CHAPTER ONE

INTRODUCTION

1.1. ESSENTIAL AND NON-ESSENTIAL ELEMENTS IN FRUITS AND VEGETABLES

The living organisms require several different types of organic and inorganic

substances to use, sustain and grow by performing several biological processes. Some of these

substances are required in small quantities but they are essential for carrying out different

processes. Without the availability of the proper amount or quantity of these substances, the

organism may face several deficiencies.

The mineral elements are defined as the inorganic elements that are required by the

body in smaller amounts in order to perform various functions. The mineral elements cannot

be synthesized by the living organism and they have to be received from other sources such as

soil, water etc. Organisms needs different types of minerals in different quantities. According

to the amount that is required by the body, the mineral elements can be divided into essential

and non-essential minerals.

Essential elements are those types of mineral elements that are required by an

organism for normal growth and development (McDowell, 2003). These mineral elements are

vital for overall development of the organism. Essential mineral elements are the most basic

blocks that are necessary for every type of biological processes occurring in the organism.

Some important essential elements are oxygen, carbon, hydrogen, nitrogen etc (Matsuura et

al., 2001). Apart from these elements, some other essential elements that are important for

living organisms are calcium, sodium, iodine, iron, phosphorus, potassium, copper and zinc.

1
 Whereas some other minerals elements are also found in the living organism in

addition to the essential minerals elements. These elements can be synthesized by the

organism and are required in small amounts (McDowell, 2003). Such types of mineral

elements are known as non-essential mineral elements. This type of mineral does not play a

significant role in meeting nutritional demands. Some of the non-essential elements are

aluminium, arsenic, bromine, cadmium, barium etc. (Marschner, 2012),

Fruits and vegetables are useful components of the diet due to their contributions in

forming a balanced diet. They are important as essential building blocks of any diet and are

loaded with vitamins and minerals (essential or non-essential).

Vegetables contain the necessary nutrients, carbohydrates, fats, and primitive proteins

required for the human body and is considered the best nutrient source. In addition to these

biomolecules, some vegetables and fruits are also crucial for human health. Micro and Macro-

elements, as well as heavy metals, are considered as a potential health risk (Basel and

Erdemoglu, 2006). Plants are also primary sources of food, minerals, vitamins, and essential

antioxidants for many communities facing economic difficulties. However, some researchers

have found similar antinutrients in many conventional and traditional plants (Kalny et al.,

2007). Although knowledge of plant materials is generally limited, there is little data on

nutrients and proximity elements (Hosseinzadeh et al., 2015).

Fresh plant material contains 80-90% of water, and the remainder over 90% consists of

C, H, and O. Organic material is removed from the dried plant samples by ashing. The

remaining 1.5% of the plants, the fresh weight represents its mineral content (Malik et al.,

2008).

2
 Elements such as carbon, hydrogen, nitrogen, phosphorus, sulfur, potassium, calcium,

magnesium, iron, boron, manganese, copper, zinc, chlorine, sodium, and silicon are present in

various medicinal plants. The vegetables also naturally produce trace metals such as zinc,

cadmium, copper, manganese, aluminum, iron, and lead. Most of the research focuses on the

role of metabolic function of trace elements throughout the world. There is a need to analyze

these fruit and vegetables detect their components, essential for normal human body function.

In the case of an abnormal quantity of these elements, the human body faces different

disorders. Moreover, even a small amount of toxic elements can harm the average human

body. Therefore, it is necessary to measure the appropriate amount of these elements in the

human body (Maiga et al., 2005). The plants produce several essential chemicals (Malik et

al., 2012). The deviation of the vegetable element content is mainly due to the difference in a

plant structure (botanical) and availability of minerals in the soil where the vegetables are

implanted. Other factors include the climate conditions, irrigation water, use of fertilizers, and

absorptive capacity of the plant (Lozak et al., 2012). Metals are categorized with macro

(primary) or micro (trace) elements. The 3rd class is the ultra-trace elements. Macro-minerals

contain Calcium, Phosphorus, Sodium, and Chloride, whereas the micro-elements include

Iron, Copper, Cobalt, Potassium, Magnesium, Iodine, Zinc, Manganese, Molybdenum,

Fluoride, Chromium, Selenium, and Sulfur (Murray et al., 2000). 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. The level of elements permitted by the WHO should not endanger the

health of consumers (WHO, 2011).

