1

CHAPTER 1

INTRODUCTION

1.1

Background of Study

One of the main causes of water pollution is from heavy metals. The presence
of heavy metals in water and sediment can cause considerable impacts on the
environment (Madzin and Shai-in et al., 2015). Heavy metals have attracted a
considerable amount of attention and raising human concerns due to their toxicity,
wide sources, non-biodegradable properties and accumulative behaviours (Yu, Yuan
et al., 2008). Both natural and anthropogenic activities are responsible for the
abundant of heavy metals in the environment (Wilson & Pyatt, 2007; Khan, Cao et
al., 2008). Rivers have always been the recipients of liquid water discharges from
human activities, such as domestic sources, industrial or agricultural effluents or
mining process waters. Over the last two centuries, since the age of industrialization,
the massive increase of industrial production accompanied by the growth of large
urban populations has led to severe water pollution problems on many rivers, turning
some of them into essentially open cloacae. Compared to other developing countries,
China suffers the most from water pollution due to rapid economic growth and
intense industrialization. The intense industrialization inevitably leads to heavy metal
pollution in this region primarily due to sewage discharge from the factories, for
example, metal and electronic industries (Ye, Huang et al., 2012; Wu, Tam et al.,
2014).
Recent studies have proven the ability of sediment as pollution indicator of
environmental health status (?). This is due to higher capability of sediment to bind

2
with metal ions as compared with other environmental matrices likes water and biota
(?). According to Marcus (1991), sediment serves as diffuse sources of contamination
to the overlying water body, slowly releasing the contaminant back into the water
column. Therefore, ensuring good sediment quality is crucial to maintain a healthy
aquatic ecosystem, which ensuring better protection of human health and aquatic life.
Therefore, sediment of Johor River has been chosen for this study due to
geographical area and it impact on various pollution loading from anthropogenic
activity nearby area.

1.2

Problem Statement

It has long been known that, in the right concentration, many metals are
essential to life and eco-systems. Chronic low exposures to metals can lead to severe
environemtal and health effects. Similarly, in excess, these same metals can be
poisonous. Unlike many organic pollutants, which eventually degrade to carbon
dioxide and water, heavy metals will tend to accumulate in the environment,
especially in lake and estuarine. Metals can also be transported from one
environment compartment to another, which complicates the containment and
treatment problem. Heavy metals are closely connected with environmental
deterioration and the quality of human life, and thus have aroused concern all over
the world. More and more countries have signed treaties to monitor and reduce heavy
metal pollution. Moreover, this field of research has been receiving increasing
scientific attention due to its negative effects on life. For example, it was found that
metals accumulate in animal and plant cells, leading to severe negative effects. The
transport and accumulation of heavy metals by air, water and soil have also been a
hot topic for research. It was found that in some cases contamination was circulate on
a global range.

1.3

Objectives of Study

1.3.1

To investigate the conncentration of heavy metals at Johor River

1.3.2 To evaluate the risk related to contamination associated with such extensive
natural events
1.3.3

To propose a flood forecast method on concentration of pollutant after flood

1.4

Scope of Study

The scope of this study will be specified into four rivers that are situated
around Kota Tinggi area. The parameters involve include water quality parameter
which is BOD, COD, TSS, ammonia, pH, DO, Total Nitrogen, Total Phosphate and
Total Phosphorus, heavy metal which is mercury, arsenic, aluminium, copper,
magnesium and zinc and pesticides which is dichlorvos and parathion-methyl.

1.5

Significant of Study

This study will help to know the effect of a major flooding on contamination
of the river sediments and soils. As flooding events are expected to increase with
climate change in certain regions around the world, it is important to have effective
proxies of flooding events to understand the broader ramifications of their
occurrences.

CHAPTER 2

LITERATURE REVIEW

This section gives an introduction of this study for the analysis of heavy metal and its
characteristics.

2.1

Johor River (Sungai Johor)

Johor River is the main river in the Malaysian state of Johor. The river is
122.7 km long with a chatchment of 2,635 km2 and flows in a roughly north-south
direction, originating from Mount Gemuruh and then empties into the Strait of Johor.
Its major tributaries are Sayong, Linggui Tiram and Lebam Rivers. Its banks are also
known to be the location of past capitals of Johor.

Figure 2. 1 Map of Sg Johor and its tributaries, and the location of treatment plant provided by
Syarikat Air Johor

Johor River is the major contributor for water supply in Johor, about 55% of
total state needs. Treatments plants in Sungai Johor supply treated water to fast
growing Iskandar Malaysia (Johor Bahru, Kulai Jaya, Pasir Gudang and partially
Pontian), projected population up to 3 million in 2025 by IRDA. Johor Water Works
of PUB with capacity 250 MGD is vital source of treated water for Singapore, with
population more than 5 million people. Most of major treatment plants have been
fully utilized, with buffer less than 10%. Population of Johor River is caused by
urbanization of Kota Tinggi City, agriculture, animal farm and also sand field.
Water from rivers in Johor is used for agriculture, domestic needs, industrial
and urbanization as well as recreational use. Sungai Johor basin had 16 crude palm
oil mills in operation with ten discharge effluents into the river and another six
discharge palm oil effluents onto land (Salleh et al., 2013). Figure 2.2 below shows
oil palm mills and land use along Sungai Johor included rubber factories that located
along its tributaries (Noramin & Jani, 2011).

