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TITLE:

COMPARISON AND EVALUATION OF HEAVY METAL FOR THE


RECREATIONAL AND INDUSTRIAL AREA IN
PENGKALAN BALAK BEACH AT MELAKA

SUBJECT NAME: PROFESSIONAL ENGLISH 2


SUBJECT CODE: WEB 20302
LECTURER NAME: SA’ADIAH BINTI HUSSIN
SECTION: LO1-T2

STUDENT NAME AND ID NUMBER:


NUR ANIS ALISYA BINTI MOHD FAIZAL
55102316087

NOR ALIA AQILI BINTI AHMAD ROS


55218118064

NURSHUHADA BINTI ADZHARI


55214118066
Malaysian Institute of Chemical & Bioengineering Technology
University Kuala Lumpur
ABSTRACT

Water can be said to be polluted, by the introduction of harmful


materials in such a way by anthropogenic contaminants that are classified into either
a point source of pollution or nonpoint source of pollution are so transformed as to
contaminate its usefulness. Due to the modern lifestyle and developing of economic
such as agriculture, tourism, transportation and industrialisation. Therefore, water
becomes highly demand resources. The Pengkalan Balak Beach was found heavily
polluted by heavy metals. Therefore, this study is carried out to identify the
concentration of heavy metals in this beach that was in Melaka. The Atomic
Absorption and Dr 900 was used to analyse dissolved and particulate concentration
of Cu, Pb, Zn, Fe, Al and K in eighteen surface seawater samples from different site.
Statistical analysis such as the average, standard deviation, correlation matrix and
analysis of variance which is used to analyse the data. The characteristics of the
heavy metal distribution, the mechanism of influence and the distribution ratio
between particulate and dissolved state were analysed. The study proved that the Fe
have the highest value of concentration and the concentration of Zn was lowest value
in all recreational area and industrial area. In the west, dissolved heavy metal has
higher concentration which was higher than in the dissolved state and the other
heavy metals in the particulate state were lower. The distribution of heavy metals in
the beach has been affected not only by natural pollutants, but also by human
activities.

I
ABSTRAK

Air boleh dikatakan tercemar, dengan pengenalan bahan-bahan


berbahaya sedemikian rupa oleh bahan cemar antropogenik yang diklasifikasikan
menjadi sama ada sumber titik pencemaran atau punca pencemaran tidak begitu
berubah untuk mencemarkan kegunaannya. Disebabkan gaya hidup moden dan
pembangunan ekonomi seperti pertanian, pelancongan, pengangkutan dan
perindustrian. Oleh itu, air menjadi sumber permintaan yang tinggi. Pantai Pengkalan
Balak merupakan salah satu pantai yang tercemar oleh logam berat. Oleh itu, kajian
ini dijalankan untuk mengenal pasti kepekatan logam berat di pantai ini di Melaka.
Sampel sembilan belas sampel air laut dari tapak yang berbeza telah dikumpulkan
untuk menganalisis kepekatan dan larutan partikel Cu, Pb, Zn, Fe, Al dan K
menggunakan metode Penyerapan Atom dan Dr 900. Analisis statistik seperti rata-
rata, sisihan piawai, matriks korelasi dan analisis varians yang digunakan untuk
menganalisis data. Ciri-ciri pengedaran logam berat, mekanisme yang
mempengaruhi dan nisbah taburan antara zarah dan keadaan terlarut telah
dianalisis. Keputusan menunjukkan bahawa kepekatan Fe adalah nilai tertinggi dan
kepekatan Zn adalah nilai terendah dalam semua kawasan rekreasi dan kawasan
perindustrian. Kepekatan logam berat yang terlarut adalah tertinggi di barat
mendekati tanah dan logam berat lain dalam keadaan zarah yang lebih rendah
daripada keadaan yang terlarut. Kesimpulannya, pencemaran logam berat zarah
menjadi lebih dan lebih serius dari laut terbuka ke kawasan laut lepas pantai.
Pengedaran logam berat di pantai tidak hanya terjejas akibat pencemaran alam
semulajadi tetapi juga berasal dari aktiviti manusia.

II
TABLE OF CONTENTS

Table of Contents

ABSTRACT..................................................................................................................................I
ABSTRAK...................................................................................................................................II
TABLE OF CONTENTS...............................................................................................................III
LIST OF TABLES........................................................................................................................IX
LIST OF FIGURES .......................................................................................................................X
LIST OF SYMBOLS.....................................................................................................................XI
LIST OF ABBREVIATION...........................................................................................................XII
INTRODUCTION........................................................................................................................1
1.1 Background of study.......................................................................................................1
1.2 Problem statement.........................................................................................................3
1.3 Objectives ......................................................................................................................4
1.4 Significance of study.......................................................................................................4
1.5 Scope and Limitation of the Project................................................................................5
LITERATURE REVIEW.................................................................................................................6
2.1 Overview of Sea in Malaysia...........................................................................................6
2.2 Water Pollution...............................................................................................................7
2.3 Sources of Water Pollution.............................................................................................8
2.3.1 Natural and Anthropogenic Sources........................................................................8
2.4 Heavy Metal....................................................................................................................8
2.5 Characteristics of Heavy Metal.......................................................................................9
2.5.1 Copper (Cu)............................................................................................................10
2.5.2 Iron (Fe).................................................................................................................11
2.5.3 Lead (Pb)................................................................................................................13
2.5.4 Zinc (Zn).................................................................................................................15
2.5.5 Potassium (K).........................................................................................................16
2.5.6 Aluminium (Al).......................................................................................................18
2.6 Atomic Absorption Spectroscopy..................................................................................19

III
2.6.1 Introduction...........................................................................................................19
2.6.2 Basic Equipment in AAS.........................................................................................20
2.7 Dr 900...........................................................................................................................23
2.7.1 Introduction...........................................................................................................23
2.8 Statistical Analysis.........................................................................................................24
2.8.1 Descriptive Statistic................................................................................................24
2.8.2 Inferential Statistic.................................................................................................24
METHODOLOGY......................................................................................................................26
3.1 Introduction..................................................................................................................26
3.2 Apparatus and Material................................................................................................26
3.3 Procedures....................................................................................................................27
3.4 Site Selection and Water Sampling...............................................................................28
3.5 Preparation of Standard Solution.................................................................................28
3.6 Preparation of Blank.....................................................................................................29
3.7 Analysis of Sample Using AAS.......................................................................................30
3.8.1 Determination of Aluminium.................................................................................30
3.8.2 Determination of Potassium..................................................................................31
RESULT AND DISCUSSION.......................................................................................................32
4.1 Introduction..................................................................................................................32
4.2 Raw Data Analysis.........................................................................................................33
4.2.1 Sampling Point 1....................................................................................................33
4.3.2 Sampling Point 2....................................................................................................34
4.3.3 Sampling Point 3....................................................................................................35
4.3.4 Sampling Point 1....................................................................................................36
4.3.5 Sampling Point 2....................................................................................................36
4.3.6 Sampling Point 3....................................................................................................37
4.4 Statistical Analysis of Data............................................................................................38
4.4.1 The Average and Standard Deviation.....................................................................38
4.4.2 The Correlation Matrix and Probability Value........................................................40
4.4.3 The Analysis of Variance (ANOVA).........................................................................43
CONCLUSION AND RECOMMENDATION.................................................................................49
5.1 Conclusion....................................................................................................................49
5.2 Recommendation.........................................................................................................50
REFERENCES...........................................................................................................................51
APPENDICES............................................................................................................................55
APPENDIX A........................................................................................................................55

IV
National Interim Water Quality Standard for Malaysia...................................................55
APPENDIX B........................................................................................................................58
Dilution Calculation.........................................................................................................58
ABSTRACT..................................................................................................................................I
ABSTRAK...................................................................................................................................II
TABLE OF CONTENTS...............................................................................................................III
LIST OF TABLES........................................................................................................................VI
LIST OF FIGURES ....................................................................................................................VII
LIST OF SYMBOLS...................................................................................................................VIII
LIST OF ABBREVIATION............................................................................................................IX
Chapter 1..................................................................................................................................1
INTRODUCTION........................................................................................................................1
1.1 Background of study................................................................................................1
1.2 Problem statement....................................................................................................3
1.3 Objectives ..................................................................................................................4
1.4 Significance of study................................................................................................4
1.5 Scope and Limitation of the Project.....................................................................4
CHAPTER 2................................................................................................................................6
LITERATURE REVIEW.................................................................................................................6
2.1 Overview of Sea in Malaysia...................................................................................6
2.2 Water Pollution..........................................................................................................7
2.3 Sources of Water Pollution.....................................................................................7
2.3.1 Natural and Anthropogenic Sources.............................................................7
2.4 Heavy Metal................................................................................................................8
2.5 Characteristics of Heavy Metal..............................................................................9
2.5.1 Copper (Cu).........................................................................................................9
2.5.2 Iron (Fe)..............................................................................................................11
2.5.3 Lead (Pb)............................................................................................................13
2.5.5 Potassium (K).......................................................................................................16
2.5.6 Aluminium (Al)......................................................................................................17
2.6 Atomic Absorption Spectroscopy......................................................................................19
2.6.1 Introduction.......................................................................................................19
2.6.2 Basic Equipment in AAS................................................................................19
CHAPTER 3..............................................................................................................................25
METHODOLOGY......................................................................................................................25
CHAPTER 4..............................................................................................................................32

V
RESULT AND DISCUSSION.......................................................................................................32
4.4.3 The Analysis of Variance (ANOVA)..............................................................42
CONCLUSION AND RECOMMENDATION.................................................................................48
REFERENCES...........................................................................................................................50
APPENDICES............................................................................................................................55
APPENDIX A............................................................................................................................55
National Interim Water Quality Standard for Malaysia..........................................55
APPENDIX B............................................................................................................................57
Dilution Calculation................................................................................................................57

TITLE PAGE

ABSTRACT
ABSTRAK TABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF SYMBOLS
LIST OF ABBREVIATION

CHAPTER 1 : INTRODUCTION
Background study
Problem statement
Objectives of the Study
Significant of Project
Scope and Limitation of study

CHAPTER 2 : LITERATURE REVIEW


2.1 Overview of Sea in Malaysia
2.2 Water Pollution
2.3 Sources of Water Pollution
2.3.1 Natural and Anthropogenic Sources
2.3.2 Direct and Indirect Sources
2.4 Heavy Metal
2.5 Characteristic of Heavy Metal
2.5.1 Copper (Cu)
a. Toxicity of Copper
2.5.2 Iron (Fe)
a. Toxicity of Iron
2.5.3 Lead (Pb)
a. Toxicity of Lead
2.5.4 Zinc (Zn)
a. Toxicity of Zinc
2.5.5 Potassium (Kb)
a. Toxicity of Potassium
2.5.6 Aluminium (Al)

VI
a. Toxicity of Aluminium
2.6 Atomic Absorption Spectroscopy
2.6.1 Introduction
2.6.2 Basic Equipment in AAS
a. Light Sources
b. Flame
c. Monochromator
d. Detector and Readout System
2.7 Dr 900
2.7.1 Introduction
2.8 Statistical Analysis
2.8.1 Descriptive Statistic
2.8.2 Inferential Statistic

