper identity of bacterial by
which corrosion may be exploited on the metal surface and the role of microbial
contaminants in a specific environment is a useful tool to prevent frequent
microbiologically influenced corrosion problems.(Videla and Herrera ,2001).

Microbial corrosion on the other hand, also called bacterial corrosion, bio-
corrosion, microbiologically influenced corrosion, or microbially induced
corrosion(MIC), is corrosion caused or promoted by microorganisms, usually
chemoautotroph. It can apply to both metals and non-metallic materials.

Some sulfate-reducing bacteria produce hydrogen sulphide, which can cause

sulphide stress cracking. Acidithiobacillus bacteria produce sulfuric acid ;
Acidothiobacillus thiooxidans frequently damages sewer pipes. Ferrobacillus
ferrooxidans directly oxidizes iron to iron oxides and iron hydroxides; the

3
reticules forming on RMS Titanic wreck are caused by bacterial activity. Other
bacteria produce various acids, both organic and mineral, or ammonia.

In presence of oxygen, aerobic bacteria like Acidithiobacillus

thiooxidans,Thiobacillus thioparus, and Thiobacillus concretivorus, all three
widely present in the environment, are the common corrosion-causing factors
resulting in biogenic sulfide corrosion.

Without presence of oxygen, anaerobic bacteria, especially Desulfovibrio and

Desulfotomaculum, are common.Desulfovibrio salixigens requires at least 2.5%
concentration of sodium chloride, but D. Vulgaris and D. desulfuricanscan grow
in both fresh and salt water. D. africanus is another common corrosion-causing
microorganism. The Desulfotomaculumgenus comprises sulfate-reducing spore-
forming bacteria;Dtm. Orientis and Dtm. Nigrificans are involved in corrosion
processes. Sulfate-reducers require reducing environment; an electrode potential
lower than -100 mV is required for them to thrive. However, even a small
amount of produced hydrogen sulfide can achieve this shift, so the growth, once
started, tends to accelerate (Barton and Larry, 2009).

Layers of anaerobic bacteria can exist in the inner parts of the corrosion
deposits, while the outer parts are inhabited by aerobic bacteria.Some bacteria
are able to utilize hydrogen formed during cathodic corrosion
processes.Bacterial colonies and deposits can form concentration cells, causing
and enhancing galvanic corrosion. (Schwermer et al ,2008)

Bacterial corrosion may appear in form of pitting corrosion, for example in

pipelines of the oil and gas industry.( Schwermer et al ,2008 ) Anaerobic
corrosion is evident as layers of metal sulfides and hydrogen sulfide smell. On
cast iron, a graphitic corrosion selective leaching may be the result, with iron
being consumed by the bacteria, leaving graphite matrix with low mechanical
strength in place.

4
Various corrosion inhibitors can be used to combat microbial corrosion.
Formulae based on benzalkonium chloride are common in oil field industry.

Microbial corrosion can also apply to metals, plastics, concrete, and many other
materials. Three examples are Nylon- eating bacteria , Plastic-eating bacteria
and sulphate reducing bacteria that corrode metals.

Hydrocarbon utilizing microorganisms, mostly Cladosporium resinae and

Pseudomonas aeruginosa, colloquially known as "HUM bugs", are commonly
present in jet fuel. They live in the water-fuel interface of the water droplets,
form dark black/brown/green, gel-like mats, and cause microbial corrosion to
plastic and rubber parts of the aircraft fuel system by consuming them, and to
the metal parts by the means of their acidic metabolic products. They are also
incorrectly called algae due to their appearance. FSII, which is added to the fuel,
acts as a growth retardant for them. There are about 250 kinds of bacteria that
can live in jet fuel, but fewer than a dozen are meaningfully harmful. (Sheridan
and Nelson 1993)

1.2 PROBLEM STATEMENT OF THE STUDY

Biocorrosion has been known to cause deterioration to many industrial materials

like mild steel. When mild steel is used for construction of various engineering
work near or in a dumpsite area containing Leachate, the material becomes
susceptible to microbial attack which may lead to pipes leakages and bursting
which may lead to fire outbreak, poor service condition of some engineering
components and deterioration of the base of metallic bridge and some other
adverse effect like collapse of bridge.

5
1.3 OBJECTIVE OF THE STUDY

1. This work aims at assessing leachate from three dumpsite areas and its
impact on mild steel and also to test, study and analyze the
physicochemical and bacteriological properties of leachate .
2. It also involves examining the biocorrosion rate of mild steel in a leachate
obtained from three dumpsite area in Lagos state which are Abule Egba ,
Olusosun and Elepe Dumpsite.

1.4 SCOPE OF THE STUDY

1. This work entails testing, studying and analyzing changes that occur
during microbiologically influenced corrosion of mild steel
graphically.
2. It also encompasses testing the physicochemical and microbial
properties of the leachate and as well the physicochemical properties
of the mild steel.

1.5 LIMITATION THE OF STUDY

1. The cost of testing the physicochemical and bacteriological properties of

the leachate is high.
2. Biocorrosion rate is a slow process, and hence requires more time to
study the microbial effect of the leachate on mild steel.
3. The leachate may contain dangerous bacteria that can enhance infection
if tangible precautionary measure is not put into consideration in the
process of the research.

6
 4. The research work requires a lot of testing and analysis whereas some
reagents and instruments needed may not be available in the laboratory
that one intends to use for the research.

1.6 MOTIVATION

Many industrial plant , equipment and pipes are usually made of mildsteel
because it is cost effective , easy to fabricate and affordable. When used for
construction or for piping and other instrumentation near dumpsite area, they
become susceptible to biocorrosion which deteriorate the pipes and instruments
with time, causing leakages along the pipeline and corrodes the plant and
equipment.As a result of the need to prevent economic losses and cost of
replacement incurred from biocorrosion attack on materials and to ensure public
safety that maybe resulting from sudden derailment, collapse of metallic bridge
and sudden fire accident from pipeline leakages gives the reason why the study
need to be work upon.

1.7 JUSTIFICATION

Some micro-organism poses threat and have adverse effect on metals such as
iron , copper ( and mild steel which is mostly used by structural engineer for
construction of bridge and railway line , and for the design of a reactor and
other unit operation equipment due to the material excellent mechanical
properties such as strength ,high ductility , toughness , ease of fabrication and
availability ). Biocorrosion study of mild steel in leachate plays significantly an
important role in economic development of any nation .It is believed that
studying the biocorrosion rate of mild steel in leachate obtained from dumpsite
area provides some information to assist the structural engineers , designers

7
,fabricators and industrialists in understanding the behaviour of available mild
steel material that is endangered .Apart from economic losses incurred as a
result of biocorrosion attack on material (which may lead to bursting of pipeline
, biodegradation of material of construction used for structural engineering
works such as metallic bridge and railway line) , biocorrosion study of mild
steel also ensures public safety and anticipate danger that may be resulted from
derailment of railway line and unprepared collapse of metallic bridge as a result
of degradation and deterioration caused by the microbial organisms.

1.8 ECONOMIC IMPORTANCE OF THE STUDY

1) Investigating the effect of leachate on mild steel minimizes cost of

replacement and increases life span of some engineering component
made of mild steel like tanks and pipelines by using appropriate inhibitors
that can reduce this microbial effect to industrial service condition.
2) The study can be used for evaluating material resistance to a specific
environment which would aid the workshop and the industries to proffer
solution to biocorrosion of the material in order to give the client some
satisfaction.

8
 CHAPTER TWO

2.0 LITERATURE REVIEW

2.1 Concept of Leachate

Leachate is any liquid that in passing through matter, extracts solutes,

suspended solids or any other component of the material through which it has
passed. Leachate is a widely used term in the environmental sciences where it
has the specific meaning of a liquid that has dissolved or entrained
environmentally harmful substances which may then enter the environment. It is
most commonly used in the context of land-filling of putrescible or industrial
waste. In the narrow environmental context, leachate is therefore any liquid
material that drains from land or stockpiled material and contains significantly
elevated concentrations of undesirable material derived from the material that it
has passed through.( Henry Heinke ,1996) .Leachate from a land fill varies
widely in composition depending on the age of the landfill and the type of waste
that it contains.( Henry and Heinke, 1996) .It can usually contain both
dissolved and suspended material. The generation of leachate is caused
principally by precipitation percolating through waste deposited in a landfill.
Once in contact with decomposing solid waste, the percolating water becomes
contaminated and if it then flows out of the waste material it is termed leachate.(
Christensen and Cossu,1992). Additional leachate volume is produced during
this decomposition of carbonaceous material producing a wide range of other
materials including methane, carbon dioxide and a complex mixture of organic

9
acids, aldehydes ,alcohols and simple sugars. The risks of leachate generation
can be mitigated by properly designed and engineered landfill sites, such as
sites that are constructed on geologically impermeable materials or sites that use
impermeable liners made of geomembranes or engineered clay. The use of
linings is now mandatory within both the United States and the European Union
except where the waste is deemed inert. In addition, most toxic and difficult
materials are now specifically excluded from land filling. However despite
much stricter statutory controls leachate from modern sites are found to contain
a range of contaminants that may either be associated with some level of illegal
activity or may reflect the ubiquitous use of a range of difficult materials in
household and domestic products which enter the waste stream legally (Singh
and Chandra, 2006).

2.2 Composition of landfill leachate

When water percolates through the waste, it promotes and assists the process of
decomposition by bacteria and fungi. These processes in turn release by-
products of decomposition and rapidly use up any available oxygen creating an
anoxic environment. In actively decomposing waste the temperature rises and
the pH falls rapidly and many metal ions which are relatively insoluble at
neutral pH can become dissolved in the developing leachate. The decomposition
processes them release further water which adds to the volume of leachate.
Leachate also reacts with materials that are not themselves prone to
decomposition such as fire ash, cement based building materials and gypsum
based materials changing the chemical composition. In sites with large volumes
of building waste, especially those containing gypsum plaster, the reaction of
leachate with the gypsum can generate large volumes of hydrogen sulphide

10
which may be released in the leachate and may also form a large component of
the landfill gas.(Obuekwe et al,1983).

In a landfill that receives a mixture of municipal, commercial, and mixed

industrial waste, but excludes significant amounts of concentrated specific
chemical waste, landfill leachate may be characterized as a water-based solution
of four groups of contaminants; dissolved organic matter (alcohols, acids,
aldehydes, short chain sugars etc.), inorganic macro components (common
cations and anions including sulfate, chloride, iron, aluminium, zinc and
ammonia), heavy metals (Pb, Ni, Cu, Hg), and xenobiotic organic compounds
such as halogenated organics, (PCBs,dioxins, etc.).

The physical appearance of leachate when it emerges from a typical landfill site
is a strongly odoured black, yellow or orange coloured cloudy liquid. The smell
is acidic and offensive and may be very pervasive because of hydrogen,
nitrogen and sulfur rich organic species such as mercaptans.

2.3 Leachate management

In older landfills and those with no membrane between the waste and the
underlying geology, leachate is free to egress the waste directly into the
groundwater. In such cases high concentrations of leachate are often found in
nearby springs and flushes. As leachate first emerges it can be black in color,
anoxic and may be effervescent with dissolved and entrained gases. As it
becomes oxygenated it tends to turn brown or yellow because of the presence of
Iron salts in solution and in suspension. It also quickly develops a bacterial flora
often comprising substantial growths of Sphaerotilus. (Ebong et al, 2007).