Figure 2. 2 Sg Johor tributaries and its land use

2.2

Streams and Rivers

All through the ages, rivers have played an important role in society. They
have provided means of transportation, water for irrigation, water supply, power
generation and many other uses. They have also caused disasters, primarily during
floods when they inundate portions of the floodplain and destroy property and
infrastructure (Parkinson and Goldenfum et al., 2010). Streams and rivers supply
important ecosystem services, such as drinking water supply, fish production,
opportunity for recreational activities and the collection, transport and processing of
pollutants and contaminants originating from the surrounding landscape (Cceres,
Diaz et al., 2005).

7
2.3

Water Pollution

Water pollution is the contamination of lakes, rivers, oceans and groundwater

with foreign substances caused by human activities, substances that can be harmful
to organisms and plants that live in the water (Palmer, 2010). Researchers suspect
that this form of pollution may be the leading worldwide cause of deaths and
diseases and that it accounts for the death of more than 14,000 people daily. That is
why research into water pollutions causes and solutions is so essential and this book
offers readers the most up-to-date and serious research in the field.

2.4

Urbanization Impacts on Water Quality

Waterways and receiving waters near urban and suburban areas often
adversely affected by urban stormwater run off. The degree and type of impact varies
from location to location, but it is often significant relative to other sources of
pollution and environmental degradation. Urban storm water runoff affects water
quality, water quantity, habitat and biological resources, public health and the esthetic
appearance of urban waterways. As stated in the National Water Quality Inventory
1996 Report to Congress (US-EPA, 1997), urban runoff is the leading source of
pollutants causing water-quality impairment related to human activities in ocean
shoreline waters and the second leading cause in estuaries across the United States.
Urban run off was also a significant impairment in rivers and lakes.
US-EPA (2005) has classified the adverse impacts of urban runoff on
receiving waters into three categories as follow:

Short-term changes in water quality during and after storm events including
temporary increases in the concentration of one or more pollutants, toxics or

bacteria levels
Long-term water-quality impacts caused by the cumulative effects associated

with repeated stormwater discharges from a number of sources

Physical impacts due to erosion, scour and deposition associated with
increased frequency and volume of runoff that alters aquatic habitat

According to Horner et al. (the Terrenes Fundamentals of Urban Runoff

Management), pollutants associated with urban runoff, which are potentially
harmful to receiving waters, are listed in Table _. These pollutants degrade the
water quality in receiving waters near urban areas and often contribute to the
impairment of use and exceedances of criteria included in water-quality
standards. The quantity of these pollutants per unit area delivered to receiving
waters tends to increase with the degree of development in urban areas.

Pollutant
Source

Solid
s

Nutrien
t

Soil erosion
Fertilizers
Human
waste
Animal
waste
Vehicle
fluids
Internal
combustion
Vehicle wear

Household
chemicals
Industrial
processes
Paints and
preservative
s
Pesticides

2.5

Pathogen
s

Oxygen
Deman
d

Metal
s

Oil
s

Organic
s

Table _. Urban Runoff Pollutant Souces and Constituents

Metal Toxicity

Out of 106 identified elements, about 80 of them are called metals. These
metallic elements can be divided into two groups which are those that are essential

9
for survival, such as iron and calcium and those that are nonessential or toxic, such as
camium and lead. These tosic metals, unlike some organic substances, are not
metabolically degradable and their accumulation in living tissues can cause death or
serious health threats. Furthermore, these metals, dissolved in wastewaters and
discharged into surface waters, will be concentrated as they travel up the food chain.
Eventually, extremely poisonous levels of toxin can migrate to the immediate
environment of the public. Metals that seep intogroundwaters will contaminate
drinking water wells and harm the consumers of the water.
Pollution from man-made sources can easily create local conditions of
elevated metal presence, which could lead to disastrous effects on animals and
humans. Actually, mans exploitation of the worlds mineral resources and his
technological activities tend to unearth, dislodge and disperse chemicals and
particularly metallic elements, which have recently been brought into the
environment in unprecedented quantities and concentration and at extreme rates.

2.6

Selected Heavy Metals

Heavy metals can be defined as forming positive ions in solution and they
have a density five times greater than that of water. They are of particular
toxicological importance. Many metallic elements play an essential role in the
function of living organisms; they constitute a nutritional requirement and fulfil a
physiological role. However, the abundance of the essential trace elements and
particularly their substitution of non-essential ones, such as the case may be, for
cadmium and nickel that can cause toxicity by symptoms or death. Humans receive
their allocation of trace elements from food and water, an indispensable link in the
food chain being plant life, which also supports animal life. It has been shown that
spectacular metal enrichment coeffients of the order 10 5-107 can occur in cells.
Imbalances or excessive amounts of a metal species along this route lead to toxicity
symptoms, disorders in the cellular functions, long-term debilitating disabilities in
human, and eventually death.