Trace elements are inorganic substances that exist in trace elements at low concentrations. The

essential elements at trace levels play a role in the human body and can cause some diseases

3
beyond the limit of average concentration. The recommended daily trace elements mineral

intake (about 1.5 grams) is considered adequate for healthy people (WHO, 2007). Trace

elements are present in all body tissues and fluids, and their presence is necessary. Although

they do not produce energy, they play an essential role in many activities in the body (Thor et

al., 2011) Trace elements comprise only a fraction of the total body weight, these are crucial

for many body functions. These include transporting oxygen, normalizing the central nervous

system (CNS), and stimulating the growth, maintenance, and repair of tissues and bones

(Feinendegen and Kasperek, 1980). It has been reported in the literature that most of the trace

elements found in the tissues and body fluids are also present in the blood (Shenkin, 1997).

Nevertheless, plants’ composition depends on several factors, such as the industrial use of

components of human activities and climatic conditions. These components are essential to

ensure the quality of plant raw materials and pollutants’ presence if human consumption is

core. (Naila-Moshood et al., 2013).

Heavy metal pollution has spread broadly over the globe, perturbing the environment

and posing serious health hazards to humans. The root causes of this problem are generally

held to be the rapid pace of urbanization, land use changes, and industrialization, especially in

developing countries with extremely high populations, such as India and China (UN-

HABITAT, 2004). Since the industrial revolution and economic globalization, the diversity of

environmental contaminants has increased exponentially, with countless anthropogenic

sources. Therefore, the diverse and emerging issues of food security have become a global

concern, particularly their inextricable association with human health (Clarke, 2011; Säumel

et al., 2012; Toth et al., 2016; Rai, 2018a). Several hazardous heavy metals and metalloids

(e.g As, Pb, Cd, and Hg) are classified as non-essential to metabolic and other biological

4
functions. Those metals are deleterious in various respects (Gall et al., 2015), and they have

therefore been included in the top 20 list of dangerous substances by the United States

Environmental Protection Agency and the Agency for Toxic Substances and Disease Registry

(ATSDR)(ATSDR, 2007; Xiong et al., 2016a, 2016b; Khalid et al., 2017; Rai, 2018a). Certain

heavy metals, such as Cu, Fe, and Zn (and even Cr (III)), are essential components of

metabolic processes, including cytochromes and enzymes, inextricably linked to the metabolic

functioning of biota (Marschner, 2012). Nickel is an integral component of urease, although it

can cause human health risks at excessive levels (Zhuang et al., 2009; Marschner, 2012).

Thus, soil–food crop/vegetable systems provide a classic example of abiotic-biotic

interactions in the environment. Soil is the fundamental sustenance of food crops, and it can

be greatly perturbed by heavy metals from point sources (e.g., energy-intensive industries,

such as thermal power plants and coal mines, and chloro-alkali chemical industries, such as

goldmines, smelting, electroplating, textiles, leather, and e-waste processing) and non-point

sources (e.g., soil/sediment erosion, agricultural runoff, and open freight storage). In addition

to their human health implications, heavy metals adversely affect soil biota through microbial

processes and soil–microbe interactions (Gadd, 2010; Gall et al., 2015; Rai, 2018a).

Beneficial soil insects (especially in agriculture), invertebrates, and small and large

mammals are all affected (Gall et al., 2015; Bartrons and Peñuelas, 2017; Rai et al., 2018).

For example, medicinal plants used for traditional human health care should be examined for

heavy metal contamination to prevent adverse effects, as demonstrated by the Chinese

medicinal plant Feng dan (Paeonia ostii) (Shen et al., 2017). Many medicinal plants have been

shown to bioaccumulate various metals (e.g., Cd, As, Cr, Cd, Cu, Pb, and Fe) when grown

near smelting or other industrial areas (Hamiani et al., 2015; Bolan et al., 2017; Kim et al.,

2017a, 2017b; Kohzadi et al., 2018). Greenhouse vegetables are also highly contaminated

5
with heavy metals such as Cu, Zn, Mn, Pb, and Cd (but not Fe) compared to open field

vegetables, possibly due to less illumination (Li et al., 2017a, 2017b).