2.4 Total Dissolved Solids (TDS)

11
High TDS levels generally indicate hard water, which can cause scale buildup
in pipes, valves, and filters, reducing performance and adding to system
maintenance costs. These effects can be seen in aquariums, spas, swimming
pools, and reverse osmosis water treatment systems.(DeZuane and John,1997).
Typically, in these applications, total dissolved solids are tested frequently, and
filtration membranes are checked in order to prevent adverse effects. In the case
of hydroponics and aquaculture, TDS is often monitored in order to create a
water quality environment favorable for organism productivity.(Hogan et
al,1987). For freshwater oysters, trouts, and other high value seafood, highest
productivity and economic returns are achieved by mimicking the TDS and pH
levels of each species' native environment. For hydrophonic uses, total
dissolved solid is considered as one of the best indices of nutrient availability
for the aquatic plants being grown. Because the threshold of acceptable
aesthetic criteria for human drinking water is 500 mg/l, there is no general
concern for odour, taste, and colour at a level much lower than is required for
harm. A number of studies have been conducted and indicate various species'
reactions range from intolerance to outright toxicity due to elevated TDS. The
numerical results must be interpreted cautiously, as true toxicity outcomes will
relate to specific chemical constituents. Nevertheless, some numerical
information is a useful guide to the nature of risks in exposing aquatic
organisms or terrestrial animals to high TDS levels. Most aquatic ecosystems
involving mixed fish fauna can tolerate TDS levels of 1000 mg/l. (Boyd and
Claude,1999).

The Fathead minnow (Pimephales promelas), for example, realizes an LD50

concentration of 5600 ppm based upon a 96 hour exposure. LD50 is the
concentration required to produce a lethal effect on 50 percent of the exposed
population. Daphnia magna, a good example of a primary member of the food
12
chain, is a small planktonic crustacean, about 0.5 millimeters in length, having
an LD50 of about 10,000 ppm TDS for a 96 hour exposure. (Boyd and
Claude,1999).

Spawning fishes and juveniles appear to be more sensitive to high TDS levels.
For example, it was found that concentrations of 350 mg/l TDS reduced
spawning of Striped bass (Morone saxatilis) in the San Francisco Bay-Delta
region, and that concentrations below 200 mg/l promoted even healthier
spawning conditions (Kaiser et al,1969) .In the Truckee River, EPA found that
juvenile Lahontan cutthroat trout were subject to higher mortality when exposed
to thermal pollution stress combined with high total dissolved solids
concentrations.

2.4.1 Water classification

Water can be classified by the amount of tds per liter:

 Fresh water < 1,000 mg/L TDS

 Brackish water 1000 to 10,000 mg/L TDS

 Saline water 10,000 to 30,000 mg/L TDS

 Brine > 30,000 mg/L TDS (Ela and Wendell, 2007).

2.5 Dissolved oxygen

The dissolved oxygen (DO) is oxygen that is dissolved in water. The oxygen
dissolves by diffusion from the surrounding air; aeration of water that has
tumbled over falls and rapids; and as a waste product of photosynthesis. A
simplified formula is given below:

13
  Photosynthesis (in the presence of light and chlorophyll):

Carbon dioxide + Water --------------> Oxygen + Carbon-rich foods

CO2 H2O O2 C6H12O6
 Fish and aquatic animals cannot split oxygen from water (H2O) or other

oxygen-containing compounds. Only green plants and some bacteria can

do that through photosynthesis and similar processes. Virtually all the
oxygen we breath is manufactured by green plants. A total of three-
fourths of the earth’s oxygen supply is produced by phytoplankton in the
oceans.

2.5.1 The temperature effect

If water is too warm, there may not be enough oxygen in it. When there are
too many bacteria or aquatic animal in the area, they may overpopulate,
using DO in great amounts.(Barthel et al, 1998).

Oxygen levels also can be reduced through over fertilization of water plants
by run-off from farm fields containing phosphates and nitrates (the
ingredients in fertilizers). Under these conditions, the numbers and size of
water plants increase. Then, if the weather becomes cloudy for several days,
respiring plants will use much of the available DO. When these plants die,
they become food for bacteria, which in turn multiply and use large amounts
of oxygen. And this depleting all the oxygen. (Hayashi,2004).

How much DO an aquatic organism needs depends upon its species, its
physical state, water temperature, pollutants present, and more.
Consequently, it’s impossible to accurately predict minimum DO levels for
specific fish and aquatic animals. For example, at 5 oC (41 oF), trout use
about 50-60 milligrams (mg) of oxygen per hour; at 25 oC (77 oF), they may

14
 need five or six times that amount. Fish are cold-blooded animals. They use
more oxygen at higher temperatures because their metabolic rates increase.

Numerous scientific studies suggest that 4-5 parts per million (ppm) of DO is
the minimum amount that will support a large, diverse fish population. The
DO level in good fishing waters generally averages about 9.0 parts per
million (ppm).In the graph below you can see the effect of the temperature in
the D.(Barthel et al, 1998).

Fig. 2.1 Temperature variation with oxygen concentration.

Source: Bjorn Lomborg

2.5.2 Environmental Impact

Total dissolved gas concentrations in water should not exceed 110 percent.
Concentrations above this level can be harmful to aquatic life. Fish in waters
containing excessive dissolved gases may suffer from "gas bubble disease";

15
however, this is a very rare occurrence. The bubbles or emboli block the flow of
blood through blood vessels causing death. External bubbles (emphysema) can
also occur and be seen on fins, on skin and on other tissue. Aquatic
invertebrates are also affected by gas bubble disease but at levels higher than
those lethal to fish. (Kaiser,1969). Adequate dissolved oxygen is necessary for
good water quality. Oxygen is a necessary element to all forms of life. Natural
stream purification processes require adequate oxygen levels in order to provide
for aerobic life forms. As dissolved oxygen levels in water drop below 5.0 mg/l,
aquatic life is put under stress. The lower the concentration, the greater the
stress. Oxygen levels that remain below 1-2 mg/l for a few hours can result in
large fish kills. (Ela and Wendell,2007).Biologically speaking, however, the
level of oxygen is a much more important measure of water quality than feacal
coliform. Dissolved oxygen is absolutely essential for the survival of all aquatic
organisms ( not only fish but also invertebrates suach as crabs, clams,
zooplankton, etc). Moreover, oxygen affects a vast number of other water
indicators, not only biochemical but esthetic ones like the odor, clarity and taste.
Consequently, oxygen is perhaps the most well-established indicator of water
quality.(shirokova, 2000).

2.5.3 River pollution

In the graph below you can see the percentage levels of Oxygen dissolved in the
river "The Thames" in the period (1890-1974), The New York harbor in the
period (1910-1997), and the river "The Rhine" in the period (1945-1997).Here
we can see how the oxygen levels for some of the majors rivers have returned to
the previous high levels after decades of low levels. This has consequences for
both marine organisms and humans. The increased levels of percentage of
dissolved oxygen have improved the possibilities of aquatic live.

16
Fig.2.2 Oxygen dissolved against year. Author: Bjorn Lomborg

Author: Bjorn Lomborg

A high DO level in a community water supply is good because it makes

drinking water taste better. However, high DO levels speed up corrosion in
water pipes. For this reason, industries use water with the least possible amount
of dissolved oxygen. Water used in very low pressure boilers have no more than
2.0 ppm of DO, but most boiler plant operators try to keep oxygen levels to
0.007 ppm or less.

2.6 Salinity and Conductivities

Salinity is a measure of the amount of salts in the water. Total Dissolved Solids
(TDS) as salinity parameter are often determined using laborious and time
consuming laboratory tests, but it may be more appropriate and economical to
develop a method which uses a more simple soil salinity index. Because
dissolved ions increase salinity as well as conductivity, the two measures are
related. (Thirumalinil and Joseph , 2009). SALINITY is a measure of the
amount of salts in the soil saturation extracts. Conductivity is the ability of
water to conduct an electrical current, and the dissolved ions are the conductors.
Electrical conductivity (EC) is a useful indicator of total dissolved solids (TDS)
because the conduction of current in an electrolyte solution is primarily

17
dependent on the concentration of ionic species. Conductivity is measured by a
probe, which applies voltage between two electrodes. Drop in voltage is used to
measure the resistance of the water, which is then converted to conductivity.
Conductivity is reciprocal to resistance and is measured in the amount of
conductance over a certain distance. The relationship between EC and TDS is
complex depending on the chemical composition and ionic strength. However,
there are many instances where the relative composition of water is reasonably
constant in a given region or study site and, hence, the TDS-EC relation can be
established in the laboratory with a reasonable accuracy over a wide
concentration range . (chang et al,1983). Measurement of EC is fast and
inexpensive. Therefore, under suitable conditions, EC measurements offer a
significant advantage over the direct determination of TDS by sampling and
chemical analysis (Barthel et al, 1998). Hem (1992) provides a detailed analysis
and discussion on the relationship of conductivity to TDS. Hem plotted TDS
versus EC data that ranged from about 500 to 3000 mg/L and observed that the
data set fit a straight line of regression with a slope of 0.59. Hem (1992) stated
that for the range of natural water evaluated the range for the ratio of TDS: EC
was 0.54 to 0.96 and that for water high in sulfate could exceed the upper end of
the range. Further, Hem (1992) indicated that the slope of the line of regression
is not constant over a wide range of dissolved solids concentration. The
relationship of TDS to EC is less well defined for waters with TDS exceeding
about 50,000 mg/L . In general, the range for the ratio of TDS: EC was (0.55 –
0.7) [10-11] & (0.55 – 0.9). (Metacalf and Eddy, 2005). This correlation is
approximate because non-ionic species do not contribute to EC and the
individual ionic species have different weights. The actual multiplier depends
on the activity of the specific dissolved ions present and the average activity of
all ions in the sample which are in turn influenced by the sample temperature,
the relative amount of the each ion and the total concentration of dissolved
solids in the sample. Measuring the TDS of the preliminary samples

18
gravimetrically and regress those results against the measured specific
conductance of the samples would determine the correlation (Howard et al ,
1985). Griffin and Jurinak (1973) proposed another equation in which EC was
related to an ionic concentration function known as ionic strength. ( Griffin and
Jurinak , 1973) .Thirumalini1, S. and K. Joseph studied the correlation ratio
between Total Dissolved Solids (TDS ) and Electrical Determine of Constant
Coefficients to RelateTotal Dissolved Solids to Electrical Conductivity.

2.7 PH of a solution

The pH of a solution is a measure of the molar concentration of hydrogen ions

in the solution and as such is a measure of the acidity or basicity of the solution.
The letters pH stand for "power of hydrogen" and numerical value for pH is just
the negative of the power of 10 of the molar concentration of H+ ions.

The usual range of pH values encountered is between 0 and 14, with 0 being the
value for concentrated hydrochloric acid (1 M HCl), 7 the value for pure water
(neutral pH), and 14 being the value for concentrated sodium hydroxide (1 M
NaOH). It is possible to get a pH of -1 with 10 M HCl, but that is about a
practical limit of acidity. At the other extreme, a 10 M solution of NaOH would
have a pH of 15. In pure water, the molar concentration of H + ions is 10-7 M and
the concentration of OH- ions is also 10-7 M. Actually, when looked at in detail,
it is more accurate to classify the concentrations as those of [H 3O]+ and [OH]-.
The product of the positive and negative ion concentrations is 10 -14 in any
aqueous solution at 25°C. (Nernst, 2005).