2.6.1

Aluminium

10
Aluminium is the most commonly available element in homes and
workplaces. It is readily available for human ingestion through the use of food
additives, antacids, buffered aspirin, astringents, nasal sprays and antiperspirants,
drinking water and others. Prolonged exposure to high concentrations of aluminium
and its accumulation causes disturbances in renal function, dialysis and
encephalopathy syndrome a degenerative neurological syndrome characterized by
the gradual loss of motor, speech and cognitive functions. The Department of Health
and Human Services (DHHS) and the U.S. Environmental Protection Agency (EPA)
have not evaluated the carcinogenic potential of aluminium in humans. However, the
International Agency for Research on Cancer (IARC) has classified aluminium under
group 1, meaning that it is a known human carcinogen.

2.6.2

Arsenic

Arsenic is a poisonous chemical that is widely distributed in nature and

occurs in the form of inorganic or organic compounds. Inorganic compounds consists
of water-soluble arsenite (As III), the most toxic form and arsenate (As V), the less
toxic form, and such pollutants have been associated with many health problems
such as skin lesions, keratosis (skin hardening), lung cancer and bladder cancer (?).
The release of arsenic into the environment occurs in a variety of ways through
industrial effluents, pesticides, wood preservative agents, combustion of fossil fuels
and mining activity (?). Indeed, arsenical insecticides have been used in agricultural
for centuries and particularly lead arsenate was quite extensively used in Australia,
New Zealand, Canada and the United States (?). Bangladesh tops the list of the
highest arsenic contamination, followed by India and China (?). In these countries,
arsenic

has

been

released

into

the

groundwater

by

oxidation

of

the

arsenopyrite/pyrites from the subsoil or oxygydroxide reduction. Volcanic action is

the most important natural source of arsenic, followed by low-temperature
volatilization. Inorganic arsenic of geological origin is found in groundwater used as
drinking water in several parts of the world, for example Bangladesh (?). Skin
disorders, including hyper/hypopigmentation changes and keratosis are the most
common external manifestation, although skin cancer has also been identified.

11
Around 5000 patients have been identified with As-related health problems in West
Bengal (including skin pigmentation changes) (?). In some areas in Bangladesh,
groundwater arsenic concentration can reach 2 mg L-1 (10 ppb) (?).

2.6.3

Cadmium

Cadmium is found in natural deposits as ores containing other elements. The

greatest use of cadmium is primarily for electroplating, paint pigments, plastics,
silver-cadmium batteries and coating operations, including transportation equipment,
machinery and baking enamels, photography and television phosphors. It is also used
in nickel-cadmium batteries, solar batteries and in pigments (?). In one review, it was
noted that the use of cadmium products has expanded in recent years at a rate of 510% annually and the potential for further growth is very high (?). The whole worlds
annual production of cadmium is around 20,000 tons. Discharge of cadmium into
natural waters is derived partly from the electroplating industry, which accounts for
about 50% of the annual cadmium consumption in the United States. Other sources
of water pollution are the nickel-cadmium battery industry and smelter operations,
which are more likely to be fewer in number, but of a greater point source
significance, often affecting the environment at distances of a 100 km order of
magnitude (?). Cadmium occurs in nature in the form of various inorganic
compounds and as complexes with naturally occurring chelating agents;
organocadmium compounds are extremely unstable and have not been detected in the
natural environment. Industrial and municipal wastes are the main sources of
camium pollution. The solubility of cadmium in water is influenced to a large degree
by the acidity of the medium. Dissolution of suspended or sediment-bound cadmium
may result when there is an increase in acidity (?). The need to determine cadmium
levels in suspended matter and sediments in order to assess the degree of
contamination of water body has been pointed out. The concentration of cadmium in
seawater averages about 0.00015 mg L-1 (?). Surface waters containing in excess of a
few micrograms of cadmium per litre have probably been contaminated by industrial
wastes from metallurgical plants, plating works, plants manufacturing cadmium

12
pigments, textile operations, cadmium-stabilized plastics, or nickel-cadmium
batteries, or by effluents from sewage treatment plants (?).
Due to its acute toxicity studied only recently, cadmium has joined lead and
mercury in the most toxic Big Three category of heavy metals with the greatest
potential hazard to humans and the environment. Cadmium is one of the metals most
strongly absorbed by living cells accumulated by vegetation. It is also among the
most toxic to living organisms and more likely to leach from industrial wastes. The
acute oral lethal dose of cadmium for humans has not been established; it has been
estimated to be several hundred milligrams (?). Doses as low as 15-30 mg from
acidic foodstuffs stored in cadmium-lined containers have resulted in acute
gastroenteritis. The consumption of fluids containing 13-15 mg of cadmium per litre
by humans has caused vomiting and gastrointestinal cramps. Symptoms of acute
poisoning include pulmonary edema, headaches, nausea, vomiting, chills, weakness
and diarrhea. A disease known as Itai-Itai in Japan is specifically associated with
cadmium poisoning, resulting in multiple fractures arising from osteomalacia (?).
Symptoms of the disease, which occurred most often among elderly women who had
many children, are the same as those of osteomalacia (softening of the bone); the
syndrome is characterized by lumbar pain, myalgia and spontaneous fractures with
skeletal deformation. There is little general agreement about acceptable safety limits
for cadmium intake. In the United States, the safety level of cadmium in drinking
water has been set at 10ppb. The World Health Organization (WHO) has
recommended that the provisional permissible intake of cadmium not exceed 0.4-0.5
mg per week or 0.057-0.071 mg d-1 (?).