1.2. AIM OF THE STUDY

The purpose of this study is to determine the levels of essential (Mg, Al, Mn, Fe, and

Cu) and non-essential elements (Cr, Cd, Ni and Pb) in vegetables and fruits grown in Iseyin

town, Oyo state and assess the health risk associated with their consumption using DIM, THQ

and ILCR indices for adults and children.

1.3. SCOPE OF THE STUDY

The study will focus on analyzing vegetable and fruits samples from selected farm

land in Iseyin town, Oyo state, Nigeria, using the result to calculate the DIM, THQ and ILCR

indices and hence assess the potential health risk.

1.4. JUSTIFICATION OF THE STUDY

Environmental contaminants, food safety and security, and human health are

inextricably linked. The concentrations of heavy metals in the environment have increased

significantly in recent decades. In developing countries, irrigation within adequately treated

effluent or sludge is the main contamination source for food crops. Heavy metal transfer from

soil to crop systems is complex and uses multifaceted mechanisms. Multi-metal toxicity in

food crops requires specific attention to determine the actual metal toxicity. The human health

risks have been widely investigated on a global scale, but only a few of those works have used

proper epidemiological methods. To prevent health risks, existing options focus on reducing

the concentration of heavy metals in soil and the food chain. Although existing research on

food chain contamination in Nigeria is fragmented and localized, past research has shown that

heavy metal contamination affects Nigeria’s food chain. The spatial distribution of these

6
toxicities in Nigeria’s food chain is the major issue that suggest the need for further research,

which should map and delineate spatially the variations in heavy metal toxicity within the

whole of Nigeria.

7
 CHAPTER TWO

LITERATURE REVIEW

All essential elements are by definition required for plant growth and completion of

the plant life cycle from seed to seed. Some essential elements are needed in large quantities

and others in much smaller quantities. However, from a practical standpoint, three of the six

essential macronutrients are most often "managed" by the addition of fertilizers to soils, while

the others are most often found in sufficient quantities in most soils and no soil amendments

are required to supply adequate supplies. From a management perspective only, the primary

nutrients are N, P, and K, because they are most often limiting from a crop production

standpoint. All of the other essential macronutrient elements are secondary nutrients because

they are rarely limiting, and more rarely added to soils as fertilizers.

The ability of soils to supply secondary nutrients to plants indefinitely is subject to the law of

conservation of matter and is therefore dependent upon nutrient cycling. Continued crop

removal of Ca, Mg, and S requires replenishment just as surely as primary nutrients, but most

likely less frequently. Calcium and magnesium are often supplied by mineral weathering,

either of natural soil materials or of aglime, ground limestone added to correct soil acidity.

Sulfur is often added to soil as either atmospheric deposition (associated with air pollution) or

as impurities in fertilizers, particularly common Phosphorus fertilizers.

To demonstrate that this classification is more responsive to soil ability to supply nutrients

than plant requirements, it should be noted that plant requirements for Calcium, a secondary

nutrient element, is greater than for Phosphorus. Calcium is found as a principle exchangeable

8
cation in most soils and an important soluble cation in the soil solution. Phosphorus, on the

other hand, is only slightly soluble in most soils, and many soils (particularly acid soils and

alkaline soils) have the potential for causing phosphorus deficiencies. Whether a

macronutrient or micronutrient, or whether a primary or secondary nutrient, the Law of the

Minimum holds: the most growth-limiting nutrient will limit growth, no matter how favorable

the nutrient supply of other elements. For example, a deficiency of Fe or Mn (most common

in soils containing calcium carbonate) can severely limit plant growth in spite of adequate N,

P, and K.

2.1 SOURCES OF HEAVY METALS IN SOIL–CROP SYSTEMS

Sources of contaminants are both natural and anthropogenic. These toxic substances

make their way to the farmland, water, and food stuff exposed in the market by mostly the

process of leaching and runoff. Anthropogenic activities contaminate different environmental

media such as the soil, water, and air which support the growth, production, and supply of

foods. Ingestion, inhalation, and dermal are the major exposure pathways through which

heavy metals in locally produced foods in most of the regions get to the consumers. Toxicity

of these heavy metals can cause potential health hazards. Thus, long term consumption of

these foods is of public health significance. There is the need for better quality control for

food crops to protect consumers from contamination exposure.