19
An important example of pH is that of the blood. Its nominal value of pH = 7.4
is regulated very accurately by the body. If the pH of the blood gets outside the
range 7.35 to 7.45 the results can be serious and even fatal.(Kuchler, 1998).

If you measure the pH of tap water with a pH meter, you may be surprised at
how far from a pH of 7 it is because of dissolved substances in the water.
Distilled water is necessary to get a pH near 7.(Leschber,2004).

Meters for pH measurement can give precise numerical values, but approximate
values can be obtained with various indicators. Red and blue litmus paper has
been one of the common indicators. Red litmus paper turns blue at a basic pH of
about 5, and blue litmus paper turns red at an acid pH of about 8. Neither
changes color if the pH is nearly neutral. Litmus is an organic compound
derived from lichens.The pH of a solution is a measure of the molar
concentration of hydrogen ions in the solution and as such is a measure of the
acidity or basicity of the solution. The letters pH stand for "power of hydrogen"
and the numerical value is defined as the negative base 10 logarithm of the
molar concentration of hydrogen ions.

pH = -log10[H+]

The measurement of the pH of a sample can be done by measuring the cell

potential of that sample in reference to a standard hydrogen electrode, as in the
accepted procedure for measuring standard electrode potentials. This procedure
would give a value of zero for a 1 Molar solution of H + ions, so that defines the
zero of the pH scale. The cell potential for any other value of H + concentration
can be obtained with the use of the Nernst equation. For a solution at 25°C this
gives

Ecell = -0.0592 log10[H+]

20
Or pH = Ecell/0.0592

2.8 Environmental impact

The risks from waste leachate are due to its high organic contaminant
concentrations and high concentration of ammonia. Pathogenic micro-
organisms that might be present in it are often cited as the most important, but
pathogenic organism counts reduce rapidly with time in the landfill, so this only
applies to the most fresh leachate. Toxic substances may however be present in
variable concentration and their presence is related to the nature of waste
deposited.Leachate also causes environmental problem to certain material such
as steel and iron. certain material such as steel are corroded by microbially
influenced bacterial.(Weismann and Lohse,2007).

2.9 Landfills

Most landfills containing organic material will produce methane, some of which
dissolves in the leachate. This could in theory be released in weakly ventilated
areas in the treatment plant. All plants in Europe must now be assessed under
the EU ATEX Directive and zoned where explosion risks are identified to
prevent future accidents. The most important requirement is the prevention of
discharge of dissolved methane from untreated leachate when it is discharged
into public sewers, and most sewage treatment authorities limit the permissible
discharge concentration of dissolved methane to 0.14 mg/l, or 1/10 of the lower
explosive limit. This entails methane stripping from the leachate.(Pomeroy and
Sawyer,1976).

2.10 Other types of leachate

21
Leachate can also be produced from land that was contaminated by chemicals or
toxic materials used in industrial activities such as factories, mines or storage
sites. Composting sites in high rainfall also produce leachate.

Leachate is also associated with stockpiled coal and with waste materials from
metal ore mining and other rock extraction processes, especially those in which
sulphide containing materials are exposed to air and thus to oxygen generating
acidic, sulphur-rich liquors, often with elevated metal concentrations.

In the context of civil engineering (more specifically reinforced concrete

design), leachate refers to the effluent of pavement wash-off (that may include
melting snow & ice with salt) that permeates through the cement paste onto the
surface of the steel reinforcement, thereby catalyzing its oxidation and
degradation. Leachates can be genotoxic in nature.( Singh and Chandra ,2007 ).

2.11 Biogenic sulphide corrosion

Biogenic sulphide corrosion is a bacterially mediated process of forming

hydrogen sulphide gas and the subsequent conversion to sulphuric acid that
attacks concrete and steel within Waste water environments. The hydrogen
sulphide gas is biochemically oxidized in the presence of moisture to form
sulphuric acid. The effect of sulphuric acid on concrete and steel surfaces
exposed to severe wastewater environments can be devastating. ( O’Dea and
Vaughn,2007).Corrosion may occur where stale sewage generates hydrogen
sulphide gas into an atmosphere Containing oxygen gas and high relative
humidity. There must be an underlying anaerobic aquatic habitat containing
sulphates and an overlying aerobic aquatic habitat separated by a gas phase
containing both oxygen and hydrogen sulfide at concentrations in excess of 2
ppm. ( Smith and William ,1967).

22
2.12 Conversion of sulfate SO42- to hydrogen sulfide H2S

Fresh domestic sewage entering a wastewater collection system contains

proteins includingmorganic sulfur compounds oxidizable to sulfates and may
contain inorganic sulfates. ( Metcalf & Eddy ,1992).Dissolved oxygen is
depleted as bacteria begin to catabolize organic material in sewage. In the
absence of dissolved oxygen and nitrates, sulfates are reduced to hydrogen
sulfide as an alternative source of oxygen for catabolizing organic waste by
sulfate reducing bacteria(SRB), identified primarily from the obligate anaerobic
species Desulfovibrio. (Barton and Larry, 2009).

2.13 Conversion of hydrogen sulfide to sulfuric acid, H2SO4

Some hydrogen sulfide gas diffuses into the headspace environment above the
wastewater. Moisture evaporated from warm sewage may condense on
unsubmerged walls of sewers, and is likely to hang in partially formed droplets
from the horizontal crown of the sewer. As a portion of the hydrogen sulfide gas
and oxygen gas from the air above the sewage dissolves into these

stationary droplets, they become a habitat for sulfur oxidizing bacteria (SOB),
of the genus Acidithiobacillus. Colonies of these aerobic bacteria metabolize the
hydrogen sulphidegas to sulfuric acid.( Schewermer et al,2008).

2.14 Corrosion Sulfidation

Sulfuric acid converts the calcium hydroxide in concrete to calcium sulfate.

This changes simultaneously destroys the polymeric nature of calcium
hydroxide and substitutes a larger molecule into the matrix causing pressure and
spalling of the adjacent concrete and aggregate particles(USDI ,1975 ) . The

23
weakened crown may then collapse under heavy overburden loads.( Metcalf &
Eddy ,1972 )

2.15 Prevention

Sewage flows more rapidly through steeper gradient sewers reducing time
available for hydrogen sulfide generation. Providing good ventilation of sewers
can reduce atmospheric concentrations of hydrogen sulphide gas and may dry
exposed sewer crowns. Acid resistant materials like PVC or vitrified clay pipe
may be substituted for concrete or steel (Hammer, 1972).

2.16 Carbon steel

Carbon steel is steel in which the main interstitial alloying constituent is carbon
in the range of 0.12–2.0%. The American Iron and Steel Institute (AISI)
defines carbon steel as the following: "Steel is considered to be carbon steel
when no minimum content is specified or required for chromium, cobalt,
molybdenum, nickel, niobium, titanium, tungsten, vanadium or zirconium, or
any other element to be added to obtain a desired alloying effect; when the
specified minimum for copper does not exceed 0.40 percent; or when the
maximum content specified for any of the following elements does not exceed
the percentages noted: manganese1.65, silicon0.60, copper 0.60. (Degarmo,
2009). As the carbon percentage content rises, steel has the ability to become
harder and stronger through heat treating; however it becomes less ductile.
Regardless of the heat treatment, higher carbon content reduces weldability. In
carbon steels, the higher carbon content lowers the melting point. ( Knowles and
Peter,1987 ).

2.17 Types

24
Carbon steel is broken down into four classes based on carbon content:

a)Mild and low-carbon steel

Mild steel, also called asplain-carbon steel, is the most common form of steel
because its price is relatively low while it provides material properties that are
acceptable for many applications, more so than iron. Low-carbon steel contains
approximately 0.05–0.3% carbon making it malleable and ductile. Mild steel
has a relatively low tensile strength, but it is cheap and malleable; surface
hardness can be increased through carburizing. It is often used when large
quantities of steel are needed, for example as structural steel. The density of
mild steel is approximately 7.85 g/cm3 (7850 kg/m3or 0.284 lb/in3) ( Elert and
Glenn 2009 ) and the Young's modulus, like all steels, is 210 GPa (30,000,000
psi). Low-carbon steels suffer from yield-point run out where the material has
two yield points. The first yield point (or upper yield point) is higher than the
second and the yield drops dramatically after the upper yield point. If a low-
carbon steel is only stressed to some point between the upper and lower yield
point then the surface may develop Lüder bands.(Degarmo et al ,2003) . Low-
carbon steels contain less carbon than other steels and are easier to cold-form,
making them easier to handle .( Nishimura, 1990).

b) Higher carbon steels

Carbon steels which can successfully undergo heat-treatment have a carbon

content in the range of 0.30–1.70% by weight. Trace impurities of various other
elements can have a significant effect on the quality of the resulting steel. Trace
amounts of sulfur in particular make the steel red-short, that is, brittle and
crumbly at working temperatures. Low-alloy carbon steel, such as A36grade,
contains about 0.05% sulphur and melts around 1,426–1,538 °C (2,599–2,800
°F). Manganese is often added to improve the hardenability of low-carbon
steels. These additions turn the material into low-alloy steel by some

25
definitions, but AISI's definition of carbon steel allows up to 1.65% manganese
by weight.

Low carbon steel contains less than 0.3% carbon content and mild or medium
carbon steel approximately 0.30–0.59% carbon content. Balances ductility and
strength and has good wear resistance; used for large parts, forging and
automotive components.( Nishimura, 1990).

High-carbon steel contains approximately 0.6–0.99% carbon content. It is Very

strong, used for springs and high-strength wires.Ultra-high-carbon steel contains
approximately 1.0–2.0% carbon content. It is Steel that can be tempered to great
hardness. Used for special purposes like (non-industrial-purpose) knives, axles
or punches. Most steels with more than 1.2% carbon content are made using
powder metallurgy. Note that steel with a carbon content above 2.14% is
considered cast iron. (Ameri ,2012)

2.18 Heat treatment

The purpose of heat treating carbon steel is to change the mechanical properties
of steel, usually ductility, hardness, yield strength, or impact resistance. Note
that the electrical and thermal conductivity are only slightly altered. As with
most strengthening techniques for steel, Young's modulus (elasticity) is
unaffected. All treatments of steel trade ductility for increased strength and vice
versa . Iron has a higher solubility for carbon in the austenite phase; therefore
all heat treatments, except spheroidizing and process annealing, start by heating
the steel to a temperature at which the austenitic phase can exist. The steel is
then quenched (heat drawn out) at a high rate causing cementite to precipitate
and finally the remaining pure iron to solidify. The rate at which the steel is
cooled through the eutectoid temperature affects the rate at which carbon
diffuses out of austenite and forms cementite. Generally speaking, cooling
26
swiftly will leave iron carbide finely dispersed and produce a fine grained
pearlite (until the martensite critical temperature is reached) and cooling slowly
will give a coarser pearlite. Cooling a hypoeutectoid steel (less than 0.77 wt%
C) results in a lamellar-pearlitic structure of iron carbide layers with α- ferrite
(pure iron) between. If it is hypereutectoid steel (more than 0.77 wt% C) then
the structure is full pearlite with small grains (larger than the pearlite lamella) of
cementitescattered throughout. The relative amounts of constituents are found
using the lever rule. The following is a list of the types of heat treatments
possible:

a) Spheroidizing: Spheroidite forms when carbon steel is heated to

approximately 700 °C for over 30 hours. Spheroidite can form at lower
temperatures but the time needed drastically increases, as this is a diffusion-
controlled process. The result is a structure of rods or spheres of cementite
within primary structure (ferrite or pearlite, depending on which side of the
eutectoid you are on). The purpose is to soften higher carbon steels and allow
more formability. This is the softest and most ductile form of steel. The image
to the right shows where spheroidizing usually occurs.( Smith and William ,
2006).

b) Full annealing: Carbon steel is heated to approximately 40 °C above Ac3 or

Ac1 for 1 hour; this ensures all the ferrite transforms into austenite (although
cementite might still exist if the carbon content is greater than the eutectoid).
The steel must then be cooled slowly, in the realm of 20 °C (68 °F) per hour.
Usually it is just furnace cooled, where the furnace is turned off with the steel
still inside.This results in a coarse pearlitic structure, which means the "bands"
of pearlite are thick. Fully annealed steel is soft and ductile, with no internal
stresses, which is often necessary for cost-effective forming. Only spheroidized
steel is softer and more ductile.