CHAPTER 3 :: METHODOLOGY
3.1 Introduction
3.2 Apparatus and Material
3.3 Procedures
3.4 Site Selection and Water Sampling
3.5 Preparation of Standard Solution
3.6 Preparation of Blank
3.7 Preparation of the Samples
3.8 Methodology for Analyzed Parameter
3.8.1 Analysis of Sample Using AAS
3.8.1 Analysis of Sample Using Dr 900

CHAPTER 4: RESULT AND DISCUSSION


4.1 Introduction
4.2 Site Selection
4.3 Raw Data Analysis
4.3.1 Sampling Point 1
4.3.2 Sampling Point 2
4.3.3 Sampling Point 3
4.3.4 Sampling Point 4
4.3.5 Sampling Point 5
4.3.6 Sampling Point 6
4.4 Statistical Analysis of Data
4.4.1 The Average and Standard Deviation
4.4.2 The Correlation Matrix and Probability Value
4.4.3 The Analysis of Variance (ANOVA)
a. Copper (Cu)
b. Iron ( Fe)
c. Lead ( Pb)
d. Zinc( Zn )
e. Potassium ( K )
f. Aluminium( Al )
4.5 Comparison of Data with National Interim Water Quality Standard for Malaysia

CHAPTER 5 : CONCLUSION AND RECOMMENDATION


5.1 Conclusion
5.2 Recommendation
REFERENCES
APPENDICES
APPENDIX A: National Interim Water Quality Standard for Malaysia

VII
APPENDIX B

VIII
LIST OF TABLES

TABLE TITLE PAGES


NO. NO.
2.1 Properties of Copper 10
2.2 Properties of Iron 12
2.3 Properties of Lead 14
2.4 Properties of Zinc 15
2.5 Properties of Potassium 17
2.6 Properties of Aluminium 18
3.1 Materials and Apparatus for each experiment 27s
4.1 Concentration of heavy metals sample 1 in 33
recreational area
4.2 Concentration of heavy metals sample 2 in 34
recreational area
4.3 Concentration of heavy metals sample 3 in 35
recreational area
4.4 Concentration of heavy metals sample 1 in 36
industrial area
4.5 Concentration of heavy metals sample 2 in 37
industrial area
4.6 Concentration of heavy metals sample 3 in 37
industrial area
4.7 The total average and standard deviation 38
value of heavy
metals concentration along
the seawater in recreational
area.
4.8 The total average and standard deviation value of 39
heavy
metals concentration along the seawater in
industrial

IX
area.
4.9 Correlation matrix for the heavy metals in 40
recreational area
4.10 Probability value between the heavy metals in 41
recreational area
4.11 Correlation matrix for the heavy metal in industrial 41
area
4.12 Probability value between the heavy metals in 42
industrial area
4.13 Average value between the heavy metals in two 43
area
4.14 The result of (ANOVA) for Copper in recreational 43
area.
4.15 The result of (ANOVA) for Copper in industrial area. 44
4.16 The result of (ANOVA) for Iron in recreational area. 44
4.17 The result of (ANOVA) for Iron in industrial area. 45
4.18 The result of (ANOVA) for Lead in recreational area 45.
4.19 The result of (ANOVA) for Lead in industrial area. 46
4.20 The result of (ANOVA) for Zinc in recreational area. 46
4.21 The result of (ANOVA) for Zinc in industrial area. 46
4.22 The result of (ANOVA) for Potassium in recreational 47
area.
4.23 The result of (ANOVA) for Potassium in industrial 47
area.
4.24 The result of (ANOVA) for Aluminium in recreational 48
area.
4.25 The result of (ANOVA) for Aluminium in industrial 48
area.

LIST OF FIGURES

X
FIGURE TITLE PAGES NO.
NO.
2.1 Heavy metals in periodic table 9
2.2 The basic diagram of AAS 20
2.3 Air-acetylene flames used in AAS 21
2.4 Basic elements of monochromator 22
2.5 Dr 900 device 23
3.1 Procedures of experiment 27
3.2 Sample storing 28
3.3 Standard solution 29
3.4 Present of aluminium in sample 31
3.5 Reagent was added to the sample 32
4.1 Drainage from recreational area 34

LIST OF SYMBOLS

XI
% - Percent
km2 -
Kilometer square
g.mol-1 -Gram per mole
g.cm-3 - Gram per cubic centimeter
0
C - Degree celcius
ppb - Part per billion
ppm - Part per million
mL - Millilitre
mg/L - Milligram per litre
km - Kilometer
mi - Miles
mg/kg - Microgram per kilogram

LIST OF ABBREVIATION

XII
Cu – Copper
Pb – Lead
Fe – Iron
Zn – Zinc
Al – Aluminium
K – Potassium
AAS – Absorption Absorption Spectroscopy
APHA – American Public Health Association
ANOVA – Analysis of Variance
O- - Oxygen
RSD – Relative Standard Deviation
UV – Ultraviolet
HCL – Hollow Cathode Lamp
PMT – Photiomultiplier Tube
HNO3 – Nitric Acid
HCL – Hydrochloric Acid
Sq. – Square
Df – Degree of Freedom

XIII
Chapter 1

INTRODUCTION

1.1 Background of study

1
The surface of earth is mostly covered by seawater and it forms from the
seas and the oceans. The composition of seawater is 96.5% water, 2.5% salts,
heavy metals, waste, and smaller quantities of other substances, including dissolved
inorganic and organic materials, particulates and a few atmospheric gases. By
referring to britannica website. , seawater is also enriched with various chemical
elements of commercial importance, which have their own advantages and
disadvantages. Much of the magnesium in the world is recovered from sea water, as
well as large amounts of bromine. Moreover, there are still some countries which use
the process of evaporation to obtain sodium chloride (salt). Other than that, sea can
provide an unlimited supply of drinking water when desalinated.

Nowadays, Malaysia is presently undergoing rapid growth in industrial


and residential area. Due to this, our surrounding environment is frequently exposed
to various types of pollution and contamination especially water pollution. Solid and
liquid wastes which contain organic and inorganic materials which is dissolved or
undissolved from industrial activities are cannot be avoided by products of
manufacturing process which will then be discharged into the water body especially
river , sea and lakes (AhmadIsmail,2008).

One of pollutants that affect the environment especially sea and river, heavy
metals are the most among all pollutants that have been released to water bodies.
According to a publication from Molecular, Clinical and Environmental Toxicology,
Springer Nature America, Inc, 2012, heavy metals are serious pollutants due to their
persistence in natural conditions, toxicity that can be harmful to humans and can be
included and accumulated in food chains. Heavy metals are known as metal
elements that have a high atomic weight compared to water with a high density.
Some of metals that can be found in the water bodies include Lead (Pb), Aluminium
(Al), Zinc (Zn), Potassium (K), Copper (Cu), Iron (Fe), Arsenic (As), and many other
more. Other than that, heavy metals are different compared to organic pollutants,
heavy metals cannot be chemically and biologically degraded and can thus
accumulate either locally or be transported over long distances. Even though some of
these metals are necessary for the environment ecosystem, but if the concentrations
of this heavy metals are high or exceed the permissible limit it can destroy the
ecosystem (Silwa, 2017).

The reason we collected this sample because heavy metal cannot be


seen but can be identified and determined. Therefore, some sea water has been

2
collected to determine heavy metal concentrations in sea water. Atomic Absorption
Spectroscopy (AAS) is the most common method used in determining the
concentrations of heavy metals but there was another device used which is Dr 900.

The method to determine this heavy metal can be refer to APHA 3010-3030
which guide the full method from the sampling until the determination of heavy metal
concentration. (APHA/AWWA, 2012). There was one application has been used for
further analysis of the data obtained from the result. The science of data collection
and the discovery of patterns and trends is statistical analysis (Statistical Analysis:
Definition, Examples,’’ N.d).

1.2 Problem statement

Nowadays, the water available is being further contaminated by


pollutants that causes sickness and death to aquatic plant and human. Almost all the
country in this world experiencing drought affecting the water supply that needed to
use in thermoelectric power plant, maintaining irrigation and for public purpose. This
happens because human not aware with the important of water and do not take it as
a serious matter. There are many factors that might causes pollutants of the sea
such as recreational activities and industrial activities. From this both area, people
are influence by modern society. Therefore, the problem of pollutants is increasingly
concerned about environmental issues relating to industrial activity and polluting
industries, which must comply with increasingly rigid environmental regulations. The
heavy metal pollution of rivers and lakes and other bodies of water has become a
global problem (Peng et al., 2009) in the 21st century.

There are many beautiful coastals in Melaka. Pengkalan Balak


Beach is one of coastal that is often visited whether by local people or foreigners for
fishing, swimming and other recreational activities. Almost every day, it can be
observed that many people came here by strolling along the beach, having a picnic,
swimming and fishing. The concern of this study stated whether this seawater is safe
and suitable for recreational area and does this seawater quality are standard with
National Interim Water Quality Standards for Malaysia ?
Issue of pig farming near industrial area is a major cause of
pollutants in water. This issue was brought for a few years back and until now there
are no strict order from government to stop the sewage from the pig farming channel

3
into Pengkalan Balak Beach and Sungai Tuang which are near to the pig farming.
Based on pervious researcher, its stated that this pig farming pollution resulted of this
pollutant are along the coast about 24 kilometer from Pengakalan Balak until Kuala
Lingi whether in seawater or river. From day by day, there are negative impact on the
tourism sector nearby this beach.In order to achieve this, techniques such as
chemical precipitation, evaporation, adsorption, ion exchange and electrodialysis
have been used to remove and recover heavy metals from wastewaters.

1.3 Objectives

 To describe the pollution status of the beach.


 To compare and evaluate the concentration of heavy metal for the
recreational area and industrial area in Pengkalan Balak Beach Melaka.

1.4 Significance of study

The project was conducted in order to determine the concentration of


heavy metals in Pengkalan Balak Beach which is in Melaka. This is because this
beach is currently in developing area which is near to town. Besides that, Pengkalan
Balak Beach area is full of industrial area, agricultural area and residential area. The
waste that are produced from these activities will be discharged into the beach and it
will contaminate the water.
Therefore, the concentration of the heavy metals pollutants in the river
need to be determined to identify the pollution status of the beach in order to create
awareness among the people about the danger and toxicity of the heavy metals
pollutants to our health and also to the environment. Since the heavy metals pollution
in the water are considered danger, people will need to comply the levels that have
been applied or regulate by the Department of Environment or in the Environment
Quality Act (EQA) 1974.
This project also is conducted to determine the location that are badly
exposed to the heavy metals’ pollutants. By doing the sampling from different
location, we can know which area has a lot more pollutants and which are safe from
the pollutants. Then, we can know the sources of the pollutants from the surrounding

4
location of the sampling point. It will be easier to prevent or reduce the pollutants
after knowing the sources of the pollutants.

