CHAPTER ONE

1.0 INTRODUCTION

1.1 BACKGROUND OF STUDY

Nigeria is considered the most populous country in Africa having a population of 182 million,

(Akhilesh et al., 2009). One of the consequences of the increased human population is

environmental pollution, and it is possible to establish relationships between over population,

poverty, and urban air pollution. Poverty as an outcome of overpopulation for a country of low

gross domestic productresults in a majority of its citizens using rickety, old, smoke-belching cars

and two-stroke engine motorcycles as a means ofpublic transport, and this has resulted in

environmental pollution in most Nigerian cities Mapandaet al., (2005).

A heavy metal is any metallic element that has a relatively high density and is toxic or poisonous

even at low concentrations. The term applies to the group of metals and metalloids with an

atomic density greater than 4g/cm, or at least 5 timesgreater than the density of water(Thomas et

al., 2015). Heavy metals include lead (Pb), cadmium (Cd), zinc (Zn), mercury (Hg), arsenic

(As),silver (Ag), chromium (Cr), copper (Cu), iron (Fe), and the platinum (Pt) group.

Heavy metal contamination is a major environmental health challenge and is potentially

dangerous because ofbioaccumulation through the food chain, which arises from rapid industrial

growth, advances in the use of agriculturalchemicals, and the urbanising activities of man. This

has led to the dispersion of heavy metals in the environment, resulting inthe impaired health of

the population, mainly by the ingestion of food crops contaminated by these harmful

elements.Uptake of heavy metals by plants through absorption and subsequent accumulation

along the food chain is a potential threatto animal and human health(Thomas et al., 2015).

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Heavy metals are natural constituents of the earth’s crust and are persistent environmental

contaminants; they are not degradable and enter the body through food, air, and water and bio-

accumulate over a period of time. They can be released into the environment by natural and

anthropogenic sources. Anthropogenic sources of heavy metal contamination include agricultural

activities, such as pesticide and herbicide application, contaminated irrigation water, municipal

waste used for fertilization, and even mineral fertilizer containing traces of heavy metals.

Additional anthropogenic sources of heavy metals include direct waste disposal on farmland,

mining activities, use of lead as antiknock in petrol, traffic emissions, cigarette smoking,

metallurgy and smelting, aerosol cans, sewage discharge, and building materials, such as paints.

The atmosphere can be loaded with heavy metals through the breakdown of applied waste

materials, which gradually release the heavy metals in them. However, lead accumulation on

Nigerian soil is a result of long-term cultivation, while a significant increase in the concentration

of zinc in pasture fields is due to the application of manure (Murray et al., 2000).

In the savannah region of Nigeria, some heavy metals have been reportedly added to the soil

through farmyard and chemical fertilizer application. Heavy metal emissions from other sources,

such as worn automobile tires and brake linings, roofs, and food remnants in residences, as well

as other domestic byproducts, such as refuse, have also been identified. Heavy metals emanating

from anthropogenic sources are more dangerous because of their instability and solubility, which

leads to a high bioavailability (Murray et al., 2000).

Minerals are inorganic substances, present in all body tissues and fluids and their presence is
necessary for the Corresponding author maintenance of certain physicochemical processes which
are essential to life. Minerals are chemical constituents used by the body in many ways.
Although they yield no energy, they have important roles to play in many activities in the body
(Malhotra, 1998; Eruvbetine, 2003). Every form of living matter requires these inorganic
elements or minerals for their normal life processes (Hays and Swenson, 1985; Ozcan, 2003).

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Minerals may be broadly classified as macro (major) or micro (trace) elements. The third
category is the ultra trace elements. The macro-minerals include calcium, phosphorus, sodium
and chloride, while the micro-elements include iron, copper, cobalt, potassium, magnesium,
iodine, zinc, manganese, molybdenum, fluoride, chromium, selenium and sulfur (Eruvbetine,
2003). The macro-minerals are required in amounts greater than 100 mg/dl and the micro-
minerals are required in amounts less than 100 mg/dl (Murray et al., 2000). The ultra trace
elements include boron, silicon, arsenic and nickel which have been found in animals and are
believed to be essential for these animals. Evidence for requirements and essentialness of others
like cadmium, lead, tin, lithium and vanadium is weak (Albion Research Notes, 1996). The
mineral elements are separate entities from the other essential nutrients like proteins, fats,
carbohy-drates, and vitamins. Animal husbandry had demon-strated the need for minerals in the
diet (Hegsted et al., 1976). In this century, biological assay methods clarified the significance
and importance of mineral elements for human and animal nutrition and modern analytical
techniques led to the detection of trace elements as essential nutrients and this is still an active
area of current research. Micronutrient deficiencies are a major public health problem in many
developing countries, with infants and pregnant women especially at risk (Batra and Seth, 2002).
Infants deserve extra concern because they need adequate micronutrients to maintain normal
growth and development (Rush, 2000). The micronutrient deficiencies which are of greatest
public health significance are iron deficiency, causing varying degrees of impairment in
cognitive performance, lowered work capacity, lowered immunity to infections, pregnancy
complications e.g. babies with low birth weight, poor learning capacity and reduced
psychomotor skills (Batra and Seth, 2002). Medical reports show that very severe anaemia is a
direct cause of maternal and child mortality (Chakravarty and Ghosh, 2000). There have been
suggestions that more than anything else, lack of adequate information about the composition of
varied feed resources in some regions have been the major drawback to their utilization, rather
than real shortage (Aletor and Omodara, 1994). For instance, there is very limited information on
the mineral elements in some plants used as human food and animal feeds consumed in Nigeria,
especially the newly-introduced varieties of diets and the lesser known legumes. Some of the
earlier information on mineral elements was based on analysis employing less sensitive methods,
which may not be reliable

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1.2 STATEMENT OF THE PROBLEM

Elevated lead levels in soils forinstance may decrease soil productivity, while a very low lead
concentration may inhibit some vital plant processes, such asphotosynthesis, mitosis, and water
absorption, leading to symptoms of toxicity, like dark green leaves, wilting of older
leaves,stunted foliage, and brown short roots. Heavy metals are potentially toxic, resulting in
chlorosis, weak plant growth, andlow yield, and they may even be accompanied by reduced
nutrient uptake, disorders in plant metabolism, and a reducedability to fix molecular nitrogen in
leguminous plants The importance of mineral elements in human, animal and plant nutrition has
been well recognized. Deficiencies or disturbances in the nutrition of an animal cause a variety
of diseases and can arise in several ways. When a trace element is deficient, a characteristic
syndrome is produced which reflects the specific functions of the nutrient in the metabolism of
the animal.
1.3 OBJECTIVE OF THE STUDY

The main objective of this study is to analyze metals and minerals on soil, feed, water, on

agricultural farms in Nigeria

1.4 JUSTIFICATION OF THE STUDY

The high level of environmental contamination by metals is dangerous because their uptake by
plants and subsequent accumulation in food crops consumed by humans and animals is
deleterious to health. There are many known sources of harmful metals, including the earth,
which releases them into food, air, and water, and anthropogenic activities, such as the
application of fertilizer in agriculture, the use of pesticides and herbicides, and irrigation. The
need for a research on the importance of mineral components in the soil, feed and water samples
in agricultural farmlands is of high importance as this helps to control the level at which farm
produce is affected or hampered.

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 CHAPTER TWO

2.0 LITERATURE REVIEW

Many heavy metals are environmentally stable and non-biodegradable, toxic to the living beings

and tend to accumulate in plants and animals, causing chronic adverse effects on human health

(Vijayaet al., 2010). Heavy metals are introduced to the soil environment through a variety of

sources such as combustion, extraction processes, agricultural runoff, transportation of dissolved

metals etc (Akhileshet al., 2009). They are priority toxic pollutants that severely limit the

beneficial use of water for domestic and industrial application (Vijayaet al., 2010). They further

stated that frequent use of heavy metal-contaminated water in agricultural field’s leads to soil

pollution and gradually enriching the soil. Different studies have revealed that the presence of

toxic heavy metals like iron (Fe), lead (Pb), mercury (Hg) reduce soil fertility and agricultural

output. Anthropogenic activities, such as mining and industrial processing, were reported as the

main sources of heavy metal contamination in the environment (Xilonget al., 2005). They also

stated that under certain conditions, these metals may accumulate to a toxic concentration level

which can lead to ecological damages. In suburban areas, the use of industrial and municipal

wastewater is a common practice in many parts of the world (Rajesh et al., 2007). There are

different sources of toxic element in urban soils (Thomas et al., 2015), their loads in and around

human settlements are a global problem. They enter the soils by different pathways, including: 1)

aerial deposition (industries, vehicles and volcanoes), 2) paints, 3) pesticide and fertilizer

application, 4) waste utilization, 5) disposal of degraded sediments, and 6) river and irrigation

waters (Aguilar et al., 2013). They pass through the air and food into the human organism, where

they are usually not degraded, and hence they accumulate and may cause cancer, neuropathy and

other diseases (Thomas et al., 2015).

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The accumulation of heavy metals in agricultural soils is of increasing concern because of food

safety issues, potential health risks, and its detrimental effects on soil ecosystem (Cui et al.,

2004). Hg, Pb, Cd and Cr are of great concern due to their toxicity to human health and other

organism, whereas Zn and Cu are essential elements for plants and human (Na et al., 2007).

Heavy metals can accumulate in the soil at toxic levels due to the long-term application of

wastewater (Rajesh et al., 2007). Heavy metals are extremely persistent in the environment

which is non-biodegradable and non-thermodegradable, thus they readily accumulate to toxic

levels (Rajesh et al., 2007). Vegetable plants take up Hg, Pb, Cd, Zn, and Cu and accumulate

them in their edible and inedible parts with various concentrations. One important dietary uptake

pathway could be through crops irrigated with contaminated waste, when the capacity of the soil

to retain heavy metals is reduced due to repeated use of wastewater, soil can release heavy

metals into the ground water or soil solution available for plant uptake (Rajesh et al., 2007).

Rajesh et al. (2007) identified important sources of heavy metals in wastewater as urban and

industrial effluents, deterioration of sewage pipe and treatment works, and the wear of household

plumbing fixtures while Mapandaet al., (2005) identified other sources of contamination of

agricultural soil as sewage sludge, fertilizers, and pesticides. Rajesh et al., (2006) further stated

that the concentrations heavy metals in soil, crops and water are compared with established safe

limits as this provides a basis for guiding further activities aimed at preventing excessive

exposure of toxic substances (heavy metals) to human beings through monitoring and control of

irrigation water and/or amelioration of uptake by crops. On the other hand mineral is a chemical

element required as an essential nutrient by organisms to perform functions necessary for life.