27
c) Process annealing: A process used to relieve stress in a cold-worked carbon
steel with less than 0.3 wt% C. The steel is usually heated up to 550–650 °C for
1 hour, but sometimes temperatures as high as 700 °C. The image rightward
shows the area where process annealing occurs.

d) Isothermal annealing: It is a process in which hypoeutectoid steel is heated

above the upper critical temperature and this temperature is maintained for a
time and then the temperature is brought down below lower critical temperature
and is again maintained. Then finally it is cooled at room temperature. This
method rids any temperature gradient. ( Smith and William F,2006).

e) Normalizing: Carbon steel is heated to approximately 55 °C above Ac3 or

Acm for 1 hour; this ensures the steel completely transforms to austenite. The
steel is then air-cooled, which is a cooling rate of approximately 38 °C (100 °F)
per minute. This results in a fine pearlitic structure, and a more-uniform
structure. Normalized steel has a higher strength than annealed steel; it has a
relatively high strength and ductility .( Smith and William ,2006).

f) Quenching: Carbon steel with at least 0.4 wt% C is heated to normalizing

temperatures and then rapidly cooled (quenched) in water, brine, or oil to the
critical temperature. The critical temperature is dependent on the carbon
content, but as a general rule is lower as the carbon content increases. This
results in a martensitic structure; a form of steel that possesses a super-saturated
carbon content in a deformed body-centered cubic (BCC) crystalline structure,
properly termed body-centered tetragonal (BCT), with much internal stress.
Thus quenched steel is extremely hard but brittle, usually too brittle for practical
purposes. These internal stresses cause stress cracks on the surface. Quenched
steel is approximately three to four (with more carbon) fold harder than
normalized steel .(Nishimura,1990).

28
g) Martempering(Marquenching): Martempering is not actually a tempering
procedure, hence the term "marquenching". It is a form of isothermal heat
treatment applied after an initial quench of typically in a molten salt bath at a
temperature right above the "martensite start temperature". At this temperature,
residual stresses within the material are relieved and some binate may be
formed from the retained austenite which did not have time to transform into
anything else. In industry, this is a process used to control the ductility and
hardness of a material. With longer marquenching, the ductility increases with a
minimal loss in strength; the steel is held in this solution until the inner and
outer temperatures equalize. Then the steel is cooled at a moderate speed to
keep the temperature gradient minimal. Not only does this process reduce
internal stresses and stress cracks, but it also increases the impact resistance.
(Ameri,2012).

h) Quench and tempering: This is the most common heat treatment

encountered, because the final properties can be precisely determined by the
temperature and time of the tempering. Tempering involves reheating quenched
steel to a temperature below the eutectoid temperature then cooling. The
elevated temperature allows very small amounts of spheroidite to form, which
restores ductility, but reduces hardness. Actual temperatures and times are
carefully chosen for each composition.Glenn and Elert, 2009).

i) Austempering: The austempering process is the same as martempering,

except the steel is held in the molten salt bath through the bainite transformation
temperatures, and then moderately cooled. The resulting bainite steel has a
greater ductility, higher impact resistance, and less distortion. The disadvantage
of austempering is it can only be used on a few steels, and it requires a special
salt bath. (Smith and William ,2006).

29
j) Case hardening: Case hardening processes harden only the exterior of the
steel part, creating a hard, wear resistant skin (the "case") but preserving a tough
and ductile interior. Carbon steels are not very hardenable; therefore wide
pieces cannot be through-hardened. Alloy steels have a better hardenability, so
they can through-harden and do not require case hardening. This property of
carbon steel can be beneficial, because it gives the surface good wear
characteristics but leaves the core tough.( Brady and George ,1997 ).

2.19 Sulfate-reducing bacteria

Desulfovibrio vulgar is the best-studied sulphate-reducing bacteria species; the

bar in the upper right is 0.5 micrometer long. Sulphate-reducing bacteria are
those bacteria that can obtain energy by oxidizing organic compounds or
molecular hydrogen(H2) while reducing sulphate (SO42−) to hydrogen
sulfide(H2S) (Ernst and Harold ,1993). In a sense, these organisms "breathe"
sulphate rather than oxygen, in a form of anaerobic respiration. Sulphate-
reducing bacteria can be traced back to 3.5 billion years ago and are considered
to be among the oldest forms of microorganisms, having contributed to the
sulphur cycle soon after life emerged on Earth. (Barton and Larry , 2009). There
are a few genera of Achaea which can also reduce sulfate). Many bacteria
reduce small amounts of sulphates in order to synthesize sulphur-containing cell
components; this is known as assimilatory sulphate reduction. By contrast, the
sulphate-reducing bacteria considered here reduce sulphate in large amounts to
obtain energy and expel the resulting sulphide as waste; this is known as
dissimilatory sulphate reduction. They use sulphate as the terminal electron
acceptor of their electron transport chain. (Larry and Barton , 2009) .Most of
them are anaerobes. Most sulfate-reducing bacteria can also reduce other

30
oxidized inorganic sulfur compounds, such as sulfite, thiosulfate, or elemental
sulfur (which is reduced to sulfide as hydrogen sulphide).

In addition, there are sulfate-reducing bacteria that can reduce fumarate, nitrate
and nitrite, iron(Fe(III)) and some other metals, dimethyl sulfoxide and even
oxygen. (Muyzer and Stams, 2008).

2.20 Ecological importance and markers

Sulphate occurs widely in seawater, sediment, or water rich in decaying organic

material. Sulphate-reducing bacteria are common in anaerobic environments
where they aid in the degradation of organic materials. In these anaerobic
environments, fermenting bacteria extract energy from large organic molecules;
the resulting smaller compounds such as organic acids and alcohols are further
oxidized by acetogens and methanogens and the competing sulphate-reducing
bacteria. (Larry and Barton , 2009).

Sludge from a pond; the black colour is due to metal sulphides that result from
the action of sulphate-reducing bacteria.

The toxic hydrogen sulphide is a waste product of sulphate-reducing bacteria;

its rotten egg odor is often a marker for the presence of sulfate-reducing bacteria
in nature. (Dexter and Betsey 2003) .Sulphate-reducing bacteria are responsible
for the sulphurous odours of salt marshes and mud flats. Much of the hydrogen
sulphide will react with metal ions in the water to produce metal sulphides.
These metal sulphides, such as ferrous sulphide (FeS), are insoluble and often
black or brown, leading to the dark colour of sludge. (Ernst and Schulze,1993 ).

During the Permian–Triassic extinction event (250 million years ago) a severe
anoxic event seems to have occurred where these forms of bacteria became the

31
dominant force in oceanic ecosystems, producing copious amounts of hydrogen
sulfide. (schewermer et al, 2008).

2.21 Uses

Some sulfate-reducing bacteria can reduce hydrocarbons such as benzene,

toluene, ethylbenzene, and xylene, and have been used to clean up contaminated
soils. Their use has also been proposed for other kinds of contaminations.
(hammer and mark, 1975).

Sulfate-reducing bacteria are considered as a possible way to deal with acid

mine waters that are produced by other bacteria (Barton and Larry,2009).

2.22 Problems caused by sulphate-reducing bacteria

In engineering, sulphate-reducing bacteria can create problems when metal

structures are exposed to sulphate-containing water: Interaction of water and
metal creates a layer of molecular hydrogen on the metal surface; sulphate-
reducing bacteria then oxidize the hydrogen while creating hydrogen sulphide,
which contributes to corrosion.

Hydrogen sulphide from sulphate-reducing bacteria also plays a role in the

biogenic sulphide corrosion of concrete. It also occurs in sour crude oil. (Barton
and Larry 2009).

Some sulphate-reducing bacteria play a role in the anaerobic oxidation of

methane: (Larry L. and Fauque, Guy D. 2009).

CH4+ SO42–→ HCO3 –+ H 2S+ H2O

An important fraction of the methane formed by methanogens below the seabed

is oxidized by sulphate-reducing bacteria in the transition zone separating the

32
methanogenes is from the sulphate reduction activity in the sediments. This
process is also considered a major sink for sulphate in marine sediments.

In hydro -fracturing fluids used to frack shale formations to recover

methane( shale gas), biocide compounds are often added to water to inhibit the
microbial activity of sulphate-reducing bacteria in order to avoid anaerobic
methane oxidation and to minimize potential production loss.

2.23 Biochemistry

Before sulphate can be used as an electron acceptor, it must be activated. This is

done by the enzyme ATP-sulfurylase, which uses ATP and sulphate to create
adenosine 5'-phosphosulfate(APS). APS is subsequently reduced to sulphite and
AMP. Sulphite is then further reduced to sulphide, while AMP is turned into
ADP using another molecule of ATP. The overall process, thus, involves an
investment of two molecules of the energy carrier ATP, which must to be
regained from the reduction. (Muyzer and Stams 2008).

2.24 Phylogeny

The sulfate-reducing bacteria have been treated as a phenotypic group, together

with the other sulfur-reducing bacteria, for identification purposes. They are
found in several different phylogenetic lines. (Pfennig and Biebel (1986). As of
2009, 60 genera containing 220 species of sulfate-reducing bacteria were
known. ( Barton and Larry ,2009 ).

2.25 Recent events

In response to increased awareness of the nature and danger of microbial

corrosion, a two-day international symposium was held in Perth, Western

33
Australia in February 2007. The symposium, originally proposed by Dr. Reza
Javaherdashti, was sponsored by EXTRIN Consultants and Curtin University of
Technology, as well as other local industries. It attracted speakers and attendees
from as far as Argentina, Brazil, New Zealand, the UK and the United States in
addition to Australian representatives. The symposium primarily focussed on
the identification of Microbial Corrosion in marine, mining and industrial
environments and the best course of action to remove and prevent further
attacks.

