DETERMINATION OF PB, CU, CR, FE, ZN,NI AND CD CONTENTS OF SOIL DUST

SAMPLES IN SCHOOLS AROUND ONITSHA METROPOLIS

INTRODUCTION

ABSTRACT

The increasing impact of exposure to heavy metals on children’s health is increasing. The city of
Onitsha in anambra state Nigeria was investigated for its heavy metal content in JUNE 2017.
Samples of sedimented dust on floors from 6 primary schools were analyzed for their contents of
Cu, Pb, Cr, Cd, Fe, Zn & Ni after digestion with nitric acid. The results of the analysis were used
to determine spatial distribution and magnitude of heavy metal pollution and also the
contribution of different heavy metal sources to floor dust contamination in these primary
schools . The schools located around the industrial areas had elevated concentration of Zn
20.22mg kg -1 in soil dust samples. two main sources of pollution inculde: (1) Pd,Cd, Cr and Zn
which are mainly derived from industrial sources combined with traffic sources; (2) Fe, Co and
Ba are mainly derived from natural sources, but also by the location of the emission sources.
The latitude of Onitsha, Nigeria is 6.15° N, and the longitude is 6.79° E. With the gps
coordinates of 6° 8' 28.7232'' N and 6° 48' 10.6164'' E. Elevation: 72 m
 CHAPTER ONE

INTRODUCTION

BACKGROUND OF THE STUDY.

Soil is a mixture of minerals, organic matter, gases, liquids, and countless organisms that
together support life on Earth. Soil is a natural body called the pedosphere which has four
important functions: it is a medium for plant growth; it is a means of water storage, supply and
purification; it is a modifier of Earth's atmosphere; it is a habitat for organisms; all of which, in
turn, modify the soil.

Soil has been called the Skin of the Earth[1] as it interfaces with the lithosphere, the
hydrosphere, the atmosphere, and the biosphere.[2] The term pedolith, used commonly to refer to
the soil, literally translates ground stone. Soil particles are subsequently entrained into the
atmosphere as dust(Diana 2007) Soils are the major sink for heavy metals released into
the environment by aforementioned anthropogenic activities and unlike organic contaminants
which are oxidized to carbon (IV) oxide by microbial action, most metals do not undergo
microbial or chemical degradation [4], and their total concentration in soils persists for a long
time after their introduction [5]

The fate and transport of a heavy metal in soil depends significantly on the chemical form and
speciation of the metal. Once in the soil, heavy metals are adsorbed by initial fast reactions
(minutes, hours), followed by slow adsorption reactions (days, years) and are, therefore,
redistributed into different chemical forms with varying bioavailability, mobility, and toxicity
[41, 42]. This distribution is believed to be controlled by reactions of heavy metals in soils such
as(i) mineral precipitation and dissolution, (ii) ion exchange, adsorption, and desorption, (iii)
aqueous complexation, (iv) biological immobilization and mobilization, and (v) plant
uptake [43].

Particulate matter emitted from the geologic media pose threats to human health and the
environment due to expansion of infrastructure development to serve increasing population.
Natural particles derive primarily from soil minerals while anthropogenic particles derive from
road construction (asphalt, concrete and road paint), automobiles (tire dust, brake dust),
industrial inputs or atmospheric depositions (Adachi and Tainosho 2005).

Soils may become contaminated by the accuulation of heavy metals and metalloids through
emissions from the rapidly expanding industrial areas, mine tailings, disposal of high metal
wastes, leaded gasoline and paints, land application of fertilizers, animal manures, sewage
sludge, pesticides, wastewater irrigation, coal combustion residues, spillage of petrochemicals,
and atmospheric deposition [1, 2] Soil particles are subsequently entrained into the atmosphere
as dust.

Dusts are solid particles, ranging in size from below 1 µm up to at least 100 µm, which may be
or become airborne, depending on their origin, physical characteristics and ambient conditions.
Particulate matter commonly referred to as dust can range in size from 1 to 10000µm (Diana
2006).

Examples of the types of dust found in the work environment include: mineral dusts, such as
those containing free crystalline silica (e.g., as quartz), coal and cement dusts;
· metallic dusts, such as lead, cadmium, nickel, and beryllium dusts;
· other chemical dusts, e.g., many bulk chemicals and pesticides:
· organic and vegetable dusts, such as flour, wood, cotton and tea dusts, pollens;
· biohazards, such as viable particles, moulds, and spores

Particles small enough to stay airborne may be inhaled through the nose (nasal route) or the
mouth (oral route). The probability of inhalation depends on particle aerodynamic diameter, air
movement round the body, and breathing rate. The inhaled particles may then either be deposited
or exhaled again, depending on a whole range of physiological and particle-related factors.

The five deposition mechanisms are sedimentation, inertial impaction, diffusion (significant only
for very small particles < 0.5 m m), interception, and electrostatic deposition.
Sedimentation and impaction are the most important mechanisms in relation to inhaled airborne
dust, and these processes are governed by particle aerodynamic diameter. There are big
differences between individuals in the amount deposited in different regions (Lippmann, 1977).

The largest inhaled particles, with aerodynamic diameter greater than about 30 mm, are
deposited in the airways of the head that is the air passages between the point of entry at the lips
or nares and the larynx. During nasal breathing, particles are deposited in the nose by filtration
by the nasal hairs and impaction where the airflow changes direction. Retention after deposition
is helped by mucus, which lines the nose. In most cases, the nasal route is a more efficient
particle filter than the oral, especially at low and moderate flow rates. Thus, people who
normally breathe part or all of the time through the mouth may be expected to have more
particles reaching the lung and depositing there than those who breathe entirely through the nose.
During exertion, the flow resistance of the nasal passages causes a shift to mouth breathing in
almost all people.

Dust generally consists of particles in the atmosphere that come from various sources such as
soil, dust lifted by weather (an aeolian process), volcanic eruptions, and pollution. Dust can be
generated through civil construction operations, farming activities and vehicle operations on un-
surfaced roads. Lead and a variety of other metals from automobile exhaust have been found to
contaminate roadway and parking site dust and sampled in Palermo, Italy (Varrica et al., 2003)
and Kayseri, Turkey,(Tokaliolu and Kartal, 2006). Upon generation, dust can be carried by wind
into sensitive environments.(Diana 2006) Dust in homes, offices, and other human environments
contains small amounts of plant pollen, human and animal hairs, textile fibers, paper fibers,
minerals from outdoor soil, human skin cells, burnt meteorite particles, and many other materials
which may be found in the local environment. (Kathleen, 2002), Small children and infants are
particularly vulnerable to pollutants because of their rapid growth and cell differentiation,
immaturity of metabolic pathways and their development of vital organ systems (Moshammer et
al. 2006; Sunyer 2008).

Millions of children and adults across the nation spend their days in school buildings, and they
need safe, healthy environments to thrive, learn, and succeed [1]. Indoor air quality has become
an important public health concern as most people spend more than 90% of their time in indoors
like houses, offices and schools [2]. Air in the indoor environment can be polluted by a number
of pollutants among which airborne microorganism (bacteria and fungi) are one of the most
important. It has been estimated that one-third of indoor air quality (IAQ) complaints may be due
to microbial contamination [3] and exposure to these may cause allergies, respiratory and
immunotoxic diseases [4]. Several investigators have reported these contaminants in different
indoor environments such as schools and hospitals [5-8]. Schools are public places inhabited by
thousands of students every day and tend to have high levels of activity that typically result in
higher levels of airborne fungi and bacteria [6]. Particular interest are the source and pathways of
hazardous particles that enter and deposit in a classroom environment and thus expose the
occupants, particularly children, in the dwelling to levels of contaminants above safe limits.
Biological contamination of indoor air is mostly caused by bacteria, moulds and yeast. They can
be dangerous as pathogenic living cells but they can also secrete some substances harmful for
health [9]. These are different kinds of toxic metabolism products, for example mycotoxins [10-
12].

Consumption of fine soil and dust particulates, especially by young

children, is the dominant route of exposure for lead and other contaminants (Laidlaw et al. 2014;
Landrigan et al. 1975; Lanphear et al. 1998, 2003). Childhood soil and dust ingestion occurs via
multiple pathways, including hand-to-mouth (PICA) transfer, mouthing of objects, and
contaminatedfood.

The ingestion of soil and dust is a potential route of exposure for both adults and children to
environmental chemicals. Children, in particular, may ingest significant quantities of soil due to
their tendency to play on the floor indoors and on the ground outdoors and their tendency to
mouth objects or their hands. Children may ingest soil and dust through deliberate hand-to-
mouth movements, or unintentionally by eating food that has dropped on
the floor. Adults may also ingest soil or dust particles that adhere to food, cigarettes, or their
hands. Thus, understanding soil and dust ingestion patterns is an important part of estimating
overall exposures to environmental chemicals. At this point in time, knowledge of soil and dust
ingestion patterns within the United States is somewhat limited. Only a few researchers have
attempted to quantify soil and dust ingestion patterns
in U.S. adults or children.

Soil ingestion is the consumption of soil. This may result from various behaviors including,
but not limited to, mouthing, contacting dirty hands, eating dropped food, or consuming soil
directly.
Soil-pica is the recurrent ingestion of unusually high amounts of soil (i.e., on the order of 1,000-
5,000 mg/day or more).
Geophagy is the intentional ingestion of earths and is usually associated with cultural
practices. Some studies are of a behavior known as “pica,” and the subset of “pica” that consists
of ingesting
soil. A general definition of the concept of pica is that of ingesting non-food substances, or
ingesting large quantities of certain particular foods. Definitions of pica often include references
to recurring or repeated ingestion of these substances. Soil-pica is specific to ingesting materials
that are defined as soil, such as clays, yard soil, and flower-pot soil. Although soil pica is a fairly
common behavior among children,
information about the prevalence of pica behavior is limited. Gavrelis et al. (2011) reported that
the prevalence of non-food substance consumption varies by age, race, and income level. The
behavior was most prevalent among children 1 to <3 years (Gavrelis et al., 2011). Geophagy, on
the other hand, is an extremely rare behavior, especially among children, as is soil-pica among
adults. One distinction between geophagy and soil-pica that may have public health implications
is the fact that surface soils generally are not the main source of geophagy materials. Instead,
geophagy is typically the consumption of clay from known, uncontaminated sources, whereas
soil-pica involves the consumption of surface soils, usually the top 2-3 inches (ATSDR, 2001).
Researchers in many different disciplines have hypothesized motivations for human soil-pica or
geophagy behavior, including alleviating nutritional deficiencies, a desire to remove toxins or
selfmedicate, and other physiological or cultural influences (Danford, 1982). Bruhn and
Pangborn (1971) and Harris and Harper (1997) suggest a religious context for certain geophagy
or soil ingestion practices. Geophagy is characterized as an intentional behavior, whereas soil-
pica should not be limited to intentional soil ingestion, primarily because children can consume
large amounts of soil from their typical behaviors and because differentiating intentional and
unintentional behavior in young children is difficult (ATSDR, 2001). Some researchers have
investigated populations that may be more likely than others to exhibit soil-pica or geophagy
behavior on a recurring basis. These populations might include pregnant women who exhibit
soil-pica behavior (Simpson et al., 2000), adults and children who practice geophagy (Vermeer
and Frate, 1979), institutionalized children (Wong, 1988), and children with developmental
delays (Danford, 1983), autism (Kinnell, 1985), or celiac disease (Korman, 1990). However,
identifying specific soil-pica and geophagy populations remains difficult due to limited research
on this topic. It has been estimated that 33% of children ingest more than 10 grams of soil 1 or 2
days a year (ATSDR, 2001).
No information was located regarding the prevalence of geophagy behavior. Because some soil
and dust ingestion may be a result of hand-to-mouth behavior, soil properties may be important.
For example, soil particle size, organic matter content, moisture content, and other soil properties
may affect the adherence of soil to the skin. Soil particle sizes range from 50-2,000 µm for sand,
2-50 µm for silt, and are <2 µm for clay (USDA, 1999), while typical atmospheric dust particle
sizes are in the range of 0.001-30 µm (Mody and Jakhete, 1987). Studies on particle size have
indicated that finer soil particles (generally <63 µm in diameter) tend to be adhered more
efficiently to human hands, whereas adhered soil fractions are independent of organic matter
content or soil origin (Choate et al., 2006; Yamamoto et al., 2006). More large particle soil
fractions have been shown to adhere to the skin for soils with higher moisture
content (Choate et al., 2006).
Soil. Particles of unconsolidated mineral and/or organic matter from the earth’s surface that
are located outdoors, or are used indoors to support plant growth. It includes particles that
have settled onto outdoor objects and surfaces (outdoor settled dust).
Indoor Settled Dust. Particles in building interiors that have settled onto objects, surfaces,
floors, and carpeting. These particles may include soil particles that have been tracked or blown
into the indoor environment from outdoors as well as organic matter.
Outdoor Settled Dust. Particles that have settled onto outdoor objects and surfaces due to either
wet or dry deposition. Note that it may not be possible to distinguish between soil and
outdoor settled dust, since outdoor settled dust generally would be present on the uppermost
surface layer of soil.

These pathways are dependent on individual behaviors, exposure time, and environmental
conditions (Zahran et al. 2013a). Accurate estimates of the soil and household dust ingestion rate
(IR) pathway are needed to assess children’s exposures and health risks associated with trace
metals and persistent organic chemical residues in the home or play environment, and to make
informed cleanup decisions.

The amount of the microbial content of indoor air of school is an important parameter because it
has a direct impact on the mental heal [13], physical development and performance of the
students. Epidemiological studies show that too high concentration of microorganisms in the air
can be allergenic; however, sometimes even very low concentrations of some particular
microorganisms can cause serious diseases [14]. Childhood asthma is one of the commonest
chronic respiratory disorders in Asian countries [15-18] also noted that allergic disease (nasal
allergy, asthma, and other allergies) is the number one chronic childhood illness. The
conditioning systems are to provide occupants with a more comfortable environment.
Nevertheless, such artificial environments may be favorable to fungi, bacteria, protozoan and
mites growth, which may bring health risks to users, either by hypersensitivity or infections.

DOMESTIC DUST AND HUMANS

House dust mites are present indoors wherever humans live. Positive tests for dust mite allergies
are extremely common among people with asthma. Dust mites are a nesting species that prefers a
dark, warm, and humid climate. They flourish in mattresses, bedding, upholstered furniture, and
carpets. Their feces include enzymes that are released upon contact with a moist surface, which
can happen when a person inhales, and these enzymes can kill cells within the human body.[3]
House dust mites did not become a problem until humans began to use textiles, such as western
style blankets and clothing.[4] Dust mites are microscopic arachnids whose primary food is dead
human skin cells, but they do not live on living people. They and their feces and other allergens
they produce are major constituents of house dust, but because they are so heavy they are not
suspended for long in the air. They are generally found on the floor and other surfaces until
disturbed (by walking, for example). It could take somewhere between twenty minutes and two
hours for dust mites to settle back down out of the air. Young children are more likely to ingest
significant quantities of dust than adults because of the behavior of mouthing non-food objects
and repetitive hand/finger sucking. Secondly, children have a much higher absorption rate of
heavy metals from digestion system and higher haemoglobin sensitivity to heavy metals than
adults (Hammond, 1982). Because of their ubiquitous distribution, non-degradable persistence
and deadly nature, heavy metals poisoning is one of the most widespread, pediatric health
problems regardless of gender, race, ethnic origin and socioeconomic status (Casey et al., 1994).