1.5 Scope and Limitation of the Project

This project was conducted to determine the concentration of heavy


metals in Pengakalan Balak Beach, Melaka. The heavy metals that’s are selected for
the research are in listed below:

 Copper (Cu)

 Iron (Fe)

 Lead (Pb)

 Zinc ( Zn)

 Potassium ( K)

 Aluminium (Al)

This project used a statistical analysis for the concentration of the


heavy metals measured or analysed. The variables selected for the statistical
analysis are listed below:
 Mean/ Average
 Standard Deviation
 Correlation Matrix
 Probability Value

There are several things that are limiting the scope of the research.
Firstly, the application of Cold-Vapor Atomic Absorption Spectroscopy (CVAAS)
should be applied for the analysis of mercury. Next, the management should provide
the standard solution for cadmium and chromium so that it can measured.

5
CHAPTER 2

LITERATURE REVIEW

6
2.1 Overview of Sea in Malaysia

Malaysia's total coastline is 4,675 kilometers (2,905 mi), while


Peninsular Malaysia's coastline is 2,068 kilometers (1,285 mi), while East Malaysia's
coastline is 2,607 kilometers (1,620 mi). Malaysia has the world's 29th longest
coastline. The two separate parts of Malaysia separated by the South China Sea
share a largely similar character. Between the Peninsula of Malaysia and East
Malaysia there is the South China Sea, Malaysia's largest body of water. Opposite
the west coast of Malaysia there is the Malacca Strait to the south and the Andaman
Sea to the north. The Malacca Strait, located between Sumatra and Malaysia
peninsular, is probably the most important (Andrew,2006).

The South China Sea is off the eastern coast of Peninsular Malaysia, while a
small part in the north is in the Gulf of Thailand. These are part of the Pacific Ocean
marginal seas. The Johor Strait off the south of the Peninsula acts as a maritime
border between Malaysia and Singapore. In East Malaysia, the west coast of
Singapore. Sabah's northeastern coast faces the Sulu Sea while Sabah's
southeastern coast faces the Celebes Sea (Marshall, 2007).

Malaysia claims that its territorial waters extend into the Coral Triangle are
12 nm (22 kilometers (14 mi)). It also calls for an exclusive economic zone of 200 nm
(370 kilometers (230 mi). Malaysia also claims 200 meters (656 ft) in the depth of the
continental shelf or the depth of exploration in the region below the South China. The
territorial claim for the Malacca Strait is shared between Malaysia and Indonesia in
accordance with a 1970 Treaty known as the Treaty between the Republic of
Indonesia and Malaysia on the establishment of the boundary lines of the two
Nations ' territorial waters in the Malacca Strait(Maritime Claims).

2.2 Water Pollution

Water pollution is water contamination, usually caused by human


activity. Water bodies, for example, include lakes, rivers, oceans, aquifers and
groundwater. Water pollution results in the introduction of waste contaminants into
and around the natural environment. For example, the release into natural water
bodies of unused treated wastewater can lead to degradation of aquatic ecosystems.
This, in turn, can lead to problems of public health for people living offshore and

7
animals in aquatic ecosystems. They can use the same polluted water and river to
drink or bathe, irrigate or other things (Larry ,2006).

2.3 Sources of Water Pollution

2.3.1 Natural and Anthropogenic Sources

Surface runoff, drainage from ground water and drainage are important
natural sources. Rainwater is reported to be acidic in urban areas. This is due to
each animal excreta, declining animal and plant bodies, solid waste landfills and the
decline of large amounts of organic matter in swamps. Anthropogenic sources are
the product of man's industrial, domestic, farming and mining activities
(Ashawani,2012).

2.3.2 Direct and Indirect Sources


Water pollution from point source refers to contaminants entering a
waterway from a single identifiable source, such as a pipe or ditch. Examples of
sources in this category include discharges from a sewage treatment plant, a plant or
a storm drain from the city. Section 502(14), Clean Water Act (CWA). Pollution from
non-source sources means diffuse contamination that does not originate from a
single source. This pollution type is often the cumulative effect of small quantities of
contaminants from a large area. The leaching of nitrogen compounds from fertilized
farmland is a common example(Brian, 2008).

2.4 Heavy Metal

A heavy metal is a dense metal which at low concentrations is (usually)


toxic. Most heavy metals have a high number of atoms, a density of atoms and a
specific gravity greater than 5.0. Heavy metals contain metalloids, transition metals,
fundamental metals and actinides. Although some metals meet certain criteria and
not others, most of the element's mercury, iron and plum are toxic metals of
sufficiently high density. (Anne Marie,2018) Heavy metals are metallic compounds
which naturally occur with a high density compared to other metals-at least five times

8
the water density(Amanda,2002). All the heavy metal can be identified through the
periodic table as shown in Figure 2.1.

Figure 2.1: Heavy Metals in Periodic Table (Steemit Beta, 2017)

Heavy metals are generally defined as metallic elements with a high density
in comparison with water. In determining the correlation between heaviness and
toxicity, heavy metals are also classified into transition metals and metalloids such as
zinc, mercury iron, arsenic, which can induce toxicity at low exposure levels
(Duffus,2002). There are some heavy metals are not in transition metals such as
magnesium and aluminium. From this periodic table, the arrangement of chemical
elements with the strongest metal character is in the lower left corner of the table and
non-metal elements are in the top right corner. It also said that as the metal moves
from left to right and from bottom to the top, the metallic value will be reduced
(Fergusson, 1990).
In recent years, there has been an increasing environmental and
global public health concern associated with the pollution and pollution of these
metals in large quantities. In addition, human exposure in several industrial,
agricultural, domestic and technological applications have increased dramatically as
a result of an exponential increase in their use. Heavy metal sources in the
environment are reported to be geogenic, industrial, agricultural, pharmaceutical,
domestic and atmospheric. Environmental pollution is very important in areas of point
source such as mining, foundries and smelters and other industrial operations based
on metals.

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2.5 Characteristics of Heavy Metal

2.5.1 Copper (Cu)

Copper is a soft, malleable and ductile metal with a very good heat and
electricity conductor. Low chemical reactivity of copper, but I have high thermal
conductivity and resist corrosion. A freshly exposed pure copper surface has a
pinkish orange colour with a facial crystalline cubic structure. Copper is used as a
conductor of heat and electricity, as a building material and as a component of
various metal alloys, such as sterling silver used in jewellery and electrical contacts,
cupronickel used in marine hardware and coins and constantly used for temperature
measurement in strain gauges and thermocouples.(McHenry, Charles) Copper is
released into the environment through human activity, industry and natural
resources. Examples of natural sources include decaying vegetation, dust and dirt
from the wind and spray from the sea. The properties of copper are summarized in
the Table 2.1.

Table 2.1 Properties of Copper (Source: ’Copper(Cu)


Properties Value
Isotopes 6
Atomic number 29
Atomic mass 63.546 g.mol-1
Density 8.9 g.cm-3 at 20 oC
Melting Point 1083 oC
Boiling Point 2595 oC
Colour Reddish-brown

a. Toxicity of Copper

10
Metals are one of the most common types of coastal contaminants in the
world and are found in high concentrations in water and sediments in many coastal
and estuarine systems.

(Bryan, Langston,1992)For example, total dissolved copper concentrations


in coastal and estuarine waters may vary from low levels of 0,004 μM (Schiff, Brown,
Diehl & Greenstein, 2007). In highly contaminated habitats, to as high as 1.61μM.
Although copper is essential for human health, but it is consumed and exposed in
high concentrations, it can cause several environmental and heat effects (Pascal,
Fleeger, Galvez & Carman,2007).

Since copper cannot break down in the environment, soon ocean,


where reduced seawater pH becomes more acidic and increases free ion availability,
greater metal toxicity of copper effects would be predicted. Some examples of how
copper can be released into the environment include electrical wiring and
electroplating, alloy production, copper piping, photography, production, anti-fouling
and pesticide formulations. Mining, smelting, refining and coal-fired industries are the
major industrial sources. Some of these anthropogenic sources may lead to
significant concentrations entering the aquatic environment (either directly through
sewage or industrial discharges or through atmospheric deposition), but copper also
enters the aquatic environment through natural sources, e.g. copper mineral
weathering or solution (CCREM 1987).

2.5.2 Iron (Fe)

Iron is thought to be the 10th most abundant element in the crust of the
Earth. Iron is also the most abundant metal per mass, 34.6 percent of the earth's
composition; the concentration of iron in the different layers of the earth's inner and
outer core. Most of this iron is found in different iron oxides, such as hematite,
magnetite and taconite minerals. The core of the earth is believed to be a metal iron -
nickel alloy. This iron is a lustrous, ductile, malevolent, silver - gray metal rusting in
moist air but not dry. Seawater is about 1 - 3 ppb of iron. The quantity varies greatly
in the Atlantic and the Pacific Oceans.
In deep-sea areas, the water often contains iron fragments of the size of a
fist, manganese and small amounts of lime, silicone dioxide and organic compounds,
and is a chemical metal. Iron is used worldwide for commercial purposes and

11
produced in an annual quantity of 500 million tons. Some 300 million tons are
recycled all the time. This is mainly because iron is used in more areas than any
other metal. Alloys reduce the corrosivity of the metal. Manufacturers of steel add
different amounts of carbon. Iron alloys finally become containers, cars, washing
machines, bridges, buildings and even small springs. Iron compounds are used as
pigments in glass and e - mail production or processed in pharmaceuticals,
chemicals, iron, or pesticides fertilizers. In wood and photography, they are also
used. Iron is a key factor in the growth and survival of almost all living organisms,
including algae and enzymes (Meija, 2016). The properties of iron are listed in Table
2.2.

Table 2.2: Properties of Iron. (Source: ‘’Iron (Fe)- Chemical properties, Health and
Environmental effects,’’ n.d)

Properties Value
Isotopes 8
Atomic number 26
Atomic mass 55.85 g.mol-1
Density 7.8 g.cm-3 at 20 oC
Melting Point 1536 oC
Boiling Point 2861 oC
Colour Silver-grey

b. Toxicity of Iron

Toxicity of iron is mainly from absorption. The higher the intake of iron,
the higher the risk of toxicity. In the ferrous state, the cells of the intestinal mucus
absorb iron. Gastric and intestinal secretions can reduce ferrous ions to the ferrous
(absorbable) state (the unusable form of iron). Ferrous iron reacts with hydrogen
peroxide (H202) to form OH, in the reaction: Fe(II) + H2O2--> OH. + OH- + Fe(III)
Under normal conditions, the free radicals formed are controlled and removed by
antioxidants, but if you have an overabundance of iron in your body, the free radicals

12
are not removed as quickly as possible and a build - up takes place. Many factors
affect iron toxicity, such as the level of copper, phosphorus and vitamin E. Factors
that improve iron absorption include Valine and Histidine, Ascorbic Acids, Vitamin E,
Succinate, Pyruvic Acid and Citric Acid or not.
Iron toxicity is not always due to an increase in dietary iron. There are
many diseases that can lead to a problem in iron absorption and in turn iron toxicity.
With acute iron poisoning, much of the damage to the gastrointestinal tract and liver
may be a result of a high localized iron concentration and free radical production,
leading to heptatoxicity via lipid peroxidation and the destruction of the hepatic
mitochondria. Therefore, the patient needs rapid removal of iron from the gut to
prevent tissue damage.