However, the four major structural elements in the human body by weight (oxygen, hydrogen,

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carbon, and nitrogen), are usually not included in lists of major nutrient minerals (nitrogen is

considered a "mineral" for plants, as it often is included in fertilizers).

The significance of the mineral elements in humans, animals and plants nutrition cannot be
overemphasized. The presence of mineral elements in animal feed is vital for the animal’s
metabolic processes. Grazing livestock from tropical countries often do not receive mineral
supplementation except for common salt and must depend almost exclusively upon forage for
their mineral requirements (McDowell et al., 1984). Mineral deficiencies or imbalances in soils
and forages account partly for low animal production and reproductive problems. Soil acidity
and season are factors affecting mineral uptake by plants. Plants use these minerals as structural
components in carbohydrates and proteins; organic molecules in metabolism, such as magnesium
in chlorophyll and phosphorus in ATP; enzyme activators like potassium, and for maintaining
osmotic balance. Calcium is highly implicated in the maintenance of firmness of fruits (Olaiya,
2006) and its requirements in fruits are related to cell wall stability and membrane integrity
(Belakbir et al., 1998).
2.1 AGRICULTURAL LAND

Agricultural land is typically land devoted toagriculture, the systematic and controlled use of

other forms of lifeparticularly the rearing of livestock and production of cropsto produce food for

humans. It is thus generally synonymous with both farmland or cropland, as well as pasture or

rangeland.

The United NationsFood and Agriculture Organization and others following its definitions,

however, also use agricultural land or agricultural area as a term of art, where it means the

collection of:

 "arable land" (a.k.a. cropland): here redefined to refer to land producing crops requiring

annual replanting or fallowland or pasture used for such crops within any five-year period

 "permanent cropland": land producing crops which do not require annual replanting

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  permanent pastures: natural or artificial grasslands and shrublands able to be used for

grazing livestock

This sense of "agricultural land" thus includes a great deal of land not devoted to agricultural use.

The land actually under annually-replanted crops in any given year is instead said to constitute

"sown land" or "cropped land". "Permanent cropland" includes forested plantations used to

harvest coffee, rubber, or fruit but not tree farms or proper forests used for wood or timber. Land

able to be used for farming is called "cultivable land"(Speira, 2008). Farmland, meanwhile, is

used variously in reference to all agricultural land, to all cultivable land, or just to the newly

restricted sense of "arable land". Depending upon its use of artificial irrigation, the FAO's

"agricultural land" may be divided into irrigated and non-irrigated land.

2.1.1 DESCRIPTION

Under the FAO's definitions above, agricultural land covers 38.4% of the world's land area as of

2011. Permanent pastures are 68.4% of all agricultural land (26.3% of global land area), arable

land (row crops) is 28.4% of all agricultural land (10.9% of global land area), and permanent

crops (e.g. vineyards and orchards) are 3.1% (1.2% of global land area). Society of China.

(Speira, 2008)

 Total of land used to produce food: 49,116,227 square kilometers or 18,963,881 square

miles

 Arable land: 13,963,743 square kilometers or 5,391,431 square miles

 Permanent pastures: 33,585,676 square kilometers or 12,967,502 square miles

 Permanent crops: 1,537,338 square kilometers or 593,570 square miles

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Globally, the total amount of permanent pasture according to the FAO has been in decline since

1998, in part due to a decrease of wool production in favor of synthetic fibers (such as polyester)

and cotton(Parshotam, 2008).

The decrease of permanent pasture, however, does not account for gross conversion (e.g. land

extensively cleared for agriculture in some areas, while converted from agriculture to other uses

elsewhere) and more detailed analyses have demonstrated this. For example, Lark et al. 2015

found that in the United States cropland increased by 2.98 million acres from 2008-2012

(comprising 7.34 million acres (29,700 km2) converted to agriculture, and 4.36 million acres

(17,600 km2) converted from agriculture)(Parshotam, 2008).

2.1.2 TYPES OF FARMLAND

 Arable Farming

Arable farming involves growing of crops only in warm climate. It is practiced on gently sloping

or flat land with deep, fertile soil. It is important that the land is neither too wet nor dry. Land

ideal for growing crops should be fairly sheltered and suitable for use of machinery. In the UK,

this type of farming is mainly adopted in the east and south (Rowling, 2009).

 Pastoral Farming

Pastoral farming is the practice of rearing animals only in cold and wet climates not ideal for

growing crops. Land with steep slopes and poor soils cannot support the use of machinery nor

provide the nutrients crops need to grow. Only heather and grasses can grow on that kind of land.

Stronger winds on the steep slopes can also easily damage crops. Therefore, they are ideal for

rearing animals such as sheep. In the UK, highland areas in the west and north allow for pastoral

farming. Sheep can easily graze on hilly areas and feed on the kind of grass growing in such

areas (Rowling, 2009).

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However, dairy animals need flat land with enough pasture to feed on. Dairy farming is also

practiced near markets because dairy products are highly perishable.

 Mixed Farming

Mixed farming involves growing of crops and rearing of animals on the same piece of land. The

two types of farming, pastoral and arable, support each other and increase farm yield. This type

of farming reduces the risk of making losses due to poor weather conditions. For instance, if the

crops are not doing well, animals on the farm are still a good source of food and money (James,

2006).

Furthermore, animals provide the manure farmers need to improve soil fertility for crops to grow

and increase yield.

 Subsistence Farming

Subsistence farming is the practice of growing crops and rearing animals for personal use. It is

done on a small-scale with the focus of feeding the farmer’s family. It can be labor-intensive in

terms of manpower in use, but little to no machinery or technology is used. Subsistence farmers

are determined to be self-sufficient (James, 2006).

 Commercial Farming

Commercial farming is practiced for the purpose of making a profit. It involves the rearing of

animals and or growing of crops on a large scale to increase production and profits. Technology

and machinery are used with a few workers to operate them. This type of farming often involves

monoculture, the growing of a single type of cash crop such as flowers or coffee (James, 2006).

 Extensive and Intensive Farming

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Extensive farming or cultivation involves land tillage with an aim of increasing output. Farmers

increase the size of land for cultivation to improve yield without changing other factors. On the

other hand, intensive farming involves increasing capital and labor on the same piece of land

being cultivated to increase yield (James, 2006).

 Nomadic Farming

Nomadic farming involves farmers moving with their animals from one place to another in

search of pasture and water. It is similar to pastoral farming and often practiced in arid and semi-

arid areas (Rowling, 2009).

Different regions across the world rear different animals under this type of farming. They include

camels, sheep, cattle, donkeys, goats and horses. As a type of subsistence farming, it provides

families with food.

 Sedentary Farming

Sedentary farming involves tilling the same piece of land for many years. Unlike nomadic

farming, land is used permanently for growing crops or rearing animals. With its origins in the

Americas and Eurasia, the practice is believed to have started in 10,000 B.C.E.

Hunters and foragers first settled in America in 20,000 B.C.E. and by 7,000 B.C.E, agriculture

had spread to South America. This type of farming fostered the development of early

civilizations (Rowling, 2009).

 Poultry Farming

Poultry farming involves the rearing of turkeys and chickens for meat and eggs. According to the

United States Department of Agriculture (USDA), the U.S exports about 18% of all its poultry

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meat. It can be practiced in large or small scale farms. However, there is increasing demand for

local poultry fed on natural pasture (Parshotam, 2008).

 Fish Farming

Fish farming is also known as aquaculture. It is the practice of raising fish in large numbers in

large tanks or fish ponds. Although farmed fish, according to Grist, have a bad reputation,

properly managed fish farms are clean, sustainable and yield protein of high quality (Parshotam,

2008).

2.1.3 VARIETIES OF AGRICULTURAL FARMLANDS AND FARMING METHODS

Agriculture is one of the most widespread activities in the world, but it is not uniform

throughout. There are a number of ways to classify agriculture, and some of the major criteria

which can be adopted include:

 Scale

 Type of crop

 Livestock combinations

 Intensity

 Means of distribution of farm produce

 Level of mechanization

The following are the major types/ varieties of agriculture around the world.

 Nomadic Herding

Nomadic herding is based upon the rearing of animals on natural pastures. This practice is

performed by the people of semi-arid and arid regions. These people stay on the move with their

animals in search of natural pastures for their livestock to graze. The type of animals reared

differs from one region to the other. Northern Africa, parts of Arabia and parts of northern

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Eurasia are the typical regions of this type of farming. This is a subsistence type of activity

(Percivalc, 2008).

 Livestock Ranching

Under this system of farming, the major emphasis is laid on rearing animals. Unlike nomadic

herding, the farmers live a settled life. This type of farming has developed on a commercial basis

in areas of the world where large plots of land are available for animal grazing, such as the low

rainfall areas of North America, South America and Australia. Animals are reared mainly for

meat and wool, and they are kept on large-scale farms called ranches (Percivalc, 2008).

 Shifting Cultivation

This type of farming is most often adopted in the tropics. Under this system, the land is obtained

by clearing forest areas using a slash and burn technique. The land is then cultivated for a few

years, or until the fertility declines or the land is overtaken by the weeds and other native flora.

At this point, farmers move on to clear another area of the forest. (Percivalc, 2008).

 Rudimentary Sedentary Tillage

This is a subsistence type of agriculture and it differs from the aforementioned types because the

same plot of land is cultivated continuously year after year (Kettlesb, 2008).

 Intensive Subsistence Farming With Rice Dominant

Intensive subsistence farming is practiced in tropical regions that have high populations and

receive a large amount of precipitation. Rice is the dominant crop when it comes to this type of

farming, as it can employ and feed a large number of people per unit of area. (Kettlesb, 2008).

 Intensive Subsistence Farming Without Rice Dominant

This is a variant of the aforementioned type of farming designed for areas where the amount of

rainfall is not very high. (Thomas, 2005).

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  Commercial Plantations

Although practiced over a rather small area, this type of farming is quite important in terms of its

commercial value. The major products of this type of farming are tropical crops such as tea,

coffee, rubber and palm oil (Thomas, 2005).

 Mediterranean Agriculture

The typically rugged terrain of the Mediterranean region has resulted in typical livestock and

crop combinations. Wheat, vineyards and citrus fruits are the major crops, and small animals are

the major livestock reared in the region (Thomas, 2005).

 Commercial Grain Farming

This type of farming is a response to farm mechanization and is the major type of farming in the

areas with low rainfall and population (Thomas, 2005).