The primary sources of heavy metals in the soil environment and agriculture are

atmospheric deposition, livestock manure, irrigation with wastewater or polluted water,

metallo-pesticides or herbicides, phosphate-based fertilizers, and sewage sludge–based

amendments (Chary et al., 2008; Cai et al., 2009; Luo et al., 2009; Mansour et al., 2009; Gall

et al., 2015; Elgallal et al., 2016; Woldetsadik et al., 2017; El-Kady and Abdel-Wahhab,

9
2018).In addition to natural sources, conventional/emerging anthropogenic contaminants pose

major human health risks through the dietary intake of food crops contaminated by root

transfer from soil to plant tissues or direct atmospheric deposition on to plant surfaces

(Samsøe-Petersen et al., 2002; Zhuang et al., 2009) (Fig. 1). Particulate matter (PM) emitted

by industries and vehicles ultimately accumulates in soil and the food chain (Rai, 2016a,

2016b; França et al., 2017). Coal-fired power plants are one major source of Hg

contamination in soil. Li et al., (2017a, 2017b) reported that the long-term consumption of

lettuce, amaranth, water spinach, cowpea, and grains (e.g., rice) grown in Hg-contaminated

soils (e.g., close to thermal power plants in China) is deleterious to human health. Likewise,

several strong source processes (e.g., waste water as an irrigation source, sewage sludge as a

soil amendment for food crops, and PM pollution/deposition on soil/plants) pose a grim

scenario for global food safety. Indeed, many countries do not have adequate water resources

to sustain their agricultural needs. To ensure agricultural productivity, inadequately treated

wastewater and sewage sludge are extensively applied to food crops; however, the quality and

safety of food crops grown in soils irrigated with poorly treated reclaimed water cannot be

guaranteed (Rai and Tripathi, 2007; Jaramillo and Restrepo, 2017).Sewage sludge is produced

in large quantities as a soil amendment for agriculture (e.g., 70, 30, and 6milliontons in Japan,

China, and USA, respectively) (Kelessidis and Stasinakis, 2012; Bourioug etal., 2015; Gall et

al., 2015), but negative environmental and public health repercussions have been reported

from using uncertainly or partially treated effluent and sewage sludge in that way (Sipter et

al., 2008;Toth et al., 2016; El-Kady and Abdel-Wahhab, 2018).

10
2.1.1 Factors Influencing Uptake of Mineral elements by Plants

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

moisture, organic matter, pH, and nutrient availability (Tangahu et al., 2011). 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 (Khan et al.,

2008). 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 (Bhattacharyya et al., 2008). 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 (Guala et al., 2010)

2.1.2 Mechanisms of action, Pathways and transport of metals in crop plants

An explicit understanding of the routes and mechanisms by which heavy metals pose a

risk to human health through the consumption of grains and vegetables enables the adoption of

suitable strategies to manage and mitigate heavy metals for the benefit of local people,

farmers, researchers, pedologists, and policy makers (Oves et al., 2012).

Heavy metals are transferred from soil pores to plants in ionic forms, which can vary

by metal (McLaughlin et al., 2011).The biospeciation of heavy metals can also vary by food

crop. Vegetables such as dandelion greens, bitter leaf, African spinach, Lagos spinach and

water leaf all accumulate heavy metals with different concentrations in the roots, leaves, and

fruits (Cobb et al., 2000). Pb uptake in lettuce was higher than that in tomatoes and beans, and

11
Cd and As uptake in the same plants was lower than Zn uptake (Cobb et al., 2000). Pb, Cd,

Cu, Zn, and As bio-accumulated in 22 vegetables grown in China in the following decreasing

order: leaves > stalk/root/solanaceous > legume/melon vegetables. The THQ reached 5,

indicating that all the vegetables had a high potential to cause severe health risks upon

ingestion (Zhou et al., 2016). Plant roots play the most vital role in the uptake and

translocation of heavy metals. The entry of metals into a root depends on its anatomy

(especially the cell wall) and environmental adaptability. For example, Zn uptake in mangrove

seedlings adversely affected their environmental adaptability through radial oxygen loss