The iron accumulating disease is Hemochromatosis. This is an iron storage


disease the results from the inability of the intestine to keep out unneeded iron.
Instead, iron accumulates in the liver causing siderosis (the accumulation of storage
iron in tissues) and damage to the storage organs. As referred in press release in
CRC press by Laufffer, a normal man will usually absorb 1 mg of iron/day, but with
this disease, he will absorb 3mg/day. This is a very common problem, 1 out of every
15 people have a form of this disease.

2.5.3 Lead (Pb)

Lead is a bluish-gray metal which is present in the crust of the earth in small
amounts. It's very soft, smooth and ductile. However, many anthropogenic activities,
such as burning fossil fuels, mining and manufacturing, contribute to high
environmental lead concentrations. Lead has many different applications in industry,
agriculture and the country. It is currently used to manufacture lead acid batteries,
ammunition, metal products, and X-ray shielding devices. In the United States, an
estimated 1,52 million metric tons of lead were used in different industrial
applications in 2004. Although the production of lead - acid batteries was 83 percent,

13
the remaining uses covered a variety of products, such as ammunition. (3.5 percent),
oxides for paint, glass, pigments, and chemicals (2.6percent), and sheet lead (1.7
percent) (Reston,2006). The properties of lead are summarized in Table 2.3.

Table 2.3: Properties of Lead (Source: ‘’Lead (Pb)- Chemical properties, Health and
Environmental Effects,’’ n.d.)
Properties Value
Isotopes 13
Atomic number 82
Atomic mass 207.2 g.mol-1
Density 11.34 g.cm-3 at 20 oC
Melting Point 327 oC
Boiling Point 1755 oC
Colour Bluish-grey/Bluish-white

c.Toxicity of Lead

Lead is a highly poisonous metal (whether inhaled or


swallowed), affecting almost every organ and system in the human body. (Luckey,
Venugopal ,1979) At airborne levels of 100 mg/m3, it is dangerous to life and health.
Most ingested lead is absorbed into the bloodstream (Rudolph,2003). The primary
cause of its toxicity its predilection for interfering with the proper functioning of
enzymes (Dart, Hurlbut, Boyer-Hassen 2004). Among the essential metals that lead
interacts with are calcium, iron, and zinc. High levels of calcium and iron tend to
provide some protection from lead poisoning; low levels cause increased
susceptibility (Kosnett,2006).
Lead waterworks were often applied in former days, and
these may still be present in old buildings. Lead from rust pipes may partially dissolve
in the water flowing through. Lead may bind to carbonate, therefore lower amounts of
lead dissolve in hard water. Inside the pipes, a layer of hardly soluble alkali lead
carbonate is formed. This layer functions as a protective coating for the underlying
lead of the pipes. Despite its toxicity, lead (II)acetate was widely used in the 19th
century for sweetening wine and other drinks and foodstuffs.

In 20 B.C., the architect Vitruvius first mentioned water pollution containing


lead compounds derived from lead ores in the mining industry when he warned about
its health effects. Lead was frequently released as a silver mining by-product. A white
pigment is the lead white, an alkaline lead carbonate (2PbCO3.Pb(OH)2). It is not
applied anymore due to its extreme toxicity. Most of the industrial lead is used in the

14
manufacture of computers and TV screens. The tetra-ethyl lead compound is used
as a fuel additive. These organic lead compounds are rapidly converted to inorganic
plum and end up in water, even in drinking water at times. Fortunately, the release of
lead is becoming less and less abundant. Lead is applied in roofs and stained-glass
windows in architecture. In general, dissolved or suspended lead in wastewater is
mainly derived from streets, pipes, and soils.

2.5.4 Zinc (Zn)

Zinc is a lustrous bluish-white metal which are commonly found in


earth crust. It is crystalline and brittle at ordinary temperature, but it becomes ductile
and malleable when heated between 1100C to 1500C. Zinc is a relatively reactive
metal that combines with oxygen and other non-metals and reacts to the release of
hydrogen with dilute acid. It is the most abundant element comprising between
0.0005% and 0.02% of the crust of the earth. The dominant ore is zinc blende also
known as sphalerite. Other important zinc ores are wurtzite, smithsonite and
hemerophyte. The properties of zinc are listed in Table 2.5.

Table 2.5: Properties of Zinc. (Source: (‘’Zinc(Zn)- Chemical properties, Health and
Environmental effects,’’n.d.)
Properties Value
Isotopes 10
Atomic number 30
Atomic mass 65.37 g.mol-1
Density 7.11 g.cm-3 at 20 oC
Melting Point 420 oC
Boiling Point 907 oC
Colour Silvery-white

d.Toxicity of Zinc

15
Zinc salts tend to be corrosive and ingestion can result in severe injury to
the mouth, throat and stomach. Initial symptoms include burning of the mouth and
pharynx with vomiting and may be accompanied by erosive pharyngitis, esophagitis,
and gastritis. Complications may include gastrointestinal haemorrhage and acute
pancreatitis. A woman who swallowed 28 g of zinc sulphate (7 g of zinc) suffered
hypoglycaemia and tachycardia and eventually died as a result of pancreatic
haemorrhage and renal damage.

Poisoning by an emetic dose of zinc sulphate (containing 1-2 g zinc)


presented symptoms that included vomiting, nausea, abdominal cramps, epigastric
pain and bloody diarrhoea. The symptoms in a 26-year old woman who was
poisoned by swallowing 10 mL of a correction fluid (containing 26% zinc chloride and
0.5% methanol) included oropharyngeal and gastric burns, epigastric tenderness,
dysphagia, diarrhoea, gross oral mucosal and pharyngeal enema; the patient
subsequently experienced hematemesis and melaena which required multiple blood
transfusions. Gastrointestinal distress and diarrhoea have also been reported in
several cases following the consumption of food and beverages stored in galvanized
zinc containers.

Gastrointestinal ulcerations and burns following ingestion of toxic amounts


of zinc salt may lead to an acute decline in haemoglobin and haematocrit levels and
may result in intravascular haemolysis. Acute exposure to zinc sulfate at a dose of 3
mg / kg per day for one week resulted in secondary anaemia to gastrointestinal
haemorrhage. Changes in serum lipid profile, serum ferritin and erythrocyte
superoxide dismutase activity have been reported in several patients with 4 zinc
toxicity in humans with high zinc doses. As a result of sustained hands to zinc
chloride solution, microcytic anaemia and decreased blood platelets have been
reported.

2.5.5 Potassium (K)

Potassium is a white, soft metal. Its melting point is 63 ° C (145 ° F)


and 770 ° C (1420 ° F). Its density is 0,862 grams per cubic centimetre (1.00 grams
per cubic centimetre) lower than water. This means that potassium can float and
dissolve in water. Like the other alkali metals, potassium is very active metals. It is
reacting with water violently and gives off hydrogen gas. Potassium is the eighth
most abundant element found in the Earth's crust. In the other hand, it believes to

16
abundance to be about 2.0 to 2.5 percent. Potassium is less dense than water, so
that water can float. However, potassium reacts violently with water chemically. It
gives off hydrogen and catches fire. It is only a little less abundant than its sodium
cousin alkali Seawater contains about 400 ppm of potassium. It tends to settle and
therefore ends mostly in sediments. The properties of potassium are listed in Table
2.5 below.

Table 2.5 Properties of potassium (Source: ‘’Potassium-(K) – Chemistry explained,


n.d.)

Properties Value
Isotopes 20
Atomic number 19
Atomic mass 39.0983 g.mol-1
Density 11.34 g.cm-3 at 20 oC
Melting Point 63 oC
Boiling Point 770 oC
Colour Silvery-white metal

e.Toxicity of Potassium

Potassium is a mineral found in food which is consumed by people.


It's an electrolyte, too. Electrolytes carry electric impulses all over the body.
Electrolytes can help in a variety of essential body functions, including blood
pressure, normal water balance, muscle contractions, nerve impulses, digestion,
cardiac rhythm and pH balance (acidity and alkalinity).

High water-soluble levels of potassium could cause damage to


germinating seedlings, inhibits of the uptake of other minerals and reduces the
quality of the crop. The consequences of low potassium levels are apparent in a
variety of symptoms such as restricted growth, reduced flowering, lower yields and
lower quality produce. Because potassium metal is highly reactive, it must be
handled with great care and with full skin and eye protection. Signs of a potassium
deficiency are extreme fatigue, muscle spasms, weakness, or cramping, irregular
heartbeat, constipation, nausea, and vomiting. Although potassium can be an
effective tool to reduce water retention, it can also be dangerous to have too much

17
potassium in the blood. The consumption of potassium via dietary sources is usually
safe.

2.5.6 Aluminium (Al)

Aluminium is a silvery-white and light weight metal. Aluminium is


soft and malleable. Generally, aluminium is the third most abundant metals element
can be found in earth’s crust. Aluminium is a very light metal with a specific weight of
2.7 g/cm3, about a third that of steel. It is ductile and has a low melting point and
density. Aluminium is a very rare in its free atoms. It is the most among metals on the
earth to refine because aluminium is oxidized very rapidly and that its oxide is an
extremely stable compound that. Aluminium are found primarily as the ore bauxite. It
is also highly reactive and does not occur freely in nature. Aluminium can be recycled
100 percent without any degradation of its quality. The properties of aluminium are
listed in Table 2.6.

Table 2.6 Properties of aluminium (Source: ‘’Aluminium-(Al) -European Aluminium


Association., n.d.)

Properties Value
Isotopes 3
Atomic number 13
Atomic mass 26.98154g.mol-1
Density 2.7 g.cm-3 at 20 oC
Melting Point 660.4 oC
Boiling Point 2467oC
Colour Silvery-white

f.Toxicity of Aluminium

Aluminium (Al), when present in high concentrations, has for long been
recognised as a toxic agent to aquatic freshwater organisms. Aluminium may cause
major harm to animals, plants, human and environment. Aluminium naturally occurs
in very low concentrations of nut in waters when it is high in concentration and can
cause several health and environmental problems.

18
Higher mining waste concentrations may have a negative effect on aquatic
bioeconomic. Aluminium is, however, is toxic to fish in acidic, unbuffered waters
beginning at 0.1 mg / L. Simultaneous shortages of electrolytes affect the
permeability of the gull and damage the cells of the surface. Aluminium is toxic to fish
with pH values from 5.0 to 5.5. Aluminium ions build up on the gulls and block them
with a slim breathing-limiting layer. When pH values decrease, aluminium ions
control the permeability of the gull by calcium and increase the toxicity of aluminium.
When pH values decrease, aluminium ions influence calcium 's adjustment of gull
permeability and increase aluminium toxicity. Approximately 5–10 mg of aluminium
enters our bodies daily through various sources such as water, food and
occupational aluminium exposure in industry. When the water is contaminated, the
aquatic, human and other animals also will be contaminated (Jiang, Chen, Zheng,
Han, Tang,Smith, 2008).