 Livestock and Grain Farming

This type of agriculture is commonly known as mixed farming, and originated in the humid areas

of the middle latitudes, except Asia (John, 2007).

 Subsistence Crop and Stock Farming

In this type of agriculture practically nothing is sold off the farm. This type of farming has been

common in areas of middle latitudes with lower fertility of soils, or in areas with rough terrain

(John, 2007).

 Specialized Horticulture

This type of farming has developed to take advantage of a large demand for horticulture

products, especially in areas of large-scale urbanisation and high-density population (John,

2007).

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  Different agricultural farming methods

Several farming methods are practiced worldwide. Some of these include:

a. Subsistence Farming

Characterized by farmers having small and scattered land areas, most farmers practicing this

method are poor who never use:

 Fertilizer

 High-yield seed varieties

They produce for local consumption. In this method, work is done manually following traditional

processes.(Zorpas, 2002).

b. Plantation Agriculture

Introduced by the British in the 19th century, this method:

 Involves planting a single crop variety over huge tracts of land.

 Requires lots of capital to run.

Also, it’s dependent on:

 Agricultural experts

 Sophisticated farm machinery

 Irrigation

 Fertilizers

 Good transport facilities(Zorpas, 2002).

c. Crop Rotation

Here, crops are grown one variety at a time on a land area, usually done to maintain land fertility.

Switching crop types on a piece of land takes time and may vary depending on:

 Crop type;

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  Duration it takes for a crop to exhaust the land’s fertility.

Cereals are often rotated with legumes which help in nitrogen fixation.

d. Bio-dynamic Agriculture

Developed in 1924 by Rudolf Steiner, this method considers farms as organisms. In this method,

fertility is maintained through planting cover crops or farm animal manure. For a farm to be

certified bio-dynamic, it must first be organically certified.

In this agricultural system, farmers follow these measures and rhythms, among other farm

customs:

 Homeopathic measures for treating compost plants and soil.

 Natural rhythms to determine planting seasons.

e. Integrated Pest Management

Also known as IPM, this farming method is based on strategies for pest management and relies

on:

 Pest observation

 Pest prevention

IPM makes use of biological controls to get rid of pests. For example, ladybugs are used to

devour aphids in farms. Also, this method helps farmers keep track of their land, making it easier

to notice arising problems. 

f. No-Till Agriculture

As the name suggests, farmers never have to break the soil and seeds are simply planted on soils.

Also, weeds are controlled by spraying herbicides. Another method to control weeds was

developed at the Rodale Institute in Pennsylvania, USA where a roller crimper does these:

 Rolls over weeds;

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  Leaving the land ready for planting.

These are just some farming methods you should know. Other farming methods include: Organic

farming, Vertical farming, multi-crop farming, Green house farming and Playhouse farming. All

farming methods are dependent on land size, soil type and other factors (Radcliff et al., 2010)

 2.1.4 SIGNIFICANCE OF AGRICULTURAL FARMING

For decades, agriculture has been associated with the production of essential food crops. At

present, agriculture above and beyond farming includes forestry, dairy, fruit cultivation, poultry,

beekeeping, mushroom, arbitrary, etc. In today’s agricultural practice: processing, marketing,

and distribution of crops and livestock products, etc. are all acknowledged as part of current

agriculture. Thus, agriculture could be referred to as the production, processing, promotion, and

distribution of agricultural products (John, 2007). Agriculture plays a critical role in the entire

life of a given economy. Agriculture is the backbone of the economic system of a given country.

In addition to providing food and raw material, agriculture also provides employment

opportunities to a very large percentage of the population.

 Source of Livelihood

 Contribution to National revenue

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  Significance to the International Trade

 Marketable Surplus

 Source of Raw Material

 Significance in Transport

 Foreign Exchange Resources

 Great Employment Opportunities

 Economic Development

 Source of Saving

 Food Security

2.3 MINERALS

In the context of nutrition, a mineral is a chemical element required as an essential nutrient by

organisms to perform functions necessary for life. However, the four major structural elements in

the human body by weight (oxygen, hydrogen, carbon, and nitrogen), are usually not included in

lists of major nutrient minerals (nitrogen is considered a "mineral" for plants, as it often is

included in fertilizers). These four elements compose about 96% of the weight of the human

body, and major minerals (macro minerals) and minor minerals (also called trace elements)

compose the remainder.

Nutrient minerals, being elements, cannot be synthesized biochemically by living organisms.

Plants get minerals from soil. Most of the minerals in a human diet come from eating plants and

animals or from drinking water (Huang, 2007). As a group, minerals are one of the four groups

of essential nutrients, the others of which are vitamins, essential fatty acids, and essential amino

acids. The five major minerals in the human body are calcium, phosphorus, potassium, sodium,

and magnesium. All of the remaining elements in a human body are called "trace elements". The

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trace elements that have a specific biochemical function in the human body are sulfur, iron,

chlorine, cobalt, copper, zinc, manganese, molybdenum, iodine, and selenium.

Most chemical elements that are ingested by organisms are in the form of simple compounds.

Plants absorb dissolved elements in soils, which are subsequently ingested by the herbivores and

omnivores that eat them, and the elements move up the food chain. Larger organisms may also

consume soil (geophagia) or use mineral resources, such as salt licks, to obtain limited minerals

unavailable through other dietary sources (Zhu, 2007)

Bacteria and fungi play an essential role in the weathering of primary elements that results in the

release of nutrients for their own nutrition and for the nutrition of other species in the ecological

food chain. One element, cobalt, is available for use by animals only after having been processed

into complex molecules (e.g., vitamin B12) by bacteria. Minerals are used by animals and

microorganisms for the process of mineralizing structures, called "biomineralization", used to

construct bones, seashells, eggshells, exoskeletons and mollusc shells (Huang, 2007)

2.3.1 EXAMPLES OF MINERALS

MACRO MINERALS

Mineral Function Sources

Sodium Needed for proper fluid balance, nerve Table salt, soy sauce; large amounts
transmission, and muscle contraction in processed foods; small amounts in
milk, breads, vegetables, and
unprocessed meats
Chloride Needed for proper fluid balance, stomach Table salt, soy sauce; large amounts
acid in processed foods; small amounts in
milk, meats, breads, and vegetables
Potassium Needed for proper fluid balance, nerve Meats, milk, fresh fruits and
transmission, and muscle contraction vegetables, whole grains, legumes
Calcium Important for healthy bones and teeth; Milk and milk products; canned fish
helps muscles relax and contract; with bones (salmon, sardines);

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 important in nerve functioning, blood fortified tofu and fortified soy milk;
clotting, blood pressure regulation, greens (broccoli, mustard greens);
immune system health legumes
Phosphorus Important for healthy bones and teeth; Meat, fish, poultry, eggs, milk,
found in every cell; part of the system that processed foods (including soda pop)
maintains acid-base balance
Magnesium Found in bones; needed for making Nuts and seeds; legumes; leafy, green
protein, muscle contraction, nerve vegetables; seafood; chocolate;
transmission, immune system health artichokes; "hard" drinking water
Sulfur Found in protein molecules Occurs in foods as part of protein:
meats, poultry, fish, eggs, milk,
legumes, nuts

TRACE MINERALS (MICRO MINERALS)

The body needs trace minerals in very small amounts. Note that iron is considered to be a trace

mineral, although the amount needed is somewhat more than for other microminerals.

Mineral Function Sources

Iron Part of a molecule (hemoglobin) found in Organ meats; red meats; fish;
red blood cells that carries oxygen in the poultry; shellfish (especially
body; needed for energy metabolism clams); egg yolks; legumes; dried
fruits; dark, leafy greens; iron-
enriched breads and cereals; and
fortified cereals
Zinc Part of many enzymes; needed for making Meats, fish, poultry, leavened
protein and genetic material; has a function whole grains, vegetables
in taste perception, wound healing, normal
fetal development, production of sperm,
normal growth and sexual maturation,
immune system health
Iodine Found in thyroid hormone, which helps Seafood, foods grown in iodine-
regulate growth, development, and rich soil, iodized salt, bread, dairy
metabolism products
Selenium Antioxidant Meats, seafood, grains
Copper Part of many enzymes; needed for iron Legumes, nuts and seeds, whole

20
 metabolism grains, organ meats, drinking
water
Manganese Part of many enzymes Widespread in foods, especially
plant foods
Fluoride Involved in formation of bones and teeth; Drinking water (either fluoridated
helps prevent tooth decay or naturally containing fluoride),
fish, and most teas
Chromium Works closely with insulin to regulate blood Unrefined foods, especially liver,
sugar (glucose) levels brewer's yeast, whole grains, nuts,
cheeses
Molybdenu Part of some enzymes Legumes; breads and grains; leafy
m greens; leafy, green vegetables;
milk; liver

2.3.2 IMPORTANCE OF MINERALS TO PLANTS AND OTHER ORGANISMS

FEEDING ON PLANT

The importance of mineral elements in human, animal and plant nutrition has been well
recognized (Underwood, 1971; Darby, 1976). Deficiencies or disturbances in the nutrition of an
animal cause a variety of diseases and can arise in several ways (Gordon, 1977). When a trace
element is deficient, a characteristic syndrome is pro-duced which reflects the specific functions
of the nutrient in the metabolism of the animal. The trace elements are essential components of
enzyme systems. Simple or conditioned deficiencies of mineral elements therefore have
profound effects on metabolism and tissue structure. To assess the dietary intake and adequacy
of minerals, information needs to be collected on mineral element content of foods, diets and
water (Rao and Rao, 1981; Simsek and Aykut, 2007). There is limited information on the trace
element content of water and numerous plant foods consumed in some less developed countries.
Mineral elements play important roles in health and disease states of humans and domestic
animals. For example, iron deficiency anaemia and goitre due to iodine deficiency are reported to
be problems of public health importance in some communities (Partwardhan, 1961; Deosthale
and Belavady, 1978). Trace elements of significance to people with HIV are zinc and selenium.
Selenium is an antioxidant that increases immune function. Zinc, usually taken to stimulate the

21
immune system, has been reported to weaken immune system function and lower calcium levels
in HIV – positive men (O’ Connor, 1995; Wood, 2000).

2.3.4 MINERAL TOXICITY AND DEFICIENCY IN AGRICULTURAL PLANTS

 Mineral toxicity

Plants work quite the same way. In fact, the whole world works on a careful balance, and every
living being in this same world must obey the law of balance. The seven essential micronutrients
have to be maintained in an exact proportion. From this, a careful conclusion can be drawn that
too much leads to toxicity while too little gives rise to deficiency, which has been discussed
earlier.