ATMOSPHERIC DUST

Atmospheric or wind-borne dust, also known as aeolian dust, comes from arid and dry regions
where high velocity winds are able to remove mostly silt-sized material, deflating susceptible
surfaces. This includes areas where grazing, ploughing, vehicle use, and other human activities
have further destabilized the land, though not all source areas have been largely affected by
anthropogenic impacts.[5] Apart from the intrinsic geochemistry of earthen dust materials,
anthropogenic activities have introduced contaminants in topsoil from atmospheric deposition by
sedimentation, impaction and interception(Li et al.,2001). One-third of the global
land area is covered by dust-producing surfaces, made up of hyper-arid regions like the Sahara
which covers 0.9 billion hectares, and dry lands which occupy 5.2 billion hectares.[6]
Dust in the atmosphere is produced by saltation and sandblasting of sand-sized grains, and it is
transported through the troposphere. This airborne dust is considered an aerosol and once in the
atmosphere, it can produce strong local radiative forcing. Saharan dust in particular can be
transported and deposited as far as the Caribbean and the Amazon basin, and may affect air
temperatures, cause ocean cooling, and alter rainfall amounts.[5]

ROAD DUST
Dust kicked up by vehicles traveling on roads[7] may make up 33% of air pollution.[8] Road
dust consists of deposits of vehicle exhausts and industrial exhausts, particles from tire and brake
wear, dust from paved roads or potholes, and dust from construction sites. Road dust is a
significant source contributing to the generation and release of particulate matter into the
atmosphere.[9] Control of road dust is a significant challenge in urban areas, and also in other
locations with high levels of vehicular traffic upon unsealed roads, such as mines and landfill
dumps.
Road dust may be suppressed by mechanical methods like street sweeper vehicles equipped with
vacuum cleaners,[10] vegetable oil sprays,[11] or with water sprayers. Improvements in
automotive engineering have reduced the amount of PM10s produced by road traffic; the
proportion representing re-suspension of existing particulates has increased as a result.

DUST CONTROL
CONTROL OF ATMOSPHERIC DUST

Dust control is the suppression of solid particles with diameters less than 500 micrometers. Dust
poses a health threat to children,[12] older people, and those with respiratory illnesses.

Most governmental EPAs, mandate that facilities that generate dust, minimize or mitigate the
production of dust in their operation. The most frequent dust control violations occur at new
residential housing developments in urban areas. United States Federal law requires that
construction sites obtain permits to conduct earth moving, clearing of areas, to include plans to
control dust emissions when the work is being carried out. Control measures include such simple
practices as spraying construction and demolition in sites with water, and preventing the tracking
of dust onto adjacent roads.

Some of the issues include:

 Reducing dust related health risks that include allergic reactions, pneumonia and
asthmatic attacks.
 Improving visibility and road safety.
 Providing cleaner air, cleaner vehicles and cleaner homes and promoting better health.
 Improving crop productivity in agriculture.
 Reducing vehicle maintenance costs by lowering the levels of dust that clog filters,
bearings and machinery. Reducing driver fatigue, maintenance on suspension systems
and improving fuel economy.
 Increasing cumulative effect - each new application builds on previous residuals reducing
re-application rate *while improving performance.
US federal laws require dust control on sources such as vacant lots, unpaved parking lots, and
unpaved roads.

Dust in such places may be suppressed by mechanical methods, including paving or laying down
gravel, or stabilizing the surface with water, vegetable oils[11] or other dust suppressants, or by
using water misters to suppress dust that is already airborne.

House dust can become airborne easily. Care is required when removing dust to avoid causing
the dust to become airborne. A feather duster tends to agitate the dust so it lands elsewhere.
Products like Pledge and Swiffer are specifically made for removing dust by trapping it with
sticky chemicals.

Components and quantity of dust deposited in roofs at schools could provide an indirect
measurement of air population integrated over varying time periods. However, there is a lack of
information on sedimented dust and consequently, most developing countries do not have
regulations, guidelines, or standard tests for heavy metal contamination in schools (Diana 2006).

Air filtering appliances differ greatly in their effectiveness. Laser particle counters are an
effective way to measure filter effectiveness, medical grade instruments can test for particles as
small as 0.3 micrometers. In order to test for dust in the air, there are several options available.
Pre weighted filter and matched weight filters Dust on the air filter made from polyvinyl chloride
or mixed cellulose ester are suitable for respirable dust (less than 10 micrometers in
diameter).[13]

DUSTS IN SCHOOLS

Preschools are an important microenvironment associated with children’s exposure to indoor

pollutants due to the large portion of time they spend at such establishments on weekdays
(Lupoli et al. 2009; Yang et al. Indoor air quality in preschools has received wide interest in
recent studies due to the possible impact of air pollutants on preschool children (Wichmann et al.
2010; Kang et al. 2011). The air quality in an environment is usually associated with children’s
respiratory illnesses (Dockery et al. 1989; Von Mutius et al. 1995; Pekkanen et al. 1997; Qian et
al. 2000; Jalaludin et al. 2004). Furthermore, several studies also indicated the influence of
indoor pollutants on the academic performance and mental stability of the children in question
(Mendell and Heath 2005; Mohai et al. 2011).

Indoor dust is one locus of indoor contaminants containing toxic materials, particularly heavy
metals, in quantities that may be potentially harmful to human health (Landrigan et al. 2004;
Roberts and Ott 2007; Hochstetler et al. 2011; Aucott and Caldarelli 2012). Indoor dust has been
found to contain a quantity of heavy metals which may potentially affect the health of young
children (Akhter and Madany 1993; Al-Rajhi et al. 1996; Kim et al. 1999; Meyer et al. 1999;
Butte and Heinzow 2002; Latif et al. 2009). A high intake of heavy metals by children has been
associated with mood swings, poor impulse control and aggressive behaviour along with a poor
attention span, depression and apathy, disturbed sleep patterns and impaired memory and
intellectual performance (Holford and Colson 2008).

It is known that the sources of heavy metals in indoor dust are varied and depend on the
condition and location of a building, the activities occurring in the indoor environment, as well
as outdoor sources (Abdul-Wahab and Yaghi 2004; Jaradat et al. 2004; Abdul-Wahab 2006;
Latif et al. 2009; Pekey et al. 2012). A study by Kumpiene et al. (2011) has suggested that
industry and city traffic, top soil and building materials, especially during renovation, are among
the sources of heavy metals in preschools. Heavy metals may be transported via ventilation
systems and by the children’s movement from outside to inside a classroom which both in turn
contribute to the presence of heavy metals in the classroom in the form of dust brought in from
outdoors. Several studies have indicated heavy traffic as a source of heavy metals in road dust,
which subsequently becomes another source of heavy metals in the indoor environment (Akhter
and Madany 1993; Tiittanen et al. 1999; Adachi and Tainosho 2004; Al-Khashman 2007;
Gaudry et al. 2008).

Contamination of roadway topsoil material from which dust may be generated by vehicular and
wind action is prevalent in developing countries, where most roads are un surfaced and in some
cases leaded gasoline has been in use. Though there are numerous studies of heavy metal
contamination of urban dusts in developed countries, little information is available on heavy
metals of urban dusts in developing countries (Barnarjee 2003). In developed countries, most of
these studies of heavy metal contamination in dusts focused on Pb, Cu and Zn (Charlesworth et
al., 2003) and little attention has been paid to other trace elements such as Cr, Cd, Ni etc.

In addition, it is possible that contaminated soils or dust ingested, either directly or indirectly as a
result of hand-to-mouth (pica) activity, represent a significant pathway of lead intake during
early childhood (Al-Rajhi et al. 1996).

AIMS AND OBJECTIVES OF THE STUDY

This study was to determine the concentrations of selected heavy metals (Pb, Zn, Cu, Cd, Fe, Ni
and Cr) in the dust inside classrooms to which children in preschool could be exposed to in six
primary schools in Onitsha, Nigeria. Furthermore, this study will investigate the correlation of
classroom dust with dust collected from the surface soils surrounding the preschool areas. This
study will also correlate the composition of heavy metals in all types of dust samples collected
with the heavy metals from children’s classrooms so as to determine the degree that preschool
children are exposed to heavy metals. This work is an earnest effort as to provide a common
picture on the current load of pollutants in the form of dust as it affects schools.

The objectives of the present investigation were to carry out a general survey of distribution of
heavy metals including Cd, Cr, Cu, Ni, Fe, Pb and Zn in outdoor dust in Onitsha with respect to
their metal content.
 CHAPTER TWO

LITERATURE REVIEW

AIR POLLUTION

Airborne contaminants occur in the gaseous form (gases and vapours) or as aerosols. In scientific
terminology, an aerosol is defined as a system of particles suspended in a gaseous medium,
usually air in the context of occupational hygiene, is usually air. Aerosols may exist in the form
of airborne dusts, sprays, mists, smokes and fumes. In the occupational setting, all these forms
may be important because they relate to a wide range of occupational diseases.

HEALTH EFFECTS

Airborne dusts are of particular concern because they are well known to be associated with
classical widespread occupational lung diseases such as the pneumoconioses, as well as with
systemic intoxications such as lead poisoning, especially at higher levels of exposure. But, in the
modern era, there is also increasing interest in other dust-related diseases, such as cancer,
asthma, allergic alveolitis, and irritation, as well as a whole range of non-respiratory illnesses,
which may occur at much lower exposure levels.

POLLUTION
Pollution is the introduction into the environment substances or energy liable to cause hazards to
human health, harm to living organisms and ecological system, damage to structure or amenity
of interference with legitimate uses of the environment by man (Holdgate, 1979). Pollution has
increased considerably in recent years as a result of increasing human activities such as burning
of fossil fuels, industrial and automobile exhaust emissions. Nigeria crude oil is known to have
about 0.003 – 42.31mg/kg of transition metals such as V, Cr, Mn, Fe, Co, Ni and Cu
(Nwachukwu et al., 1995)
some of which cannot be completely removed during the crude refining processes and can
therefore readily be emitted during combustion.
Man, animals, vegetation, dust and soil act as ‘sinks’ for atmospheric pollutants (Osibanjo and
Ajayi, 1980; Ogunsola et al., 1994; Bada et al., 2001).

Metals in dust/smoke emitted by vehicles can enter the human food chain through the milk and
meat of the animals fed on plants (Cannon and Bowels, 1962). Several studies have shown that
metals such as Pb, Cd, Ni, amongst others, are responsible for certain diseases that have effects
on man (especially children and street traders who spend up to 10 h daily selling their goods
along the streets) and animals (Giddings, 1973; Gustav, 1974). Work has been done on the heavy
metal content of roadside soil and vegetation in IleIfe, Osun State (Bada et al., 2001) and on the
metals content of roadside dusts in Lagos, Nigeria (Ogunsola et al., 1994).But much work has
not been done on the heavy metal content of soil/dusts in primary schools in Onitsha, Anambra
state Nigeria.

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, man’s exploitation of
the world’s 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 concentrations and at extreme rates. Man’s new
technologies involving nuclear fission opened up a whole new area of hope and concern at the
same time.

HEAVY METALS
Heavy metals can be defined in several ways. One possible definition is the following: Heavy
metals form 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 fulfill a
physiological role. Key heavy metals are thereby Pb from leaded gasoline, cu, zn and cd from car
components, tyre abrasion, lubricants and industrial and incinerator emissions (Markus and
McBratney, 1996; Thornthon, 1991; Wilcke et al., 1998).
Out of 106 identifed elements, about 80 of them are called metals. These metallic elements can
be divided into two groups: those that are essential for survival, such as iron and calcium, and
those that are nonessential or toxic, such as cadmium and lead. These toxic 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 into groundwater’s will contaminate drinking water wells and harm the
consumers of that water.

Such heavy metal (such as Cu and Zn) at small amounts are harmless but some (notably Pb and
Cd) even at extremely low concentrations are toxic and are potential cofactors initiators o
promoters in many diseases including cardiovascular disease and cancer (Willers et al., 2005;
Diana 2006). The most common heavy metals found at contaminated sites, in order of abundance
are Pb, Cr, Zn, Cd, Cu, and Ni [40]. Those metals are important since they are capable of
decreasing crop production due to the risk of bioaccumulation and biomagnification in the food
chain. There’s also the risk of superficial and groundwater contamination.

Heavy metals constitute an ill-defined group of inorganic chemical hazards, and those most
commonly found at contaminated sites are lead (Pb), chromium (Cr), arsenic (As), zinc (Zn),
cadmium (Cd), copper (Cu), mercury (Hg), and nickel (Ni) [3] Heavy metal contamination of
soil may pose risks and hazards to humans and the ecosystem through: direct ingestion or contact
with contaminated soil, the food chain (soil-plant-human or soil-plant-animalhuman), drinking of
contaminated ground water, reduction in food quality (safety and marketability) via
phytotoxicity, reduction in land usability for agricultural production causing food insecurity, and
land tenure problems [7–9].

However, overabundance of the essential trace elements and particularly their substitution by
nonessential ones, such as the case may be for cadmium, nickel, or silver, can cause toxicity
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 is a well-
established fact that assimilation of metals takes place in the microbial world as well as in plants,
and these elements tend to get concentrated as they progress through the food chain. It has been
shown that spectacular metal enrichment coeffcients of the order of 105–107 can occur in cells
[1]. 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 humans, and
eventually death.