2.6 Atomic Absorption Spectroscopy

2.6.1 Introduction

Atomic absorption (AAS) spectroscopy uses light absorption to


measure gas-phase atomic concentration. Since samples are usually liquids or
solids, the atoms or ions of the analyte must be sprayed in a flame or graphite
furnace (B. Welz, M. Sperling,199). The atoms absorb UV or visible light and
transition to higher levels of electronic energy. The concentration of the analyte is
determined by the amount of absorption. It is difficult to apply the Beer-Lambert law
directly in AAS due to variations in the atomization efficiency of the sample matrix
and the non-uniformity of the concentration and track length of the analyte atoms (in
graphite furnace AA). Concentration measurements are usually determined from the
work curve after the instrument has been calibrated with known concentration
standards (Haswell,1991). By measuring the amount of light absorbed, the
quantitative can be obtained and measured. Figure 2.2 shows block diagram of AAS.

19
Figure 2.2: The basic diagram of AAS. (Source: (Reynolds,1970)

2.6.2 Basic Equipment in AAS

a. Light Sources

There are several types of light sources used by the AAS depend
on its usage such as Hollow Cathode Lamp (HCL) and Electrode Discharge Lamp
(ECL) The commonly used light source is a hollow cathode lamp. For each element
determination, a different element hollow cathode lamp is required because HCL is
an excellent, bright, intense and stable line source for most elements. Cathode is
made from the same metal in the sample. Single element lamps are commonly used,
although there are also multi - element lamps. Lamps are made of quartz windows in
glass and are filled with an inert gas like argon or neon gas (Schrenk, 1975).

b. Flame
Flame Atomic Absorption is a very common technique for detecting
metals present in samples and a sensitive technique for the quantitative
determination of more than sixty metals. The technique is based on the principle that
ground state metals absorb light at a specific wavelength is used to breakdown
complexes into atoms or molecules and destroy any analyte ions. Metal ions in a
liquid are converted to atomic state by means of a flame (David,2017). The process
of converting a liquid to a free gaseous atom is called atomization. There are two
main atomizer types that are discreet and constant. Continuous atomizers are always
steadily introduced to the analyte, while discrete atomizers discontinuously introduce
the analyte. A flame is the most common continuous atomizer used in AAS. The
atomisation of the sample limits the accuracy, precision and detection limit of the

20
analytical tool. When the temperature of flame is higher, the sensitivity of the
quantitative analysis is increase. The common types of flames used in AAS are the
air-acetylene flames which the acetylene acts as fuel and air as an oxidant. Flames
are shown in Figure 2.3.

Figure 2.3: Air-acetylene flames used in AAS

c. Monochromator

The monochromator generally produces monochromatic light by dispersing


unwanted wavelengths from the light source beam. A monochromator can also be
called a wavelength selector to isolate light emitted by a single or narrow spectral line
from a wavelength by the light source. A monochromator consists of an input slit that
limits the light by selecting a defined beam light from the source, a dispersion device
that helps to spread or disperse the light into the desired wavelength causes the
different wavelengths of light in the source beam to be dispersed at different points.
and finally, the light will exit the monochromator through the exit slit and enables
selection of a wavelength to produce the required monochromatic light (Douglas,
2007). Figure 2.4 is a simple representation of a monochromator that uses a
diffraction grating (Douglas, 2007).

21
Figure 2.4: Basic Elements of a Monochromator

d. Detector and Readout System

A detector may be a mechanical, chemical or electrical device that measures


the environmental change of a variable. It is used to measure the light intensity and
amplifies the signal. The amount of radiation passing through a sample is measured
in atomic absorption spectroscopy and quantitatively described by transmission.
When light passes through a sample, power is reduced because it is absorbed in the
sample by the analyte. The common type of detector used in AAS is photomultiplier
tube (PMT). The role of the photomultiplier tube is used for low radiant power
measurements. The amount of light absorbed by a sample is directly related to the
concentration of the element in the sample.

Photomultiplier tube is highly sensitive, dynamic and can be used for many
types of elements. The photomultiplier tube is a vacuum tube which generates an
electrical signal proportional to the light intensity when the device is reached. Light in
the photomultiplier tubes admitted through a window falls directly on a photosensitive
material of the photocathode. The cathode is covered with a material that emits
electrons when lit. The higher the light intensity of the light incident, the more
electrons are emitted. The emitted electrons are accelerated to an adjacent electrode
with a positive electrical potential in relation to cathode. It is called a dynode. When
electrons are reached the dynode, it liberates a few other electrons which in turn
attached to another dynode, emitting even more electrons. The electrical current
measured at the anode is then used as a relative measure of the intensity of the
radiation reaching the photomultiplier. Then, the light intensities that are obtained are
led to an electric current of useful magnitude which can be further amplified to

22
provide the requirement of quantitative measurement. This is achieved by an
electronic component that displays information in a format that can be used
effectively by the researcher. Therefore, it is possible to compare the sample
absorbance with that of standard solutions using a calibration curve and hence
determine the element concentration.

2.7 Dr 900
2.7.1 Introduction
The Dr 900 is device which can test multiple parameters. It is
portable, rugged and time tested. This device simplified testing in the field by using
the DR900. This device has an intuitive user interface, data storage for up to 500
tests, and an integrated USB port for easy data and information transfer. The
portable colorimeter enables you to quickly and easily access your most used test
methods in less than four clicks. The portable colorimeter also supports the basic
testing requirements by offering at least 90 of the most common test parameters.

This colorimeter is waterproof, stainless steel, resistant to shock and has


been tested for higher quality. Combining all these features with a backlit push button
for use in low light areas, this device has a portable colorimeter that is ready for field
testing and makes testing a little less challenging in harsh field environments.
Figure 2.5 shows Dr 900 device.

Figure 2.5: Dr 900 device

23
2.8 Statistical Analysis
2.8.1 Descriptive Statistic

Descriptive statistics is the term used to describe brief descriptive


coefficients that summarize a given set of data that can be either a representation of
the whole population or a sample. Descriptive statistics are broken down into central
tendency measurements and variability measurements (spread). Measures of
variability, or the measures of spread, aid in analysing how spread-out the
distribution is for a set of data.

Central tendency measurements include mean, median and mode, while


variability measurements include standard deviation, variance, minimum and
maximum variables and curtosis and skewing is the way to describe the central
frequency distribution position for a data group. Variability measurements help to
communicate this by describing the form and distribution of the data set. Variability,
quartiles, absolute variation and variance are all examples of variability
measurements.

2.8.2 Inferential Statistic


Inferential statistics is one of the two main branches of
statistics. With inferential statistics, it helps reach conclusions that extend
beyond the immediate data alone. For instance, with using inferential statistics
to try to infer from the sample data what the population might think and can
use inferential statistics to make judgments of the probability that an observed
difference between groups is a dependable one or one that might have
happened by chance in this study. Thus, by using inferential statistics to make
inferences from sample data to more general conditions and relate with
descriptive statistics simply to describe what is going on in sample data
(William, 2006).
Inferential statistics, unlike descriptive statistics, is the attempt
to apply the conclusions that have been obtained from one experimental study
to more general populations. This means inferential statistics tries to answer
questions about populations and samples that have not been tested in the
given experiment (Siddharth, Lyndsay, 2010). Inferential statistics is the branch
of statistics that deals with generalizing outcomes from small samples to much
larger populations. Inferential statistics are concerned with making inferences

24
based on relations found in the sample, to relations in the population.
Inferential statistics help to decide, for example, whether the differences
between groups that we see in sample data are strong enough to provide
support for the hypothesis that group differences exist in general, in the entire
population.

There are some data to consider the basic principles of


significance testing: the sampling and test statistic distribution, p-value,
significance level, power and type I and type II errors. Then, the large number
of statistical tests and techniques will help to make inferences for different
types of data and different types of research designs. For each individual
statistical test will show how it works, for what data and design it is
appropriate and how results should be interpreted. This sample data can also
be learned on how to perform these tests by using freely available software.

25
CHAPTER 3

METHODOLOGY

3.1 Introduction
In this project, the main objective is to determine the
composition of the heavy metals in Pengkalan Balak Beach, Melaka. The
experiment was conducted for 3 weeks in Laboratory 25 and 17, Environmental
Lab at Unikl MICET. The samples from the beach were selected at six different
locations whether in recreational area and industrial along the beach. Then,
equipment that is used to determine these heavy metals are Atomic Absorption
Spectroscopy (AAS) and Dr 900. This device is to measure the concentrations
of the heavy metals which has been most common method used nowadays.
The concept of AAS is by the absorption of light by the elements which is used
to measure their concentrations. The sample will be vaporized and become
free atom which is visible light will past through it and the monochromator will
be disperse the light according to the desired wavelength. Then the detector
detects the light intensity and transfer the result into the monitor. For Dr 900,
this equipment is more user-friendly as it has data storage for up to 500 tests
and a built-in USB port for the easy transfer of information. After that,
statistical analysis was conducted using the result from the analysis.

3.2 Apparatus and Material.


List of material used in each experiment , Dr 900 were used for aluminium and
potassium with 10 mm and 25 mm sample cell. For AAS method to identify
zinc,lead,iron and copper the material and apparatus use is micro pipette,
glass dropper, 100 mL volumetric with stopper as listed in Table 3.1

26
Table 3.1 Material and Apparatus Used for Each Experiment
EXPERIMENTS MATERIAL AND APPARATUS
Dr 900 : Aluminium, Potassium 10 mm and 25 mm sample cell

Atomic Absorption Spectroscopy: Micro pipette, glass dropper, 100mL


Zinc, Lead, Iron , Copper volumetric with stopper

3.3 Procedures
This experiment was started by selecting the suitable site or place
for water sampling. Then, for Atomic Absorption Spectroscopy (AAS) the
standard solution for copper, lead, zinc and iron was prepared from its stock
solution followed by the blank solution and the samples. Then, for Dr 900, the
sample are prepared according their reagents of aluminium and potassium.
And lastly is the analysis of the sample to determine the heavy metals
concentrations. It is summarized as shown in Figure 3.1.

Selection
location for
sampling.

AAS Method: Dr 900 Method:

Preparation of Preparation of
standard solution for reagent powder
Cu, Fe, Pb and Zn. pillow for Al and K.

Preparation of blank
solution.

Preparation of sample.

Analysis of sample 27
concentration.
Figures 3.1: Procedures of experiment

3.4 Site Selection and Water Sampling

First and foremost, the suitable location for water sampling need to
be identified. The sampling was done at Pengkalan Balak Beach, Melaka. It is
located near the town of Masjid Tanah. This place is tourist attraction. There
are many of human activities were done here include fishing, swimming and
other recreational activities. Most sample points are taken near the drainage
area and there were six different are been collected, three points are from
recreational area and three more are from industrial area. For each points,
three sample was taken to get average readings when analyse. This sample
was taken in morning. The sample collected was kept in cold storage filled with
ice which is 24oC of temperature. The sample was taken at knee-high level of
the sea to avoid any debris such as plastic bottles, floating leaves and wood or
branches around the sampling area. Figure 3.2 shows sample storage after
being collected.