Mineral elements hold diverse functions in all plants, including electron carriers, enzyme
activation, providing osmoticum for turgor and growth, maintaining charge balance, structural
components and more.

 Effects of Mineral Toxicity

The effects of mineral nutrient deficiencies in plants result in roots and leaf cessation, reduced
growth, massive disruption in cell and cell walls, reduced branching, small changes in the pH of
the cytosol, an inability of an enzyme to align correctly with a reactant, stunting,
abnormal thickening, and darkening of roots, iron chlorosis, oxidative stress, chlorosis,
destruction of chloroplasts, and death of cells and tissue.

This raises the question, how is this delicate balance or exact proportion determined? There lies a
straightforward answer for this; the concentration of the mineral ion in tissue, decrease the dry
weight of tissues by 10 per cent and is said to be toxic. These concentrations do vary among
different plants since every plant has different nutritional needs, varying weights, energy
requirements, and more.

Also, another issue to be considered is that an excess intake of one element inhibits the uptake of
another element. For instance, the presence of manganese toxicity is observed by the appearance
of brown spots encompassed by chlorotic veins. Here the manganese competes with magnesium

22
and iron for absorption and also hinders calcium translocation in the shoot apex of the plant.
Consequently, the abundance of manganese in plants induces a deficiency of iron, copper, and
calcium. So it is apparent that toxicity and deficiency are closely interlinked.

 Deficiency in agricultural plants

A first step in diagnosing nutrient deficiencies is to describe the symptoms. Each deficiency
symptom is related to some function of the nutrient in the plant (Havlin et al., 1999).. Symptoms
caused by nutrient deficiencies are generally grouped into five categories: 1) stunted growth, 2)
chlorosis, 3) interveinal chlorosis, 4) purplish-red coloring and 5) necrosis. Stunting is a common
symptom for many deficient nutrients due to their varied roles in the plant.
 Nitrogen (N)
Nitrogen is needed by plants for the production of proteins, nucleic acids (DNA and RNA) and
chlorophyll. Symptoms of N deficiency are general chlorosis of lower leaves, stunted and slow
growth and necrosis of older leaves in severe cases (Jacobsen and Jasper, 1991).
 Phosphorus (P)
Plants require P for the development of ATP (energy), sugars and nucleic acids. Cool soils
during the early growing season may be a factor causing P deficiency. P deficiency symptoms
are usually more noticeable in young plants, which have a greater relative demand for P than
more mature plants (Grundon, 1987). P deficient plants generally turn dark green (both leaves
and stems) and appear stunted.
 Potassium (K)
Potassium is utilized by plants in the activation of enzymes, photosynthesis, protein formation
and sugar transport. K deficiency does not immediately result in visible symptoms (hidden
hunger). Initially, there is only a reduction in growth rate, with chlorosis and necrosis occurring
in later stages (Mengel and Kirkby, 2001).

 Chloride (Cl)
Chloride is required by the plant for leaf turgor and photosynthesis. Until recently, little
information was documented on Cl deficiencies, as symptoms were often misdiagnosed as
physiological leaf spot. However, more recent studies have shown Cl deficiencies to exist in

23
Montana, with visual symptoms observed in winter wheat and durum wheat cultivars (Engel et
al., 1998; Engel et al., 2001).
2.3.5 SOURCES OF MINERALS TO PLANT
Sedimentary rock covers 75-80% of the Earth's crust, and it forms parent materials for a large
majority of soils. Soil parent material has a significant direct influence on the nutrient element
contents of the soil; this influence is more pronounced in young soils and diminishes somewhat
with increasing soil age and soil weathering. In order to better understand the effect of soil parent
materials on the soil elemental composition, it is useful to review the mineralogical composition
of common rocks that make up the soil parent material. Primary minerals form at elevated
temperatures from cooling magma during the original solidification of rock or during
metamorphism, and they are usually derived from igneous and metamorphic rocks in soil
(Lapidus 1987). In most soils, feldspars, micas, and quartz are the main primary mineral
constituents, and pyroxenes and hornblendes are present in smaller amounts.
Mineral constituent Igneous Shal Sandstone Nutrient element constitutents
rock e
  % Major Minor
Feldspars 59.5 30.0 11.5 K, Ca, Na Cu, Mn
Amphiboles & 16.8 – sm Mg, Fe, Ca Ni, Co, Cu, Mn,
pyroxenes Zn, Mo
Micas 3.8 – sm K, Ca, Na, Ni, Mn, Co, Zn,
Mg, Fe Cu
Titanium minerals 1.5 – sm Ti, Fe, Ca Co, Ni
Apatite 0.6 – sm Ca, P  
Clay – 25.0 6.6 K, Mg, Fe, Ca,  
Na
Iron oxides – 5.6 1.8 Fe Mn, Zn, Ni, Co
Carbonates – 5.7 11.1 Ca, Mg, Fe  
Other minerals – 11.4 2.2 – –
Table 1: Average mineralogical and nutrient element composition of common rocks on the
Earth's land surface (Klein & Hurlbut 1999, based on data of F. W. Clarke).

2.4 METALS

A metal (from Greek μέταλλον métallon,"mine, quarry, metal") is a material that,when freshly

prepared, polished, orfractured, shows a lustrous appearance,and conducts electricity and heat

24
relativelywell. Metals are typically malleable (theycan be hammered into thin sheets) orductile

(can be drawn into wires). A metalmay be a chemical element such as iron;an alloy such as

stainless steel; or a molecular compound such as polymeric sulfur nitride (Zheng, 2007).

In physics, a metal is generally regarded asany substance capable of conductingelectricity at a

temperature of absolutezero. Many elements and compoundsthat are not normally classified as

metalsbecome metallic under high pressures. Forexample, the nonmetal iodine graduallybecomes

a metal at a pressure of between40 and 170 thousand times atmosphericpressure. Equally, some

materialsregarded as metals can becomenonmetals. Sodium, for example, becomesa nonmetal at

pressure of just under twomillion times atmospheric pressure(Facchinelli et al. 2001; Wei and

Yang 2010).

In chemistry, two elements that would otherwise qualify (in physics) as brittle metals arsenic and

antimony are commonly recognized as metalloids due to their chemistry (predominately non-

metallic for arsenic, and balanced between metallicity and non-metallicity for antimony). Around

95 of the 118 elements in the periodic table are metals (or are likely to be such). The number is

inexact as the boundaries between metals, nonmetals, and metalloids fluctuate slightly due to a

lack of universally accepted definitions of the categories involved.

In astrophysics the term "metal" is cast more widely to refer to all chemical elements in a star

that are heavier than the lightest two, hydrogen and helium, and not just traditional metals. A star

fuses lighter atoms, mostly hydrogen and helium, into heavier atoms over its lifetime. Used in

that sense, the metallicity of an astronomical object is the proportion of its matter made up of the

heavier chemical elements.

Metals, as chemical elements, comprise25% of the Earth's crust and are present in many aspects

of modern life. The strength hand resilience of some metals has led to their frequent use in, for

25
example, high-rise building and bridge construction, as well as most vehicles, many home

appliances, tools, pipes, and railroad tracks. Precious metals were historically used as coinage,

but in the modern era, coinage metals have extended to at least 23 of the chemical elements.

The history of refined metals is thought tobegin with the use of copper about 11,000years ago.

Gold, silver, iron (as meteoriciron), lead, and brass were likewise in use before the first known

appearance of bronze in the 5th millennium BCE. Subsequent developments include the

production of early forms of steel; the discovery of sodium the first light metal in 1809; the rise

of modern alloy steels; and, since the end of World War II, the development of more

sophisticated alloys (Facchinelli et al. 2001).

 Properties

Metals are shiny and lustrous, at least when freshly prepared, polished, or fractured. Sheets of

metal thicker than a few micrometres appear opaque, but gold leaf transmits green light.

The solid or liquid state of metals largely originates in the capacity of the metal atoms involved

to readily lose their outer shell electrons. Broadly, the forces holding an individual atom's outer

shell electronsin place are weaker than the attractiveforces on the same electrons arising

frominteractions between the atoms in thesolid or liquid metal. The electronsinvolved become

delocalised and the atomic structure of a metal can effectively be visualised as a collection of

atoms embedded in a cloud of relatively mobile electrons. This type of interaction is called a

metallic bond. The strength of metallic bonds for different elemental metals reaches a maximum

around the center of the transition metal series, as these elements have large numbers of

delocalized electrons (Duruibe et al., 2007).

Although most elemental metals have higher densities than most nonmetals, there is a wide

variation in their densities, lithium being the least dense (0.534 g/cm3) and osmium (22.59

26
g/cm3) the most dense. Magnesium, aluminum and titanium are light metals of significant

commercial importance. Their respective densities of 1.7, 2.7 and 4.5 g/cm3 can be compared to

those of the older structural metals, like iron at 7.9 and copper at 8.9 g/cm3. An iron ball would

thus weigh about as much as three aluminum balls.

2.4.1 CLASSIFICATION OF METALS

Metals can be categorised according to their physical or chemical properties. Categories

described in the subsections below include ferrous and non-ferrous metals; brittle metals and

refractory metals; white metals; heavy and light metals; and base, noble, and precious metals

(Huang, 2007). The Metallic element stable in this section categories the elemental metals on the

basis of their chemical properties into alkali and alkaline earth metals; transition and post-

transition metals; and lanthanides and actinides. Other categories are possible, depending on the

criteria for inclusion. For example, the ferromagnetic metals those metals that are magnetic at

room temperature are iron, cobalt, and nickel (Huang, 2007).

 Ferrous and non-ferrous metals

The term "ferrous" is derived from the Latin word meaning "containing iron". This can include

pure iron, such as wrought iron, or an alloy such as steel. Ferrous metals are often magnetic, but

notexclusively. Non-ferrous metalsalloyslack appreciable amounts of iron (Huang, 2007).

 Brittle metal

While nearly all metals are malleable orductile, a fewberyllium, chromium,manganese, gallium,

and bismuthare brittle. (Thomas et al., 2015).Arsenic, and antimony, if admittedas metals, are

brittle. Low values of theratio of bulk elastic modulus to shearmodulus (Pugh's criterion) are

indicative ofintrinsic brittleness.

 Refractory metal

27
In materials science, metallurgy, andengineering, a refractory metal is a metalthat is

extraordinarily resistant to heat and wear. Which metals belong to this category varies; the most

common definition includes niobium, molybdenum, tantalum, tungsten, and rhenium. They all

have melting points above 2000 °C, and a high hardness at room temperature.