2.6.4

Chromium

Chromium is used in many industrial applications. It can be either used

melted with other metals to produce alloys or plated. Other applications of chromium
range from tanning agents, paint pigments and catalysts to impregnation solution for
wood and photography. Chromium concentrations in natural waters are very limited
by the low solubility of Cr(III) oxides. Thus, a major part of chromium in waters is in

13
the hexavalent state. Main contamination is generated by industrial wastewaters.
Chromium was recognized to be hazardous element in the early years after it was
discovered. However, no reports indicate that chromium salts (III) have severe toxic
effects. The U.S. Standards Institute listed a maximum acceptable concentration
(MAC) of 0.1 mg m-3 for chromic acid.

2.6.5

Copper

Copper ions are prone to complexation, especially with hydroxide and

carbonate ligands. In water above neutral pH, the Cu(OH) 3- complex is formed and a
strong CuCO3 (aq) ion pair predominates in aerated neutral waters containing
dissolved carbonate species. The complexes are slightly soluble and may keep the
copper concentration in water below 10 g l-1. Moreover, adsorption and
coprecipitation with ferric oxyhydroxides may cause even smaller copper
concentrations (Hem, 1989). Copper is an essential micronutrient that is a constituent
of many enzyme systems. Animals and humans need copper to be able to use iron
properly. Humans need between 1 mg and 3 mg each day. It takes several days for
copper to leave the body. Copper contamination of soils may cause phytotoxicity.
The bioavailability of copper decreases with increasing pH, so the toxicity to plants
can be mitigated by liming soils contaminated with copper, to bring the pH up to 7

2.6.6

Iron

Iron is required for the normal body functions of animals and humans and of
all living cells. It is essential for basic metabolic processes such as oxygen transport,
DNA synthesis, cytochrome P-450 enzyme oxidative metabolism and electron
transport. Iron is the most abundant trace mineral in the body and is an essential
element in most biological systems. Iron concentration in surface water ranges for
the most part 61 tp 2680 ppm (? Sciencedirect). A study has reported that, due to
agricultural activities and increased water extraction, ground water levels have

14
generally decreased in large areas of the peaty lowlands in the Netherlands (?-sc). As
a result, iron-containing seepage has decreased in many region, while alakaline
Rhine river, which is rich in sulfates and poor in iron, has been used to compensate
for the shortage of water. This has resulted in increased alkalinity and organic
sediment breakdown. Increased sulfate reduction leads to iron sulphide precipitation
and internal alkalinity generation. As a result of these processes, phosphate and
ammonium levels in sediment pore water have increased strongly. Release of these
nutrients to the water layer has resulted in internal eutrophication of the peatland
ecosystems. Furthermore, iron levels have decreased strongly as a result of decreases
seepage and iron sulphide precipitation. As a result, sulphide accumulates in
sediment pore water and reaches toxic levels. Furthermore, decreased iron levels
appear.
The direct and indirect effects of iron on structure and function of lotic
ecosystems have been reviewed (?-sc). In addition to the mining of iron enrich ores,
intensified forestry, peat production and agricultural water runoff have increased the
load of iron in many river ecosystems. The effects of iron on aquatic animals and
their habitats are mainly indirect, although the direct toxic effects of Fe 2+ are also
important in some lotic habitats that receive iron-enriched effluents particularly
during cold seasons. Iron hydroxide and iron-humus precipitates on both biological
and other surfaces, indirectly affect lotic organisms by disturbing the normal
metabolism and osmoregulation and by changing the structure and quality of benthic
habitats and food resources. The bioaccumulation of iron in the organs and tissues of
the freshwater crab, Potamonautes warren Calman, from three metal-polluted
aqualtic ecosystems was examined (?). Differences in iron concentrations in the crab
occurred in the gills, suggesting this organ to be the prime site for the absorption
and/or loss of iron to and from the aquatic environment.
The toxicity of iron is governed by absorption. Chronic iron overload is an
insidious tissue that often does not produce obvious symptoms until substantial tissue
damage to tissue damage to vital organs has occurred. Large amounts of free iron in
the circulation are known to cause damage to critical cells in the liver, heart and other
metabolically active organs. Industrial workers exposed to fumes of iron compounds
show potential symptoms of poisoning such as irritation of eyes, skin and respiratory,

15
cough, metal fume fever (MFF), severe vomiting, diarrhea, abdominal pain,
dehydration and siderosis (a benign pneumoconiosis). Reports have indicated that
severe siderosis leads to myocardial diseases and death. Iron toxicity is usually the
result of more chronic iron overload syndromes associated with genetic diseases, the
liver becomes cirrhotic. Hepatoma, the primary cancer of liver, has become the most
common cause of death among patients with hemochromatosis. Workers and the
general public with hemochromatosis absorb iron very efficiently, which can result in
build-up of excess iron and cause organ damage such as cirrhosis of the liver and
heart failure.