Figure 3.2 : Sample storing

28
3.5 Preparation of Standard Solution

The heavy metals that have been analysed using Atomic


Absorption Spectroscopy (AAS) is copper (Cu), iron (Fe), lead (Pb), zinc (Zn). The
preparation of standard solution are done by diluting 1000 mg/L of stock solution.
The standard was 1 ppm, 2ppm and 3ppm. The volume of the stock solution
needed to be diluted was calculated using the formula below:

M1V1 = M2V2
M1 = Concentration of the standard needed .(mg/L)
V1 = Volume of the standard solution needed. (mL)
M2 = Concentration of the stock solution (mg/L)
V2 = Volume of the stock solution need to be diluted.(mL)

Based on the formula for 1ppm, 0.1 mL of the stock solution was
measured using the micro pipette and transferred into 100mL volumetric flask.
After that, ten drops of concentrated nitric acid (HNO 3) was added and distilled
water was filled up until it reached the mark. The volumetric flask was shaken
and inverted several times to mix the content properly. This step was repeated
by measuring 0.2mL for 2ppm and 0.3mL for 3ppm. These steps were also
repeated to prepare another stock for other parameters. Figures 3.3 shows
standard solution that have been prepared.

Figure 3.3: Standard solution

29
3.6 Preparation of Blank
The preparation of blank solution was started by prepared by measuring
100mL of distilled water and then it was transferred into 100mL volumetric
flask. Then, add 10 drops of concentrated nitric acid (HNO3) into the volumetric
flask were added and shaken to mix the content properly.

3.7 Analysis of Sample Using AAS


Only iron, copper, lead and zinc are analysed using the Atomic
Absorption Spectroscopy, AAS (Perkin Elmer 5100), to determine their
concentration. Firstly, the Acetylene gas was switched on and was set to 2
bars for its pressure. Next, the compressor was also switched on and it was
set to 4 bars. After that, the AAS switch and suction hood was switched on.
First, the lamp page was selected, and copper are selected as the element to
be analysed and need to wait until the absorbance reading to be constant.
Next, the parameter page was selected with calibration tab was filled with
1ppm, 2ppm and 3ppm for calibration value. Then the flame page was selected.
The air pressure, the acetylene pressure, the nebulizer interlock, the burned
head and the drain interlock was ensured to be in good before starting the
analysis.

Then, the ‘analyse’ page was selected. The blank solution was
analysed first. After that, first copper standard solution that was1 ppm was
introduced and analysed. This was repeated for 2ppm and 3ppm. The display
calibration was selected to display the calibration curve. Lastly, the sample
was introduced and analysed. This step were repeated for replicated sample 2
and sample 3. The result obtained was recorded and the experiment was
repeated for determination of iron (Fe), lead (Pb) and zinc (Zn) metals.

3.8 Analysis of Sample Using Dr 900


3.8.1 Determination of Aluminium
The experiment began by preparing blank and sample cells. The
blank cells were filled with 10 mL of the reacted sample into a sample cell and one
Bleaching 3 Reagent powder pillow are added to the blank and instrument arande
started with 30 second reactions while shaking it. After that, for preparing the sample,
sample were filled in 50 mL mixing cylinder until mark level and then one Ascorbic
Acid Powder Pillow were added. The mixing cylinder were inverted several times to
dissolve the powder. Next, one AluVer 3 Aluminium reagent powder pillow were

30
added, then an orange to orange-red colour appeared if aluminium present.
Instrument timer of 1 minute a started and cylinder were inverted repeatedly during
reaction time. It was shaken well to let the chemical dissolve and was left for 15
minutes. Next, 10 mL of solution from the cylinder were poured into a second sample
cell. When the timer expires, blank cell was read first by set to ZERO by using Dr 900
spectrophotometer and followed by sample cell for aluminium testing. The Figure
3.4 shows aluminium were present in the sample. The measurement was recorded,
and the step was repeated for next sample.

Figure 3.4: Present of aluminium in sample

3.8.2 Determination of Potassium


The experiment was conducted by preparing sample and blank cells.
The sample cell are filled with 25 mL of seawater into the mixing cylinder. Next, One
Potassium 1 Reagent Pillow were added and follow by one Potassium 2 Reagent
Pillow. The mixing cylinder was inverted until the solution became clear. After that,
one Potassium 3 Reagent Pillow are added by inserted the stopper on the mixing
cylinder and solution was shaken for 30 seconds until white turbidity formed because
there were potassium in the sample. Instrument were started for about 3 minutes and
poured 10 mL of the solution from the mixing cylinder to sample cells. For blank
preparation, a sample cell with 10 mL of fresh sample were added. When the timer
expires, the blank sample cell cleaned, and blank were inserted into the cell holder
and the prepared sample cell were cleaned. Within 7 minutes after the timer expires,
prepared sample were inserted into the cell holder. Blank sample was read first by
set it to ZERO by using spectrophotometer. The measurement was recorded, and the
step was repeated for the next sample. Figure 3.5 shows reagent was added to
sample.

31
Figure 3.5: Reagent added to the sample

CHAPTER 4

RESULT AND DISCUSSION

4.1 Introduction
This chapter presents the results and analysis of the data that was
done. The water sample was collected from six different points from two locations
along the Pengkalan Balak Beach, Melaka for recreational and industrial area. The
concentration of six heavy metals were measured: Copper (Cu), Iron (Fe), Lead (Pb),
Zinc (Zn), Potassium (Kb) and Aluminium (Al). The results obtained from the
collected sample were analysed statistically, such as average, standard deviation
and correlation matrix.

32
4.2 Raw Data Analysis
From Recreational Area,
4.2.1 Sampling Point 1
The concentrations of the heavy metals measured from the first sampling
point are presented in Table 4.1.

Table 4.1: Concentration of heavy metals for sample 1

Sample Concentration of Heavy Metals (mg/L)


Cu Fe Pb Zn K Al
1.1 0.566 1.109 0.180 0.134 0.240 0.261
1.2 0.534 0.932 0.165 0.109 0.250 0.263
1.3 0.539 0.905 0.169 0.108 0.240 0.260

The experiment was conducted three times in order to get more


accurate result. Based on the result, iron has the highest concentration compare to
the other metals that is 1.109mg/L, 0.932 mg/L and 0.905 mg/L. This is because
waste and residual that come from the nearby recreational area contain amount of
iron. Iron can also come from the rusting and corrosion of the pipeline that have been
channel from the nearby hotel and chalet area which flow towards the sea.

Copper is also one of metals that high in seawater, this is because


copper piping used in plumbing and also as an anti-fouling agent in paint on the hulls
of boats. Potassium and aluminium detected in a slightly medium concentration level
in seawater because of people threw alloys tin in the sea but the concentration is not
high enough because dustbin have been provided nearby so it prevented them from
throwing trash into the sea. However, the concentrations of potassium high could be
attributed to the agricultural runoff from fertilized land that channel the drain into the
water as in the Figure 4.1.

33
Figure 4.1: Drainage from recreational area

Zinc and lead are detected as low concentrations level from others metal
in the water. Zinc mainly came from the pesticides and fertilizer used for agriculture.
Since zinc present in the water, it can be said that nearby area use fertilizer for
agriculture activities. The concentrations of lead in water are due to old buildings in
the vicinity. The leads which comes out from the pipe will partially dissolved in the
water. The presence of lead will bind carbonate and dissolve lower amounts of plum
in hard water. The formation of hard soluble alkaline lead carbonate is found inside
the pipes.

4.3.2 Sampling Point 2


The concentrations of the heavy metals measured from second sampling
point in recreational area are presented in Table 4.2.

Table 4.2 : Concentration of heavy metals for sample 2

Sample Concentration of Heavy Metals (mg/L)


Cu Fe Pb Zn K Al
2.1 0.505 0.161 0.148 0.240 0.260
0.923
2.2 0.500 0.147 0.147 0.250 0.263
1.115
2.3 0.522 0.141 0.106 0.240 0.264

34
1.042

Based on the result obtained, the iron concentration was the highest
that is 0.923 mg/L, 1.115 mg/L and 2.066 mg/L. This is because, this area is located
near a rubbish bin and the leachate are channel to water. Copper also slightly high in
this point because the location is near to boat parking which means old paint and
metal may deprived from boat and cause anti-fouling agent in paint are high in this
area. Potassium and aluminium are presented in this area too because near to waste
trash. The concentration of lead is presented because of pipeline of the leachate are
corrodes in the seawater. Zinc mainly came from the waste produced from the
nearby farm such as food waste and the dunk produced. This source effects the high
concentration that are presented in the seawater.

4.3.3 Sampling Point 3


The concentrations of the heavy metals measured form the third point in
recreational area are presented in Table 4.3.
Table 4.3: Concentration of heavy metals for sample 3

Sample Concentration of Heavy Metals (mg/L)


Cu Fe Pb Zn K Al

3.1 0.521 0.932 0.141 0.118 0.220 0.259

3.2 0.514 0.974 0.119 0.150 0.230 0.260

3.3 0.494 1.238 0.160 0.151 0.240 0.258

The result obtained from the third sampling point are quite similar
the result from the first and second sampling point as shown in Tables 4.1 and 4.2.
This is because this third sampling point are near to recreational area which near to
developing residential area, hotels and chalet and this show that the sources of the
heavy metals are the same from each sampling point. Iron was detected the highest
in this area that is 0.932 mg/L, 0.974 mg/L and 1.238 mg/L. The difference in this
area compare to another both sampling location is the concentration of potassium
measured was lower. This is because this area there are no farming or agriculture
activities. This sampling point have highest concentrations of zinc because of the

35
nearby food stall washes dishes with plain water which contain zinc and flow towards
the sea.

From Industrial Area,


4.3.4 Sampling Point 1
The concentrations of the heavy metals measured form the first point are
presented in Table 4.4.

Table 4.4 Concentration of heavy metals for sample 1


Sample Concentration of Heavy Metals (mg/L)
Cu Fe Pb Zn K Al
1.1 0.544 1.020 0.135 0.132 0.210 0.249
1.2 0.552 0.904 0.150 0.121 0.210 0.252
1.3 0.520 0.961 0.164 0.137 0.210 0.253

For each parameter, experiment was replicate three times in


order to get more accurate and average value. Based on the result obtained, iron has
the highest concentration compare other metals which is 1.020, 0.904 and 0.961
same as in recreational area. This is because in industrial area, people used
abundantly pharmaceutics, chemicals, iron fertilizers, or pesticides in industry and
channel it to seawater. Iron also come from rusting of the piping from the building in
the industry.
Copper also are detected to be medium highest concentration as
there are major industrial sources such as smelting,coal-burning, mining and refining
industries. Potassium and aluminium are identified to be slightly lower because of the
waste from nearby industrial area. Resident nearby are set up stall beside the sea
and cause all the wastewater channel towards the water and aluminium can also
been used so some of it are pollutants the seawater same as in recreational area.
Lead and zinc have the lowest concentrations of metals among all metals this is
because fertilizer that cause concentration of zinc higher are not being use for
agriculture and only pesticides are been used. Lead are low because there is not
excess leachate are channel to water.

36
4.3.5 Sampling Point 2

The concentrations of the heavy metals measured form the second point
are presented in Table 4.5.