2.26 Corrosion

Corrosion is the deterioration of materials by chemical interaction with their

environment. The term corrosion is sometimes also applied to the degradation
of plastics, concrete and wood, but generally refers to metals. The most widely
used metal is iron (usually as steel) and the following discussion is mainly
related to its corrosion. (El-Etr et al, 2003)

The environment consists of the entire surrounding in contact with the material.
The primary factors to describe the environment are the following:

(a) Physical state — gas, liquid, or solid; (b) Chemical composition —

constituents and concentrations; and (c) Temperature. Other factors can be
important in specific cases. Examples of these factors are the relative velocity of
a solution (because of flow or agitation) and mechanical loads on the material,
including residual stress within the material. To summarize, corrosion is the
deterioration of a metal and is caused by the reaction of the metal with the
environment. It is useful to identify both natural combinations and unnatural
combinations in corrosion. Examples of natural or desirable combinations of
material and environment include nickel in caustic environments, lead in water,
and aluminium in atmospheric exposures. In these environments, the interaction
34
between the metal and the environment does not usually result in detrimental or
costly corrosion problems. The combination is a natural combination to provide
good corrosion service.(Ekpe et al,1995).

One manifestation was the “dry bellyache” with accompanying paralysis, which
was mentioned by Franklin in a letter to a friend. This malady was actually
caused by the ingestion of lead from corroded lead coil condensers used in
making brandy. The problem became so wide spread that the Massachusetts
legislature passed a law in the late 1700s that outlawed the use of lead in
producing alcoholic beverages. (Morgan, and Wilson, 1999).

2.27 Chemistry of corrosion

Common structural metals are obtained from their ores or naturally-occurring

compounds by the expenditure of large amounts of energy. These metals can
therefore be regarded as being in a metastable state and will tend to lose their
energy by reverting to compounds more or less similar to their original states.
Since most metallic compounds, and especially corrosion products, have little
mechanical strength a severely corroded piece of metal is quite useless for its
original purpose. (El-Etre et al, 2005)

Virtually all corrosion reactions are electrochemical in nature, at anodic sites on

the surface the iron goes into solution as ferrous ions, this constituting the
anodic reaction. As iron atoms undergo oxidation to ions they release electrons
whose negative charge would quickly build up in the metal and prevent further
anodic reaction, or corrosion. Thus this dissolution will only continue if the
electrons released can pass to a site on the metal surface where a cathodic
reaction is possible. At a cathodic site the electrons react with some reducible
component of the electrolyte and are themselves removed from the metal. The
rates of the anodic and cathodic reactions must be equivalent according to
35
Faraday’s Laws, being determined by the total flow of electrons from anodes to
cathodes which is called the “corrosion current”, Icor. (Morgan et al, 1999).The
most common and important electrochemical reactions in the corrosion of iron
are thus,

Anodic reaction (corrosion)

Fe → Fe2+ + 2e .............
(1)Cathodic reactions (simplified)

2H+ + 2e → H2 ............. (2a)

Or H2O + ⅟2O2 + 2e → 2OH− ............... (2b)

Reaction 2a is most common in acids and in the pH range 6.5 – 8.5 the most
important reaction is oxygen reduction 2b. In this latter case corrosion is usually
accompanied by the formation of solid corrosion debris from the reaction
between the anodic and cathodic products.

Fe2+ + 2OH− → Fe (OH)2, iron (II) hydroxide.

Pure iron (II) hydroxide is white but the material initially produced by corrosion
is normally a greenish colour due to partial oxidation in air.

2Fe (OH)2 + H2O + ⅟2O2 → 2Fe(OH)3, hydrated iron (III) oxide.

Further hydration and oxidation reactions can occur and the reddish rust that
eventually forms is a complex mixture whose exact constitution will depend on
other trace elements which are present. Because the rust is precipitated as a
result of secondary reactions it is porous and absorbent and tends to act as a sort
of harmful poultice which encourages further corrosion.(E-Awady et al,1992).

36
For other metals or different environments different types of anodic and
cathodic reactions may occur. If solid corrosion products are produced directly
on the surface as the first result of anodic oxidation these may provide a highly
protective surface film which retards further corrosion, the surface is then said
to be “passive”. An example of such a process would be the production of an
oxide film on iron in water, a reaction which is encouraged by oxidising
conditions or elevated temperatures.(Ekpe et al ,1995)

2.28 Factors that control corrosion rate

Certain factors can tend to accelerate the action of a corrosion cell.

These include:

(a) Establishment of well-defined locations on the surface for the anodic and
cathodic reactions. This concentrates the damage on small areas where it may
have more serious effects, this being described as “local cell action”. Such
effects can occur when metals of differing electrochemical properties are placed
in contact, giving a “galvanic couple”. Galvanic effects may be predicted by
means of a study of the Galvanic Series which is a list of metals and alloys
placed in order of their potentials in the corrosive environment, such as sea
water. Metals having a more positive (noble) potential will tend to extract
electrons from a metal which is in a more negative (base) position in the series
and hence accelerate its corrosion when in contact with it. The Galvanic Series
should not be confused with the Electrochemical Series, which lists the
potentials only of pure metals in equilibrium with standard solutions of their
ions. Galvanic effects can occur on metallic surfaces which contain more than
one phase, so that “local cells” are set up on the heterogeneous surface.
Localised corrosion cells can also be set up on surfaces where the metal is in a

37
varying condition of stress, where rust, dirt or crevices cause differential access
of air, where temperature variations occur, or where fluid flow is not uniform.
(b) Stimulation of the anodic or cathodic reaction. Aggressive ions such as
chloride tend to prevent the formation of protective oxide films on the metal
surface and thus increase corrosion. Sodium chloride is encountered in marine
conditions and is spread on roads in winter for de-icing. Quite small
concentrations of sulphur dioxide released into the atmosphere by the
combustion of fuels can dissolve in the invisibly thin surface film of moisture
which is usually present on metallic surfaces when the relative humidity is over
60-70%. The acidic electrolyte that is formed under these conditions seems to
be capable of stimulating both the anodic and the cathodic reactions. In practical
terms it is not usually possible to eliminate completely all corrosion damage to
metals used for the construction of industrial plant. The rate at which attack is
of prime importance is usually expressed in one of two ways:
(1) Weight loss per unit area per unit time, usually mps (milligrams per square
decimetre per day).
(2) A rate of penetration, i.e. the thickness of metal lost. This may be expressed
in American units, mpy (mils per year, a mil being a thousandth of an inch) or
in metric units, mmpy (millimetres per year).
Taking as an example the corrosion of heat exchanger tubes in industrial
cooling water atypical corrosion rate in untreated water would be 40-50 mpy
(210-260 mdd); the use of a corrosion inhibitor could reduce this to less than 5
mpy (26 mdd). The mild steel tubing used in heat exchangers is a maximum of
200 thousandths of an inch thick, thus with corrosion rates of 40-50 mpy in
untreated water, severe problems might be expected within four or five years. If
suitable water treatment with corrosion inhibitors is used a life of at least twenty
years might be expected. This, of course, is ignoring the fact that at some time
before the metal corrodes away the tubing may have thinned to a point where its
required mechanical strength is not attained. When designing equipment for a

38
certain service life engineer’s often add a “corrosion allowance” to the metal
thickness, permitting a certain amount of thinning before serious weakening
occurs. In a cooling water system the factors influencing the rate of attack are:

(a) The condition of the metal surface.

(i) Corrosion debris and other deposits - corrosion under the deposits, with a
possibility of pitting (severe attack in small spots).

b) The nature of the environment.

(i) pH- in the range of 4-10 corrosion rates is fairly independent of pH, but it
increases rapidly when the pH falls below 4.

(ii) Oxygen content - Increase in oxygen concentration usually gives an increase

in corrosion rate.

(iii) Flow rate - Increased water flow increased oxygen access to the surface and
removes protective surface films, so usually increases corrosion, but can
sometimes improve access for corrosion inhibiting reactants.

(iv) Water type - Very important, in general low corrosion rates are found with
scale-forming (hard) waters. Aggressive ions which accelerate corrosion are
Cl-, SO42-but quite complex interactions may occur between the various
dissolved species in natural waters. (El-Etre et al, 2005)

2.29 The consequence of corrosion

39
The consequences of corrosion are many and varied and the effects of these on
the safe, reliable and efficient operation of equipment or structures are often
more serious than the simple loss of a mass of metal. Failures of various kinds
and the need for expensive replacements may occur even though the amount of
metal destroyed is quite small. The effects of corrosion in our daily lives are
both direct, in that corrosion affects the useful service lives of our possessions,
and indirect, in that producers and suppliers of goods and services incur
corrosion costs, which they pass on to consumers. At home, corrosion is readily
recognized on automobile body panels, charcoal grills, outdoor furniture, and
metal tools. Preventative maintenance such as painting protects such items from
corrosion. A principal reason to replace automobile radiator coolant every 12 to
18 months is to replenish the corrosion inhibitor that controls corrosion of the
cooling system. Corrosion protection is built into all major household
appliances such as water heaters, furnaces, ranges, washers, and dryers. Of far
more serious consequence is how corrosion affects our lives during travel from
home to work or school. The corrosion of steel reinforcing bar (rebar) in
concrete can proceed out of sight and suddenly (or seemingly so) result in
failure of a section of highway, the collapse of electrical towers, and damage to
buildings, parking structures, and bridges, etc., resulting in significant repair
costs and endangering public safety. For example, the sudden collapse because
of corrosion fatigue of the Silver Bridge over the Ohio River at Point Pleasant,
OH in1967 resulted in the loss of 46 lives and cost millions of dollars.

Perhaps most dangerous of all is corrosion that occurs in major industrial plants,
such as electrical power plants or chemical processing plants. Plant shutdowns
can and do occur as a result of corrosion. This is just one of its many direct and
indirect consequences. Some consequences are economic, and cause the
following:

40
1. Reduction of metal thickness leading to loss of mechanical strength and
structural failure or breakdown. When the metal is lost in localised zones so as
to give a crack like structure, very considerable weakening may result from
quite a small amount of metal loss.

2. Hazards or injuries to people arising from structural failure or breakdown

(e.g. bridges, cars, aircraft).

3. Loss of time in availability of profile-making industrial equipment.

4. Reduced value of goods due to deterioration of appearance.

5. Contamination of fluids in vessels and pipes (e.g. beer goes cloudy when
small quantities of heavy metals are released by corrosion).

6. Perforation of vessels and pipes allowing escape of their contents and

possible harm to the surroundings. For example a leaky domestic radiator can
cause expensive damage to carpets and decorations, while corrosive sea water
may enter the boilers of a power station if the condenser tubes perforate.

7. Loss of technically important surface properties of a metallic component.

These could include frictional and bearing properties, ease of fluid flow over a
pipe surface, electrical conductivity of contacts, surface reflectivity or heat
transfer across a surface.

8. Mechanical damage to valves, pumps, etc, or blockage of pipes by solid

corrosion products.

9. Added complexity and expense of equipment which needs to be designed to

with standard certain amount of corrosion, and to allow corroded components to
be conveniently replaced.

41
10. Other consequences include: contamination of the product, loss of valuable
product, shutdown of equipment due to corrosion failure, and replacement of
corroded equipment.(El-Awady et al 1992).

2.30 Mechanical properties of mild steel:-

Strength, hardness, toughness, elasticity, plasticity, brittleness, and ductility and
malleability are mechanical properties used as measurements of how metals
behave under a load. These properties are described in terms of the types of
force or stress that the metal must withstand and how these are resisted.