2.6.7

Manganese

Manganese is a naturally occurring metal that is found in many types of

rocks. The metal is reactive chemically and decomposes slowly. It is an important
component of steel. The common organic manganese compounds include pesticide
such as Maneb or Mancozeb. Metallic manganese is used in the manufacturing of
steel, carbon steel, stainless steel, cast iron and super alloys to increase hardness,
stiffness and strength. Manganese chloride is used in dyeing, disinfecting, batteries,
as a paint drier and dietary supplement. Manganese oxide (MnO) is used in textile
printing, ceramics, paints, coloured glass, fertilizers and as a food additive.
Manganese toxicity, manganism, injures the part of the brain that helps to control
body movements and affects motor skills such as holding ones hand steady. The
symptoms of manganese poisoning include but not limited to headache, insomnia,
disorientation, speech disturbances, memory loss, languor, weakness, emotional
disturbances, spastic gait, recurring leg cramp and paralysis. Continuation of
exposure to manganese causes disturbance to motor function, tremors, unsteady
walking and exaggerated reflexes similar to Parkinsonism. However, there are no
reports indicating that manganese causes cancer in humans. The U.S. EPA has
included manganese in group D, meaning not classifiable as a human carcinogen.

16
2.6.8

Mercury

Mercury and its compounds are used in dental preparations, thermometers,

fluorescent and ultraviolet lamps, and pharmaceuticals and as fungicides in paints,
industrial process waters and seed dressings. The pulp and paper industry also
consumes mercury in significant amounts in the form of phenyl mercuric acetate, a
fungicide, and in caustic soda, which may contain up to 5 mg kg -1 as an impurity.
Mercury in air can be washed out by rain. In industrial areas, mercury concentrations
as high as 0.0002 mg L-1 have been reported in raun. In most surface water, Hg(OH) 2
and HgCl2 are the predominant mercury species. In reducing sediments, however,
most of the mercury is immobilized as the sulphide. Concentrations of mercury in
surface and drinking waters are generally below 0.001 mg L -1 (?). The presence of
higher levels of mercury in water is due to effluents from the chlor-alkali industry,
the pulp and paper industry, mining, gold and other ore-recovering processes, and
irrigation or drainage of areas in which agricultural pesticides are used.
Inorganic mercury in sediments, under anaerobic conditions, can be
transformed by microorganisms into organic mercury compound, the most common
of which is methyl mercury (?). These compounds can readily associate with
suspended and organic matter and be taken by aquatic organisms. Methyl mercury
has a high affinity for lipids and is distributed to the fatty tissues of living organisms
(?). Although methyl mercury is estimated to constitute only 1% of the total mercury
content of water, more than 90% of the mercury in biota is in the form of methyl
mercury (?). It has been estimated that about 5000 tons of mercury are annually
released into the environment by mans activities. Mercury is readily scavenged by
organic matter. Mercury salts from industrial effluents deposit in the river or lake
sediments and are then acted upon by anaerobic bacteria, which convert them into
toxic methyl mercury and dimethyl mercury. Soluble mercury is readily incorporated
into organisms in the aquatic environment and ultimately finds its ways into higher
members of the food chain such as man. The progress of mercury through the food
chain successively increases its concentration to such an extent that natural levels in
some commercial fish are close to or exceed the lowest level that was set by health
authorities in the countries. Analyses of the Greenland ice cap revealed that while

17
mercury levels worldwide have been constant since 800 B.C., since 1950, the
amounts present seems to have doubled.
Although it had been known for many centuries that mercury is poisonous to
animals and humans, it was not until the late 1950s that its extreme toxicity to
humans was appreciated as it made headlines worldwide. In 1953, the mysterious
death of 52 persons living in fishing villages along Minamata Bay in Japan was
unmistakably linked with mercury poisoning. High levels of mercury originating
from the nearby plastics factory were found in the shellfish eaten by the villagers.
The minamata disease, mercury poisoning, has been linked to many more death
around the globe ever since and symptoms of mercury poisoning crippled countless
more. Advanced analytical methods made it possible recently to monitory low levels
of mercury in the environment, which however, are sufficient to cause these serious
problems on the large scale. A particularly disturbing feature of mercury poisoning is
that the effects are not immediately obvious. Methyl mercury is particularly toxic
because it readily passes from the bloodstream into the cerebellum and cortex,
causing damage that is symptomized by numbness, awkwardness of gait, and
blurring vision. Clinical tests to determine mercury poisoning are based on the levels
of this element in whole blood. Identifiable symptoms of mercury poisoning occur
with levels 0.2-0.6 ppm. The WHO proposed an acceptable daily intake (ADI) of 0.3
mg Hg, of which not more than 0.2 mg should be in the form of methyl mercury.