 White metal

A white metal is any of range of white coloured metals (or their alloys) with relatively low

melting points. Such metals include zinc, cadmium, tin, antimony (he recounted as a metal), lead,

and bismuth, some of which are quite toxic. In Britain, the fine art trade uses the term "white

metal" in auction catalogues to describe foreign silver items which do not carry British Assay

Office marks, but which are none the less understood to be silver and are priced accordingly

(Zheng, 2007).

 Heavy and light metals

A heavy metal is any relatively dense metalor metalloid(Xilonget al., 2005).More specific

definitionshave been proposed, but none haveobtained widespread acceptance. Someheavy

metals have niche uses, or arenotably toxic; some are essential in traceamounts. All other metals

are light metals.

 Base, noble and precious metals

In chemistry, the term base metal is used informally to refer to a metal that is easily oxidized or

corroded, such as reacting easily with dilute hydrochloric acid (HCl) to form a metal chloride

28
and hydrogen. Examples include iron, nickel, lead and zinc. Copper is considered a base metal

asit is oxidized relatively easily, although itdoes not react with HCl.

The term noble metal is commonly used in opposition to base metal. Noble metals areresistant to

corrosion or oxidation, (Thomas et al., 2015).unlikemost base metals. They tend to be precious

metals, often due to perceivedrarity. Examples include gold, platinum, silver, rhodium, iridium

and palladium.

In alchemy and numismatics, the term base metal is contrasted with precious metal, that is, those

of high economic value. A longtime goal of thealchemists was the transmutation of base metals

into precious metals including such coinage metals as silver and gold. Most coins today are made

of base metals with no intrinsic value, in the past, coins frequently derived their value

primarilyfrom their precious metal content.Chemically, the precious metals (like thenoble

metals) are less reactive than mostelements, have high luster and highelectrical conductivity.

Historically,precious metals were important ascurrency, but are now regarded mainly

asinvestment and industrial commodities.Gold, silver, platinum and palladium eachhave an ISO

4217 currency code. The bestknownprecious metals are gold and silver.While both have

industrial uses, they arebetter known for their uses in art, jewelry,and coinage. Other precious

metalsinclude the platinum group metals:ruthenium, rhodium, palladium, osmium,iridium, and

platinum, of which platinum is the most widely traded (Zheng, 2007).

The demand for precious metals is drivennot only by their practical use, but also bytheir role as

investments and a store of value. Palladium and platinum, as of fall2018, were valued at about

three quartersthe price of gold. Silver is substantiallyless expensive than these metals, but is

often traditionally considered a precious metal in light of its role in coinage and jewelry.

2.5 COMMON HEAVY METALS FOUND IN NIGERIAN AGRICULTURAL SOILS

29
Lead: 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 (NSC, 2009). 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 (Raymond and

Felix, 2011).

Heavy Metals Ground Water Effect on lifting

maximum minimum
Lead 0.05 - Toxic plumb solvency

diseases, burning in

mouth, several

inflammations in

gastro

intestinal track, causes

paralysis mental

confusion, visual

disturbance anemia

etc.
Chromium 0.05 - Carcinogenic acuity

(cancer), can produce

coetaneous and nasal

mucous membrane

ulcer and Dermatitis,

Hexavalent Cr causes

30
 lung tumors.
Copper 1.5 0.05 Astringent taste but

essential elements for

metabolism,

deficiency results is

anemia in infants,

excess may results in

liver damage.
Mercury 0.01 - Causes minimata

disease also causes

blue baby disease in

Infants the color of

skin in baby is turn

into blue. Paralysis.

Nickel 0.02 - May be carcinogenic,

can react with DNA.

Resulting in DNA

damage.
1 PPM = 1000 PPB, Source; (Akhileshet al., 2009)

Lead is particularly a 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 (Akhileshet al., 2009). In general, plants do not absorb or

accumulate lead. However, in soils containing high concentration of 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).

31
Higher concentrations of Pb 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) (Raymond and Felix, 2011). Generally, it has been considered

safe to use garden produce grown in soils with total Lead levels less than 300 ppm (Taylor et al.

2010; Dasguptaet al. 2006). The risk of Lead poisoning through the food chain increases as the

soil Lead level rises above this concentration. Raymond and Felix (2011) stated further that 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. The Joint FAO/ World Health

Organization Expert Committee on Food Additives (JECFA) established a Provisional Tolerable

Weekly Intake (PTWI) for Lead as 0.025 mg/kg/bodyweight (bw) (JECFA, 2004). The WHO

provisional guideline of 0.01 mg/L has been adopted as the standard for drinking water (WHO,

2004).

Chromium: Chromium 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 (Shankeret al., 2005).

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 (Raymond and Felix, 2011). Major Cr (VI) species include

chromate (CrO42−) and dichromate (Cr2O72−) which precipitate readily in the presence of

32
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). 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 chromium hydroxides (Cr(OH)3) (Sutle,

2010). 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 (Raymond and Felix, 2011).

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 (Shankeret al., 2005).

Chromium is associated with allergic dermatitis in humans (Requejo and Tena, 2005).

Copper (Cu): Copper is the third most used metal in the world (VCI 2011).Copper is an

essential micronutrient required in the growth of both plants and animals while in humans, it

helps in the production of blood hemoglobin (Raymond and Felix, 2011). In plants, Cu is

especially important in seed production, disease resistance, and regulation of water. Copper in

high doses can cause anemia, liver and kidney damage, and stomach and intestinal irritation in

human (Yrule, 2005). Copper normally occurs in drinking water from Cu pipes, as well as from

additives designed to control algae 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 (Raymond and Felix,

2011). He also added that the solubility of Cu is drastically increased at pH 5.5, which is rather

close to the ideal farmland pH of 6.0–6.5. Copper and Zn are two important essential elements

33
for plants, microorganisms, animals, and humans (Cambell, 2006). 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 (Raymond and Felix, 2011). Most countries that imports

agricultural products now specifies acceptable maximum contents of metals in food, which might

limit the possibility for the farmers to export their contaminated crops (Bjuhr., 2007).

Mercury: The primary source of mercury is the Sulphide ore cinnabar, mercury(II)forms strong

complexes with a variety of both inorganic and organic ligands, making it very soluble in

oxidized aquatic systems (Alysson and Fabio, 2014). He also stated that mercury may also be

removed from solution by co-precipitation with sulphides. Under anaerobic conditions, both

organic and inorganic forms of Hg may be converted to alkylated forms by microbial activity,

such as by sulfur reducing bacteria. Elemental mercury may also be formed under anaerobic

conditions by demethylation of methylmercury, or by reduction of Hg (II). Acidic conditions

(pH<4) also favor the formation of methyl mercury, whereas higher pH values favor

precipitation of HgS (s) (Sharma and Dubey 2005). It has been established medically that

mercury is associated with kidney damage (Scragg, 2006). In the year 2003, JECFA revised its

risk assessment on methylmercury in fish and adopted a lower PTWI of 1.6 μg/kg body

weight/week to replace the previous PTWI of 3.3μg/kg body weight/week of total mercury for

the general population (JECFA, 2004).

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). It is neutral to slightly

34
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 its alkaline conditions;

it forms nickelite ion (HNiO2) which is soluble in water. In oxidizing and alkaline conditions,

nickel exists in the form of stable nickelo-nickelic oxide (Ni3O4) which 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+ (Alysson and Fabio, 2014). 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 (Sreekanthet al., 2013). This can cause

various kinds of cancer on different areas within the bodies of animals and humans, especially

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 (Khodadoustet al.,

2004). 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 longtime for nickel to be removed

from air. Nickel can also end up in surface water when it is a part of wastewater streams

(Alysson and Fabio, 2014). 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 (shankeret al., 2005). Alysson and Fabio, (2014) also

stated that nickel is not known to accumulate in plants or animals and as a result Ni has not been

35
found to biomagnify up the food chain, but for animals, Ni is an essential foodstuff in small

amounts.

2.6 SOURCES OF HEAVYMETALS INCONTAMINATED SOILS

Heavy metals occur naturally in the soil environment fromthe pedogenetic processes of

weathering of parent materialsat levels that are regarded as trace (<1000mg kg−1) and rarely

toxic (Zheng, 2007). Due to the disturbance and accelerationof nature’s slowly occurring

geochemical cycle of metalsby man, most soils of rural and urban environments mayaccumulate

one or more of the heavy metals above definedbackground values high enough to cause risks to

humanhealth, plants, animals, ecosystems, or other media. Theheavy metals essentially become

contaminants in the soilenvironments because (i) their rates of generation via manmadecycles are

more rapid relative to natural ones, (ii) theybecome transferred from mines to random

environmentallocations where higher potentials of direct exposure occur,(iii) the concentrations

of the metals in discarded productsare relatively high compared to those in the

receivingenvironment, and (iv) the chemical form (species) in whicha metal is found in the

receiving environmental system may render it more bioavailable. A simple mass balance ofthe

heavy metals in the soil can be expressed as follows:

Mtotal =(Mp+Ma +Mf +Mag +Mow +Mip )− (Mcr +Ml),where “M” is the heavy metal, “p” is

the parentmaterial, “a”is the atmospheric deposition, “ f ” is the fertilizer sources,“ag” are the

agrochemical sources, “ow” are the organic waste sources, “ip” are other inorganic pollutants,

“cr” is crop removal, and “l” is the losses by leaching, volatilization, and soforth. It is projected

that the anthropogenic emission into theatmosphere, for several heavy metals, is one-to-three

ordersof magnitude higher than natural fluxes. Heavy metalsin the soil from anthropogenic

sources tend to be moremobile, hence bio-available than pedogenic, or lithogenicones. Metal-

36
bearing solids at contaminated sites canoriginate froma wide variety of anthropogenic sources in

theform of metal mine tailings, disposal of high metal wastesin improperly protected landfills,

leaded gasoline and leadbasedpaints, land application of fertilizer, animal manures,biosolids

(sewage sludge), compost, pesticides, coal combustionresidues, petrochemicals, and atmospheric

deposition are discussed hereunder(shankeret al., 2005).

2.6.1. Fertilizers.

Historically, agriculture was the first major human influence on the soil. To grow and complete

thelifecycle, plants must acquire not only macronutrients (N, P,K, S, Ca, and Mg), but also

essential micronutrients. Somesoils are deficient in the heavy metals (such as Co, Cu, Fe, Mn,

Mo, Ni, and Zn) that are essential for healthy plant growth, and crops may be supplied with these

as an addition to the soil or as a foliar spray. Cereal crops grown on Cu deficient 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, applicationmay significantly increase their content in the

soil.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 (shanker et al., 2005).