Sources of Heavy Metals in

Contaminated Soils
Heavy metals occur naturally in the soil environment from the pedogenetic processes of
weathering of parent materials at levels that are regarded as trace (<1000 mg kg-1) and
rarely toxic [10, 13]. Due to the disturbance and acceleration of nature’s slowly occurring
geochemical cycle of metal by man, most soils of rural and urban environments may
accumulate one or more of the heavy metals above defined background values high enough to
cause risks to human health, plants, animals, ecosystems, or other media [14]. The heavy metals
essentially become contaminants in the soil environments because (i) their rates of generation via
manmade cycles are more rapid relative to natural ones, (ii) they become transferred from mines
to random environmental locations where higher potentials of direct exposure occur, (iii) the
concentrations of the metals in discarded products are relatively high compared to those in the
receiving environment, and (iv) the chemical form (species) in which a metal is found in the
receiving environmental system may render it more bioavailable [14]. Heavy metals in the soil
from anthropogenic sources tend to be more mobile, hence bioavailable than pedogenic, or
lithogenic ones [18, 19]. Metal-bearing solids at contaminated sites can originate from a wide
variety of anthropogenic sources in the form of metal mine tailings, disposal of high metal
wastes in improperly protected landfills, leaded gasoline and leadbased paints, land application
of fertilizer, animal manures, biosolids (sewage sludge), compost, pesticides, coal combustion
residues, petrochemicals, and atmospheric deposition. [1, 2, 20]

FERTILIZERS. Historically, agriculture was the first major human influence on the soil [21].
To grow and complete the lifecycle, plants must acquire not only macronutrients (N, P, K, S, Ca,
and Mg), but also essential micronutrients. Some soils are deficient in the heavy metals (such as
Co, Cu, Fe, Mn, Mo, Ni, and Zn) that are essential for healthy plant growth [22], and crops may
be supplied with these as an addition to the soil or as a foliar spray. Cereal crops grown on
Cudeficient soils are occasionally treated with Cu as an addition to the soil, and Mn may
similarly be supplied to cereal and root crops. Large quantities of fertilizers are regularly added
to soils in intensive farming systems to provide adequate N, P, and K for crop growth. The
compounds used to supply these elements contain trace amounts of heavy metals (e.g., Cd and
Pb) as impurities, which, after continued fertilizer, application may significantly increase their
content in the soil.[23].Metals, such as Cd and Pb, have no known physiological activity.
Application of certain phosphatic fertilizers inadvertently adds Cd and other potentially toxic
elements to the soil, including F, Hg, and Pb [24].

PESTICIDES. Several common pesticides used fairly extensively in agriculture and

horticulture in the past contained substantial concentrations of metals. For instance in the recent
past, about 10% of the chemicals have approved for use as insecticides and fungicides in UK
were based on compounds which contain Cu, Hg, Mn, Pb, or Zn. Examples of such pesticides
are copper-containing fungicidal sprays such as Bordeaux mixture (copper sulphate) and copper
oxychloride [23]. Lead arsenate was used in fruit orchards for many years to control some
parasitic insects. Arsenic containing compounds were also used extensively to control cattle ticks
and to control pests in banana in New Zealand and Australia, timbers have been preserved with
formulations of Cu, Cr, and As (CCA), and there are now many derelict sites where soil
concentrations of these elements greatly exceed background concentrations. Such contamination
has the potential to cause problems, particularly if sites are redeveloped for other agricultural or
nonagricultural purposes. Compared with fertilizers, the use of such materials has been more
localized, being restricted to particular sites or crops [8].

BIOSOLIDS AND MANURES. The application of numerous biosolids (e.g., livestock

manures, composts, and municipal sewage sludge) to land inadvertently leads to the
accumulation of heavy metals such as As, Cd, Cr, Cu, Pb, Hg, Ni, Se, Mo, Zn, Tl, Sb, and so
forth, in the soil [20]. Certain animal wastes such as poultry, cattle, and pig manures produced
in agriculture are commonly applied to crops and pastures either as solids or slurries [25].
Although most manures are seen as valuable fertilizers, in the pig and poultry industry,
the Cu and Zn added to diets as growth promoters and as contained in poultry health products
may also have the potential to cause metal contamination of the soil [25, 26].
The manures produced from animals on such diets contain high concentrations of As, Cu, and Zn
and, if repeatedly applied to restricted areas of land, can cause considerable buildup of these
metals in the soil in the long run.

Biosolids (sewage sludge) are primarily organic solid products, produced by wastewater
treatment processes that can be beneficially recycled [27]. Land application of biosolids
materials is a common practice in many countries that allow the reuse of biosolids produced by
urban populations [28]. The term “sewage sludge” is used in many references because of its
wide recognition and its regulatory definition.
However, the term biosolids is becoming more common as a replacement for sewage sludge
because it is thought to reflect more accurately the beneficial characteristics inherent
to sewage sludge [29]. It is estimated that in the United States, more than half of approximately
5.6 million dry tonnes of sewage sludge used or disposed of annually is land applied, and
agricultural utilization of biosolids occurs in every region of the country. In the European
community, over 30% of the sewage sludge is used as fertilizer in agriculture
[29]. In Australia over 175 000 tonnes of dry biosolids are produced each year by the major
metropolitan authorities, and currently most biosolids applied to agricultural land are used in
arable cropping situations where they can be incorporated into the soil [8].

There is also considerable interest in the potential for composting biosolids with other organic
materials such as sawdust, straw, or garden waste. If this trend continues, there
will be implications for metal contamination of soils. The potential of biosolids for
contaminating soils with heavy metals has caused great concern about their application in
agricultural practices [30]. Heavy metals most commonly found in biosolids are Pb, Ni, Cd, Cr,
Cu, and Zn, and the metal concentrations are governed by the nature and the intensity of the
industrial activity, as well as the type of process employed during the biosolids treatment [31].
Under certain conditions, metals added to soils in applications of biosolids can be leached
downwards through the soil profile and can have the potential to contaminate groundwater
[32]. Recent studies on some New Zealand soils treated with biosolids have shown increased
concentrations of Cd, Ni, and Zn in drainage leachates [33, 34].

WASTEWATER. The application of municipal and industrial wastewater and related effluents
to land dates back 400 years and now is a common practice in many parts of the world
[35]. Worldwide, it is estimated that 20 million hectares of arable land are irrigated with waste
water. In several Asian and African cities, studies suggest that agriculture based on
wastewater irrigation accounts for 50 percent of the vegetable supply to urban areas [36].
Farmers generally are not bothered about environmental benefits or hazards and are primarily
interested in maximizing their yields and profits.
Although the metal concentrations in wastewater effluents are usually relatively low, long-term
irrigation of land with such can eventually result in heavy metal accumulation in the
soil.
METAL MINING AND MILLING PROCESSES AND INDUSTRIAL WASTES.
Mining and milling of metal ores coupled with industries have bequeathed many countries, the
legacy of wide distribution of metal contaminants in soil. During mining, tailings (heavier and
larger particles settled at the bottom of the flotation cell during mining) are directly discharged
into natural depressions, including onsite wetlands resulting in elevated concentrations [37].
Extensive Pb and zinc Zn ore mining and smelting have resulted in contamination of
soil that poses risk to human and ecological health. Many reclamation methods used for these
sites are lengthy and expensive and may not restore soil productivity.

Soil heavy metal environmental risk to humans is related to bioavailability. Assimilation

pathways include the ingestion of plant material grown in (food chain), or the direct ingestion
(oral bioavailability) of, contaminated soil [38].
Other materials are generated by a variety of industries such as textile, tanning, petrochemicals
from accidental oil spills or utilization of petroleum-based products, pesticides, and
pharmaceutical facilities and are highly variable in composition. Although some are disposed of
on land, few have benefits to agriculture or forestry. In addition, many are
potentially hazardous because of their contents of heavy metals (Cr, Pb, and Zn) or toxic organic
compounds and are seldom, if ever, applied to land. Others are very low in plant nutrients or
have no soil conditioning properties [25].
AIR-BORNE SOURCES. Airborne sources of metals include stack or duct emissions of air,
gas, or vapor streams, and fugitive emissions such as dust from storage areas or waste
piles. Metals from airborne sources are generally released as particulates contained in the gas
stream. Some metals such as As, Cd, and Pb can also volatilize during high-temperature
processing. These metals will convert to oxides and condense as fine particulates unless a
reducing atmosphere is maintained [39]. Stack emissions can be distributed over a wide area by
natural air currents until dry and/or wet precipitation mechanisms remove them from the gas
stream.
Fugitive emissions are often distributed over a much smaller area because emissions are made
near the ground. In general, contaminant concentrations are lower in fugitive emissions
compared to stack emissions. The type and concentration of metals emitted from both types of
sources will depend on site-specific conditions. All solid particles in smoke from fires and in
other emissions from factory chimneys are eventually deposited on land or sea; most forms of
fossil fuels contain some heavy metals and this is, therefore, a form of contamination which has
been continuing on a large scale since the industrial revolution began. For example, very
high concentration of Cd, Pb, and Zn has been found in plants and soils adjacent to smelting
works. Another major source of soil contamination is the aerial emission of Pb from the
combustion of petrol containing tetraethyl lead; this contributes substantially to the content of Pb
in soils in urban areas and in those adjacent to major roads. Zn and Cd may also be added to soils
adjacent to roads, the sources being tyres, and lubricant oils [40].

VEHICLE TRAFFIC FROM THE CLOSEST ROAD. The contribution of vehicle traffic
from the closest road
was not important regarding the response variable (no more than an approximate 10%
increase), and there was no evidence at all of its effect.
DEMOLITION. The demolition of old buildings increased the dust lead level by approximately
30%. This effect was observed previously by Rabito et al. (2007) in the BLL of children when
multiple demolitions occurred. Dixon et al. (2012) found a greater contribution, but their
variable “nearby demolition” also included the presence of smelters, battery plants, or other
potential lead sources. Thus, our results confirm the role of demolitions around the dwelling
in the lead contamination of interior floor dust.
POLLUTING SITES AND CONTAMINATED SITES. Soil abatement near polluting sites
such as smelters or
milling plants was found to reduce the lead level in interior floor dust (Lanphear et al. 2003).
Our findings confirm the influence of such polluting sites: they increased the lead level in dust
by 40 to 50%. A change from its 0.25 quantile to its 0.75 quantile produced an increase

among the top 3 contributions. An unexpected result was obtained for the “Contaminated
sites” covariate, but there was no evidence of its negative contribution.
Lead emissions in air. The contribution of lead emissions in the air to the contamination of
interior floor dust was estimated as very low (only a few percent), even for the highest
observed values; moreover, there was no evidence of its effect. Layton and Beamer (2009)
demonstrated that airborne lead was the main source of lead in interior floor dust by analyzing
data on lead contamination in Sacramento, CA, United States, in the early 1980s and assumed
that after the phase-out of leaded gasoline, soil track-in was the major source of lead
contamination of interior floor dust.

SOURCES RELATED TO THE BUILDING INDOOR FEATURES

Floor DPb of the landing of the apartment. The lead in dust of the apartment landing was the
most important contributor to the lead contamination of the interior floor dust. We previously
reported (Lucas et al. 2012) that lead loadings were 4 times higher in common areas than
inside apartments; the prevalence of LBP was also higher: 7.1% (CI 95% = 1.8-12.4%) vs.
4.7% (CI = 2.4-6.9%). These previous findings and the results of the present study are
consistent with Dixon et al. (2005), who studied the influence of common-area lead hazards.
DPb from the landing is tracked into the home through the natural flow caused by the
movements of people or on clothing and shoes. Dixon et al. (2005) assumed that leaded paint
was a source of floor DPb in the common areas as well as exterior soil and dust tracked into
the common areas. To verify this assumption, we replaced in our model the “DPb-landing”
covariate with a covariate indicating the maximal XRF value measured in paints of the
landing of the apartment. The coefficient of this covariate was estimated to be close to zero:
0.004 (95% CI = -0.13; 0.138) compared to 0.369 (95% CI = 0.189; 0.549) for the “DPblanding”
covariate. Moreover, little change occurred in estimates of other source coefficients.

LEAD
Lead is the most common of the heavy elements. Several stable isotopes exist in nature, 208Pb
being the most abundant. The average molecular weight of lead is 207.2. Lead is a soft metal that
resist corrosion and has a low melting point (327°C). From a drinking water perspective, the
almost universal use of lead compounds in plumbing fittings and as a solder in water distribution
systems is important. Distribution systems and plumbing installed before 1945 were made from
lead pipes [2].

Solid and liquid (sludge) wastes account for more than 50% of the lead discharged into
the environment, usually into landfills, but lead has been dispersed more widely in the general
environment through atmospheric emissions—particularly from car exhausts. With the
introduction of unleaded fuel, lead emissions from this source declined. The annual consumption
of lead is in the order of 3 million tons, of which 40% is used in the production of electrical
accumulators and batteries, 20% is used in gasoline as alkyl additives, 12% in building
construction, 6% in cable coatings, 5% in ammunition, and 17% in other usages. It is estimated
that approximately 2 million tons are mined yearly. Probably 10% of this total is lost in treatment
of the ore to produce the concentrate, and a further 10% is lost in making pig lead. The amount
of lead discharged into the environment is equal to the amount weathered from igneous rocks. In
global lead level terms, the power storage battery industry may have a relatively low impact on
the environment because about 80% of all batteries are recycled.

Exposure

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 [3]. Food can be contaminated by naturally occurring lead in the
soil as well as by lead from sources such as atmospheric fallout or water used for cooking.

The total intakes and uptakes of lead from all sources are 29.5 and 12.5 mg/d,
respectively, for children and 63.7 and 6.7 mg/d, respectively, for adults in urban areas [4]. The
relative contribution of water to average intake is estimated to be 9.8% and 11.3% for children
and adults, respectively.

The total intake of lead from three of the four major sources air, food, and dust appears
to have dropped significantly since the mid-1980s as a result of regulatory and voluntary actions
to control lead from air (via gasoline) and food (via cans).

Other sources of lead intake include ceramic ware, activities involving arts and crafts, peeling
paint, and renovations resulting in dust or fumes from paint [5]. No allowance was made for the
contribution of lead from these sources, because they occur on a highly sporadic basis and
because no quantitative data are available. It has been pointed out [5] that old paint has been an
important source of excess lead intake for inner-city children living in older housing stock in the
United States.

Although the lead pollution from mining activities presents a relatively localized problem, its
magnitude is significant, and particularly on the water pollution side it is compounded by the
occurrence of other heavy metals. The obvious danger of pollution from smelting operations has
long been recognized. Pollution control practices, however, leave a great deal to be desired.
Primary smelters process the ore material and are usually large but few in number,
whereas secondary smelters process scrap from old batteries, cable sheathing, etc. and represent
more dispersed point sources of heavy metal pollution.

Health Effects of lead

Lead can be absorbed by the body through inhalation, ingestion, dermal contact (mainly as a
result of occupational exposure), or transfer via the placenta. In recent decades there has been a
growing concern for the potential contribution of ingested dust to metal toxicity in humans
(Chirenje et al., 2006; Inyang and Bae, 2006). In adults, approximately 10% of ingested lead is
absorbed into the body. Young children absorb from 40% to 53% of lead ingested from food.
Once lead is absorbed, it enters either a “rapid turnover” biological pool with distribution to the
soft tissues (blood, liver, lung, spleen, kidney, and bone marrow) or a “slow turnover” pool with
distribution mainly to the skeleton [6]. 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 [6] and about 17–27 years in bones [6].