2.6.9

Nickel

Nickel has many uses in industry and in the manufacture of consumer

products such as stainless steel, magnets, coinage and special alloys. Human
exposure to these nickel compounds in jewelry, soaps, fats and oils is known. Nickel
sulfate is used in electroplating, as a mordant in dyeing, in preparation of other nickel
compounds, in paints, varnishes and ceramics. Prolonged exposure to high
concentrations of nickel and nickel compounds causes poisoning and health disorders
in humans. These include but are not limited to headache, dizziness, nausea,
vomiting, epigastric pain, substernal pain, eye and respiratory irritation, cough and

18
others. Nickel-induced contact dermatitis is well documented for humans and is the
most prevalent effect of nickel exposure in humans. Nickel and nickel compounds
are known to be human carcinogens based on sufficient evidence of carcinogenicity
from studies in humans, including epidemiological and mechanistic information,
which indicates a casueal relationship between exposure of nickel compounds and
human cancer.

2.6.10 Lead

Lead is the most common of the heavy elements. Lead is present in tap water
as a result of dissolution from natural sources or from household plumbing systems
containing lead in pipes. The amount of lead from the plumbing system that may be
dissolved depends on several factors, including acidity (pH), water softness and
standing time of the water (?). Other sources of lead intake include ceramic ware,
activities involving arts and crafts, peeling paint, and renovations resulting in dust or
fumes from paint (?). Lead can be absorbed by the body through inhalation,
ingestion, dermal contact (mainly as a result of occupational exposure), or transfer
via the placenta. Of the total body lead, approximately 80 95% in adults and about
73% in children accumulate in the skeleton. The biological half-life of lead is
approximately 16-40 days in blood and about 17-27 years in bones (?). Lead is a
cumulative general poison, with infants, children up to six years of age, and pregnant
women (because of their foetuses) being more susceptible to adverse health effects.
Young children that are affected can suffer mental retardation and semipermanent
brain damage as it can severely affect the central nervous system. Overt signs of
acute intoxication include dullness, restlessness, irritability, poor attention span,
headaches, muscle tremor, hallucinations and loss of memory (?), which occurring at
blood levels of 100-120 g dL-1 in adults and 80-100 g dL-1 in children. Signs of
chronic lead toxicity, including tiredness, sleeplessness, irritability, headaches, joint
pain and gastrointestinal symptoms, may appear in adults with blood lead levels of
50-80 g dL-1. After one or two years of of exposure, muscle weakness,
gastrointestinal symptoms, lower scores on psychometric tests, disturbances in mood,

19
and symptoms of peripheral neuropathy were observed in occupationally exposed
populations at blood lead levels of 40-60 g dL-1.

2.6.11 Zinc

Normal average zinc intake by adult humans through the diet ranges from 7
mg d-1 to 16 mg d-1. In humans and animals, long-term exposure to excess levels of
zinc may result in copper deficiency, reduced immune function, reduced levels of
high-density lipoproteins (the good cholesterol), anaemia, death of foetuses, and
damage to the liver, pancreas and kidneys (ATSDR, 2006). However, in the context
of pollution, zinc is more a cause of phytotoxicity rather than being toxic to animals
and humans. Anthropogenic sources of zinc are galvanised steel, sewage sludge,
waste disposals and industrial releases. Galvanised steel is used in roofs, gutters,
drainpipes and wire fences. Exposure to acid rain slowly dissolves these materials
and the zinc ends up in soil or runoff water. Zinc is also widely used in domestic
products such as skin care products (cosmetics, baby creams, shampoos). Together
with drainage water from galvanised surfaces, these are the main sources of zinc
pollution of sewage water, effluent from wastewater treatment plants and sewage
sludge. Hence, spreading sewage sludge on land as a fertiliser progressively
increases the zinc concentrations in agricultural soils. The other major sources of
zinc in domestic waste in adition to discarded galvanised materials and domestic
products containing zinc are batteries, pigment and paints. Waste disposal can
therefore lead to local soil and groundwater pollution around landfills.

2.7

Agricultural and Urbanization Effect to River

Land-use changes in river basins, as a result of agricultural intensification and

expansion, as well as urbanization, can affect various characteristics of river
ecosystem integrity, such as water quality, community structure, and primary and
secondary production, organic matter decomposition, ecosystem metabolism and

20
energy fluxes (Allan, 2004; Young and Matthaei et al., 2008; Rosa, Aguiar et al.,
2013).

2.8

Sediment

Sediments are vital and integral parts of aquatic environments. Sediments can
be valuable indicators for monitoring pollutants in aquatic ecosystem. Sediments act
as a potential sink for various pollutants. Many contaminants such as hazardous and
toxic metals are accumulated in sediments that can be extremely harmful for the
aquatic environments (Nilin, Moreira et al., 2013). The legacy of polluted sediments
is a major problem for urban catchments. There is, therefore a need to reduce the
impact of such sediments on urban regions. Among others, urban storm flow
discharges can provoke displacement of contaminated sediments and lead to
ecological disruptions of riverbed sediments downstream of urban areas (Rossi,
Chvre et al., 2013). To date, strong acid digestion has been widely applied for the
determination of total heavy metals in sediments, especially for Singapore. However,
this approach can be misleading when assessing environmental effects due to the
potential for an overestimation of exposure risk (Cuong & Obbard, 2006).
In the urban development basin scenario, two stages of solids production can
be identified. At the initial stage of development, a large amount of sediment is
present, compared to natural conditions, because of construction and loss of vegetal
cover. Rainfall energy and increase in velocity of runoff from impervious areas
increase soil erosion and transport more sediment into nearby urban creeks. After
urbanization has stabilised, sediments remain as an important part of total solids.
Neves (2006) (?) showed that in a basin which is 67% urbanized, 77% of total solids
come from sediments, stones and vegetation, and 23% constitute refuse. Solid waste
increases mainly due to human activities lack of efficient services and lack of
education concerning street cleaning and waste collection.