1) Strength:-Strength is the property that enables a metal to resist deformation

under load. The ultimate strength is the maximum strain a material can
withstand. Tensile strength is a measurement of the resistance to being pulled
apart when placed in a tension load. Fatigue strength is the ability of material to
resist various kinds of rapidly changing stresses and is expressed by the
magnitude of alternating stress for a specified number of cycles. Impact strength
is the ability of a metal to resist suddenly applied loads.
2) Hardness:-Hardness is the property of a material to resist permanent
indentation. Because there are several methods of measuring hardness, the
hardness of a material is always specified in terms of the particular test that was
used to measure this property. Rockwell, Vickers, or Brinell are some of the
methods of testing. Of these tests, Rockwell is the one most frequently used.
The basic principle used in the Rockwell testis that a hard material can penetrate
a softer one. We then measure the amount of penetration and compare it to a
scale. For ferrous metals, which are usually harder than nonferrous metals, a
diamond tip is used.

42
3) Toughness:-Toughness is the property that enables a material to withstand
shock and to be deformed without rupturing. Toughness may be considered as a
combination of strength and plasticity.
4) Elasticity:-When a material has a load applied to it, the load causes the
material to deform. Elasticity is the ability of a material to return to its original
shape after the load is removed. Theoretically, the elastic limit of a material is
the limit to which a material can be loaded and still recover its original shape
after the load is removed.
5) Plasticity:-Plasticity is the ability of a material to deform permanently
without breaking or rupturing. This property is the opposite of strength. By
careful alloying of metals, the combination of plasticity and strength is used to
manufacture large structural members. For example, should a member ofa
bridge structure become overloaded, plasticity allows the overloaded member to
flow allowing the distribution of the load to other parts of the bridge structure.
6) Brittleness:-Brittleness is the opposite of the property of plasticity. A brittle
metal is one that breaks or shatters before it deforms. White cast iron and glass
are good examples of brittle material. Generally, brittle metals are high in
compressive strength but low in tensile strength. As an example, you would not
choose cast iron for fabricating support beams in a bridge.
7) Ductility and malleability:-Ductility is the property that enables a material
to stretch, bend, or twist without cracking or breaking. This property makes it
possible for a material to be drawn out into a thin wire. In comparison,
malleability is the property that enables a material to deform by compressive
forces without developing defects. A malleable material is one that can be
stamped, hammered, forged, pressed, or rolled into thin sheets.(Morgan et
al,1999).

2.31 Chemical Composition of mild steel

43
Carbon, C0.14 - 0.20 % Iron, Fe98.81 - 99.26 % (as remainder) Manganese,
Mn0.60 - 0.90 % Phosphorous, P≤ 0.040% Sulfur, S≤ 0.050 %.

2.32 Physical properties of mild steel

Mild steel is very strong due to the low amount of carbon it contains. In
materials science, strength is a complicated term. Mild steel has a high
resistance to breakage. Mild steel, as opposed to higher carbon steel, is quite
malleable, even when cold. This means it has high tensile and impact strength.
Higher carbon steels usually shatter or crack under stress, while mild steel
bends or deforms. Mild steel has density of .248pounds per cubic inch. It melts
at 2570degrees Fahrenheit. It has a specific heat of around .122British Thermal
Unit (BTU) per pounds per cubic inch.(David ,2010).

2.33 Dumpsite Location In Lagos State

Olushosun Landfill Site: Situated in the Northern part of Lagos within Ikeja
Local Government and receives approximately 40%  of the total waste deposits
from Lagos. The size is 42.7 hectares and a residual life span of 20 years.

 Abule-Egba Landfill Site: The site occupies a land of about 10.2 hectares in
the Western part of Lagos in Alimosho Local Government and receives waste
from the densely populated area. The residual life span is approximately 8
years.

 The Solous Sites: Situated along Lagos State University – IBA Road.
Soluos II - is on 7.8 hectares of land with average life span of5 years.
  Soluos III- a new site with approximately 5 hectares of land with average life
span of 5 years. Each site  receives an average of about 2,250 m3 of waste per
day.

44
2.34 Satellite Sites

These Satellite Sites comprise of Ewutu Elepe (Ikorodu), Sangotedo (Eti–Osa)

and Temu (Epe) dumpsites. These sites serve as back–ups for other three main
landfill sites, and also have an advantage of proximity. They are temporary
sites, and receive an average waste of about 1,864.29m3 per day.

2.35 GEOLOGY OF STUDY AREA

The city of Lagos lies in southwestern Nigeria, on the Atlantic Coast in the Gulf
of Guinea, within latitudes 6023′N and 6041′ N and longitudes 2042′E and
3042′E. Abule-Egba dumpsite lies within longitude 3 017.94'E and 3018.48'E
and latitude 6038.19'N and 6038.64'N , Olushoshun dumpsite lies within
longitude 3022.32'E and 3023.1'E and latitude 6035.4'N and 6036.0'N while
Ewutu Elepe dumpsite lies within longitude 7018.64'E and 3018.48'E and
latitude 11048.10'N and 15018.84'N . The two sites are easily accessible through
major state roads.

Geologically, the study areas fall within the Dahomey basin. The sediment was
accumulated during the Cenozoic to Mesozoic. Depositional materials in the
basin vary in texture and in thickness from place to place for the identified
lithostratigraphic units. Abeokuta Formation is the oldest sedimentary
Formation overlying the basement . It consists of sandstones and grits towards
the basal conglomerates. It has good groundwater potential except that the
bituminous materials associated with the sand could affect the groundwater
quality . Though there may be associating low yield due to the presence of
Borehole failures could be due to the frequent occurrence of clayey material
which tends to seal the pores. This study evaluates quality of 26 water and 2 soil
samples around Abule Egba and Olushoshun landfill sites in Lagos, Nigeria.
This was enhanced through the determination of the major ions and their origin,
45
suitability of well and borehole water for drinking purpose and analysis of
geotechnical properties of the underlying soil. Piper’s was used to interpret
water suitability for drinking. Results showed that Abule Egba is dominated by
Ca-MgCl and CaHCO3 while Oloshoshun dumpsite is generally dominated by
(Na+K)-HCO3 with few samples as CaSO4 suggesting incursion of saline
water into the fresh aquifer. The mean concentration of Fe2+ at Oloshoshun
measures above the permissible limits of WHO standard for drinking water.
Grain size analysis revealed that the soils are sandyclay with average hydraulic
conductivity of 10-5cm/s which makes them potential barrier material in
modern landfills. Though quality of groundwater shows little anthropogenic
influence, pre-treatment due to dominance of Cl- and SO-24 is recommended.
(Olasunkanmi ,2010).

46
 CHAPTER THREE

3.0 METHODOLOLGY

3.1 APPARATUS/EQUIPMENT:

Equipment and apparatus needed for the research work are:

1. Three 1000ml beakers

2. Thermometer (mercury in glass type)

3. 4 test tubes

4. 100ml beaker (1)

5. Filter paper

6. Stirrer

7. PH meter

8. Colony counter

9. Incubator

10. Conductivity meter

47
11. Desiccator

12. Pipette

13. Conical flask

3.2 USES OF THE EQUIPMENT AND APPARATUS

a) Beaker: - It is made of borosilicate glass and it was used in the

experiment as a container that contained both the leachate and the mild
steel.

b) Pipette: It is made of soda glass and it was used in the experiment to take
specific volume of the effluent from the beaker.

c) Test tube: It is also made of soda glass cylindrical in shape and it was
used in the experiment to hold filterate while removing the suspended
solid.

d) Incubator: This was used in the experiment to keep the bacterial at

constant temperature (which is 370C).

e) PH meter: This is an equipment that is used to know the degree of

alkalinity or acidity of the leachate samples.

48
 f) Weighing balance: It was used to know the weight loss as the corrosion
process continued.

Thermometer: Mercury in glass thermometer was used to read the temperature

of the effluent

3.3 MATERIAL

1. Leachate sample from three dumpsites in Lagos State (Elepe, Olusosun and
Abule Egba)

2. Distilled water

3. Commercial mild steel plate of thickness 0.8mm

3.4 EXPERIEMENTAL PROCEDURE

Leachate samples from three dumpsites (Olusosun(A), Elepe(B) and Abule

Egba(C) ) were initially taken to Lagos State Environmental Agency to analyse
their physico-chemical and their bacteriological properties before immersion of
the coupon samples. After that, three 100ml beaker A, B, C were half filled
with the leachate sample i.e. 500ml. Mild steel was cut into three equal size and
weight (M1=100g by mass and 109cm2 in area) and were perforated at one end
to facilitate the immersion. The coupons were tied with rope and immersed
completely into leachate sample A, B and C. The coupons were allowed to
remain in the sample for 168hours and then reweighed (M2) to know the weight
loss ( M ).

Also, electrical conductivity, oxygen dissolved, temperature, pH of the leachate

and total bacteria count (TBC) were then determined. The process was repeated

49
every 168hours for other five times and their results were tabulated and
represented graphically.

50
DIAGRAM OF THE EXPERIMENT :
Rope handle

Leachate sample A

1000ml beaker

500ml
Mild steel

Fig.3.1.1 Leachate sample A from Olusosun Dumpsite

Rope handle

Leachate sample B

1000ml beaker
500ml

Mild steel

Fig.3.1.2 Leachate sample B from Elepe Dumpsite

51
 Rope handle

Leachate sample c

1000ml beaker

500ml
Mild steel

Fig.3.1.3 Leachate sample c from Abule egba Dumpsite

52
3.5 METHOD OF CLEANING AND REWIGHING COUPONS

After exposure, according to America standard Testing material (ASTM 1985),

the following chemical method of cleaning specimen was adopted :

(1) The samples were rinsed in water to remove excess acid.

(2) The coupon were then dried in methanol, hot air and kept in desiccator
for final reweighing M2.

3.6 DETERMINATION OF TOTAL DISSOLVED SOLID USING

GRAVIMETRY METHOD.

TDS was determined using pipette (2ml), 100ml beaker, weighing balance and
filter paper 2ml of each effluent was filtered into separate test tube to remove
suspended particle.

One 100ml beaker was dried and weighed when empty (w 1). 2ml of the leachate
sample A was put into the beaker and then heated to dry all the water.The
beaker was allowed to cool and then reweighted (w2) to know the total
dissolved solid. Similar step were taken for sample B and C.

TDs = (w2-w1) g/2ml

3.7 DETERMINATION OF ELECTRICAL CONDUCTIVITY

Electrical Conductivity of the effluents was determined using equation

suggested by Hem in 1992.The relationship is TDS = K C * EC where KC is
correction factor which is 0.92.

53
3.8 DETERMINATION OF TOTAL BACTERIAL COUNT (TBC)

TBC was determined using pipette, petri dish, incubator and Agar.

1ml of each leachate sample (A,B,C) was taken and put into three separate
Petridishes. The dishes were then half filled with agar and then allowed to
solidify. The three samples were incubated at 37 0c for 24 hours for the bacteria
to grow and then counted using colony counter. Bacterium = 1cfu/ml = 1cell/ml.

3.9 PRECAUTIONS
1. Hand gloves were worn during the experiment to avoid contact with the
effluent sample which might contain dangerous bacteria.
2. Error due to parallax was avoided when taking reading from thermometer
and pipette.
3. The effluent was passed through filter paper so that suspended particle
can be removed from the sample
4. The coupons were first dried and deemed complete in a dessicator before
reweighing to avoid additional weight.