Acute and Chronic Exposure

Perhaps no other metal, not even arsenic, has had its toxicology so extensively studied as has
lead.
Lead poisoning has been actually linked to the fall of the Roman Empire. The high lead content
in bones from the roman period supports the hypothesis that the use of lead containers for wine
and other liquids, the use of lead water pipes, and lead-containing ceramic glazing of
earthenware containers contributed to the decimation of the ruling class, who were more able to
afford the lead containers [7]. The lead poisoning of children has been linked to contemporary
earthenware glazed surfaces and pigments of older paints. The toxicology of lead has been
extensively studied. Inorganic lead is a general metabolic poison and enzyme inhibitor (like most
of the heavy metals). Organic lead is even more poisonous than inorganic lead. The earliest
symptoms of lead poisoning seem to be psychical (e.g., excitement, depression, and irritability).
Young children are particularly affected and can suffer mental retardation and semi-permanent
brain damage. One of the most insidious effects of inorganic lead is its ability to replace
calcium in bones and remain there to form a semi-permanent reservoir for long-term release well
after the initial absorption. The usual indicator of the degree of inorganic lead poisoning in
humans is the content of this element in whole blood.

Different authorities suggest safety levels in the range of 0.2–0.8 ppm. The figure 0.2 ppm seems
to reflect a worldwide minimum. The disturbing fact is that the natural levels in human blood are
already very close to what is considered a reasonable toxicological limit, not leaving us with any
margin for exposure to lead.

Lead is a cumulative general poison, with fetuses, infants, children up to six years of age, and
pregnant women (because of their fetuses) being most susceptible to adverse health effects. Lead
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 [8], with encephalopathy occurring at blood lead levels of 100–120 μg dL-1 in adults
and 80–100 μg 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 μg dL-1 [8]. After one or two years of exposure, muscle
weakness, gastrointestinal symptoms, lower scores on psychometric tests, disturbances in mood,
and symptoms of peripheral neuropathy were observed in occupationally exposed populations at
blood lead levels of 40–60 μg dL-1 [9]. At levels of 30–50 μg dL-1, there were significant
reductions in nerve conduction velocity.

Renal disease has long been associated with lead poisoning; however, chronic nephropathy in
adults and children has not been detected below blood lead levels of 40 μg dL-1. Finally, it has
been demonstrated that interactions between calcium and lead were responsible for a significant
portion of the variance in the scores on general intelligence ratings, and that calcium had a
significant effect on the deleterious effect of lead [10]. Several lines of evidence demonstrate
that both the central and peripheral nervous systems are principal targets for lead toxicity.
These include sub-encephalopathic neurological and behavioral effects in adults and
electrophysiological evidence of both central and peripheral effects on the nervous system in
children with blood lead levels well below 30 μg dL-1. The carcinogenicity of lead in humans
has been investigated in several epidemiological studies of occupationally exposed workers [11].
The International Agency for Research on Cancer considered the overall evidence for the
carcinogenicity of lead to humans to be inadequate [11].

Lead. Lead is a metal belonging to group IV and period 6 of the periodic table with atomic
number 82, atomic mass 207.2, density 11.4 g cm-3, melting point 327.4◦C, and boiling point
1725◦C. It is a naturally occurring, bluishgray metal usually found as a mineral combined with
other elements, such as sulphur (i.e., PbS, PbSO4), or oxygen (PbCO3), and ranges from 10 to
30 mg kg-1 in the earth’s crust [44]. Typical mean Pb concentration for surface soils worldwide
averages 32 mg kg-1 and ranges from 10 to 67 mg kg-1 [10]. Lead ranks fifth behind Fe, Cu, Al,
and Zn in industrial production of metals. About half of the Pb used in the U.S. goes for the
manufacture of Pb storage batteries. Other uses include solders, bearings, cable covers,
ammunition, plumbing, pigments, and caulking. Metals commonly alloyed with Pb are antimony
(in storage batteries), calcium (Ca) and tin (Sn) (in maintenance-free storage batteries), silver
(Ag) (for solder and anodes), strontium (Sr) and Sn (as anodes in electrowinning processes),
tellurium (Te) (pipe and sheet in chemical installations and nuclear shielding), Sn (solders), and
antimony (Sb), and Sn (sleeve bearings, printing, and high-detail castings) [45].
Ionic lead, Pb(II), lead oxides and hydroxides, and leadmetal oxyanion complexes are the general
forms of Pb that are released into the soil, groundwater, and surface waters. The most stable
forms of lead are Pb(II) and lead-hydroxy complexes. Lead(II) is the most common and reactive
form of Pb, forming mononuclear and polynuclear oxides and hydroxides [3]. The predominant
insoluble Pb compounds are lead phosphates, lead carbonates (form when the pH is above 6),
and lead (hydr)oxides [46]. Lead sulfide (PbS) is the most stable solid form within the soil
matrix and forms under reducing conditions, when increased concentrations of sulfide are
present. Under anaerobic conditions a volatile organolead (tetramethyl lead) can be formed due
to microbial alkylation [3].
Lead(II) compounds are predominantly ionic (e.g., Pb2+ SO42-), whereas Pb(IV) compounds
tend to be covalent (e.g., tetraethyl lead, Pb(C2H5)4). Some Pb (IV) compounds,
such as PbO2, are strong oxidants. Lead forms several basic salts, such as Pb(OH)2·2PbCO3,
which was once the most widely used white paint pigment and the source of considerable
chronic lead poisoning to children who ate peeling white paint. Many compounds of Pb(II) and a
few Pb(IV) compounds are useful. The two most common of these are lead dioxide and lead
sulphate, which are participants in the reversible reaction that occurs during the charge and
discharge of lead storage battery.
In addition to the inorganic compounds of lead, there are a number of organolead compounds
such as tetraethyl lead. The toxicities and environmental effects of organolead compounds are
particularly noteworthy because of the former widespread use and distribution of tetraethyllead
as a gasoline additive. Although more than 1000 organolead compounds have been synthesized,
those of commercial and toxicological importance are largely limited to the alkyl (methyl and
ethyl) lead compounds and their salts (e.g., dimethyldiethyllead, trimethyllead chloride, and
diethyllead dichloride).
Inhalation and ingestion are the two routes of exposure, and the effects from both are the same.
Pb accumulates in the body organs (i.e., brain), which may lead to poisoning (plumbism) or even
death. The gastrointestinal tract, kidneys, and central nervous system are also affected by the
presence of lead. Children exposed to lead are at risk for impaired development, lower IQ,
shortened attention span, hyperactivity, and mental deterioration, with children under
the age of six being at a more substantial risk. Adults usually experience decreased reaction time,
loss of memory, nausea, insomnia, anorexia, and weakness of the joints when exposed
to lead [47]. Lead is not an essential element. It is well known to be toxic and its effects have
been more extensively reviewed than the effects of other trace metals. Lead can cause serious
injury to the brain, nervous system, red blood cells, and kidneys [48]. Exposure to lead can result
in a wide range of biological effects depending on the level and duration of exposure. Various
effects occur over a broad range of doses, with the developing young and infants being more
sensitive than adults. Lead poisoning, which is so severe as to cause evident illness, is now very
rare. Lead performs no known essential function in the human body, it can merely do harm after
uptake from food, air, or water. Lead is a particularly dangerous chemical, as it can accumulate
in individual organisms, but also in entire food chains.
The most serious source of exposure to soil lead is through direct ingestion (eating) of
contaminated soil or dust. In general, plants do not absorb or accumulate lead. However, in soils
testing high in lead, it is possible for some lead to be taken up. Studies have shown that lead does
not readily accumulate in the fruiting parts of vegetable and fruit crops (e.g., corn, beans, squash,
tomatoes, strawberries, and apples). Higher concentrations are more likely to be found in leafy
vegetables (e.g., lettuce) and on the surface of root crops (e.g., carrots). Since plants do not take
up large quantities of soil lead, the lead levels in soil considered safe for plants will be much
higher than soil lead levels where eating of soil is a concern (pica). Generally, it has been
considered safe to use garden produce grown in soils with total lead levels less than 300 ppm.
The risk of lead poisoning through the food chain increases as the soil lead level rises above this
concentration. Even at soil levels above 300 ppm, most of the risk is from lead contaminated soil
or dust deposits on the plants rather than from uptake of lead by the plant [49].

Cadmium
Cadmium is a silvery-white, lustrous, but tarnishable metal; it is soft and ductile and has a
relatively high vapor pressure. Cadmium is nearly always divalent; chemically it closely
resembles zinc and occurs in almost all zinc ores by isomorphous replacement [12]. 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, in solar batteries, and in
pigments [13]. In one review, it was noted that the use of cadmium products has expanded in
recent years at a rate of 5–10% annually, and the potential for further growth is very high [14].
The whole world’s 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 USA.

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 [15].

Occurrence
Cadmium is a relatively rare element. It is uniformly distributed in the Earth’s crust, where it is
generally estimated to be present at an average concentration of between 0.15 and 0.2 mg kg-1
[16].

Cadmium occurs in nature in the form of various inorganic compounds and as complexes with
naturally occurring chelating agents; organo-cadmium compounds are extremely unstable and
have not been detected in the natural environment. Industrial and municipal wastes are the main
sources of cadmium 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 [17]. The need to determine cadmium levels in suspended matter and
sediments in order to assess the degree of contamination of a water body has been pointed out.
The concentration of cadmium in unpolluted fresh waters is generally less than 0.001 mg L-1
[16]; the concentration of cadmium in seawater averages about 0.00015 mg L-1 [17]. Surface
waters containing in excess of a few micrograms of cadmium per liter have probably been
contaminated by industrial wastes from metallurgical plants, plating works, plants manufacturing
cadmium pigments, textile operations, cadmium-stabilized plastics, or nickel–cadmium batteries,
or by effluents from sewage treatment plants [17].

High concentrations of cadmium in air are associated with heavily industrialized cities, notably
those having refinery and smelting activities [16], where levels may be several hundred times
those found in non-contaminated areas [18]. According to the earlier (1969) data from the U.S.
National Air Sampling Network, the annual average cadmium concentrations at 29 nonurban
stations were all less than 0.000003 mg m-3; those for the 20 largest cities ranged from 0.000006
to 0.000036 mg m-3 [18].

The presence of cadmium in vegetation may arise from the deposition of cadmium-containing
aerosols directly on plant surfaces and by the absorption of cadmium through roots. Plants vary
in their tolerance to cadmium in soil and in the amounts they are able to accumulate. Certain
shellfish, such as crabs and oysters, may concentrate cadmium to extremely high levels in certain
tissues, even if they inhabit waters containing low levels of cadmium. Reported concentrations of
cadmium in foodstuffs vary widely; concentrations in most foods average about 0.05 mg kg-1 on
a wet-weight basis. Other fresh meats generally contain less than 0.05 mg kg-1; cadmium
concentrations in fish are usually less than 0.02 mg kg-1 [18]. In cadmium-polluted areas,
cadmium levels may be significantly elevated; rice and wheat from contaminated areas of Japan
have been found to contain concentrations near 1 mg kg-1, at least a factor of 10 higher than
those for most parts of the world [18].

Health Considerations
Cadmium is not at present believed to be an essential nutrient for animals or man. Several studies
on human subjects indicate that 4–7% of a single dose of ingested cadmium is absorbed from the
intestine. The absorption of cadmium nitrate or cadmium chloride in animal studies ranged from
0.5% to-13% [18]. The total amount absorbed by humans has been estimated as 0.0002–0.005
mg day [19].
Absorbed cadmium accumulates mainly in the renal cortex and liver. The pancreas, thyroid, gall-
bladder, and testes can also contain relatively high concentrations. Several studies suggest that
accumulation of cadmium in the human body is a function of age [20]; one author claims that
there is a 200-fold increase in the cadmium content of the body in the first three years of life, and
that in this early period humans accumulate almost one-third of their total body burden.
Cadmium accumulates with age until a maximum level is reached at about age 50; the total body
burden of a person of 50 years of age ranges from 5 to 40 mg. About half the body burden is
found in the kidneys and Concentrations of cadmium in the renal cortex are normally 5–20 times
those in the liver [17].

Toxic Effects
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 [21]. Doses as low as 15–30 mg [21] from
acidic foodstuffs stored in cadmium-lined containers have resulted in acute gastroenteritis. The
consumption of fluids containing 13–15 mg of cadmium per liter by humans has caused vomiting
and gastrointestinal cramps.

Acute cadmium poisoning has occurred following exposure to fumes during the melting or
pouring of cadmium metal [22]. Fatalities have resulted from a 5 h exposure to 8 mg m-3,
although some individuals have recovered after exposure to 11 mg m-3 for 2 h. Acute
pneumonitis resulted from inhalation of concentrations between 0.5 and 2.5 mg m-3 for 3 days.
Symptoms of acute poisoning include pulmonary edema, headaches, nausea, vomiting, chills,
weakness, and diarrhea. Cadmium has been established as a very toxic heavy metal. A disease
known as “Itai-Itai” in Japan is specifically associated with cadmium poisoning, resulting in
multiple fractures arising from osteomalacia [23].
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. It is
accompanied by the classical renal effects of industrial cadmium poisoning: proteinuria, and
often glucosuria, and aminoaciduria [18].
Cadmium tends to accumulate in the human body (30 mg in an average American male), with
33% in the kidneys and 14% in the liver. Chronic cadmium poisoning produces proteinuria and
causes the formation of kidney stones. There is evidence of a link between cadmium and
hypertension. The main problem with cadmium in humans appears to be that the body seldom
excretes as much cadmium as is absorbed. There is little general agreement about acceptable
safety limits for cadmium intake. In the USA, the safety level of cadmium in drinking water has
been set at 10 ppb.
Sampling of surface waters revealed some dangerously high cadmium levels. Chronic exposure
to airborne cadmium results in a number of toxic effects; the two main symptoms are lung
emphysema and proteinuria [22]. Emphysema appears after approximately 20 years of exposure;
levels of exposure that result in disability have not been systematically determined. It has been
proposed that the minimum critical level of cadmium in the kidney required to produce renal
tubular damage is approximately 0.2 mg g-1 [24]. 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 [24].