(Cheng et al., 2010). Heavy metals enter the roots from the soil through the intake of water

mixed with minerals and nutrients and then bind to low-methyl esterified pectins, whose

levels increase under metal stress (Krzeslowska, 2011). Pb binds to the cell wall of the root

primarily through esterified pectins, as demonstrated in the protonemata of a moss plant

(Funaria hygrometrica), and can be remobilized (Krzeslowska et al., 2010). Polysaccharides

(with –COOH,–OH, and–SH functional groups assisting in binding heavy metals to the root)

in the root cell walls of food crops also play an important role in the avoidance and tolerance

of metal stress. Polysaccharide remodeling under heavy metal stress in food crops results in

perturbations of the structural integrity of the cell membrane and organelles (especially

chloroplasts and mitochondria), enzyme inactivation through the replacement of integral

components or binding to the sulfhydryl or carboxyl group, and nucleic acid conformation

changes. Proper investigation of the mechanisms involved in the foliar uptake of heavy metals

is also necessary to manage health risks. As demonstrated in a series of studies by Schreck et

al., (2012, 2013, 2014) on Pb uptake by Lactuca sativa, foliar uptake of the heavy metal

occurred mainly via adsorption to the cuticle or stomatal pores. Heavy metals are transported

from the roots to the aerial parts of the plant through xylem loading, whereas foliar transport

12
involves the phloem vascular system. With regard to the mechanisms of heavy metal uptake in

crops, foliar translocation has been studied less than the root uptake mechanism (Shahid et al.,

2016).

2.1.3 Potential Health Hazards of Some Selected Heavy Metals and Metalloids

• Lead (Pb)

Toxicological review of lead has shown inhibition of the activity of d-aminolaevulinic

dehydratase (porphobilinogen synthase, one of the major enzymes involved in the

biosynthesis of heme) and developmental problems such as impaired cognitive function,

behavioral disorder, stunted growth, and impaired hearing at blood lead level as low as 5 μg/l

(Ihedioha et al., 2017). Lead also interferes with calcium metabolism, both directly and by

interfering with vitamin D metabolism; it concentrated largely in bones in animals and

humans and interferes with the normal maturation of erythroid elements in the bone marrow

(Plant et al., 2000). These effects have been observed in children at blood lead levels ranging

from 12 to 120 μg/l. Lead is toxic to both the central and peripheral nervous systems, inducing

subencephalopathic neurological and behavioral effects. Other effects include epidemiological

effects (blood lead level of 30 μg/l), intelligence quotient deficits of about four points in

children due to prenatal/postnatal exposure to lead (blood lead level ranging from 11 to 33

μg/l), headache, irritability, constipation, weight loss, fatigue, hypertension, miscarriages,

stillbirths, and renal tumors (Hobbs et al., 2005). However, there is evidence from studies in

humans that adverse neurotoxic effects other than cancer may occur at very low

concentrations of lead, and that a guideline value derived on this basis would also be

protective for carcinogenic effects (WHO, 2004). A report of prevalence dental caries in

children in the Tamar Valley, England, and in Ceredigion, Wales, was associated with a high

level of Pb in soils which were available to plants (Plant et al., 2000).

13
 • Manganese (Mn).

Adverse effects of Mn can result from both deficiency and overexposure, causing neurological

effects due to high level in drinking water, which can cause tremor, gait disorders (seen in

primate), psychological symptoms such as irritability, and emotional liability (Hubbs-Tait et

al., 2005). For instance, amyotrophic lateral sclerosis, according to Hubbs-Tait et al., (2005) is

a progressive neurological disorder, which appears to be a disease that may reflect a

deficiency of Mg or Mn. The decreased intake of Mg or Mn leads to a decreased ability to

store and use thiamin (vitamin B1). These authors further noted that there is some evidence

suggesting that

Parkinson’s disease may be casually related to Mn, but in this case, to an excess of it.