Table 4.5 Concentration of heavy metals for sample 2


Sample Concentration of Heavy Metals (mg/L)
Cu Fe Pb Zn K Al
2.1 0.503 0.947 0.162 0.112 0.210 0.247
2.2 0.493 0.938 0.151 0.112 0.220 0.250
5.3 0.495 0.940 0.154 0.147 0.220 0.251

Based on the result obtained, the iron concentration in this area was
the highest that is 0.947 mg/L, 0.938 mg/L and 0.940 mg/L. The area is located near
to industry involving usage of iron fertilizers and chemical waste. Copper mainly
came from the coal-burning and have higher sensitivity of saltwater that increase
absorption of copper in water. This source effects the high concentration of copper
presented in seawater. Aluminium and potassium are detected to be slightly high due
to waste from nearby. The zinc and lead are the lowest concentration that are
presented in this area.

4.3.6 Sampling Point 3


The concentrations of the heavy metals measured form the third point in
recreational area are presented in Table 4.6.
Table 4.6 Concentration of heavy metals for sample 3
Sample Concentration of Heavy Metals (mg/L)
Cu Fe Pb Zn K Al
3.1 0.497 0.941 0.161 0.115 0.210 0.251
3.2 0.477 0.956 0.147 0.147 0.210 0.250
3.3 0.497 0.913 0.161 0.132 0.200 0.255

The result obtained from third sampling in industrial area have low
copper concentration compare to recreational area and others point in industrial area.
This is due to there are less waste from coal-burning, smelting and mining from
industry are channel towards the water. Iron mainly came from the pig farm nearby
such as chemical waste, pesticides and iron- fertilizer. For aluminium and potassium
the result obtained are similar to the result in point 1 and point 2 this is because all of
this point have been pollutants by waste. Since there are lesser aluminium can, tin ,

37
glass bottle and medication waste are disposed in seawater. Lead and zinc are the
lowest in all sampling point because there are rubbish bin are provided so there are
not much leachate are channel to water. There were barrier in this point cause
seawater to coagulate with sewage from pig farm. But zinc concentration are mainly
from pig farm that use fertilizer and pesticides use. The average concentration for
each sampling point are presented in Table 4.6 below .

Average
Recreational Area,

Sample Concentration of Heavy Metals (mg/L)


Recreational Cu Fe Pb Zn K Al
Area
1 0.546 0.982 0.171 0.117 0.24 0.261

2 0.509 1.027 0.150 0.134 0.24 0.262

3 0.539 1.048 0.14 0.140 0.23 0.259

Industrial Cu Fe Pb Zn K Al
Area
1 0.539 0.962 0.150 0.130 0.210 0.251

2 0.539 0.942 0.156 0.124 0.220 0.250

3 0.491 0.937 0.156 0.131 0.210 0.252

Tables 4.6 The average value of the heavy metals at each sampling point

4.4 Statistical Analysis of Data


4.4.1 The Average and Standard Deviation

Table 4.7 The total average and total standard deviation value of the heavy metals
concentration along the seawater in recreational area.
Metals Cu Fe Pb Zn K Al

Average 0.531 1.019 0.154 0.130 0.240 0.261


(mg/L)

38
Standard 0.020 0.034 0.016 0.012 0.006 0.002
Deviation

In general, table 4.7 shows the average and the standard deviation
of the heavy metals concentration that have been calculated in recreational area.
Firstly, the highest average value among all elements was for iron that is 1.019 mg/L.
This is because iron present in all sampling point with high concentration because
iron to be discharged in water is fertilizer and pesticides use for agriculture.
The present of the copper in the water was also high due to uses of
copper alloy for plumbing and anti-fouling paint at point 2. The other metals were
present have lower concentration compare to iron and copper such as potassium and
aluminium. The least concentration of heavy metals in the seawater are zinc. The
concentration of zinc lower because there are rubbish bin provided and prevent
people from throwing trash into the sea in point 1.
By referring to the table 4.7, the standard deviation was the highest is
iron. This is because in all three point there are agriculture activity.

Table 4.8 The total average and total standard deviation value for the heavy metals
concentration along the seawater in industrial area.
Metals Cu Fe Pb Zn K Al

Average 0.523 0.947 0.154 0.128 0.213 0.251


(mg/L)
Standard 0.028 0.013 0.003 0.004 0.006 0.001
Deviation

Table 4.8 shows the average and standard deviation of the heavy
metals are obtained in all sampling point in industrial area. This is because iron
present in all sampling point with high concentration. Iron alloys are eventually
processed to containers, cars, laundry machines, bridges, buildings, and even small
springs are produced from industrial area which cause iron to be discharged to the
seawater. The glass and email production, pharmaceutics, chemicals, iron fertilizers,
or pesticides used for agriculture purpose is discharged into the seawater.
The present of the copper are high in the seawater due to uses of
chemical for refining and coal-burning especially in point 1 and point 2. Another
reason is copper are mainly came from industrial sector and treatment plant. The
other metals present are aluminium and potassium which have medium level of
concentration. The present of this both element in this three-sample point because

39
people threw the trash inside the water. Next, the least concentration of heavy metal
in the water is zinc. This is because waste from farm in point 3 have barrier and
cause the water to coagulate.

By referring to Table 4.9, the highest standard deviation was iron.


This is because iron were present in all sampling point as shown in the figure 4.0.
figure below show comparison of recreational and industrial area.

Concentration of heavy metals for recreational and industrial area


0.04
0.04
0.03
0.03
0.02
0.02
0.01
0.01
0
Cu Fe Pb Zn K Al

Recreational Industry

Figure 4.2 The comparison of heavy metals concentration for recreational and
industry area.
The standard deviation was the lowest for aluminium
from both areas. This is standard deviation for aluminium have low value and
concentration between sampling point are approximately equal. Since others
concentration heavy metals from each sampling point are in low value, therefore their
standard deviation is low.

4.4.2 The Correlation Matrix and Probability Value


Recreational Area
The correlation matrix between heavy metals are shown in Table 4.9
below.
Table 4.9 The correlation matrix for the heavy metals.
Cu Fe Pb Zn K Al

Fe -0.943

40
Pb 0.941 -1.000

Zn -0.962 0.998 -0.998

K 0.479 -0.745 -0.748 -0.702

Al 0.166 -0.485 0.490 -0.430 0.945 1.000

Based on result we obtain in recreational area, copper have


positive correlation with lead, potassium and aluminium. Its means that when there is
an increase in copper concentration in the seawater, the lead, potassium and
aluminium will also increase. For iron and zinc metals, it shows negative correlation.
This means that the concentration of iron and zinc will decreases as the copper
decreases. Then, iron have positive correlation with zinc, this shows when iron is
high, zinc element also increases. However, for lead, potassium and aluminium
element show negative correlation with iron means that they decrease together.
Next, lead have positive correlation with aluminium, but it has negative correlation
zinc and potassium. On the other hand, zinc have no correlation with potassium and
aluminium. Lastly, potassium has correlation with aluminium only. The probability
value between the heavy metals are presented in Table 4.10 below.

Table 4.10 The probability value between the heavy metals in recreational area.
Cu Fe Pb Zn K
Fe 0.217
Pb 0.220 0.003
Zn 0.177 0.040 0.043
K 0.682 0.465 0.462 0.505
Al 0.894 0.677 0.674 0.717 0.212

Industrial Area
The correlation matrix between the heavy metals are shown in Table 4.11
below.
Table 4.11 The correlation matrix for the heavy metals in industrial area.
Cu Fe Pb Zn K Al

Fe 0.998

Pb -0.991 -0.982

41
Zn 0.256 0.200 0.381

K -0.381 -0.327 0.500 0.991

Al -0.132 -0.189 0.000 0.924 -0.866 1.000

As part of this experiment, the concentration values of heavy metals


were calculated for each measured parameter. Based on the result above, the
copper has positive correlation with iron and zinc. It is means when the concentration
of copper increases, iron and zinc element will increase. Secondly, iron have positive
correlation only with zinc same as in recreational area, but not with lead, potassium
and aluminium. This means iron decreases when lead, potassium and aluminium
decreases. Next, lead have positive correlation with zinc, potassium and aluminium
compare to recreational area lead only has positive correlation with aluminium only.
In industrial area, it can be observed that zinc has positive correlation with potassium
and aluminium but in recreational area both has negative correlation. Lastly,
potassium has negative correlation with aluminium but in recreational area they have
positive correlation. The probability value between heavy metals in industrial area are
presented in Table 4.12 below.

Table 4.12 The probability value between the heavy metals.


Cu Fe Pb Zn K
Fe 0.037
Pb 0.084 0.121
Zn 0.835 0.872 0.751
K 0.751 0.788 0.667 0.084
Al 0.916 0.879 1.000 0.249 0.333

4.5 Comparison of Data with National Interim Water Quality Standard for
Malaysia.

Table 4.13 The average value between the heavy metals in two area.

Site Cu Fe Pb Zn K Al
Recreational 0.523 0.947 0.154 0.128 0.213 0.251
Area (mg/L)
Industrial 0.531 1.019 0.154 0.130 0.240 0.261

42
Area (mg/L)

The result obtained was compare with the National Interim Water
Quality Standard that was under by the Department of Environment (DOE) as shown
in Table A1 in the appendixes. Firstly, by referring the table above, copper which
have concentration 0.523 mg/L and 0.531 from difference area it is classified as
Class V because it exceed 0.2 mg/L. Secondly, iron which have concentration is
quite higher than other metal with 0.947 and 1.019 it is classified as Class I and
Class II A/ II B because in recreational area the concentration is less than 1mg/L and
for industrial area the concentration is exceed 1 mg/L. Then, for third heavy metals
which is lead have same concentration from two area with 0.154 mg/L it is classified
as Class III because the concentration exceeds 0.02 mg/L. For zinc with
concentration 0.128 and 0.130 it is classified as Class I which is natural level.
Furthermore, for potassium with concentration 0.213 and 0.240 it was identified that
no class for lead because it is natural present. Next, for aluminium concentration with
0.251 and 0.261 it is classified as Class III because it exceeds 0.06 mg/L.
Therefore, almost most of the metals present in recreational area and
industrial area are same in seawater was in Class I that is iron, and zinc shows it is
safe to be consume. Potassium identified as natural present because it has low
concentration. Lead and aluminium was classified as Class III. This means only
chemical precipitation, evaporation, and coagulation are needed for water treatment.
Lastly, only copper is classified as Class V which the water can be used for irrigation.
So, it can be concluded that this beach is not so polluted even there are one metals
classifies as Class III, however the concentration of all heavy metals is not high
enough to categorized as polluted.

4.4.3 The Analysis of Variance (ANOVA)


a. Copper (Cu)
The result for analysis of variance for aluminium from recreational area and
industrial area are presented in Table 4.14 and Table 4.15 below.

Table 4.14 The result of (ANOVA) for Cu in recreational area.

Df Sum Sq Mean Sq. F value Pr(>F)

Site 2 0.002739 0.001369 6.57 0.031

43
Residual 6 0.001251 0.000209

Table 4.15 The result of (ANOVA) for Cu in industrial area.