2.6.2 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

37
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(Rajesh et

al., 2007). 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

formulationsof Cu, Cr, and As (CCA), and there are now manyderelict sites where soil

concentrations of these elements

greatly exceed background concentrations. Such contaminationhas the potential to cause

problems, particularly ifsites are redeveloped for other agricultural or nonagriculturalpurposes.

Compared with fertilizers, the use of such materialshas been more localized, being restricted to

particular sites or crops (shankeret al., 2005).

2.6.3. Biosolids and Manures.

The application of numerous biosolids (e.g., livestock manures, composts, and municipalsewage

sludge) to land inadvertently leads to the accumulationof heavy metals such as As, Cd, Cr, Cu,

Pb, Hg, Ni, Se, Mo, Zn, Tl, Sb, and so forth, in the soil. Certain animalwastes such as poultry,

cattle, and pig manures producedin agriculture are commonly applied to crops and pastureseither

as solids or slurries. Although most manures areseen as valuable fertilizers, in the pig and poultry

industry,the Cu and Zn added to diets as growth promoters andAs contained in poultry health

products may also have thepotential to cause metal contamination of the soil.

The manures produced from animals on such diets containhigh concentrations of As, Cu, and Zn

and, if repeatedlyapplied to restricted areas of land, can cause considerablebuildup of these

metals in the soil in the long run.Biosolids (sewage sludge) are primarily organic solidproducts,

produced by wastewater treatment processes thatcan be beneficially recycled. Land application

38
of biosolids materials is a common practice in many countries thatallow the reuse of biosolids

produced by urban populations. The term sewage sludge is used in many referencesbecause of its

wide recognition and its regulatory definition(Xilonget al., 2005).

However, the term biosolids is becoming more common asa replacement for sewage sludge

because it is thought toreflect more accurately the beneficial characteristics inherentto sewage

sludge. It is estimated that in theUnited 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, over30% of the

sewage sludge is used as fertilizer in agriculture. In Australia over 175 000 tonnes of dry

biosolids areproduced each year by the major metropolitan authorities,and currently most

biosolids applied to agricultural landare used in arable cropping situations where they can be

incorporated into the soil.

There is also considerable interest in the potential forcomposting biosolids with other organic

materials such assawdust, straw, or garden waste. If this trend continues, therewill be

implications for metal contamination of soils. Thepotential of biosolids for contaminating soils

with heavymetals has caused great concern about their application in agricultural practices

(Rajesh et al., 2007). Heavy metals most commonly found in biosolids are Pb, Ni, Cd, Cr, Cu,

and Zn, and themetal concentrations are governed by the nature and theintensity of the industrial

activity, as well as the type ofprocess employed during the biosolids treatment. Under certain

conditions, metals added to soils in applications of biosolids can be leached downwards through

the soil profileand can have the potential to contaminate groundwater. Recent studies on some

New Zealand soils treated with biosolids have shown increased concentrations of Cd, Ni, and Zn

in drainage leachates (Xilonget al., 2005).

39
2.5.4. Wastewater.

The application ofmunicipal and industrialwastewater and related effluents to land dates back

400 yearsand now is a common practice in many parts of the world. Worldwide, it is estimated

that 20 million hectares ofarable land are irrigated with waste water. In several Asianand African

cities, studies suggest that agriculture based onwastewater irrigation accounts for 50 percent of

the vegetable supply to urban areas. Farmers generally are not botheredabout environmental

benefits or hazards and areprimarily interested in maximizing their yields and profits.

Although the metal concentrations in wastewater effluentsare usually relatively low, long-term

irrigation of land withsuch can eventually result in heavymetal accumulation in the soil.

2.5.5. MetalMining andMilling Processes and IndustrialWastes.

Mining and milling of metal ores coupled with industrieshave bequeathed many countries, the

legacy of wide distributionof metal contaminants in soil. During mining,tailings (heavier and

larger particles settled at the bottomof the flotation cell during mining) are directly

dischargedinto natural depressions, including onsite wetlands resulting in elevated concentration.

Extensive Pb and zinc Znore mining and smelting have resulted in contamination ofsoil that

poses risk to human and ecological health. Manyreclamation methods used for these sites are

lengthy andexpensive and may not restore soil productivity. Soil heavymetal environmental risk

to humans is related to bioavailability.Assimilation pathways include the ingestion of

plantmaterial grown in (food chain), or the direct ingestion (oralbioavailability) of, contaminated

soil.Other materials are generated by a variety of industriessuch as textile, tanning,

petrochemicals from accidental oil spills or utilization of petroleum-based products, pesticides,

and pharmaceutical facilities and are highly variable in composition(Rajesh et al., 2007).

40
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.

2.6.6. 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 (Rajesh et

al., 2007). Stack emissions can be distributed over a wide area by natural air currents until dry

and/or wetprecipitationmechanisms remove them from the gas stream (James, 2010).

Fugitive emissions are often distributed over a much smallerarea because emissions are made

near the ground. In general,contaminant concentrations are lower in fugitive emissionscompared

to stack emissions. The type and concentrationof metals emitted from both types of sources will

dependon site-specific conditions. All solid particles in smoke fromfires and in other emissions

from factory chimneys areeventually deposited on land or sea; most forms of fossilfuels contain

some heavy metals and this is, therefore, aform of contamination which has been continuing on a

largescale since the industrial revolution began. For example, veryhigh concentration of Cd, Pb,

and Zn has been found inplants and soils adjacent to smelting works. Another majorsource of

soil contamination is the aerial emission of Pbfrom the combustion of petrol containing tetraethyl

lead; thiscontributes substantially to the content of Pb in soils in urbanareas and in those adjacent

41
to major roads. Zn and Cd mayalso be added to soils adjacent to roads, the sources beingtyres,

and lubricant oils (James, 2010).

2.6 FACTORS INFLUENCING UPTAKE OF HEAVY METALS AND MINERALS

BY PLANTS

Absorption and accumulation of heavy metals in plant tissues depend upon temperature,

moisture, organic matter, pH, and nutrient availability. Heavy metal accumulation also depends

on plant species, while the efficiency of plants in absorbing metals is determined by either plant

uptake or soil-to-plant transfer factors of the metals. Elevated lead levels in soils for instance

may decrease soil productivity, while a very low lead concentration may inhibit some vital plant

processes, such as photosynthesis, mitosis, and water absorption, leading to symptoms of

toxicity, like dark green leaves, wilting of older leaves, stunted foliage, and brown short roots.

Heavy metals are potentially toxic, resulting in chlorosis, weak plant growth, and low yield, and

they may even be accompanied by reduced nutrient uptake, disorders in plant metabolism, and a

reduced ability to fix molecular nitrogen in leguminous plants (James, 2010).

2.7 EFFECTS OFHEAVY METALS ON SOIL

Soil contamination by heavy metals is of most important apprehension throughout the

industrialized world. Heavy metal pollution not only result in adverse effects on various

parameters relating to plant quality and yield but also cause changes in the size, composition

and activity of the microbial community. Therefore, heavy metals are considered as one of the

major sources of soil pollution. Heavy metal pollution of the soil is caused by various metals

especially Cu, Ni, Cd, Zn, Cr, and Pb. The adverse effects of heavy metals on soil biologicaland

biochemical properties are well documented. The soil properties i.e. organic matter, clay

contents and pH have major influences on the extent of the effects of metals on biological

42
and biochemical properties. Heavy metals indirectly affect soil enzymatic activities by shifting

the microbial community which synthesizes enzymes. (Nnorom, 2015).

Heavy metals exhibit toxic effects towards soil biota by affecting key microbial processes and

decrease the number and activity of soil microorganisms. Conversely, long-term heavy metal

effects can increase bacterial community tolerance as well as the tolerance of fungi such as

arbuscularmycorrhizal (AM) fungi, which can play an important role in the restoration of

contaminated ecosystems. (Nnorom, 2015).

Chauhan et al. suggested that heavy metals caused a decrease in bacterial species richness

and a relative increase in soil actinomycetes or even decreases in both the biomass and

diversity of the bacterial communities in contaminated soils.

Chauhan et al reported that the enzyme activities are influenced in different ways by different

metals due to the different chemical affinities of the enzymes in the soil system. Cd is the more

toxic to enzymes than Pb because of its greater mobility and lower affinity for soil colloids. Cu

inhibits b-glucosidase activity more than cellulose activity. Pb decreases the activities of urease,

catalase, invertase andacid phosphatase significantly. Phosphatase andsulfatase are inhibits by

As (V) but that urease was unaffected. Cd contamination has a negative effect on the

activities of protease, urease, alkaline phosphatase and arylsulfatase but no significant

effect on that of invertase. Each soil enzyme exhibits a different sensitivity to heavy metals.

(Ayenimoet al., 2010).

The order of inhibition of urease activity generallydecreased according to the sequence Cr >

Cd > Zn >Mn>Pb. Diversity and activity of soil microbes play significant roles in

recycling of plant nutrients, maintenance of soil structure, detoxification of noxious chemicals

and the control of plant pests and plant growth communities are important indices of soil

43
quality. It is important to investigate the functioning of soil microorganisms in ecosystems

exposed to long-term contamination by heavy metals. Chromium is commonly present in soils

as Cr (III) and Cr (VI), which are characterized by distinct chemical properties and toxicities.

Cr (VI) is a strong oxidizing agent and is highly toxic, whereas Cr (III) is a micronutrient a non-

hazardous species 10 to 100 times less toxic than Cr (VI). Cr (VI) has been reported to cause

shifts in the composition of soil microbial populations, and known to cause detrimental

effects on microbial cell metabolism at high concentrations. (Ayenimoet al., 2010).

Ashraf and Ali also reported that the heavy metals exert toxic effects on soil

microorganism hence results in the change of the diversity, population size and overall

activity of the soil microbial communities and observed that the heavy metal (Cr, Zn and

Cd) pollution influenced the metabolism of soil microbes in all cases. In general, an increase of

metal concentration adversely affects soil microbial properties e.g. respiration rate, enzyme

activity, which appears to be very indicators of soil pollutions. In case of soil contaminated with

lead (Pb) slight change was observed in the soil microbial profile. (Gardner, 2013).