• Nickel (Ni)

Nickel is an essential trace element in animals. Some of its health risk includes fibrosis,

chronic bronchitis, impaired pulmonary function, and emphysema (USDHHS, 2005). Allergic

contact dermatitis is the most prevalent effect of toxicity of nickel in the general population

(WHO,

2006). However, it is suspected to be an essential element for some plants and animals

(APHA, 1999). According to Plant and Thornton (1983) and Carla (2002), Ni deficiency

results in decreased plasma cholesterol, increased liver cholesterol, ultra-structural changes in

the liver calls, rough hair, impaired reproduction, and poor growth of the offspring.

• Zinc (Zn)

Zinc is an essential trace element whose threshold value in surface and groundwater normally

do not exceed 0.01 and 0.05 μg/l, respectively (Vinodhini and Narayanan, 2009). However,

concentrations in tap water can be much higher as a result of dissolution of zinc from pipes. It

14
should be noted that drinking water containing zinc levels above 3 μg/l may not be acceptable

for consumers (WHO, 2003).

• Cobalt (Co)

Cobalt is an essential microelement for humans in the form of vitamin B 12 with a complex

pathway through the food to man. Deficiency of Co results in pernicious anemia syndrome,

whereby the intrinsic factor from the stomach that facilitates B12 absorption is absent,

characterized by larger than normal (macrocytic) red blood cells plus neurologic

abnormalities. Excessive Co added to the foam stabilizer in beer however produced severe

cardiomyopathy, haematologic, neurologic, and thyroid abnormalities in humans (Davies et

al., 2013). A relationship between Co/ iodine (I) ratios in geochemical environment showed

an inverse correlation between Co in water and soil and thyroid enlargement in animal and

man.

• Copper (Cu) and Chromium (Cr)

These are important essential elements but when consumed in excess, they cause toxicity

(McDowell, 2013). It should be noted that the threshold for the effects of copper on the

gastrointestinal tract still leaves some uncertainty regarding the long-term effects of Cu on

sensitive populations, such as carriers of gene for Wilson disease and other metabolic

disorders of copper homeostasis (WHO, 2004).

Copper deficiency results in kinky and steely hair syndrome in humans and abnormal wool in

sheep, while excessive Cu intake results to hepatolenticular degeneration with progressive

impairment of Cu-laden tissues until death results (WHO, 2004). It also helps in

interconversion of the major neurotransmitters, dopamine, noradrenaline, and adrenaline, and

in pigment production. Zinc-Cu interaction has shown hypothesis of ischemic heart disease,

which proposes that decreased Cu intake with excessive Zn may play an aetiologic role in

15
cardiac deaths in both animals and man (Davies et al., 2013). Contamination and pollution of

vegetable and soils near smelters does occur, and excessive Cu in drinking water has been

reported to have caused a toxic syndrome in an infant called pink disease. Chromium helps to

maintain blood glucose levels, but its toxicity can result in allergic dermatitis such as eczema

(Bradhurst and Domenico, 2006).

• Arsenic (As)

Arsenic is a metalloid whose chronic exposure effects include tingling, numbness, and

peripheral neuropathy according to Plant and Thornton (Plant and Thornton, 1983). These

authors also argued that arsenic toxicity in cattle has been found to cause dysentery and

respiratory distress. An ecological correlation between the arsenic level of well water and

mortality from various malignant neoplasm in China (Province of Taiwan) demonstrated a

significant association with the arsenic level in well water ranging from 0.35 to 1.14 mg/l with

a median of 0.78 mg/l for cancer of the liver, nasal cavity, lung, skin, bladder, and kidney and

hyperpigmentation, hyperkeratosis, Blackfoot disease (a type of gangrene) in both males and

females, and prostate cancer in males (Chen and Wang, 1990).

16
Table 2.1: Risk/implications of food chain contamination for humans, domestic life, and
wildlife in Nigeria
Region Common Major sources Risk/implications
heavy