Df Sum Sq Mean Sq. F value Pr(>F)

Site 2 0.004117 0.002058 14.08 0.005

Residual 6 0.000877 0.00146

The P value measure for copper in recreational area is 0.031 and for
industrial area is 0.005. By comparing for both areas, it was identified that P value of
industrial is lower than recreational area, but both are lower than 0.05 which means
that copper concentration was significant. This is because there is large difference in
the copper in each sampling point in different area.
Based on table 4.7 and table 4.8, we can observe that concentration of
copper in recreational area is higher than industrial area. This is because copper
alloy are release to the seawater that use for plumbing, and fishing from recreational
area and industries activity are always involve with uses of copper for fossil-fuels
which is to produce steam in industries and anti-fouling paint use in both area for
boat painting. The concentration of copper present in both areas are approximately
equal because water runoff from the rain and cause the seawater to mix.

b. Iron ( Fe)
The result for analysis of variance for iron from recreational area and
industrial area are presented in Table 4.16 and Table 4.17 below.

Table 4.16 The result of (ANOVA) for Fe in recreational area.

Df Sum Sq Mean Sq. F value Pr(>F)

Site 2 0.00692 0.00346 0.47 0.648

Residual 6 0.04452 0.00742

44
Table 4.17 The result of (ANOVA) for Fe in industrial area.

Df Sum Sq Mean Sq. F value Pr(>F)

Site 2 0.00105 0.00053 0.41 0.682

Residual 6 0.0073 0.00129

The P value obtained in recreational area is lower than industrial area which
is 0.648 mg/L and 0.682 mg/L. This P value was more than 0.05 which means for the
each sampling point from each area the level is insignificant. Moreover, there are not
much different in the concentration of iron in each sampling. However, based on
table 4.7 and 4.8 the concentration from recreational area are 1.019 mg/L and
industrial are 0.947 mg/L which is recreational are higher a bit from industrial. This is
because in both side there was uses of fertilizer and pesticides for agriculture which
is more near to recreational area and pesticides used in industrial area to kill pest
and for insect's repellent especially in food industry. So, the amount of all these
chemicals used contribute in high amount of iron in seawater.

c. Lead (Pb)
The result for analysis of variance for lead from recreational area and
industrial area are presented in Table 4.18 and Table 4.19 below.

Table 4.18 The result of (ANOVA) for Pb in recreational area

Df Sum Sq Mean F value P


Sq.
Site 2 0.001545 0.00072 3.95 0.80

Residual 6 0.001173 0.000196

Table 4.19 The result of (ANOVA) for Pb in industrial area.

Df Sum Sq Mean Sq. F value P(F<f)

Site 2 0.000081 0.000040 0.39 0.691

Residual 6 0.000616 0.000103

45
The P value is 0.80 and 0.691 from recreational and industrial area for lead
concentration. This shows that P value of recreational area are more than industrial
area and the value are more than 0.005 which shows that lead level is significant. By
referring table 4.7 and table 4.8 the value for recreational area and industrial area are
same which is 0.154 mg/L. This is because nearby area has old buildings whether
hotel, chalet and factory that cause corrosion from old buildings and pipeline that are
channel into the water. Furthermore, the lead are absorbed by soil and water from
runoff when it was raining. Therefore, the concentration is equal from both area
because the amount of lead used is same.

d. Zinc(Zn )
The result for analysis of variance for lead from recreational area and
industrial area are presented in Table 4.20 and Table 4.20 below.

Table 4.0 The result of (ANOVA) for Zn in recreational area

Df Sum Sq Mean Sq. F value Pr(>F)


Site 2 0.00082 0.0001778 3.20 0.43
8
Residual 6 0.00228 0.0000556
7

Table 4.0 The result of (ANOVA) for Zn in industrial area.

Df Sum Sq Mean F value Pr(>F)


Sq.
Site 2 0.000101 0.00005 0.39 0.691
0
Residual 6 0.001463 0.00024
4

For recreational area the P value was 0.43 and from industrial
area the P value was 0.691 this means industrial area have higher value. Since, the
P value are higher than 0.05. it can be said that zinc level is insignificant because by
referring table 4.7 and 4.8 there are not much difference in the concentration of zinc
which is 0.130mg/L and 0.128mg/L from each area. This cause the result to be highly
insignificant since there is no huge difference in the concentration of zinc from both
areas. Factors that cause zinc high in both areas are resulted by corrosion of metallic

46
zinc appliance and food waste from nearby stall which is release to the atmosphere
and it mix with water through the rain.

e. Potassium ( K )
The result for analysis of variance for potassium from recreational area and
industrial area are presented in Table 4.20 and Table 4.20 below.

Table 4.22 The result of (ANOVA) for K in recreational area

Df Sum Sq Mean Sq. F value Pr(>F)

Site 2 0.0003556 0.0001778 3.20 0.43

Residual 6 0.0003333 0.0000556

Table 4.23 The result of (ANOVA) for K in industrial area.

Df Sum Sq Mean Sq. F value Pr(>F)

Site 2 0.000155 0.0000778 3.50 0.098


6
Residual 6 0.000133 0.0000222
3

The P value that was measured are 0.43 from recreational and 0.0098
from industrial this is a large difference from both areas. Therefore, 0.05 is less than
this P value which means that the concentration of the potassium measured are
insignificant. By referring table 4.7and 4.8, the concentration from recreational area
are 0.130 mg/L and industrial are 0.128 mg/L. the concentration of both area are
approximately equal because along this sampling site, there was waste that channel
in the water from nearby stall. This is because urban area is developing area so there
are much waste have been threw inside the water. And lastly, potassium that found
in water have lower value level compared to iron and copper.

f. Aluminium( Al )
The result for analysis of variance for aluminium from recreational area and
industrial area are presented in Table 4.20 and Table 4.20 below.

47
Table 4.24 The result of (ANOVA) for Al in recreational area

Df Sum Sq Mean Sq. F value Pr(>F)

Site 2 0.0000176 0.000008 3.43 0.101


8
Residual 6 0.0000329 0.000002
6

Table 4.25 The result of (ANOVA) for Al in industrial area.

Df Sum Sq Mean Sq. F value Pr(>F)

Site 2 0.0000116 0.0000058 1.11 0.390

Residual 6 0.0000313 0.0000052

Based on table 4.24 and 4.25 that was measured 0.0101 from
recreational area and 0.390 from industrial area of P value. This P value are higher
than 0.05 and it means that the aluminium is insignificant. This is because there is
not much difference in concentration between recreational area and industrial area
which is 0.261 mg/L and 0.251 mg/L based on table 4.7 and 4.8 above. The factors
of high aluminium were due to uses of aluminium can or tin are disposed into the
water. Since, along this beach there are only rubbish bin and not any systematic and
proper rules waste management. This activity causes the concentration of the
aluminium to increase whether in industrial area or in recreational area. But
concentration of aluminium in both areas are slightly low because rubbish bin are
provided.

48
CHAPTER 5

CONCLUSION AND RECOMMENDATION

5.1 Conclusion
As the conclusion, the experiment was onducted to compare
and evaluate the concentration of heavy metals in recreational area and
industrial area in Pengkalan Balak Beach, Melaka. Based on the results
obtained, iron was the highest concentration in the seawater whether in
recreational and industrial area and the lowest concentration was zinc. Based
on the report ,. It can be identified for recreational area, concentration of
iron(Fe) with 0.537 mg/L followed by opper (Cu) with 0.537 mg/L,
aluminium(Al) with 0.261 mg/L, potassium(K) with 0.240 mg/L, lead(Pb) with
0.154 and zinc (Zn) with 0.130 mg/L.

49
Next, the result for industrial area, concentration of iron(Fe) with
0.947 mg/L followed by copper(Cu) with 0.523 mg/L, aluminium(Al) with 0.251
mg/L, potassium(K) with 0.213 mg/L, lead(Pb) with 0.154 and zinc (Zn) with
0.128 mg/L. By using correlation matrix, most of the metals in the seawater is
correlate and cause the concentration are significant same. These shows that
all these metals have different concentration at each point due to surrounding
activities.
Overall, it can be concluded that all the parameters that had been
evaluated shows that the sea water is safe to be used and not harmful upon
skin contact. As stated before, Pengkalan Balak is one of the place where
tourism and recreational activity is done, so there a lot of people who would
come by to swim, having picnic, taking a stroll, people set up a stall, and also
fishing. From the research that had been done, it shown that the water is safe
to be used for recreational activity. Some of them may be affected by the
wastewater that came from drainage from the recreational area and industrial
area around the coastal area but as long it do not exceed the exposure limit. So
, by comparing the result of recreational area and industrial area with the
National Interim Water Quality Standard, it can be said Pengakalan Balak Beach,
Melaka is not polluted due to low concentration of heavy metals.

5.2 Recommendation
There were several recommendations that can be done for the
improvement of sea water quality and on getting good result for the analysis in the
research. For improvement of sea water quality, National Interim Water Quality
Standard must be aware of current situation on the sea water quality because people
there are all the time for recreational activity and set up a food stall. Moreover, the
government must act because the pig farming waste is one of the sources that can
highly affect the sea water quality.
For getting the good result of analysis, the water must be taken using
pail to fill up the bottle sample so that concentration of nitric acid is same for all
sample. Next, it is necessary to ensure that no suspended particles in the water
during sampling process. Lastly, the analysis of each samples needs to be repeated
several times in order to get precise and accurate result.

50
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54
APPENDICES
APPENDIX A

55
National Interim Water Quality Standard for Malaysia

Table A1: National Interim Water Quality Standards for Malaysia (Source: (DoeOE
Malaysia, ’’n.d.)
PARAMETER UNIT CLASS ? ? ? ?
??? I II A/B III IV V
Al mg/l - 0.06 0.5
Cu mg/l 0.02 - 0.2
Fe mg/l 1 1 5
Pb mg/l 0.05 0.02 5
Zn mg/l 5 0.4 2
K - - -
mg/l

Table A2: Water Classes and Uses ( Source: (‘’Doe Malaysia,’’n.d)


CLASS USES
Class 1 Conservation of natural enviroment.

Water supply I – Practically no


treatment necessary

Fishery I- Very sensitive aquatic species

Class IIA Water Supply II- Conventional treatment


required
Class IIB Fishery II-Sensitive aquatic species
Recreational use with body contact

Class III Water Supply III – Extensive treatment

56
required
Fishery III-Common of economic value
and tolerant species; livestock drinking.
Class IV Irrigation
Class V None of the above

57
APPENDIX B
Dilution Calculation

Calculation for volume needed to dilute the standard solution.


1. 1 ppm

M1V1 = M2V2

Where,
M1 = 1.0 mg/L

V1 = 100 mL

M2 = 1000 mg/L

M 1V 1
V2 =
M2

mg
1.0 × 100 mL
V2 = L
1000 mg/ L

V2 = 0.1 mg/L

2. 2 ppm

M1V1 = M2V2

Where,
M1 = 2.0 mg/L

V1 = 100 mL

M2 = 1000 mg/L

M 1V 1
V2 =
M2

58
mg
2.0 × 100 mL
V2 = L
1000 mg/ L

V2 = 0.2 mg/L

3. 3 ppm

M1V1 = M2V2

Where,
M1 = 3.0 mg/L

V1 = 100 mL

M2 = 1000 mg/L

M 1V 1
V2 =
M2

mg
3.0 × 100 mL
V2 = L
1000 mg/ L

V2 = 0.3 mg/L

59

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