Cadmium. Cadmium is located at the end of the second row of transition elements with atomic
number 48, atomic weight 112.4, density 8.65 g cm-3, melting point 320.9◦C, and boiling point
765◦C. Together with Hg and Pb, Cd is one of the big three heavy metal poisons and is not
known for any essential biological function. In its compounds, Cd occurs as the divalent Cd(II)
ion. Cadmium is directly below Zn in the periodic table and has a chemical similarity to that of
Zn, an essential micronutrient for plants and animals. This may account in part for Cd’s toxicity;
because Zn being an essential trace element, its substitution by Cd may cause the malfunctioning
of metabolic processes [54].
The most significant use of Cd is in Ni/Cd batteries, as rechargeable or secondary power sources
exhibiting high output, long life, low maintenance, and high tolerance to physical and electrical
stress. Cadmium coatings provide good corrosion resistance coating to vessels and other
vehicles, particularly in high-stress environments such as marine and aerospace. Other uses of
cadmium are as pigments, stabilizers for polyvinyl chloride (PVC), in alloys and electronic
compounds. Cadmium is also present as an impurity in several products, including phosphate
fertilizers, detergents and refined petroleum products. In addition, acid rain and the resulting
acidification of soils and surface waters have increased the geochemical mobility of Cd, and as a
result its surface-water concentrations tend to increase as lake water pH decreases [54].
Cadmium is produced as an inevitable byproduct of Zn and occasionally lead refining. The
application of agricultural inputs such as fertilizers, pesticides, and biosolids (sewage sludge),
the disposal of industrial wastes or the deposition of atmospheric contaminants increases the
total concentration of Cd in soils, and the bioavailability of this Cd determines whether plant Cd
uptake occurs to a significant degree [28]. Cadmium is very biopersistent but has few
toxicological properties and, once absorbed by an organism, remains resident for many years.
Since the 1970s, there has been sustained interest in possible exposure of humans to Cd through
their food chain, for example, through the consumption of certain species of shellfish or
vegetables. Concern regarding this latter route (agricultural crops) led to research on the possible
consequences of applying sewage sludge (Cd-rich biosolids) to soils used for crops meant for
human consumption, or of using cadmium-enriched phosphate fertilizer [54]. This research has
led to the stipulation of highest permissible concentrations for a number of food crops [8].
Cadmium in the body is known to affect several enzymes.
It is believed that the renal damage that results in proteinuria is the result of Cd adversely
affecting enzymes responsible for reabsorption of proteins in kidney tubules. Cadmium also
reduces the activity of delta-aminolevulinic acid synthetase, arylsulfatase, alcohol
dehydrogenase, and lipoamide dehydrogenase, whereas it enhances the activity of
deltaaminolevulinic acid dehydratase, pyruvate dehydrogenase, and pyruvate decarboxylase [45].
The most spectacular and publicized occurrence of cadmium poisoning resulted from dietary
intake of cadmium by people in the Jintsu River Valley, near Fuchu, Japan. The victims were
afflicted by itai itai disease, which means ouch, ouch in Japanese. The symptoms are the result
of painful osteomalacia (bone disease) combined with kidney malfunction. Cadmium poisoning
in the Jintsu River Valley was attributed to irrigated rice contaminated from an upstream mine
producing Pb, Zn, and Cd. The major threat to human health is chronic accumulation in the
kidneys leading to kidney dysfunction. Food intake and tobacco smoking are the main routes by
which Cd enters the body [45].

Chromium
As any other transition metal, chromium can be found at a degree of oxidation ranging from (-II)
to (+VI). However, the most common oxidation states of chromium are (0), (III), and (VI). In
natural deposits, chromium is present in complex cubic isomorphic minerals called spinel.
Most of the chromium found in nature is in its trivalent state (the most stable one), but small
amounts of the hexavalent form have been found along with the divalent oxidation state.
Chromium is used in many industrial applications. It can be either used melted with other metals
to produce alloys or plated.

Chromium steel alloys provide high corrosion resistance and good hardenability. Other
applications of chromium range from tanning agents, paint pigments, and catalysts to
impregnation solution for wood or photography. The world production of chromite ore is several
millions of tons per year. Ferrochromite is obtained by direct reduction of the ore while
chromium metal is produced either by chemical reduction (aluminothermic process) or by
electrolysis of either CrO3 or chrome alum solutions.

Chemical Pathways
Chromium concentrations in both air and soil are subject to large variations. In air the
concentrations range from 0.3 ng m-3 in remote sites to 50 ng m-3 in urban areas, and in soil
they vary from traces to 250 mg kg-1, where it may be from phosphate fertilizers. 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 the hexavalent state. Main contaminations are generated
by industrial waste waters. Since the trivalent state is predominant in soils, it is unlikely that even
heavily polluted farmland would result in chromium accumulation in the food chain via plants.
No common plant used as animal feed or food has been reported with a tendency to concentrate
chromium.

Clinical Effects
Chromium was recognized to be a hazardous element in the early years after it was discovered.
No reports indicate that chromium salts (+III) have severe toxic effects. Hexavalent chromium is
considered to be lethal for a dose higher than 3 g for adult humans. The first symptoms are
vomiting and persisting diarrhea. After a week, hemorrhagic diathesis and epitasis are commonly
observed. Convulsions occur during the final stages of the illness. Repeated occupational
inhalation of hexavalent chromium compounds causes perforations of the nasal septum
and skin ulceration “chrome holes.” The sense of smell and acute irritative dermatitis or allergic
eczematous dermatitis have frequently been reported in case of chronic exposure to chromic acid
vapors as well as an Increased incidence of cancer in the respiratory organs. Bronchial asthma
due to chromate dust or Chromic acid fumes has been experienced by a number of workers.
Environmental contamination with chromium seems trivial compared to mercury or cadmium.
Nevertheless, severe toxic effects -1 on plants have been reported at Cr(VI) concentrations of
approximately 0.5 mg L .

Monitoring and Legislations

It is accepted that monitoring both atmosphere and biological material from exposed workers is
essential. Chromium concentrations can be determined using colorimetry, atomic absorption, or
emission spectroscopy. The US Standards Institute listed a maximum acceptable
concentration (MAC) of 0.1 mg m-3 for chromic acid. The U.S. National Institute of
Occupational Safety and Health (US-NIOSH) makes a difference between non carcinogenic
Cr(VI) and carcinogenic Cr(VI). The time-weighted average values at a workplace are 25 mg
m-3 for airborne carcinogenic chromium and 50 mg m-3 for non carcinogenic chromium.
Ingestion Rate Background: Consumption of fine soil and dust particulates, especially by young
children, is the dominant route of exposure for lead and other contaminants (Laidlaw et al. 2014;
Landrigan et al. 1975; Lanphear et al. 1998, 2003). Childhood soil and dust ingestion occurs via
multiple pathways, including hand-to-mouth transfer, mouthing of objects, and contaminated
food. These pathways are dependent on individual behaviors, exposure time, and environmental
conditions (Zahran et al. 2013a).

Accurate estimates of the soil and household dust ingestion rate (IR) pathway are needed to
assess children’s exposures and health risks associated with trace metals and persistent organic
chemical residues in the home or play environment, and to make informed cleanup decisions.
Early estimates of soil/dust IRs in children were based on studies of trace elements in soil and
feces, yielding uncertain estimates due to analytical uncertainty, limited sample size, and short
study duration (Batelle 2005; Doyle et al. 2010; Sedman and Mahmood 1994; Stanek et al. 2012;
USEPA 2011, 2012). Currently, national U.S. Environmental Protection Agency (USEPA)
central tendency soil/dust IRs of 60 mg/day (children age 6 weeks-<12 months) and 100 mg/day
(children age 1-<6 years) are based on these tracer studies (USEPA 2011).

More recent studies have used dermal transfer to estimate soil and dust IRs. Ozkaynak et al.
(2010) modeled the frequency of hand and object mouthing in children aged 3-<6 years,
resulting in a mean total soil/dust IR of 68 mg/day (95th percentile of 224mg/day). Similarly,
Wilson et al. (2013) used a mechanistic model including parameters for particle loading on skin,
transfer to hands, hand surface area, mouthing surface area, hand-to-mouth frequency, saliva
dissolution, and exposure time, to estimate an average combined soil/dust IR of 61 mg/day for
children aged 7 months-4 years. Meta-analysis of four major studies using stochastic modeling
of the most reliable tracers resulted in an average soil ingestion estimate of 26 mg/day (95th
percentile of 79 mg/day) for children aged 1-8 years (Stanek et al. 2012). Findings from large-
scale reviews and integration of data from tracer, mechanistic, validation
modeling/measurement, and empirical relation (biomonitoring/environmental concentration)
studies suggest that mean IRs in children are less than 100 mg/day and may be as low as 40-80
mg/day (Bierkens et al. 2011; Moya and Phillips 2014).

Soil/dust IR and bioavailability are sensitive parameters in the USEPA Integrated Exposure
Uptake Biokinetic (IEUBK) Model for Lead in Children. The IEUBK model currently uses
default IRs ranging from 85 to 135 mg/day for 6 month-6 year old children and 30% absolute
bioavailability for ingested soil and indoor dust (USEPA 2013). The first use of the IEUBK
model to develop site-specific cleanup levels was at the Bunker Hill Mining and Metallurgical
Complex Superfund Site (BHSS) in northern Idaho (CH2MHill 1991; TerraGraphics 1990;
USEPA and IDHW 1991, 1992).

Chromium. Chromium is a first-row d-block transition metal of group VIB in the periodic table
with the following properties: atomic number 24, atomic mass 52, density 7.19 g cm-3, melting
point 1875◦C, and boiling point 2665◦C. It is one of the less common elements and does not
occur naturally in elemental form, but only in compounds.
Chromium is mined as a primary ore product in the form of the mineral chromite, FeCr2O4.
Major sources of Cr contamination include releases from electroplating processes and the
disposal of Cr containing wastes [39]. Chromium(VI) is the form of Cr commonly found at
contaminated sites. Chromium can also occur in the +III oxidation state, depending on pH and
redox conditions. Chromium(VI) is the dominant form of Cr in shallow aquifers where aerobic
conditions exist. Chromium(VI) can be reduced to Cr(III) by soil organic matter, S2- and Fe2+
ions under anaerobic conditions often encountered in deeper groundwater. Major Cr(VI) species
include chromate (CrO42-) and dichromate (Cr2O72-) which precipitate readily in the presence
of metal cations (especially Ba2+, Pb2+, and Ag+). Chromate and dichromate also adsorb on soil
surfaces, especially iron and aluminum oxides. Chromium(III) is the dominant form of Cr at low
pH (<4). Cr3+ forms solution complexes with NH3, OH-, Cl-, F-, CN-, SO42-, and soluble
organic ligands.
Chromium(VI) is the more toxic form of chromium and is also more mobile. Chromium(III)
mobility is decreased by adsorption to clays and oxide minerals below pH 5 and low solubility
above pH 5 due to the formation of Cr(OH)3(s) [50]. Chromium mobility depends on sorption
characteristics of the soil, including clay content, iron oxide content, and the amount of organic
matter present. Chromium can be transported by surface runoff to surface waters in its soluble or
precipitated form. Soluble and un-adsorbed chromium complexes can leach from soil into
groundwater.
The leachability of Cr(VI) increases as soil pH increases. Most of Cr released into natural waters
is particle associated, however, and is ultimately deposited into the sediment [39].
Chromium is associated with allergic dermatitis in humans [21].
Zinc. Zinc is a transition metal with the following characteristics: period 4, group IIB, atomic
number 30, atomic mass 65.4, density 7.14 g cm-3, melting point 419.5◦C, and boiling point
906◦C. Zinc occurs naturally in soil (about 70 mg kg-1 in crustal rocks) [52], but Zn
concentrations are rising unnaturally, due to anthropogenic additions. Most Zn is added during
industrial activities, such as mining, coal, and waste combustion and steel processing. Many
foodstuffs contain certain concentrations of Zn. Drinking water also contains certain amounts of
Zn, which may be higher when it is stored in metal tanks. Industrial sources or toxic waste sites
may cause the concentrations of Zn in drinking water to reach levels that can cause health
problems.
Zinc is a trace element that is essential for human health. Zinc shortages can cause birth defects.
The world’s Zn production is still on the rise which means that more and more Zn ends up in the
environment. Water is polluted with Zn, due to the presence of large quantities present in the
wastewater of industrial plants. A consequence is that Zn polluted sludge is continually being
deposited by rivers on their banks. Zinc may also increase the acidity of waters. Some fish can
accumulate Zn in their bodies, when they live in Zn-contaminated waterways. When Zn enters
the bodies of these fish, it is able to biomagnify up the food chain.
Water-soluble zinc that is located in soils can contaminate groundwater. Plants often have a Zn
uptake that their systems cannot handle, due to the accumulation of Zn in soils. Finally, Zn can
interrupt the activity in soils, as it negatively influences the activity of microorganisms and
earthworms, thus retarding the breakdown of organic matter [53].

Copper. Copper is a transition metal which belongs to period 4 and group IB of the periodic
table with atomic number 29, atomic weight 63.5, density 8.96 g cm-3, melting point 1083◦C and
boiling point 2595◦C. The metal’s average density and concentrations in crustal rocks are 8.1 ×
103 kg m-3 and 55 mg kg-1, respectively [52].
Copper is the third most used metal in the world [55]. Copper is an essential micronutrient
required in the growth of both plants and animals. In humans, it helps in the production of blood
haemoglobin. In plants, Cu is especially important in seed production, disease resistance, and
regulation of water. Copper is indeed essential, but in high doses it can cause anaemia, liver and
kidney damage, and stomach and intestinal irritation. Copper normally occurs in drinking water
from Cu pipes, as well as from additives designed to control algal growth. While Cu’s interaction
with the environment is complex, research shows that most Cu introduced into the environment
is, or rapidly becomes, stable and results in a form which does not pose a risk to the
environment. In fact, unlike some man-made materials, Cu is not magnified in the body or
bioaccumulated in the food chain. In the soil, Cu strongly complexes to the organic implying that
only a small fraction of copper will be found in solution as ionic copper, Cu(II). The solubility of
Cu is drastically increased at pH 5.5 [56], which is rather close to the ideal farmland pH of 6.0–
6.5 [57].
Copper and Zn are two important essential elements for plants, microorganisms, animals, and
humans. The connection between soil and water contamination and metal uptake by plants is
determined by many chemical and physical soil factors as well as the physiological properties of
the crops.
Soils contaminated with trace metals may pose both direct and indirect threats: direct, through
negative effects of metals on crop growth and yield, and indirect, by entering the human food
chain with a potentially negative impact on human health. Even a reduction of crop yield by a
few percent could lead to a significant long-term loss in production and income. Some food
importers are now specifying acceptable maximum contents of metals in food, which might limit
the possibility for the farmers to export their contaminated crops [36]

NICKEL. Nickel is a transition element with atomic number 28 and atomic weight 58.69. In low
pH regions, the metal
exists in the form of the nickelous ion, Ni(II). In neutral to slightly alkaline solutions, it
precipitates as nickelous hydroxide, Ni(OH)2, which is a stable compound. This precipitate
readily dissolves in acid solutions forming Ni(III) and in very alkaline conditions; it forms
nickelite ion, HNiO2, that is soluble in water. In very oxidizing and alkaline conditions, nickel
exists in form of the stable nickelo-nickelic oxide, Ni3O4, that is soluble in acid solutions. Other
nickel oxides such as nickelic oxide, Ni2O3, and nickel peroxide, NiO2, are unstable in alkaline
solutions and decompose by giving off oxygen. In acidic regions, however, these solids dissolve
producing Ni2+ [58].
Nickel is an element that occurs in the environment only at very low levels and is essential in
small doses, but it can be dangerous when the maximum tolerable amounts are exceeded. This
can cause various kinds of cancer on different sites within the bodies of animals, mainly of those
that live near refineries. The most common application of Ni is an ingredient of steel and other
metal products. The major sources of nickel contamination in the soil are metal plating
industries, combustion of fossil fuels, and nickel mining and electroplating [59]. It is released
into the air by power plants and trash incinerators and settles to the ground after undergoing
precipitation reactions. It usually takes a long time for nickel to be removed from air. Nickel can
also end up in surface water when it is a part of wastewater streams.
The larger part of all Ni compounds that are released to the environment will adsorb to sediment
or soil particles and become immobile as a result. In acidic soils, however,
Ni becomes more mobile and often leaches down to the adjacent groundwater. Microorganisms
can also suffer from growth decline due to the presence of Ni, but they usually develop
resistance to Ni after a while. Nickel is not known to accumulate in plants or animals and as a
result Ni has not been found to biomagnify up the food chain. For animals Ni is an essential
foodstuff in small amounts.