Metals
East Pb, Al, Zn, Heavy metals and metalloids from municipal Potential heavy metal toxicity in the
Cr, and industrial wastes in Onitsha/Awka and body system that can lead to
Abagana in Anambra and Abia States, hemoglobinuria, gastrointestinal
Fe, Mn, Cu, respectively, mining and quarrying (e.g., Pb- disorders, ataxia, pneumonia,
Co, As, Zn mining and igneous rock quarrying and diarrhea, stomatitis and paralysis .
limestone mining at Ishiagu and Nkalagu,
Ni, Hg
respectively, in Ebonyi State), air pollution
from transportation and agrochemicals.
South Zn, Cd, Pb, Petroleum extraction and refineries, e.g., Environmental degradation resulting to
Fe, Cu, Cr, consumers of seafood from these excessive social unrest destruction and
contaminated sites in Ogonib land may be incessant harm to the physical, social,
Co, and environmental, and economic health of
exposed to metal pollution
Mn its inhabitants.
West Pb, Al, Zn, Aerial deposition by emissions from Long-term consumption of ( leafy )
Cr, Lagos traffic, leaching and runoffs of Amaranthus from Lagos highway
Fe, Mn, contaminants from Ekiti State dumpsites. soils poses potential health risk due to
Cu, Co, Contaminated Fresh water bodies in Osun its heavy metal concentrations.
Mo, Se, State. Health risk index (HRI) and daily
As, Ni, Accumulation of heavy metals from battery intake of metal (DIM) estimation
Hg waste in topsoil, surface indicate higher health risk indexes
water, and garden grown maize at
in vegetables containing Pb, Ca, and
Omilende area, Olodo, Nigeria Hg. Osun freshwater bodies showed
high carcinogenic risk from high
concentrations of heavy metals
North Pb, Zn, Cr, Some heavy metals are introduce into the Increase concentration of zinc in
Fe, Mn, Cu, environment from farmyard and chemical pasture fields. Anthropogenic sources
Co, Ni fertilizer application (agrochemicals). Others usually produce heavy metals that are
include domestic by-products, worn automobile high in instability and solubility and in
tires, roofs, brake linings, and waste food. There turn, result in high bioavailability
are also iron mining sites (Itakpe, Kogi State). which
Sample of tested sediment from the river Ngada, increases potential health risk.
Maiduguri in Borno State revealed provocative Decrease in soil productivity by high
amounts of heavy metals. Evidence of mobility Pb concentration, while extreme low
of heavy metals from dumpsites to farmlands concentration can inhibit some
through leaching and runoff in Lafia, Nasarawa essential plant processes such as
mitosis, water adsorption, and
State.
photosynthesis. This can lead to brown
short roots and stunted growth/foliage.
Toxicity of heavy metals on the other
hand can lead to reduced ability in
leguminous plants to fix molecular
nitrogen.

17
Source: Izah et al., 2016

2.2 CONTAMINATION OF SOIL AND FOOD CROPS IN NIGERIA

Fruits and leafy vegetables are widely used with other foods for culinary purposes, especially

for increasing the quality of soups and for their nutritional value (Sobukola et al., 2007). They

are part of the daily diet in many households in Nigeria and are a source of vitamins and

minerals. They are made chiefly of cellulose, hemi-cellulose, and pectin, which give them

their texture and firmness (Sobukola et al., 2007). Consumer perception of better quality

vegetables is subjective as they consider dark green and big leaves as characteristics of good

quality. However, the external morphology of vegetables cannot guarantee wholesomeness

because heavy metals rank high amongst the major contaminants of leafy vegetables

(Mapanda et al., 2004).

Northern Nigeria

A study aimed at assessing heavy metal bioaccumulation in spinach, jute mallow, and tomato

in farms within Kaduna State revealed that the concentrations of heavy metals in agricultural

soil samples were generally higher than the World Health Organization/Food and Agriculture

Organization of the United Nations (WHO/FAO) maximum permissive limits for lead and

cadmium, but lower for nickel (Ni) and chromium (Cr) (John and Kakulu, 2012). The mean

concentrations of heavy metals in vegetables were found to be above the permitted limits for

all the heavy metals, except nickel. This calls for urgent attention, especially for lead and

cadmium, which are highly toxic and have no known biological use (Singh et al., 2011). In

another investigation of the variation of metal contents of irrigated vegetable farms in Kano

metropolis, it was found that the relative abundance of heavy metals in the farm produce

18
followed the sequence Fe > Zn > Mn > Cu > Ni > Pb > Co > Cr (Audu and Lawal, 2005). The

relative abundance of heavy metals affects the toxicity of metals to plants and the uptake of

these metals by plant roots. Therefore, good quality control for food crops is important to

protect consumers from exposure and toxicity (Audu and Lawal, 2005).