21

2.9

Particulate Trace Metals

Particulate trace metals are key components in the biogeochemical cycles of

many elements of the water column. They represent an intermediate stage in the
transport of the chemical components in seawater to the seafloor sediments.
Particulate enters the marine environment through waterways, runoff, eolic transport,
groundwater and others (Palenik, Grimwood et al., 2007; Tiefenthaler and Stein et
al., 2008).

2.10

Flame Atomic Absorption Spectroscopy

Among the spectrometric methods used to determine metal concentrations,

FAAS is particularly useful to perform water analysis. It is relatively inexpensive
method, which presents an adequate sensitivity sufficiently high for the
determination of major metals in most of aquatic systems. Considering the most of
atomic absorption instruments are also equipped to operate in an emission mode,
large number of alkali metals are typically determined by flame photometry or flame
atomic emission spectrometry 9FAES) due to their relative low excitation and
simplicity of the emission techniques. This technique is relative free from spectral
interferences and considering its versatility and simplicity of opration, it has become
the most extensively used method for the determination of metals within water
samples.

22

CHAPTER 3

RESEARCH METHODOLOGY

3.1

Reagents and Standards

Analytical grade (AR) chemicals will be use throughout the study without
any further purification. To prepare all the reagents and calibration standards, double
glass distilled water was used. The metal standards were prepared from stock
solution of 1000 mg/L (Merck, Germany)* by successive dilution with ultra-pure
water. Deionized water was used throughout the study. Before digestion, the sample
flasks and digestion vessels is soaking into 10% HNO 3 for 24 hours and then washed
with de-ionized water. All the experiments will be carried out in triplicate.

23
3.2

Samples Collection and Preservation

Sampling is schedule to done between months of September to November

2015 from five different stations, all along Sungai Pemandi, Sungai Kemang, Sungai
Kampung Kelantan, and river situated near to Masjid Jamek. Three to four samples
of base flow is expected to be collected between these months and another two to
three samples of storm flow is expected to be collected between these months. The
coordinates of the sampling areas are:
Sampling area
Sungai Kelantan
Sungai Kemang
Sungai Masjid
Sungai Pemandi

3.2.1

Coordinates
1 4340.53 N
103 53 33.25 E
1 44 14.54 N
103 53 31.87 E
1 44 17.71 N
103 54 10.21 E
1 44 13.44 N
103 54 34.79 E

Water Sampling

The water samples are going to be collected using method described by

APHA in sterile capped containers. To avoid contaminations disposable gloves
washes with HCl 1N should be worn during water sampling. Store the water samples
in polythene bottles.
For total recoverable metals, all samples must be acidified at the time of
collection with 5 mL of HNO3. For dissolved metals, all samples must be filtered
through a 0.45 m filter and then acidified at the time of collection with 5 mL of
HNO3. Make sure that the sampling bottles are kept in airtight large plastic ice-cold
containers at 4C and were transported to laboratory with 6 hours of their collection
for further processing.

24
3.2.2

Sediment Sampling

Collect freshly deposited upper sediments layer from shallow water near bank
at each sampling point of Sungai Pemandi, Sungai Kemang, Sungai Kampung
Kelantan and river situated near to Masjid Jamek. Place the sediment that has been
collected into pre-cleaned polythene bags. Oven dried ground, homogenized and seal
the sediment samples in clean polythene bags. Store the sediment samples in a
refrigerator.

3.3

Digestion of Water Samples for Determination of Metals

Transfer a 100 mL aliquot well-mixed sample to a beaker. For metals that are
to be analyzed, add 2 mL of concentrated HNO 3 and 5 mL of concentrated HCl. The
sample is covered with a ribbed watch glass or other suitable covers and heated on a
stream bath, hot plate or other heating source at 90 to 95C until the volume has been
reduced to 15-20 mL. Remove the beaker and allow to cool. Wash down the beaker
walls and watch glass with water and when necessary, filter or centrifuge the sample
to remove silicates and other insoluble material that could clog the nebulizer.
Filtration should be done only if there is concern that insoluble materials may clog
the nebulizer; this additional step is liable to cause sample contamination unless the
filter and filtering apparatus are thoroughly cleaned and prerinsed with diluted
HNO3. Adjust the final volume to 100 mL with reagent water.

3.4

Acid Digestion of Sediments

25

This method is to explain the preparation of sediments for analysis of samples

by inductively coupled plasma atomic emission spectrometry (ICP-MS).