Iron (Fe) is a constant and necessary component of the animal and human.

Iron is a member of the first row transition series of elements, consisting of Sc, Ti, V, Cr, Mn,
Fe, Co, Ni, Cu and Zn, and belongs to group 8 of the periodic table, along with Ru and Os.
The element has an atomic number of 26, an atomic mass of 56, two main oxidation states (+2
and +3) and four naturally occurring isotopes (54Fe, 56Fe, 57Fe and 58Fe), although 56Fe is the
major isotope at 92% of the total mass.

Iron is the fourth most abundant element and second most abundant metal in the Earth’s crust
(after aluminium). It is one of the seven metals known in antiquity (along with gold, silver,
copper, mercury, tin and lead). It has both lithophile and chalcophile properties, forming several
common minerals, including pyrite FeS2, magnetite Fe3O4, haematite Fe2O3 and siderite
FeCO3. It is also present in many rock-forming minerals, including mica, garnet, amphibole,
pyroxene and olivine. Iron becomes concentrated in mid-stage fractionates during magmatic
processes and is generally enriched in mafic rocks relative to felsic, intermediate or ultramafic
types.
There is a wide range of Fe concentrations within different rock classifications depending on
their mineralogical composition but, as a guide, Mielke (1979) and Williamson (1999) report Fe
values as: ultramafic 9.6%; basaltic 8.6%; granitic 2.2% (1.4-3.0%); syenite 3.7%; and a crustal
average of 7%.

Anthropogenic sources of iron include the iron and steel industry, sewage and dust from iron
mining (Reimann and de Caritat 1998). Iron sulphate is also used as a fertiliser and herbicide
(Reimann et al. 2003).
Iron is an essential nutrient for plants and animals. Between 10 and 18 mg per day is needed for
adults (Mertz 1987) and iron deficiency is a common medical condition. Its main role in humans
is in the production of haemoglobin in red blood cells (WHO 1996).
High intakes of cobalt, zinc, cadmium, copper and manganese interfere with iron absorption in
the human body, which can lead to anaemia (Mertz 1987).

Used for the synthesis of hemoglobin and myoglobin muscle. The daily requirement of iron is
covered in food. When the deficiency disorders are formed (anemia), which is treated with the
administration of iron salts as a medicament [7]. Iron is found in all organs and tissuesand the
largest quantities are stored in the liver and spleen. Iron salts taken orally do not poison, but can
produce side effects such as constipation and vomiting [10].
 CHAPTER THREE

Study area
The city of Onitsha in Anambra state 6° 8' 28.7232'' N and 6° 48' 10.6164'' E is located in south
eastern part of Nigeria. Abeokuta contains few but emerging industries, many commercial
centers and schools of various levels of learning, hospitals and
residential buildings. The main occupation of people in the town is trading, thus is referred to as
the trade capital of anambra state. Other occupations are, civil service etc.
it has a population of (7,425,000.) in 2006 (npc 2010).
Onitsha as a trade capital of Anambra State has been experiencing an increase in both population
and traffic density and upspring of institutions of basic learning. This is evidenced by the
continued expansion of central business district, residential areas and traffic congestion at peak
hours.

However, information on roadside dust contamination with heavy metals in relation to

class room dust contamination in Onitsha is limited and the attempt to bridge this gap formed the
thrust of this study. Therefore, the objective was to investigate effect of location on heavy metal
accumulation in classroom dust.

The study was carried out in two commercial roads (Sapon and Omida) and two residential roads
(Ibara and Asero Housing Estate) as shown in Figure 1 and their traffic counts were carried out.
However, no industrial activity is apparent near the vicinity of the sampling location.

Sample collection
Dust samples were randomly collected from both sides of the road by sweeping roadsides with a
plastic brush into a plastic waste packer and kept in well sealed polythene sample bags for
analysis. However, no industrial activity is apparent near the vicinity of the sampling location.
Dust samples from the interior of classrooms and surface soils were collected using soft brush.
selected heavy metals in the indoor dust were dominated by Fe with a concentration of
4,801±1,873 μgg-1 followed by Pb>Zn>Cr and Cd with concentration of 253.5±83.2, 144.9±
73.4, 11.9±6.8 and 0.23±0.10 μgg-1, respectively. Fe also had the highest concentration of all the
heavy metals investigated in the samples taken of soil dust (8,225±6,800 μgg-1)

samples were gently filtered using a <63 μm size sieve prior to sample digestion.
Dust was also collected by wiping 0.09 m2 (0.03 m×0.03 m) of the surface of the indoor walls
and the children’s palms with dried and pre-weighed Kimwipes. The dust from the children’s
palms was collected after the children had finished their first activities at around 10:00 a.m. in
the morning

Analytical procedure

SAMPLES WERE TAKEN FROM SCHOOLS LOCATED AROUND MARKETS,

DIFFERENT AREAS OF INDUSTRIAL ACTIVITIES AND MAJOR ROADS Collected dust
samples were dried at 100”c and pass through a 200µm mesh screen (sand). This size was chosen
because finer fractions generally contains higher metal concentrations (Duggan and Inskip, 1985;
Gulson et al., 1994, 1995; Whicker et al., 1997) and particles below this size are considered
hazardous as they easily adhere to children’s hands (Duggan and Inskip, 1985). Heavy metals
were determined using a ….. AAS.

Chemical analysis
Dust samples were dried for 24 h at a temperature of 100 0C and sieved through 100 (0.1 mm)
nylon mesh. In addition, 0.5 g of the fractionated dust samples was digested by adding 10 ml 65
% HNO3 and 2 ml concentrated HF. This was heated to dryness on a water bath. Then 10 ml of 1
% HNO3 was added and heated to boiling and the solution allowed to cool to room temperature
and finally made up to 50 ml (Ogunsola et al., 1994). The digested sample solutions were then
analysed for the heavy metals using Atomic Absorption Spectrophotometer (AAS, Varian Spectr
AA-400 plus, Varian Techtron Pty limited Mulgrave, Victoria, Australia). Replicate analyses
were carried out on each sample.

Statistical analysis
The data obtained were subjected to descriptive statistics and analysis of variance. Means were
separated using Duncan’s Multiple Range (DMR) test. Pearson’s correlation coefficient was used
to determine the relationship between the metals.

Results
The results of the heavy metals concentrations as determined by AAS were presented in Table1.
It was observed that of all the four metals, Pb had the highest concentration followed by Zn, Ni
and Cd. This trend was observed for all the six primary schools . The higher the traffic density
the more was the
concentration of the metals investigated (Table 1). Sapon road which had the highest traffic
density also had the highest concentrations of Pb, Zn, Cd and Ni. This was followed by Omida,
Ibara and Asero respectively. Commercial roads (Sapon and Omida) had significantly (p < 0.05)
higher Pb concentration than the residential roads (Ibara and Asero).

In order to establish inter-metal relationships in the samples, correlation coefficient of the metals
at the four sampling roads was carried out (Table 2). There was significant (p < 0.05) positive
correlation among the four metals investigated. The positive relation among the four metals
indicated that they are from the same source. The level of
heavy metals in this study, Abeokuta, Ogun State was compared with the work carried about in
Osun and Lagos States (Table 3). Pb concentration in Abeokuta, Ogun Sate (this study) was
higher than that of Osun State but lower than that of Lagos State. Lagos State had higher
concentrations of heavy metals investigated followed by Ogun State (this study) and Osun State

Discussion
Commercial roads (Sapon and Omida) had higher traffic density compared to the residential
roads (Ibara and Asero). This might be due to the commercial activities in Sapon and Omida
most especially from 7 a.m. to 7 p.m. when buying and selling activities are going on. Besides,
the two roads (Sapon and Omida) serve as link road to different places in Abeokuta. Roadsides
dusts of the four roads had highest concentrations of Pb, followed by Zn, Ni and Cd. Motor
vehicles introduce a number of toxic metals into the atmosphere adjacent to roadways (Moore
and Moore, 1976;
Ogunsola et al., 1994; Bada et al., 2001). The metals are considered to arise from motor vehicle
tyre wear and motor vehicle emissions (Lagerwerff and Specht, 1970); both account for 80 % of
the air pollution problems in urban areas of Southwestern Nigeria (Osibanjo and Ajayi, 1980).
Sapon with highest traffic density had highest concentration of the heavy metal investigated
followed by Omida, Ibara and Asero. Elevated metal concentration in street soil of industrialized
and /or populated cities resulted from increased automobile circulation (Smith, 1976; Ho, 1979).
As in this study, elevated concentrations of Pb, Cd, Ni, V and Zn in roadside soil and vegetation
were reported by Bada et al. (2001) to vary with traffic densities. Levels of heavy metals in bark
and fruit of trees along roads in Nigeria vary according to traffic volume (Ademoroti, 1986). The
concentration of Pb and, to some extent, a few other toxic elements are strongly correlated with
traffic density (Ogunsola et al., 1994). Significant positive correlation was observed between the
heavy metals investigated. The positive correlation among the four metals indicated that they are
from the same source. Zn and Ni in street soils and dusts emanate from vehicle parts and wear
including wear and tear of tyres (Lagerwerff and Specht, 1970). The higher concentration of
heavy metals observed in Lagos State compared to Ogun and Osun States might be due to the
variation in traffic density.

Conclusion
Commercial centre roads with the highest traffic density had the highest concentrations of the
heavy metals investigated while residential area road with the least traffic density also had the
least heavy metals. There was positive correlation among the heavy metals investigated.

Potential health implications

Due to frequent winds and deposits of soil in play grounds and major roads which cause it to be
disturbed and deposited into indoor areas (classroom)

The present study was designed to document the quantity of heavy metals that preschool
children, between the ages of 5–6, were exposed to from indoor dust in their classrooms.
Generally speaking, preschools are home to 20 to 40 preschool children and the school’s indoor
environment contains furniture and toys for them to use. All school children’s shoes are kept
outside the classroom and the classrooms are cleaned daily after the children go home. In the
mornings, these children usually take part in outdoor activities.

The measurement of heavy metals in indoor dust and soil were measured in units of μgg-1 (mass
of heavy metal (μg)/ mass of sample (g))

Quality control
Quality control was practiced throughout the analysis to avoid any interference and minimize the
risk of error. Powderless gloves were used while performing all stages of the experiment, most
notably when handling the Kimwipes and indoor dust.
Furthermore, all analyses of samples involving Kimwipes were conducted in a laminar flow
chamber. All the polyethylene bottles and glassware utilized for heavy metal analysis were
pre-cleaned by being soaked in nitric acid overnight before being rinsed with deionised water.
Additionally, any instruments involved in this analysis were calibrated before use.

Statistical analysis
All statistical calculations were performed using the Student Version of the Statistical Package
for Social Sciences (SPSS Version 17.0) for Windows. Correlation coefficients and correlation
significance among measured heavy metals were analysed using the one-way variance test with a
95 % level

The heavy metal concentrations (Pb, Zn, Cd, Fe and Cr) in the indoor dust samples collected
from the selected preschools are presented in Table 2. Fe was recorded as having the highest
concentration among the heavy metals tested, with an average concentration of 4,801±1,873 μgg-
1, followed by Pb (253.5± 83.2 μgg-1), Zn (144.9±73.4 μgg-1), Cr (11.91±6.75 μgg-1)
and Cd (0.23±0.10 μgg-1). Fe concentrations across the samples ranged from 1,439±2,810 μgg-1
(S5) to 7,969± 1,216 μgg-1 (S7). There were significant differences (p <0.05) between Fe
concentrations in indoor dust among the sampling stations. The level of Fe found in indoor dust
was expected due to the abundance of Fe as one the major components of the earth’s crust
(Wang et al. 2006; Sultan and Shazili 2009; Hunt et al. 2011). At the same time, the differences
in Fe concentrations in indoor dust sampled at different stations were also estimated because of
the influence of soil dust entering the indoor environment through the movement of students and
also the influence of the wind blowing from outdoors. The concentrations of Zn ranged from
25.0±13.3 μgg-1 (S10) to 256.8±30.0 μgg-1 (S3) and there were significant
differences in Zn concentrations between stations (p <0.05).

The highest concentration of Zn recorded was at S3, a preschool located in the city centre area,
while the lowest concentration of Zn recorded was at S10, which is located in a residential area.
Pb concentrations ranged from 57.0±83.7 μgg-1 (S10) to 328.6±27.6 μgg-1 (S3). There
were significant differences (p <0.05) between Pb concentrations in the indoor dust collected
from different stations. S3 (the sampling site located in the city centre) recorded the highest
concentration of Pb. Cd and Cr were found at lower concentrations than the other metals
investigated. The Cd concentration ranged from 0.07±0.03 μgg-1 (S10) to 0.38±0.14 μgg-1 (S9)
and there were significant differences (p <0.05) between Cd concentrations among the sampling
stations. S10, which is located in a residential area a distance from any main road, recorded a
very low Cd concentration compared to those recorded at other stations.

However, the results for the other stations were nearly the same as the highest concentration
recorded at S9. The Cr concentration in the indoor dust samples ranged from 4.79±1.75 μgg-1
(S10) to 24.29±13.96 μgg-1. Like Cd, the lowest concentration of Cr was found in the preschool
located at S10

Overall concentrations of the heavy metals recorded in the preschools are higher compared to
those in the surface soils collected around each preschool compound, that is, except for
Fe and Cr (Table 4). Fe is the major element in the surface soil and hence has the ability to
influence the level of Fe in indoor dust. In this study, the level of Cr in the surface soil collected
from several school compounds showed a higher concentration compared to that in indoor dust A
comparison of our findings with those of a previous study undertaken by (Mohd Tahir et al.
2007) at a nursery/ child care centre in the small Terengganu town of Dungun on the east coast
of the Malaysia Peninsular (Table 5), shows the concentrations of all heavy metals but Zn in the
indoor dust samples of this study to be higher. This is hardly surprising since the sampling
locations for this study are nearer to urban and industrial areas than is the case for the small town
of Dungun. It is this proximity to urban and industrial areas that can be expected to exacerbate
heavy metal contamination in our samples, especially from street and blown-soil dust.