2.8 EFFECTS OFHEAVY METALS ON PLANT

Many industries produce waste, which contain trace metals, either in the form of liquid effluent

or as solid residues. Many liquid wastes are directly discharged into the sewers and the metals

contained are eventually concentrated in sewage sludge, which may be applied to the land as

manure or soil conditioners (Webber, 1981). The quality of the water has the vital role, which

influences the seed germination, because of the presence of moisture and aqueous environmental

condition. Germinating seeds are highly sensitive to foreign material so that highly polluted

effluents from industry often prevent seed germination (Noggle and Fritz, 1991). However, in

many instances municipal wastewater and effluents from certain industries (e.g. paper mills,

44
brewereis, distilleries, sugar mills, dairies etc.) are widely used to irrigate agricultural fields.

Jerath and Sahai (1982) observed the toxic effect of fertilizer factory effluent, containing high

concentration of various forms of nitrogen, on seed germination and seedling growth of maize.

Sahaiet al. (1983) studied on the effect of distillery waste on seed germination and seedling

growth of rice (Oryza sativa) and showed that the effluent concentration more than 25% had

significantly retarded both germination percentage and seedling growth. They found root growth

was more adversely affected than the shoot growth due to the effluent. They concluded that

distillery effluent contained excessive amount of various forms of cations and anions might be

injurious to germination and seedling growth.

Chaudhary (1983) observed concentration above 5% of the effluent from Bansbari Leather and

Shoe Factory, Kathmandu, suppressed seed germination, seedling growth, fresh weight, dry

weight and biochemical products of wheat (Triticumaestivum) and rice (Oryza sativa). He

concluded high concentration of chromium and high pH present in the effluent may be the chief

cause for such inhibitory effect.

Sharma and Naik (1991) observed effect of a steel mill effluent in Abelmoschusesculentus(L)

moench in its germination parameters (% of germination, speed of germination, germination

relative index and seedling growth). They found more than 7% decrease in germination and

about 12%, 30% and 33% in speed of germination, germination relative index and seedling

growth respectively.

Patel and Kumar (1991) analyzed the germination experiment of mustard (Brassica junceaL.)

soaked in different concentrations 10%, 20%, 30%, 40%, 50% and 60% of the effluent of

pharmaceutical factory and he found that the increasing concentration (above 20%) of effluent

45
induced a gradual decrease in the germination percentage, seedling growth as well as pod

production.

Ramanujan (1991) studied the inhibitory effect of sewage waste containing industrial discharge

on seed germination and seedling growth of Phaseolusmungo.

Chapagain (1991) concluded that the toxicity of polluted water of Dhobikhola containing tannery

industry waste and sewage waste was also associated with the inhibition of seed germination and

seedling growth of vegetable. However, the magnitude of toxicity varied with the species.

Goel and Kulkarni (1994) after their study concluded that the industrial effluents at higher

concentration suppressed and at low concentration promoted germination and growth of

agricultural and vegetable crops.

Sharma (2000) and Pokhrel (2000) studied about the effect of heavy metals on germination and

growth of crop plants of Brassicaceae. Pokhrel concluded that Pb imposed significant effect on

germination of seeds, while growth was more significantly affected. The crops were found to

accumulate this metal ion in considerable amount. Similar results were reported by Sharma for

Cr.

Pokharelet al. (2000) studied about the toxic effect of some industrial effluent (Hulas Wire

Industry, Shah Udhyog and Strawboard Industry) on Allium cepa. The result showed that the root

growth and number of roots per bulb were adversely inhibited in all effluents compared to

control. The highest relative toxicity of root growth was found in 100% concentrated effluent of

Hulas Wire Industry and in all the cases, they concluded that the 100% concentrated effluents

had more toxic effect than the other lower concentrations.

Pokhrel and Lekhak (2001) studied about the effects of different concentration of lead (Pb) on

seed germination, seedling growth and moisture content in three vegetable crops,

46
Raphanussativus, Brassica oleraceaVar. botrytis and Brassica juncea. The effect of Pb on seed

germination differed according to the test species and concentration of treatments. The study

showed increase in accumulation of Pb with the increased concentration. Roots accumulated

more Pb than the shoots.

Acharya (2001) studied about the effect of brewery industrial effluents on some agricultural

crops. She found that the industrial effluent at higher concentration suppressed seed germination

and seedling growth.

2.9 TREATMENT OF AGICULTURAL FARMLAND

Soil can be contaminated by many different human activities when hazardous substances are not

used, stored or disposed of safely. Instances of soil contamination are highest in urban areas and

former industrial sites, where manufacturing, industrial dumping, land development, waste

disposal, and excessive pesticide or fertilizer use could potentially occur (Alysson and Fabio,

2014).

Some contaminants, such as agricultural chemicals, are applied to the soil surface. Others are

released below the surface, due to leaks from buried tanks, sewage pipes, or landfills.

Atmospheric contaminants containing hazardous substances can also cause problems.

Furthermore, contamination is not always limited to a specific site and can seep through the soil

into groundwater or be carried to nearby land and waterways in rainwater, or as dust.

Common treatment methods for contaminated soil

After testing to determine the type and level of contaminants present, soil can be subjected to

remediation techniques for the purposes of site decontamination. This can be carried out in-situ,

or soil may excavated and removed for treatment ex-situ (Alysson and Fabio, 2014).

47
Options for treating contaminated soil include:

 Biological treatment/bioremediation uses bacteria to break down substances in the soil

 Chemical oxidation converts contaminated soils into non-hazardous soils

 Soil stabilisation involves the addition of immobilizing agents to reduce a contaminants’

leachability

 Physical methods, like soil washing, use water to separate or remove contaminants

Bioremediation

Bioremediation is the use of biological processes to degrade, transform, or essentially remove

contaminants from soil and water (Thomas, 2007). This process relies on micro-organisms

including bacteria and/or fungi, which use the contaminant as a food source. For this reason,

bioremediation is widely used to remediate organic contaminants and can be an effective means

of mitigating:

 hydrocarbons

 halogenated organic solvents

 halogenated organic compounds

 non-chlorinated pesticides and herbicides

 nitrogen compounds

 metals (lead, mercury, chromium)

 radionuclides

Often, bioremediation presents a more economic option to disposal, however it can take anything

from one to several months to carry out.

48
Chemical oxidation

Chemical decontamination methods generally focus on chemical oxidation, whereby reactive

chemical oxidants are injected into the soil and groundwater for the purpose of rapid and

complete contaminant destruction. In situchemical oxidation (ISCO) is a versatile solution,

particularly when remediating contaminants located in difficult to access areas such as soils at

depth or soils beneath buildings. Chemical oxidation has wide ranging applications and can be

used to treat various organic contaminants including TPH, BTEX and PCBs (Alysson and Fabio,

2014).

CHAPTER THREE

3.0 MATERIALS AND METHODS

3.1 MATERIALS

3.1.1 Samples

 Soil

 Water

 Manure

3.1.2 Project site

Samples were gotten from, Sagamu, Ipara and Isara

3.1.3 Apparatus

 Heating mantle

49
  Crucible

 Glass rod flame photometer

 100ml volumetric flask

 Whatman n0.1 filter pape

 Wash bottle

 10ml pipette

 Funnel

3.1.4 Reagents

 2MHCL

 Vandate- molybdateyellowsolution

3.2 METHODS

3.2.1 Collection of sample at project site

The soil, water and manure were collected at 3 different agricultural farms, located at Isara, Ipara

and Sagamu in Remo north.

3.2.2 Preparation of sample

The soil samples were collected at different point on each farmland which were later mixed

together and air-dried at 25 °C, plantresidues removed, and ground up to pass through 2-

mmnylon sieves, then stored in plastic bags Soil pH was determined using a pH meter. Other

samples like the water and manure were taken to the laboratory after gotten from the sample site

and worked on to distinguish the presence of minerals and heavy metals in the farm land

samples.

3.2.3 Determination of ash content of the sample

50
The Ash content represented the inorganic residue (minerals) remaining after ignition and

complete oxidation of organic matter. The Dry ashing used involved heating the sample in a

muffle furnace at 500 – 600 oC. Since some elements such as Fe, Se, Pb and Hg may be partially

volatized during dry ashing, wet ashing was also done using acids or oxidizing agents or

combination to oxidize organic substances. This method is especially preferred when ashing is a

preliminary step for elemental analysis (i.e. determination of specific minerals present in the

sample). Ash content determination is widely used in the flour milling industry as a quality

measure for flour extraction. When ash is too high in flour, this indicates too much

contamination of flour with bran (outer covering of wheat kernel). The Miller made sure it was

put on reset to extract a purer flour stream. Ashing of food samples is done using a muffle

furnace.   

Method   

5 grams of food sample (turkey sausage, apple, vegetable oil, bread, vinegar, ground mineral

supplement) in a tared crucible was Weighed (in duplicate) Place crucibles in cool muffle

furnace

1. Burnt for 12-18 hours (or overnight) at 550oC

2. Turned off muffle furnace and allow to cool to at least 250oC

3. Opened door gently to avoid losing ash that may be fluffy

4. Used safety tongs, transfer crucibles to a desiccator

5. Covered crucibles and close desiccator

6. Cooled to room temperature and then weigh

7. Calculated the ash content and record your findings

51
3.2.4 Determination of mineral element

 Calcium potassium and sodium Determination

Determination: the ash of each sample obtained was digested by adding 5ml of 2MHCLto the

ash in thecrucible and heat to dryness on a heating mantle. 5ml of 2MHCL was added again, heat

to boil and filtered through a whatman no.1 filter paper into a100mlvolumetric flask. The filtrate

was made up to mark with distilled water stoppered and made ready for reading of concentration

of calcium, potassium and sodium on the jenway digital flame photometer (pfp7 model ) using

the filter corresponding to each mineral element.

The concentration of each of the element was calculated using the formula: %Ca or %K or %Na

= Meter reading (MR) X Slope x Dilution factor / 1000

NB: MR X slope X dilution factor will give you the concentration in part per million (ppm or

mg/kg). You get concentration in % when you divide by 10000

 Phosphorous determination (spectrometric method)

Phosphorous was determined routinely by the vanado-molybdate colorimetric or

spectrophotometric method

Determination: the ash of each sample obtained was treated 2MHCL solution as described for

calcium determination above. 10ml of the filtrate solution was pipette into 50ml standard flask

and 10ml of vandate yellow solution was added and the flask was made to mark with distilled

water stoppered and left for 10minutes for full yellow development. The concentration of

phosphorous was obtained by the optical density (OD) or absorbance of the solution on a

spectronic 20 spectrophotometer or colorimeter at a wavelength of 470nm.