54
 CHAPTER FOUR

4.0 CALCULATIONS

Chemical composition of the mild steel:

Table 4.0: Chemical Analysis of the Mild Steel

Run Chromium Molybdenum Vanadium Copper Tungsten Titanium

(Cr) (Mo) (V) (Cu) (W) (Ti)
Average 0.03240 0.00149 0.00260 0.05823 0.00204 0.00147
Sd 0.00069 0.00024 0.00035 0.00172 0.00027 0.00050
Sd % 2.14055 16.36337 13.62603 2.96075 13.1551 34.1946

Table 4.1: Chemical Analysis of the Mild Steel (Contd.)

Run Tin Cobalt Aluminium Niobium Iron

(Sn) (Co) (Al) (Nb) (Fe)
Average 0.00277 0.00609 0.01857 0.00160 99.3552
Sd 0.00008 0.00001 0.00264 0.00039 0.0066
Sd % 2.88655 0.16030 14.21488 24.36785 0.0067

DATE SAMPLED: 18/08/2014

SECTOR: GENERAL

55
TYPE OF ANALYSIS: COMPREHENSIVE

TYPE OF SAMPLE: LEACHATE A (OLUSOSUN)

Table 4.1: Physicochemical and Bacteriological Properties Of Leachate A

S/N PARAMETER RESULT LASEPA REMARK

STANDARD S
A PHYSICAL
Colour 88,550 250Pt.Co.APH Very high
A
Appearance Dark brown with Clear
particles and odour
0
Temperature C 28.80 C <400 C
Ph 5.49 5.5-.9.0
Turbidity 243 FTU
Conductivity 8,62 uS/cm
Total Suspended 1,070 100mg/l Very high
Solids
Total dissolved Solids 18,686 2100mg/l Very high
Total Solids 19,686 2200mg/l Very high

B CHEMICAL
Total acidity (mg/l) 2,820 NS
Total alkalinity (mg/l) 6,800 NS
Chloride 174 250mg/l
Nitrate 0mg/l
Phosphate 6.72mg/l
Sulphate 20mg/l
Phenol NA 1.0mg/l
Oil and Grease 0.8 10.0mg/l
Dissolved Oxygen 2.81mg/l Not less than 2
Chemical Oxygen 2,947 200mg/l
Demand
Biological Oxygen 736.8 50mg/l
Demand

56
C TRACE/TOXIC
HEAVY METAL
Calcium NA 200mg/l
Magnesium NA 5.0gmg/l
Zinc 0.5151 5.0gmg/l
Copper NA 3.0mg/l
Iron 4,0430 10.0mg/l
Chromium NA 0.1mg/l
Sodium 1.7585
Cobalt NA
Manganese 0.3284 5.0mg/l
Lead 0.0052 0.1mg/l
Cadmium NA 2.0mg/l

Potassium 3,3724 200.00mg/l

Nickel 0.0188 3.mg/l
Silver 0 <0.10mg/l
Mercury NA 0.01mg/l
D MICROBIOLOGY
Total Plate Count 100 350cfu/ml
Presence of Coliform +VE Nill/Negative Positive
(MCA)
Feacal Coliform +VE Negative/Nill Positive
Confirmation (EMB)
NA= NOT ANALYSED NS = NOT SPECIFIED ND = NOT DETECTED
TNTC=TOO NUMEROUS TO COUNT .

57
DATE SAMPLED: 18/08/2014

SECTOR: GENERAL

TYPE OF ANALYSIS: COMPREHENSIVE

TYPE OF SAMPLE: LEACHATE B (ELEPE)

Table 4.2: Physicochemical and Bacteriological Properties Of Leachate B

58
S/N PARAMETER RESUL LASEPA REMARKS
T STANDAR
D
A PHYSICAL
Colour 88,632 250Pt.Co.A Very high
PHA
Appearance Brown Clear
with
particles
C TRACE/TOXIC
and
HEAVY METAL
odour
Temperature C Calcium
0
27.60 C <400 C NA 200mg/l
Ph Magnesium
5.34 5.5-.9.0NA 5.0gmg/l
Turbidity Zinc 238 FTU 0.3215 5.0gmg/l
Conductivity Copper
8,83 uS/cm NA 3.0mg/l
Total Iron 1,245
Suspended 100mg/l3.1204 Very10.0mg/l
high
Chromium NA 0.1mg/l
Solids Sodium 1.0624
Total dissolved Solids 20,024
Cobalt 2100mg/lNA Very high
Total Solids 21,024
Manganese 2200mg/l0.2089 Very5.0mg/l
high

Lead 0.0031 0.1mg/l

B CHEMICAL
Cadmium NA 2.0mg/l
Total acidity (mg/l) 2,340 NS
Potassium 2.3456 200.00mg/l
Total alkalinity (mg/l) 6,890 NS
Nickel 0.0098 3.mg/l
Chloride 174 250mg/l
Silver 0 <0.10mg/l
Nitrate 0mg/l
Mercury NA 0.01mg/l
Phosphate 6.89mg/l
D MICROBIOLOGY
Sulphate 19.2mg/l
Total Plate Count 100 350cfu/ml
Phenol NA 1.0mg/l
Presence of Coliform +VE Nill/Negative Positive
Oil and Grease 0.7 10.0mg/l
Dissolved Oxygen(MCA) 2.94mg/l Not less
Feacal Coliform +VE Negative/Nill Positive
than 2
Chemical Confirmation
Oxygen 2,732 (EMB)
200mg/l
Demand
Biological Oxygen 749.9 50mg/l
Demand
59
NA= NOT ANALYSED NS = NOT SPECIFIED ND = NOT DETECTED
TNTC=TOO NUMEROUS TO COUNT

pt. Co. APHA = Platinum cobalt APHA Metho

DATE SAMPLED: 18/08/2014

SECTOR: GENERAL

TYPE OF ANALYSIS: COMPREHENSIVE

TYPE OF SAMPLE: LEACHATE C (ABULE EGBA)

Table 4.3: Physicochemical and Bacteriological Properties Of Leachate C

S/N PARAMETER RESULT LASEPA REMARKS

STANDARD
A PHYSICAL
Colour 98,550 250Pt.Co.APHA Very high
Appearance Brown with Clear
particles and odour
0
Temperature C 28.80C <400 C
Ph 5.28 5.5-.9.0
Turbidity 241 FTU
Conductivity 7.93 uS/cm
Total Suspended Solids 1005 100mg/l Very high

60
 Total dissolved Solids 18,652 2100mg/l Very high
Total Solids 19,686 2200mg/l Very high

B CHEMICAL
Total acidity (mg/l) 1,730 NS
Total alkalinity (mg/l) 5,980 NS
Chloride 158 250mg/l
Nitrate 0mg/l
Phosphate 5,92mg/l
Sulphate 18mg/l
Phenol NA 1.0mg/l
Oil and Grease 0.5 10.0mg/l
Dissolved Oxygen 2.72mg/l Not less than 2
Chemical Oxygen 2,830 200mg/l
Demand
Biological Oxygen 720.1 50mg/l
C Demand
TRACE/TOXIC
HEAVY METAL
Calcium NA 200mg/l
Magnesium NA 5.0gmg/l
Zinc 0.4200 5.0gmg/l
Copper NA 3.0mg/l
Iron 5.0210 10.0mg/l
Chromium NA 0.1mg/l
Sodium 2.0012
Cobalt NA
Manganese 0.4101 5.0mg/l
Lead 0.00 0.1mg/l
Cadmium NA 2.0mg/l

Potassium 2.34572 200.00mg/l

Nickel 0.0253 3.mg/l
Silver 0 <0.10mg/l
Mercury NA 0.01mg/l
D MICROBIOLOGY
Total Plate Count 100 350cfu/ml
Presence of Coliform +VE Nill/Negative Positive
61
(MCA)
Feacal Coliform +VE Negative/Nill Positive
Confirmation (EMB)
NA= NOT ANALYSED NS = NOT SPECIFIED ND = NOT DETECTED
TNTC=TOO NUMEROUS TO COUNT

pt. Co. APHA = Platinum cobalt APHA Method

Mild steel coupons of dimensions 10 cm, 5 cm, and 0.3 cm which are the
length, breadth, and height respectively. The surface area of the mild steel was
calculated using the mathematical relation of surface area of a Cuboid;

Where,l = Length of the mild steel = 10cm

b = Breadth of the mild steel =5cm

h = Height of the mild steel =0.3cm

Surface Area =A = 2(10*5 + 10*0.3 + 5*0.3) = 109cm2

The corrosion rate under weight loss method is calculated in mils per year using
the recommended relation (ASTM ,1985).

Corrosion rate = KW /DAT …………………………………. (1)

K =534 (corrosion rate constant) and A = total area of exposure (cm2)

W = weight loss (g) and Density of the material = 7.86g / cm3

Mpy =mils per year (corrosion rate unit) and T =Exposure time in hours

CR = Corrosion Rate

62
Table 4.4 Variation in physico-chemical properties of Leachate sample (A)
with Time.

Time Init Final Weight TDS Cond. TBC PH DO Temp

(hour) ial weight( loss( (g/ml) (Us/c (CFU (mg/l) (oC)
weigh M2) M) m) /ml)
t(M1) (g) (g) *103
(g)

0.0 100 100.0000 0.0000 18,686 8.62 100 5.49 2.81 28.8
168 100 99.7307 0.2693 33,167 15.22 118 5.43 2.75 29.5
336 100 99.6787 0.3213 54,900 25.19 125 5.39 2.73 29.0
504 100 99.6269 0.3731 67908 31.16 132 5.35 2.69 30.0
672 100 99.5731 0.4269 82,395 37.80 122 5.32 2.80 28.9
840 100 99.5213 0.4787 96,882 44.45 118 5.19 2.97 27.9
1008 100 99.4695 0.5305 111,369 51.10 115 5.03 2.68 32.3
1174 100 99.4177 0.5823 125,856 57.75 111 5.01 2.78 29.6

Table 4.5 Corrosion rate of mild steel in sample (A)

S/N W(g) T(hr) CR * 10-4(mils per

year)
1 0.0000 0.0 0.00
2 0.2693 168 9.99
3 0.3213 336 5.96
4 0.3731 504 4.61
5 0.4269 672 3.96
6 0.4787 840 3.552
7 0.5305 1008 3.28
8 0.5823 1174 3.09

CR1 = KW/DAT

63
When k = 534 , w= M = 0.2693g , A = 109cm 2, T = 168 hr and D =
7.86g/cm3

CR1 = 534 * 0.2693 / 7.86 * 109 * 168

= 9.99 * 10-4mil per year

When w= 0.3213g and T = 336hr

CR2 = 534 * 0.3213 / 7.86 * 109 * 336

= 5.96 * 10-4 mil per year

When w = 0.3731g and T = 504hr

CR3 = 534 * 0.3731 / 7.86 * 109 * 504= 4.61 * 10-4mil per year

Table 4.6 Variation in physico-chemical properties of Leachate sample (B)

with Time.