Nevertheless, comparison with a study by Tong and Lam (1998) and a more recent study by
Wang et al. (2011) in nursery schools (childcare centres) and kindergartens (preschools) in Hong
Kong and China, respectively, showed that the concentration of heavy metals in this study are
still low, apart from Pb. Further comparison with the composition of heavy metals in households,
e.g. by Al-Rajhi et al. (1996) in a wide range of rural, suburban, urban, industrial and motorway
environments in Riyadh, Saudi Arabia; Rasmussen et al. (2001) in Ottawa, Canada;
Chattopadhyay et al. (2003) in Sydney, Australia; Turner and Simmonds (2006) in four regions
(Birmingham, the Midlands, Plymouth and Devon) in the UK; Jaradat et al. (2004) in industrial
areas of Jordan; and Habil et al. (2013) near roadside and residential areas in Agra, India,
indicated that the concentrations of heavy metals in indoor dust from this study are still within
the range of those recorded in many other areas around the world.

Conclusions
This study presents an analysis of selected heavy metals (Zn, Fe, Pb, Cd and Cr) which are found
in indoor dust and which are associated with surface soil and interior walls. The average
concentrations of the selected heavy metals in the indoor dust were dominated by Fe with a
concentration of 4,801± 1,873 μgg-1 followed by Pb>Zn>Cr and Cd with an average
concentration of 253.5±83.2, 144.9±73.4, 11.9±6.8 and 0.23 ±0.10 μgg-1, respectively. Fe also
showed the highest concentration of the heavy metals investigated in samples of soil dust
(8,225±6,800 μgg-1), interior walls (1,865±756 μgm-2) and children’s palms (3,882±3,401 μgm-
2). The enrichment factor results showed that most of the heavy metals determined in indoor dust
are influenced by anthropogenic sources. The re-suspension of accumulated heavy metals in road
dust is expected to contribute to the amount of heavy metals in the indoor environment. The high
EF value for heavy metals, such as: Zn, Cd and Cr on the inside walls and children’s palms,
shows that particulate matter from outdoor dust, building materials, wall surfaces and other
indoor materials touched by the children can influence their exposure to heavy metals. The high
levels of heavy metals on their palms could be an important indicator, signalling the exposure of
heavy metals to the children. These toxic heavy metals are a source of health concern as they can
be transferred to other organs in the body through ingestion via children’s hand to mouth
activities. According to Järup (2003) and Llop et al. (2013), the effects of heavy metals to
children include neurotoxicity.
The study showed that preschool children can be exposed to heavy metals from a variety of
sources from the outdoor and indoor environment. Comprehensive investigation into the
existence of heavy metals in and around the school environment is crucial if children are to
reduce being exposed to such metals. At the same time, various mitigation procedures, such
as: the daily cleaning of indoor dust and a reduction in the use of materials containing heavy
metals should be implemented so as to reduce the exposure of heavy metals to those children
in a preschool environment.

Analysis of some heavy metals present in soil dusts of PRIMARY SCHOOLS IN ONITSHA,
South East Nigeriawas carried out. Soil dust samples were collected from five different sections
in the market and a control sample was collected 500 m away from the market. The samples
were analyzed after aqua regia digestion with Flame Atomic Absorption Spectrophotometer for
Lead, Iron, Nickel, Copper, ZINC, CHROMIUM and Cadmium. The result showed a variation,
which indicated that concentration of Fe > Cu > Pb > Cd > Ni.
The levels of some of these metals were higher than the recommended allowable limit for such
metals in soil by regulating agencies.

INTRODUCTION
The presence of high concentration of heavy metals in street dusts and soils have become a
matter of serious concern of late. Street dust is derived from anthropogenic activities by
interaction of natural elements with pollution sources (Turer et al., 2001; Al-Khashman, 2004;
Bhattacharya et al., 2011). Reports (Archer and Barratt, 1976; Ayodele and Gaya, 1998; Jaradat
and Momani, 1999; Shinggu et al., 2007; Osakwe, 2010) indicate increasing contamination of
street dust and soils with heavy toxic metals poses serious threat to healthy living and
environmental sustainability. For instance, human exposure to heavy metals has risen
dramatically in the last 50 years as a result of an exponential increase in the use of heavy metals
in industrial processes and products (Ano et al., 2007). Ultimately, they enter the food chain
and affect human and animals. There is consensus among scientists that the increasing rate of
heavy metals contamination of soil ecosystem is due to anthropogenic activities such as
industrial and energy production, construction and fuel combustion (Murphy, 1981; Nasralla,
1984; Li et al., 2001; Li et al., 2006, 2007; Sharma et al., 2007; Nyangababo and Hamuya, 1986;
Sutherland, 2000; White head, 1975). In humans, heavy metals are systemic toxins with specific
neurotoxic, nephrotoxic, fetotoxic and teratoxic effects (Murphy, 1981). The specific type of
metal contamination found in a contaminated soil is directly related to the operation that
occurred at the site. The range of contaminant concentrations and the physical and chemical
forms of contaminants will also depend on activities and disposal patterns for contaminated
wastes on the site. Other factors that may influence the form, concentration, and distribution of
metal contaminants include soil and ground-water chemistry and local transport mechanisms [3].
Heavy metal pollution can affect all environments but its effect is most long lasting in soils due
to relatively strong adsorption of many metals on loamy and clay colloid of soil. Many reagents
such as Calcium chloride, ammonium nitrate, and ammonium acetate have been employed to
extract the mobile or bioavailable forms of heavy metals in single extraction method (Ahumada
et al., 1999; He and Singh, 1995; Karezewska, 1996). Sequential extraction method has also been
adopted (Narwal et al., 1996). However, acid digestion using aqua regia appears to be most
common (Fazeli et al., 2009).

AIMS AND OBJECTIVES OF THE STUDY

-To determine the level of lead, copper, chromium, iron, zinc, nickel, and cadmium contents of
soil dust collected from six primary schools in Onitsha metropolis .
-To compare the results obtained with other works and standard limits set by regulatory agencies
-To determine the level of contamination and the possible way out in the management of heavy
metals in the environment.

Soil Concentration Ranges and Regulatory

Guidelines for Some Heavy Metals
Contaminant concentrations can be measured directly in metals-contaminated water. These
concentrations are most commonly expressed as total dissolved metals in mass concentrations
(mg L-1 or gL-1) or in molar concentrations (mol L-1). In dilute solutions, a mg L-1 is
equivalent to one part per million (ppm), and a gL-1 is equivalent to one part per billion (ppb).
Riley et al. [64] and NJDEP [65] have reported soil concentration ranges and regulatory
guidelines for some heavy metals (Table 1). In Nigeria, in the interim period, whilst suitable
parameters are being developed, the Department of Petroleum Resources [60] has recommended
guidelines on remediation of contaminated land based on two parameters intervention values and
target values (Table 2).
The intervention values indicate the quality for which the functionality of soil for human, animal,
and plant life are, or threatened with being seriously impaired. Concentrations in excess of the
intervention values correspond to serious contamination. Target values indicate the soil quality
required for sustainability or expressed in terms of remedial policy, the soil quality required for
the full restoration of the soil’s functionality for human, animal, and plant life. The target values
therefore indicate the soil quality levels ultimately aimed at.

Table 1: Soil concentration ranges and regulatory guidelines for

some heavy metals.
Metal Soil concentration range† Regulatory limits‡
(mg kg-1) (mg kg-1)
Pb 1.00–69 000 600
Cd 0.10–345 100
Cr 0.05–3 950 100
Hg <0.01–1 800 270
Zn 150–5 000 1 500
†
[64]; ‡Nonresidential direct contact soil clean-up criteria [65].

Table 2: Target and intervention values for some metals for a standard soil [60].
Metal Target value Intervention value
(mg kg-1) (mg kg-1)
Ni 140.00 720.00
Cu 0.30 10.00
Zn — —
Cd 100.00 380.00
Pb 35.00 210.00
As 200 625
Cr 20 240
Hg 85 530

This study investigates the concentration of Heavy Metals in soil sample from 15 different
locations in Garki area of Federal Capital Territory (F.C.T) Abuja, Nigeria. The level of Cu, Cd,
Pb, Ni, Mn, and Zn were determined using flame atomic absorption spectrophotometer. The
results obtained indicated that these metals on dry weight basis in the soil ranged between
(36.60-525.0 µg/g) Pb, (15.00-74.40 µg/g) Cu, (17.50-29.80 µg/g) Zn, (0.7-2.20 µg/g) Cd,
(16.16-24.60 µg/g) Ni, and (270-558.0 µg/g) Mn. From the results, areas with high traffc density
seem to be relatively high in concentration of tested metals than those from less traffc density.

Ever since life began on earth, the atmosphere has been an important resource for chemicals
elements and a medium for deposition of wastes. The deposition of waste in the atmosphere will
lead to change in the natural levels of chemical substances in the atmosphere and hence causes
pollution of the atmosphere. Pollution is defined as the introduction by man into the
environment, substances or energy liable to cause hazard to human health, harm to living
resources or amenity or interference with legitimate uses of environment [1]. Any substance
which is present in nature beyond permissible limits, as well as has detrimental effects not only
on the environment but also on living organisms is called Pollutant [2]. Emission from Heavy
trafc on roads contains lead (Pb), cadmium (Cd), zinc (Zn) and nickel (Ni), which are present in
fuel as anti-knock agents [3,4].Te deposition of vehicle derived metal and the relocation of
metals deposited on road surface by air and runoff water have led to contamination of soil [5-8].
Te level of lead in petrol in Nigeria was estimated as 0.7 g/liter and the national Consumption of
petrol in the country is estimated at 20 million liters per day with about 150 people per Car [9]. It
was therefore predicted that at least 15,000 kg of lead is emitted into the environment through
burning [10]. Hence, automobile exhaust were believed to account for more than 80% of the air
pollution and lead content in Nigeria’s super grade gasoline is 600 – 800 mg/liter [11,12], which
is much higher than permissible levels in some pollution conscious countries. Analysis of
household dust in Sydney suggests that lead in ‘‘contaminated’’ households can originate from
either gasoline or paint, depending on the proximity to major traffic thoroughfares and Pb in
household dust is more consistent with gasoline lead [13]. Sources of lead by the road side was
attributed to the settled out from burned leaded gasoline, settle dust from industrial sources and
lead around houses from lead paint that has been scraped off during the continuing repainting of
the house [14]. Smoking of cigarettes, cosmetics and paint chips could result in elevated Cd, Zn
and Cr content [15]. It was proved that worn construction; furnishing and carpet materials can
lead to elevated heavy metal content [16]. Nickel is one of many trace metals widely distributed
in the environment, with both natural and anthropogenic sources. It fnds its way into the ambient
air as a result of the combustion of coal, diesel oil and fuel oil, the incineration of waste and
sewage, and miscellaneous sources. Tobacco smoking in the form of gaseous nickel carbonyl,
Stainless steel in kitchen, inexpensive jewelry utensils also contributes to lower level of nickel
[17].
Carcinogenic transition metals such as Ni and Cu catalyze the generation of reactive oxygen
species that may result in damage to cell membranes, mitochondria, proteins and DNA [18]. Te
excessive Mn exposure is associated with neurologic and neuropsychiatric disorders, including
the subclinical signs and symptoms of Parkinsonism, reduced speed of movements, and
alterations in gait, posture and facial expressions [19]. Pb at low levels causes nausea, irritability
while large dose causes brain damage [20]. Low levels of Cd (0.2 mg/day) cause hypertension,
and degenerative bone disease at high levels [21]. Zn Deficiency cause dwarfism, dermatitis, loss
of taste, immature gonads and delay wound healing, its toxicity causes anemia [22].

Contamination of soils by Heavy Metals (HM) is the most serious environmental problem and
has significant implications for human health [23]. The environmental problems associated with
Heavy metal pollution have increased during the last decade. It has become increasing evident
that this type of pollution is affecting plants, human, and animals resources.
Thus, the aim of this study is to investigate the level of heavy metals including Pb, Mn, Cu, Ni,
Cd and Zn in Garki Area of Abuja and to elucidate the relationships between the levels of metals
in these areas and traffic density.
Study area
Abuja, the Federal Capital Territory (F.C.T) is located in the geographical center of Nigeria and
lies between longitudes 60 45 and 70 45E and latitudes 80 25 and 90 25N.Te total landmass of
Abuja is 713 sqKms and it is bounded to the south by kogi state, northwest by Niger, south- east
by Nasarawa and Kaduna in the north –east. The population of Abuja as at 2006 census was
776,298 [24]. Although this figure would have been exceeded as at 2015.
Materials and Methods
Sampling sites
Fifteen sites were selected for the study from Garki area of F.C.T. These sampling sited were
chosen to reflect commercial, residential, public office areas with peculiar characteristics like
refuse dumps. The volume of traffic per hour was determined for all the sites. Table 1 below
shows the description of samples sites and their trafgic density.

Sampling preparation/treatment of soil sample

Characteristics and road side soils were taken (3 m away) from fifteen different locations in
Federal Capital Territory - F. C. T representing areas of different traffic density. The volume of
traffic per hours was computed for different areas by taking a traffic census over a period of 12
hours for seven days between 0700 -1900 h daily. The results were used to categorise the areas
into high (above 1000 per hour), and low (below 1000 per hour) traffic density areas. The
sampling was carried out both during the dry and rainy seasons of the year. Sample (in duplicate)
were collected at the distance not more than 3 m from the road side. The samples were kept in
polythene bags. They were dried in an oven at about 80%c. the dried samples were ground in
porcelain motar, and sieved with 2 mm size nylon. The fraction passing through the sieve were
subsequently store and used for metal determination using a pye unican atomic absorption
spectrophotometer model sp9 in the flame mode.
Metal determination choice of method
Two methods of samples preparation were used to prepared a sample for metal determinations.
This was to test the extraction efciency of the methods. Te frst method was described by
Anderson and it involved subjection of 5 g of the soil to 3 hours constant extraction
with 2 M HNO 3 acids [26]. Te second method was described by HO and Tai and it involved
treating 1 g of the soil sample with 10 ml of 14 M HNO
3 acid. This was heated in steam bath were it was evaporated to dryness and then cooled. Te
procedure was repeated with another 10 ml of 14 M HNO 3 followed by 10 ml of 12 M HCl
[27].The digested soil sample was then warmed in 20 ml of 14 M HCl to re-dissolve the metal
salt. The mixture was finally filtered and the filtrate was diluted to 25 ml in a volumetric flask
with distilled water. Te results obtained with the methods are listed in Table 2. A comparison of
the two methods shows that the means were signficantly different (t-test) at 95% confidence
interval. Since the second method showed much lower results, the Anderson method was
therefore used to prepare all other samples prior to metal determination.