3.4.1

Preparation of Sediment

Mix the sample thoroughly to achieve homogeneity and sieve. All equipment
used for homogenization should be cleaned to minimize the potential of crosscontamination. For each digestion procedure, weigh to the nearest 0.01 g and transfer
a 1-2 g sample (wet weight) or 1 g sample (dry weight) to a digestion vessel. For
samples with high liquid content, a larger sample size may be used as long as
digestion is completed.

3.4.2

EPA Method 3050B

A procedure recommended by Environmental Protection Agency (EPA,

Method 3050B) was used as the conventional acid extraction method. Place 1 g of
sample in 250 mL flask for digestion. Heat the sample to 95C with 10 mL of 50%
HNO3 without boiling. After cooling the sample, reflux with repeated additions of
65% HNO3 until no brown fumes were given off by the sample. Allow the solution to
evaporate until the volume is reduce to 5 mL. After cooling, add 10 mL of 30% H 2O2
slowly without allowing any losses. Reflux the mixture with 10 mL of 37% HCl at
95C for 15 minutes. Filter the mixture through 0.45 m membrane paper to obtain
digestate and dilute to 100 mL with deionized water and store the solution a 4C for
analysis. The total extraction procedure lasted for 180-200 min.

26
3.5

Instrumentation for Determination of Heavy Metals in Water and

Sediment

All the determinations are going to be done with inductively coupled plasma
mass spectrometry. ICP-MS is a relatively new method for determining multielement analysis and ideal for water, since the vast majority of target compounds can
be detected below 0.1 mg/L. The operating conditions are listed below:
Nebulizer Gas flow rates
Auxiliary Gas Flow
Plasma Gas Flow
Lens Voltage
ICP RF Power
CeO/Ce

3.5.1

List of Wavelengths selected and Standards used

Analytes
Al
As
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Hg

3.6

0.95 l/min
1.2 l/min
15 l/min
7.25 V
1100 W
0.031

Wavelength (nm)
396.153
188.979
226.502
267.716
327.393
259.939
257.610
231.604
220.353
206.200
250.320

Standards (mg/L)
1.000 10.00
0.100 - 1.00
0.100 - 1.00
0.100 - 1.00
0.100 - 1.00
5.000 - 50.00
1.000 10.00
1.000 10.00
0.100 - 1.00
0.100 - 1.00
0.050 1.00

Quality Control

For each analytical batch of samples processed, blanks should be carried

throughout the entire sample preparation and analytical process. These blanks will be
useful in determining if samples are being contaminated.

27
Replicate sample should be processed on a routine basis. A replicate sample is
a sample brought through the whole sample preparation and analytical process.
Replicate samples will be used to determine precision. The sample load will dictate
the frequency, but 5% is recommended. Spiked samples or standard reference
material should be employed to determine accuracy. A spiked sample should be
included with each batch.

3.7

Calculation

The concentrations determined are to be reported on the basis of the actual

weight of the sample. If a dry weight analysis is desired, then the percent solids of
the sample must also be provided. If percent soilds is desired, a separate
determination of percent solids must be performed on a homogeneous aliquot of the
sample.
Determine the concentration of heavy metals in each sample by referring to
the calibration curve. Alternatively, calibrate the spectrophotometer and read directly
in concentration mode. Calculate the concentration of heavy metals in milligrams per
litre:
Metal, mg/L = C (100/V)
where,
C Concentration from curve, mg/L
V Volume of aliquot, mL

28

CHAPTER 4

EXPECTED RESULTS

4.1

Concentration of Heavy Metals in Sediment

From the research conducted, the concentrations of heavy metals are

estimated to be very high during storm flow. A recent study by Graham, Vinogradoff
et al. (2006) revealed that storm flow can play a major role in the release of dissolve
Pb from peatland soils. Thus the concentration of Pb in water is expected to be high
during storm flow compared to base flow.

4.2

Concentration of Heavy Metals in Water

According to Byrne and Reid et al. (2009), it has been shown that in their

studies, that rain-fed floods substantially increase the potential toxicity of river water
in the Afon Twymyn. Measured metal concentrations were significantly greater than
Environmental Quality Standards (EQSs). This source was most likely because
highly mobile and bioavailable metals adsorbed to the sediment of the river
bed/margins.

29

CHAPTER 5

CONCLUSION AND RECOMMENDATION

This work is set out to determine the concentration of heavy metals during base
flow and storm flow all along Sungai Pemandi, Sungai Kemang, Sungai Kampung
Kelantan, and river situated near to Masjid Jamek. Besides that, this study is to evaluate
the risk related to contamination associated with such extensive natural events. The
expected outcome of this project is that there could be possible adverse impacts to the
residing aquatic life as a result of the exposure to high concentration of the studied
metals.
Monitoring heavy metals at Sungai Pemandi, Sungai Kemang, Sungai Kampung
Kelantan, and river situated near to Masjid Jamek should be continued during dry and
wet weathers. Biological toxicity surveys should be undertaken in order to provide
definite decision regarding the possible adverse effects.

30

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