Tim Initial Final Weight TDS Cond. TBC PH DO Tem

e weight(M1) weight(M2) loss( (g/ml) (US/cm) *103 (mg/L) (oC
(ho (g) (g) M)(g) (CFU/ml)
ur)

0.0 100 100.0000 0.0000 20024 8.83 100 5.34 2.94 27.6
168 100 99.9531 0.0469 27309 12.53 112 5.31 2.98 29.3
336 100 99.8951 0.1049 31929 14.65 117 5.28 3.20 29.1
504 100 99.8482 0.1518 37988 17.43 122 5.27 3.40 30.2
64
672 100 99.8013 0.1887 43873 20.13 128 5.24 3.45 28.1
840 100 99.7544 0.2456 51479 23.62 125 5.21 3.49 27.2
1008 100 99.7075 0.2625 59107 27.12 121 5.19 3.57 32.3
1174 100 99.6617 0.2838 68327 31.35 108 5.11 3.59 29.7

Table 4.7 Corrosion rate of mild steel in sample (B)

S/N W(g) T(hr) CR * 10-4(mils per

year)
1 0.0000 0.0 0.00
2 0.0469 168 1.75
3 0.1049 336 1.95
4 0.1518 504 1.88
5 0.1987 672 1.84
6 0.2456 840 1.82
7 0.2925 1008 1.80
8 0.3383 1174 1.79

CR1 = KW/DAT

When k = 534 , w= M = 0.0469g , A = 109cm 2, T = 168 hr and D =

7.86g/cm3

CR1 = 534 * 0.0469 / 7.86 * 109 * 168

= 1.74 * 10-4mil per year

When w= 0.1049g and T = 336hr

CR2 = 534 * 0.1049 / 7.86 * 109 * 336

= 1.95 * 10-4 mil per year

When w = 0.1518g and T = 504hr

CR3 = 534 * 0.1518 / 7.86 * 109 * 504

= 1.88 * 10-4mil per year

65
 Tim Initial Final Weight TDS Cond. TBC PH DO Tem
e weight(M1) weight(M2) loss( (g/ml) (Us/cm) (CFU/ml) (Mg/l) (oC
(ho (g) (g) M)(g)
ur)

0.0 100 100 0.0000 18652 7.93 100 5.28 2.72 28.8
168 100 99.9751 0.0249 24606 11.29 110 5.25 2.81 27.9
336 100 99.8951 0.1049 33499 15.37 117 5.24 3.10 29.5
504 100 99.7861 0.2139 42347 19.43 123 5.22 3.32 29.0
672 100 99.6171 0.3829 50478 23.16 126 5.21 2.91 30.1
840 100 99.5989 0.4011 62355 28.61 119 5.18 3.42 28.5
1008 100 99.5234 0.4766 68305 31.34 114 5.10 2.80 31.2
1174 100 99.5008 0.4992 78679 36.10 104 5.00 3.45 29.4
4.8 Variation in physico-chemical properties of Leachate sample (B) with
Time.

66
Table 4.9 Corrosion Rate of mild steel in sample C

S/N W(g) T(hr) CR * 10-4(mils per

year)
1 0.0000 0.0 0.00
2 0.0249 168 0.92
3 0.1049 336 1.94
4 0.2139 504 2.65
5 0.3345 672 3.10
6 0.4011 840 2.98
7 0.4766 1008 2.94
8 0.4992 1174 2.65

CR1 = KW/DAT

When k = 534 , w= M = 0.0249g , A = 109cm 2, T = 168 hr and D =

7.86g/cm3

CR1 = 534 * 0.0249 / 7.86 * 109 * 168

= 0.92 * 10-4mil per year

When w= 0.1049g and T = 336hr

CR2 = 534 * 0.1049 / 7.86 * 109 * 336

= 1.94 * 10-4 mil per year

When w = 0.2139g and T = 504hr

CR3 = 534 * 0.2139 / 7.86 * 109 * 504

= 2.65 * 10-4mil per year

DISCUSSIONS

67
As Shown in the above table 4.4, 4.6 and 4.8, dissolved oxygen (DO) increased
from 2.81mg/l to 2.98mg/l for sample A, 2.94mg/l to 3.59mg/l for sample B and
2.74mg/l to 3.45mg/l depending on the temperature of the surrounding.
Increase in temperature decreased the concentration of oxygen in the Leachate
sample. Oxygen is an agent of corrosion and is therefore a necessary element to
all form of life.

Increase in Dissolved Oxygen (DO) in Leachate obtained from the dumpsites

enhanced the microbial activities of the micro-organism.Its presence caused the
bacteria to increase exponentially and got over populated using the DO in great
amount.

TDS is necessary for the survival of biological life. TDS increased from
18,606g/ml to 125,856g/ml for sample A , 20024g/ml to 68327g/ml for sample
B and 18652g/ml to 78679g/ml for sample C.This increase may be due to metal
particle dissolved in the samples. Increased in TDS promotes the exponential
growth of the microbes since TDS helps the microbe to prevent perpetual
temperature variation and hence causing micro-biologically induced corrosion.

pH signifies the presence of hydrogen ion in the solutions. Its values decreased
from 5.49 to 5.01 for sample A, 5.34 to 5.11 for sample B and 5.28 to 5.00 for
sample C. This is due to the presence of numerous number of bacteria count.
Bacterial that may cause this acidic effect may be sulphur reducing bacteria
which reduced the sulphate to sulphide and sulphur oxidizing bacteria which
convert H2S to H2SO4 causing the acidic properties of the Leachate to increase
dramatically and hence, causing aggressive corrosion of various engineering
component like pipes and other component made of mild steel in a dumpsite
area containing over populated bacteria.

Bacteria best operated under optimum temperature range of 29.0 0C to 32.3 0C.
This temperature variation may be due to the atmospheric condition of the place

68
i.e during rainfall, temperature drop from optimum and increased the dissolved
oxygen (DO) and during sunshine period, temperature increased and decreased
the dissolved oxygen.

Therefore, DO, Temperature and TDS contribute in one way or the other to
increase Total Bacteria Count (TBC) which can cause corrosion of mild steel.

69
Fig 4.1 Corrosion Rate – Time graph for A, B and C

DISCUSSIONS

70
As shown in the graph above (Fig.4.1), the corrosion rate - Time graph rises
from zero to maximum value of 9.99 x 10-4 mils/year and falls continuously to
3.09 x 10-4 mils/ year for Leachate sample A, it also rises from zero to
maximum value of 1.95mls/year and falls continously to 1.79 x 10 -4 mils/year
for Leachate sample B and from Zero to maximum value of 3.10 x 10 -4 mls/year
and falls to 2.65 x 10-4 mils/year for Leachate sample C over a time range of
168-1174hours. Increase in corrosion rate may be due to the presence of TDS,
TBC and DO in large amount. Increase in corrosion rate also maybe to higher
level of conductivity of the Leachate and stable optimum temperature which
promote the microbial growth and hence decreases the pH of the Leachate
which is corrosion aggressive.

Decrease in corrosion Rate may be due to temperature deviation from the

optimum condition during wet or dry seasons which is undesirable for microbial
growth. Another reason is that, the decrease may be due to brownish precipitate
deposited around the coupons which reduced the corrosion rate of mild steel.

71
Fig.4.2 Total Bacteria count Variation with time

DISCUSSIONS

As shown in the figure 4.2 above, increase in total bacteria count may be due to
the presence of suspended particle in the leachate which acted as substrate and
were fed upon by micro-organism to promote their activeness and growth.

Also increase in DO, TD, TDS,optimum temperature and P H of the leachate

might have caused the curve to rise rapidly.

When the substrate had been used up and the concentration of DO reduced
continuously, the growth rate of the micro-organism reduced with time as
shown in the curve. Therefore, Total bacteria count (TDC) increased in
leachate A followed by C and lower in B indicating that the corrosion rate of
mild steel in A will be faster followed by C and then B.

72
Fig. 4.3 Weight Loss as a function of Time

DISCUSSIONS

As shown in figure 4.3 above, the weight of mild steel in sample A reduced
from 100g to 99.4177g, in sample B it reduced from 100g to 99.6617g and
sample C from 100g to 99.5008g over a time range of 168 – 1174hours. The
weight loss of mild steel increases continuously depending on the total time of
exposure of mild steel into the Leachate sample as indicated by the curve above.
The increase in corrosion rate may be due to increase in the number of bacteria
in each of the sample caused by the presence of TDS, Conductivity, Optimum
Temperature, and PH change.

73
DISCUSSION OF RESULTS

The surface appearance of the coupon in each of the sample become dull and
then become brownish in colour after the first week of immersion. The
brownish appearance was as a result of suspended particle in the effluents. It
was also observed that the coupons were visibly affected by the leachates
obtained from Olusosun, Elepe and Abule Egba dumpsites. This is because the
weight of the coupons decreased with increase in the total time of exposure.
Also, the number of bacteria in the effluent were observed to be function of pH
i.e. increase in the microbial activities decreased the pH of the leachate and vice
versa. Meanwhile some bacteria in the samples tends to increase the sulphur
content of the leachates which reacted with the dissolved oxygen to form acid
and hence, enhanced weight loss of the coupons.
The dissolved oxygen was also observed to be function of temperature since
dissolved oxygen is needed for the survival of the microbes, at lower
temperature dissolved oxygen increased and hence promoted the effect of
microbes on the coupons.
Results obtained indicate that biocorrosion of mild steel in leachate is not only
dependent on total dissolved solid (TDS), acidic pH, temperature, dissolved
oxygen but also on total bacteria count (TBC).
The effect of each physico-chemical property as shown in the table and graph
shows that the corrosion rate of mild steel increased with time after the first
week of immersion and then decreased continuously with time. The decrease in
the corrosion rate must have been as a result of flocculent precipitates deposited
on the surface of the coupons. Also, weight loss due to corrosion increased with
total bacteria count, total dissolved oxygen, and total dissolved and then with
acidic pH of the leachate. The acidic pH was as result of microbial activities in
the leachate samples. The pH values in the acidic domain were attributed to the
present of acid resulting from microbes.The physicochemical properties as

74
shown in the graph shows that pH and conductivity have the highest effect, then
by dissolved oxygen which is an agent of corrosion and slightly by total
dissolved solid. The presence of dissolved solid in the effluent helps the micro-
organism to maintain their biological life.
Finally, the results shows that if mild steel is used for engineering work such as
pipeline or bridge near 0r in a dumpsite area containing Leachate, the corrosion
rate of such material will be faster in Olusosun dumpsite (A), slower in Abule
Egba dumpsite(C) and very slower in Elepe dumpsite(B).

75
 CHAPTER FIVE
5.0 CONCLUSION AND RECOMMENDATION
5.1 CONCLUSION:
This work has shown that the corrosion rate of mild steel is essentially
dependent on total bacteria present, electrical conductivity and total dissolved
solid of the leachate. The work has also shown that micro-organism also
contribute greatly and adversely to the corrosion rate of mild steel when used
for construction of various articles such as pipeline and bridge near or in a
dumpsite area, the material will be susceptible to corrosion leading to increase
in pipeline failure for instance in oil producing area.

5.2 RECOMMENDATION:
The research work should also be done under anaerobic condition i.e. in the
absence of air to be able to study and compare the effect of anaerobic bacteria
on underground material of construction such as pipeline with the effect of
aerobic bacteria on the mild steel.

In this research work, bacterial growth continued up to a certain point and then
declined rapidly and continuously since no substrates to sustain their growth.
Research work can also be performed in such a way that the leachate samples
are fed with substrate to enhance the microbial activity and study their effect on
mild steel experimentally as they are growing . The reason for this is that, the
leachate samples were obtained from dumpsites where there is adequate
substrate for microorganisms to sustain their lives which promote the growth of
the microorganism.

76
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