Results and Discussion

Tables 3 and 4 showed the PH and organic carbon content of the soils from all sites. Data
presented in these Tables indicated that soils have a low organic matter (0.66%) mean value. Soil
pH value ranged between 6.44 and 7.24 with an average of 6.97 in water indicating only a
slightly acidic to neural. Acidic nature of the soil could be attributed to the effect of bush burning
and the harmatten dust [28]. Te mean concentrations of Pb, Cu, Zn, Cd, Ni and Mn elements in
soil samples are summarized in Table 5. Soil samples generally show a high level of metals
concentration. Te range of heavy metals concentration found in soil was 0.7 to 558 µg/g. Tis
results obtained indicated that, these metals on dry weight basis in the soil ranged between
(36.60-525.0 µg/g) Pb, (15.00-74.40 µg/g) Cu, (17.50-29.80 µg/g) Zn, (0.7-2.20 µg/g) Cd,
(16.16-24.60 µg/g) Ni, and (270-558.0 µg/g) Mn. Pb concentration in soil shows a mean of 332.8
µg/g and a range of 36.60 to 525.0 µg/g. Te value of Pb in all the samples areas was found to be
high except in the central district area which shows a low level of Pb 36.6 µg/g. Tis value
however, is higher than the maximum value obtained for Zn, Cd, and Ni except for Mn and Cu.
Te range value for Pb (36.60- 525.0 µg/g) is lower than (89.9 -754.4 µg/g) in Bauchi soils [29],
1,925 mg/kg Pb in Urban soils of amman, Jordan [30] and 1,999 mg/kg Pb in urban soils of
Sidney, Australia [31] but higher than 0.013 ± 0.006- 0.225 ± 0.020 µg/g in soils of Malaysia
[32], (10.06 ± 0.36 – 29.71 ± 1.56 mg/kg) in Aba soils [33] and 280 mg/kg in soils of Honolulu,
USA [34].Te high Pb content of the soil could be attributed to vehicular emissions as well as
metal plating and lubricating oils. It could also be due to rough surfaces of the roads which
increase the wearing of tyres, and run-offs from the roadsides [35]. Lead pollution in urban soil
has been attributed to combustion of gasoline that contains tetraethyl lead as anti-knock agent
[8,36-38]. It was revealed by Atuanya et al. [39] that higher lead concentration in soils has toxic
effect on microorganisms inhabiting the soil which consequently alters the flora and fauna of a
location. Lead has been found to be the major cause of hypertension, impairment of central
nervous system and other respiratory problems in adult [40]. Zinc and Pb are amongst the metal
referred to as common urban pollutants [41,42]. Te fragmentation of tires has been implicated
for higher concentrations of Zn in heavy trafc zones [43,44]. Te concentration of Zn was found
in the range of (17.50-29.80 µg/g). Te level of Zn in this study is lower than 9.0-400 mg/kg
obtained in urban soils of Poznan municipality, Poland [45], 0.90-169 mg/kg in Florida soils
[46], 58 -330 mg/kg in roadside soils of Dortmund, Germany [47] but higher than 0.774 ± 0.070-
13.40 ± 1.52 in soils of Malaysia [32]. Te ranged value for Cd in the soil sample was 0.7 – 2.20
µg/g, the level of Cd in this study higher than 0.006 ± 0.002 - 0.030 ± 0.005 μg/g in soils
of Malaysia [31]. As such the source of Cd in soil may be attributed to vehicular emissions.
Cadmium is released as a combustion product in the accumulators of motor vehicles or in
carburetors [48,49]. Te main concentration of Ni in the soils determine were within the ranged
of 16.16 µg/g and 24.60 µg/g and the mean nickel content in soils, of the world vary between 8-
33 and 20-92 µg/g for light and heavy soils respectively. Ni concentration determined in the
present study remained within the target Values of 35 mg/kg and lower than EU value [50,51].
Soil generally contains 200 – 3000 mg/kg of manganese with an average value of 600 mg/kg
[52]. Te levels of manganese in this study were relatively high. Te highest level of manganese
obtained was 558.0 µg/g which is higher than what was reported in Bauchi (419.1 µg/g) [29] and
in Kaduna (132 mg/kg) [53]. But lower than the results obtained in the United States (2532
mg/kg), China (1740 mg/kg), Poland (1122 mg/kg) and Yauri (608.11 mg/kg) [54-57]. Mn and
Ni are associated with trafc related sources such as corrosion of metallic part, concrete materials,
reentrained dust from roads and tear and wear of tyres and engine parts [58]. Te correlation
coefcient between the concentrations of heavy metals in soils and trafc density in the study area
is summarized in Table 6. Te correlation analysis of the results for heavy metals concentrations
in soil samples indicated a signifcant correlation between trafc Density and Zinc with correlation
value of (r2=0.753) and (r2=0.964) for Zn and Cd respectively. Tis value indicates that
automobile tires are also sources of Cd in the environment [28]. It was also found a signifcant
correlation between concentrations of Pb and Cu in the soil sample with (r2=0.79). Te high level
of Pb which correlated with trafc density confrmed that automobile emission is the major sources
of Pb in this study area. Tere was no correlation between trafc density and Ni. Te non-signifcant
correlation signified that these metals might have resulted from sources other than vehicular
emission [32]. From the results, the metal concentration values are arranged in the decreasing
order: CMn > CPb > CCu > CZn > CNi > CCd where C stands for concentration. Te
concentration level of the heavy metals determined in the present study was signifcantly higher
than the soils permissible limits as prescribed by WHO, 1971, DPR 1991, FEPA, 1991. Table 7
for the safe environment [59-61].
Sources DPR (1991), FEPA (1991), and WHO (1971).
Conclusions
In this study, Heavy Metals (Pb, Cu, Zn, Cd, Ni and Mn) concentration in soil in Garki area of
Federal Capital Territory, Abuja, Nigeria, was investigated. Te results obtained showed that the
soil samples from various site have a high level of heavy metals concentration. Te result also
showed a positive correlation between heavy metals and Trafc density indicating that emission
from automobile is majorly responsible for such level of pollution.
Conclusion
The soil dusts from the SCHOOLS studied indicated pollution of the soil environment by heavy
metals. The values obtained from the contamination/pollution index corroborated this view.
Further more, analysis of the enrichment coefficient indicated a range of minimal to significant
enrichment for the metal contents studied. he target value was obtained by using the standard
formulated by the Department of Petroleum Resources (Osakwe, 2010) in Nigeria as cluster
abundant values for maximum allowable concentration of heavy metals in soil in mg/kg {5000
for Fe; 85 for Pb; 36 for Cu}.C/P index of some metals in the soil dusts.
Sample Fe Cu Pb
I 0.14 1.78 0.37
II 0.06 0.61 0.41
III 0.15 0.94 1.12
IV 0.13 1.33 0.57
V 0.12 1.75 1.02

The presence of high concentration of heavy metals in street dusts and soils have become a
matter of serious concern of late. Street dust is derived from anthropogenic activities by
interaction of natural elements with pollution sources (Turer et al., 2001; Al-Khashman, 2004;
Bhattacharya et al., 2011). Reports (Archer and Barratt, 1976; Ayodele and Gaya, 1998; Jaradat
and Momani, 1999; Shinggu et al., 2007; Osakwe, 2010) indicate increasing contamination of
street dust and soils with heavy toxic metals poses serious threat to healthy living and
environmental sustainability. For instance, human exposure to heavy metals has risen
dramatically in the last 50 years as a result of an exponential increase in the use of heavy metals
in industrial processes and products (Ano et al., 2007). Ultimately, they enter the food chain
and affect human and animals. There is consensus among scientists that the increasing rate of
heavy metals contamination of soil ecosystem is due to anthropogenic activities such as
industrial and energy production, construction and fuel combustion (Murphy, 1981; Nasralla,
1984; Li et al., 2001; Li et al., 2006, 2007; Sharma et al., 2007; Nyangababo and Hamuya, 1986;
Sutherland, 2000; White head, 1975). In humans, heavy metals are systemic toxins with specific
neurotoxic, nephrotoxic, fetotoxic and teratoxic effects (Murphy, 1981). Heavy metal pollution
can affect all environments but its effect is most long lasting in soils due to relatively strong
adsorption of many metals on loamy and clay colloid of soil. Many reagents such as Calcium
chloride, ammonium nitrate, and ammonium acetate have been employed to extract the mobile or
bioavailable forms of heavy metals in single extraction method (Ahumada et al., 1999; He and
Singh, 1995; Karezewska, 1996). Sequential extraction method has also been adopted
(Narwal et al., 1996). However, acid digestion using aqua regia appears to be most common
(Fazeli et al., 2009).

Sampling site description

Samples were taken from coal camp Industrial market, Enugu,
Nigeria at five different areas of industrial activities. These areas include (i) Automobile
mechanic (ii) road side (iii) Battery and brick works (iv) Motor park. soil dusts were sampled
using plastic brush and a plastic scoop. The soil dust samples were passed through 62 µm sieve
prior to analysis. Another sampling site was selected 500 m from the market to serve as a
control.
Dust samples were collected and transferred to clean polyethene bags. Each of the samples was
dried in an oven at 100-110°C to drive out moisture until a constant weight was obtained.
Particular like slag stones were separated from the samples and the samples ground into a fine
powder. The ground samples were sieved using a 250 µm sieve mesh diameter.
All experiments were performed with analar grade chemicals. One gramme of each sample was
digested using aqua regia, 3:1 ratio of HCl to HNO3 (Ayodele and Gaya, 1994; Xianagding et
al., 2001) to incipient dryness. Then 5 ml HClO4 was added and the mixture heated until a
homogeneous solution was obtained. During the digestion, the samples were heated in a water
bath at 100°C. Calibration standards were prepared from the stock solution of the metals. The
digested samples were then analyzed for desired heavy metals using Buck Scientific Model 210
VGP Atomic Absorption Spectrophotometer.

RESULTS AND DISCUSSION

The concentrations of the assayed heavy metals are presented in Table 1.
The concentration of Iron had a range of 752.0 to 12.5 mg/kg soil dust, with a concentration
trend in sampling sites of III > I > IV > V > 11 > VI. Iron had the highest concentration in soil
dust from welding work section and lowest in the automobile mechanic section. Iron also had the
highest concentration among all the metals in the reference station, some 500 m from the border
of the industrial market. Earlier studies (Xianagding et al., 2001; Dara, 1993) found out that
natural soils contain appreciable amount of Iron. The levels of iron observed in this study were
higher than some reported elsewhere (Ahumada et al., 1999; He and Singh, 1995; Karezewska,
1996). Iron in industrial areas result from construction, filing and other metal works.

The levels of Copper in the samples studied ranged from 64.0 to 2.8 mg/kg. These were
significantly higher than values reported elsewhere (Rashad and Shalaly, 2007; Dara, 1993). The
presence of Cu in industrial street dust is attributable to smelting, battery, soldering works.
Lead levels in the soil dust studied ranged from 87.0 to 4.8 mg/kg, greatly higher than some
earlier reported works (Rashad and Shalaly, 2007; Ayodele and Gaya, 2003). Lead enters dust
through the actions of electrical smelting and soldering workers. Lead is noted as toxin and it has
adverse effects on humans and animals (Murphy, 1981). The concentrations of Cadmium ranged
from 2.3 to 0. 2 mg/kg. Cadmium presence in the soil dusts results from industrial works such as
battery and other electrical works. Nickel levels ranged from 0.8 to 0.1 mg/kg. The element has
the lowest concentration of all the metals analyzed. The levels of the metals found in the
industrial market soil dust are appreciably higher than those found in the reference station, an
indication of pollution of the market soils. The result of this work has far reaching
implications to the environment. Heavy metals are widely distributed from the pollution sources
into various components of the environment ranging from the humans to air, vegetation and
water. For instance, in a study of heavy metal pollution of ground water in the same market
(Ekere, 2011), many heavy metals were found to be in excess of the maximum allowable limit.
Health risks associated with Cd, Pb, Cu, Ni, and Fe have been
 Heavy metal concentrations of soil dusts in some primary schools in Onitsha Metropolis
(mg/kg)
S/N Sites Pb Cu Cr Fe Zn Ni Cd

1 D1 74.06±0.03 11.56±0.01 23±0.01 96.74±0.16 23.64±0.07 3.67±0.01 1.23±0.04

2 D2 83.64±0.03 32.51±0.03 28±0.02 93.05±0.08 27.53±0.03 12.56±0.02 1.20±0.03

3 D3 84.64±0.03 7.86±0.03 13.02±0.03 76.49±0.12 9.45±0.05 32.61±0.06 0.68±0.16

4 D4 65.08±0.02 18.04±0.01 15.06±0.13 105.85±0.31 17.48±0.02 2.45±0.02 1.18±0.06

5 D5 94.43±0.07 54.93±0.13 21.00±0.05 82.93±0.06 22.65±0.10 5.65±0.04 1.06±0.03

6 D6 72.00±0.06 36.06±0.03 21.67±0.02 89.96±0.21 23.54±0.04 11.84±0.05 1.19±0.16

7 Control 1 176.97±0.13 84.94±0.07 53.95±0.03 216.05±0.34 76.54±0.03 31.32±0.08 21.01±0.04

8 Control 2 169.05±0.10 92.49±0.14 61.86±0.06 197.97±0.34 85.50±0.10 43.86±0.13 24.43±0.03

Key
D1- ALL SAINTS PRIMARY SCHOOL AWKA ROAD ONITSHA
D2- UNITED PRIMARY SCHOOL NKPOR
D3- OTUMOYE PRIMARY SCHOOL AWADA OKPOKO
D4- TRINITY PRIMARY SCHOOL, HOLY TRINITY
D5- OYE OLU PRIMARY SCHOOL 33-ONITSHA
D6- LEARNING FIELD INTERNATIONAL SCHOOL AWKA ROAD.
 DETERMINATION OF PB, CU, CR, FE, ZN,NI AND CD
CONTENTS OF SOIL DUST SAMPLES IN SCHOOLS AROUND

ONITSHA METROPOLIS

BY

UCHE EMMANUEL C.

13/89262

DEPARTMENT OF PURE AND INDUSTRIAL CHEMISTRY,

FACULTY OF BIOLOGICAL AND PHYSICAL SCIENCES

ABIA STATE UNIVERSITY, UTURU

DECEMBER, 2017
 DETERMINATION OF PB, CU, CR, FE, ZN,NI AND CD
CONTENTS OF SOIL DUST SAMPLES IN SCHOOLS AROUND

ONITSHA METROPOLIS

BY

UCHE EMMANUEL C.

13/89262

A PROJECT WORK SUBMITTED TO THE DEPARTMENT OF

PURE AND INDUSTRIAL CHEMISTRY FACULTY OF
BIOLOGICAL AND PHYSICAL SCIENCES ABIA STATE
UNIVERSITY, UTURU

IN PARTIAL FUFILMENT OF THE REQUIREMENTS FOR

THE AWARD OF BACHELOR OF SCIENCE (B.Sc) DEGREE IN
PURE AND INDUSTRIAL CHEMISTRY

SUPERVISOR: MR PRINCE UKAOGO

DECEMBER, 2017
 DECLARATION

I, UCHE EMMANUEL .C. hereby declare that this project is original

and was carried out by me, that this project has not been submitted
previously for any degree in the school or elsewhere and that the project
is submitted to the department of pure and industrial chemistry in partial
fufilment of the requirement for the award of Bachelor of science (B.Sc)
degree industrial chemistry.

Students Name Signature Date

Uche Emmanuel C. ………………. ………………..

13/89262
 CERTIFIFCATION
ABIA STATE UNIVERSITY, UTURU