52
The percentage phosphorous was calculated from using the formula:

% phosphorous = Absorbance X slope X Dilution factor / 10000

 Determination of se, mg ,pb, cd, cu, mn, fe, ni, zn using buck 200 AAS

The digest of the ash of each sample above as obtained in calcium and potassium determination

was washed into 100ml volumetric flask with demonized or distilled water and made up to mark.

These diluents were aspirated into the Buck 200 atomicAbsorption Spectrophotometer (AAS)

through suction tube. Each of the trace mineral elements was read at their perspective

wavelengths withtheir respective hollow cathode lamps using appropriate fuel and oxidant

combination.

3.3 INSTRUMENT SETTING FOR ATOMIC SPECTROPHOTMETRY

MODEL: BUCK 211, MADE BY BUCK SCIENTIFIC

H=ELEMEN, A= WAVELENGTH (nm), B= SLIT WIDTH (nm),C= WORKING RANGE

(ug/ml) D= SENSITIVITY (ug/ml) E=LAMP CURRENT F= FLAME TYPE

H A B C D E F

Al 309.3 0.5 25-135 1.0 25.0 N2O-C2H2

Al 396.2 0.5 25-110 1.0 25.0 N2O-C2H2

As 193.7 0.7 1-100 45.0 300.0 MHS

Ca 422.7 0.5 1-4 0.02 10.0 N2O-C2H2

Ca 422.7 0.5 1-10 0.09 10.0 AIR-C2H2

Cd 228.8 0.5 0.5-5 0.03 15.0 AIR-C2H2

Co 240.7 0.2 1-20 0.2 6.0 AIR-C2H2

Cr 357.9 0.2 2-20 0.2 25.0 AIR-C2H2

Cr 425.4 0.2 7-40 0.5 25.0 AIR-C2H2

53
Cu 324.7 0.5 1-20 0.1 15.0 AIR-C2H2

Cu 217.9 0.2 7.5-30 0.2 15.0 AIR-C2H2

Fe 248.3 0.2 2-20 0.1 30.0 AIR-C2H2

Fe 372.0 0.2 20-80 0.5 30.0 AIR-C2H2

Hg 253.7 0.7 1-200 4.2 150.0 MHS

K 766.5 0.5 1-10 0.01 6.0 AIR-C2H2

Mg 285.2 0.5 0.1-2 0.01 6.0 AIR-C2H2

Mg 202.6 1.0 5-20 0.1 6.0 AIR-C2H2

Mn 279.5 0.2 1-10 0.06 5.0 AIR-C2H2

Mn 403.1 0.2 7-27 0.2 5.0 AIR-C2H2

Mo 313.3 0.2 10-50 0.8 7.0 N2O-C2H2

Na 589.0 0.2 0.03-1 0.02 8.0 AIR-C2H2

Ni 232.0 0.2 2-20 0.2 25.0 AIR-C2H2

Ni 352.4 0.5 6-30 0.2 25.0 AIR-C2H2

Pb 283.3 0.5 4-40 0.2 440.0 AIR-C2H2

Se 196.1 1.0 45-180 1.0 10.0 N2O-C2H2

Si 251.6 0.2 20-200 2.0 15.0 N2O-C2H2

Zn 213.9 0.5 0.5-5 0.03 15.0 AIR-C2H2

The meter reading for each element was used to calculate for the concentration of each element

using the formula:

Ppm or mg/kg (any of the elements ) = Meter reading X Slope or gradient X dilution factor. %

(any of the elements ) = ppm or mg/kg divided by 10000

54
 CHAPTER FOUR

4.0 RESULTS AND INTERPRETATION

4.1 HEAVY METALS RESULT FROM THE SAGAMU FARM SAMPLES

FIGURE TABLE 1: THE RESULTS OF THE HEAVY METALS ANALYSED FROM

FEED, WATER AND FERTILIZER GOTTEN FROM SAGAMU IS STATED IN TABLE

1 BELOW

SAMPLE PARAMETERS
MINERALS METALS

CALCIUM MAGNESIU IRO LEAD ZINC ARSENIC MERCURY

Ca2+ M N Pb2+ Zn As Hg

(ppm) Mg2+ Fe2+ (Mg/kg) (Mg/kg (Mg/kg) (Mg/kg)

(ppm) (ppm )

55
 )

SOIL 6.69 0.28 0.206

WATER 10.00 10.00 0.384 0.008
MANUR 2765 0.027 0.049 0.0007

4.2 HEAVY METALS AND MINERALS RESULT FROM THE IPARA FARM

SAMPLES

FIGURE TABLE 2: THE RESULTS OF THE HEAVY METALS AND MINERALS

ANALYSED FROM FEED, WATER AND FERTILIZER GOTTEN FROM IPARA IS

STATED IN TABLE 2 BELOW

SAMPLE PARAMETERS
MINERALS METALS

CALCIUM MAGNESIU IRO LEAD ZINC ARSENIC MERCURY

Ca2+ M N Pb2+ Zn As Hg

(ppm) Mg2+ Fe2+ (Mg/kg) (Mg/kg (Mg/kg) (Mg/kg)

(ppm) (ppm )

SOIL 7.38 0.72 4.16 0.324

56
 WATER 15.00 15.00 0.318 0.23

4.3 HEAVY METALS AND MINERALS RESULT FROM THE ISARA FARM

SAMPLES

FIGURE TABLE 3: THE RESULTS OF THE HEAVY METALS AND MINERALS

ANALYSED FROM FEED, WATER AND FERTILIZER GOTTEN FROM ISARA IS

STATED IN TABLE 3 BELOW

SAMPLE PARAMETERS
MINERALS METALS

CALCIUM MAGNESIU IRO LEAD ZINC ARSENIC MERCURY

Ca2+ M N Pb2+ Zn As Hg

(ppm) Mg2+ Fe2+ (Mg/kg) (Mg/kg (Mg/kg) (Mg/kg)

(ppm) (ppm )

SOIL 6.28 0.37 3.85 0.195

WATER 10.00 10.00 0.516 0.012

57
4.5 INTERPRETATION

In relating this research to the study areas in respect of Sagamu as a study area, the level of

minerals and heavy metals can be said to be high as they posses industries capable of releasing

certain heavy metals and minerals into the environment. During this research it was discovered

that the presence of heavy metals in the study area was mild but the presence of iron with a range

of 6.69 ppm was higher than that of the other heavy metals that were examined.

For the other farmlands which are Ipara and Isara it was discovered that the presence of heavy

metals and minerals were mild unlike that of Sagamu possessing industries that can cause the

release of these metals and minerals into the soil, water and manure produced by the animals.

Comparing all the farmlands with the presence of heavy metals and minerals in the study area

specifically the soil sample, it was discovered that iron was the highest in all the farmland

starting with Sagamu having it range to be 6.69 ppm, Ipara to be 7.38 ppm, Isara to be 6.28ppm.

Therefore, the concentrations of heavy metals in thestudy area generally indicate low levels of

contamination, except for soil iron (fe2+). Comparedto some industrialized areas of Ogun state

58
such as Sagamu, (see Table 1), most of the heavy metals in soils of the study area showed lower

concentrations, especially Pb, As, Hg and Zn.

The risk of low and high concentration ofiron in arable soils wasrevealed in the study area, as

low or minute quantity of iron in soils and plants is essential for healthy plant growth and is

classed as a micronutrient while excess iron in the soil leads to plant toxicity.

CHAPTER FIVE

DISCUSSION, CONCLUSION AND RECOMMENDATION

5.1 DISCUSSION OF RESULT

From the analysis gotten from Sagamu, it was discovered that magnesium as a heavy metal was

higher than Lead, Arsenic and Mercury in fertilizer with a figure of 2765mg/kg while lead was

found to be 0.0027 ppm, Arsenic 0.049 mg/kg and mercury 0.0007 mg/kg. High levels of

magnesium in fertilizers when taken in large amounts (greater than 350 mg daily) magnesium is

possibly unsafe. Large doses might cause too much magnesium to build up in the body, causing

serious side effects. Although excess magnesium is bad for the human system, it’s highly needed

in farm manure/ fertilizer for plant growth.

Analysis gotten from Sagamu site on the minerals, showed that magnesium and calcium were

dominant in water sample gotten at Sagamu site compared to iron which was at a considerable

amount. For the soil sample, iron was higher than lead, zinc, Arsenic. A high level of iron in the

soil sample is detrimental to the growth of plant.

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Analysis from Ipara site showed a dominant trace of calcium and magnesium which is of high

importance to both plant and animal compared to other minerals present in the water sample. For

the soil sample, iron was also dominant as a heavy metal by 6.69 ppm followed by zinc which

was 3.97 ppm, lead and arsenic were lesser than other metals present.

Analysis from Isara farm land showed similar results to that of Ipara farm land in both water and

soil samples.

5.2 CONCLUSION

Heavy metals maychange the physical, chemical and biological propertiesof soil. These metals

uptake by plants from the soil, itreduces the crop productivity by inhibiting physiological

metabolism. Heavy metals uptake byplants and successive accumulation in human tissues and

biomagnifications through the food chain causesboth human health and environment concerns.

The present study examined the heavy metal contents and mineral content in a farming area of

ogun state. Except for Fe, the mean values of all theheavy metal concentrations were less than

the averagelocal background values, and showed lower Pb, As, Hg and Zn content when

compared with agricultural soils frommore industrialized regions.

From the result gotten it can be clearly stated that the presence of heavy metals and minerals

were minimal thus proving safe for agricultural productions.

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5.3 RECOMMENDATION

Background knowledge of the sources, chemistry, and potential risks of toxic heavy metals and

minerals in contaminated soils is necessary for the selection of appropriate remedial options.

Remediation of soil contaminated by heavy metals and minerals is necessary in order to reduce

the associated risks, make the land resource available for agricultural production, enhance food

security, and scale down land tenure problems. Immobilization, soil washing, and

phytoremediation are frequently listed among the best available technologies for cleaning up

heavy metal contaminated soils but have been mostly demonstrated in developed countries.

These technologies are recommended for field applicability and commercialization in the

developing countries also where agriculture, urbanization, and industrialization are leaving a

legacy of environmental degradation.

Enlightenment programs can also be held in order to reduce the risk at which soil, water and

manure for crop production gets contaminated. Implementing laws that stand against improper

disposal of sewage or industrial waste should also be considered by the governing bodies of a

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particular location, so at to curb the dangerous effects of heavy metals in the soil and improve the

level of soil mineral and nutrients.

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