Central Nigeria

In the Itakpe iron ore mining site of Kogi State, heavy metal concentrations in crops were

reportedly higher than those grown on control soil even though the observed concentrations of

heavy metals were below the WHO/FAO limit for food (Omono and Kakulu, 2012). The

presence of zinc and copper in plants and the higher level of metals observed in the mining

site indicate that agrochemicals and mining contribute to high levels of heavy metals in the

environment. Vegetables constitute the lowest source of essential trace elements for people in

developing countries like Nigeria. A study of copper and zinc contents in vegetable samples in

this region showed that copper concentrations were 5 mg/kg in peppers, 4 mg/kg in onions,

and 5.5 mg/ kg in tomatoes, while zinc levels were 13.5 mg/kg in peppers, 16.75 mg/kg in

onions, and 15.5 mg/kg in tomatoes (Iyaka, 2007). These findings indicate that vegetables

from this region could serve as good dietary sources for essential trace metals, and the levels

were within the safety margin for human consumption (Mapanda et al., 2004).

Western Nigeria

Amaranthus grown along major highways in Lagos State showed a decrease in heavy metal

concentrations with an increase in distance from the road. Concentrations in Amaranthus

cultivated on soils characterized by heavy traffic were higher than those cultivated on

reference soil (Atayese et al., 2008) suggesting that Amaranthus can concentrate heavy metals

19
in their tissues and that aerial deposition may be a major source of contamination. It is also

true that a strong relationship exists between heavy metals in the soil and contamination of

farm produce; therefore, the consumption of leafy vegetables and crops produced on

contaminated soils can pose a health risk (Nduka et al., 2008). In another study aimed at

assessing the levels of zinc, manganese, cobalt, selenium, copper, molybdenum, chromium,

iron, aluminium, lead, and cadmium in different plant parts and the index of bioaccumulation

(ratio in plant/soil) in Ekiti State, zinc and iron were mostly concentrated in the plant organs,

while manganese was found in very few plants (Adeyeye, 2005). The indices of

bioaccumulation for zinc and iron ranged from medium to intensive in iron but only intensive

for zinc (Adeyeye, 2005). Similarly, the heavy metal concentrations in plant leaves and crops

showed high levels of cobalt (0.33mg/kg) and iron (0.32mg/kg) in Roselle leaves, copper

(0.71mg/kg) and arsenic (0.37mg/kg) in groundnut, copper (0.48mg/kg) and arsenic

(0.28mg/kg) in maize grains, arsenic (0.36mg/kg) and cobalt (0.32mg/ kg) in spinach leaves,

and copper (0.36mg/kg) and cobalt (0.32mg/kg) in Okro (Opaluwa et al., 2012). The samples

from dumpsites had higher levels of contamination, suggesting a possible mobility of metals

from dumpsites to farmlands through leaching and runoffs. Iron levels reduced by 8.25% in

onions and nickel by 45.19% in okro in rainy season samples over those of the dry season, and

the mean levels of metals in the okro samples for the dry season were in the order Fe > Cu >

Zn > Mn > Ni > Pb > Co > Cr, while those of the rainy season indicated Fe > Cu > Zn > Mn >

Ni > Co > Pb > Cr (Zhou et al., 2016). This trend suggests that okro has a higher retention

capacity for essential metals, zinc, manganese, and copper, than for the toxic ones, nickel,

lead, cobalt, and chromium (Adeyeye 2005). It was observed that the general transfer factors

(potentiality of heavy metals to be absorbed by plants) for vegetables are in the order of Cd >

Zn > Hg > Pb. These might be due to a higher mobility of cadmium occurring naturally in soil

20
(Alam et al., 2003) and the low retention of cadmium in the soil than other toxic cations. The

associated health risk assessment of heavy metals to consumers shows that lead, zinc, and

mercury in the vegetables studied were above the FAO/WHO permissible limits (Olayiwola et

al., 2017). The health risk values of estimated daily intake of metal (DIM) (the presumed daily

exposure to or consumption of a heavy metal) and health risk index (HRI) (the capacity of a

toxicant to pose a danger on exposure if it is greater than one for any metal in food crops is an

indication that the consumer population faces a health risk) indicate that lead, cadmium, and

mercury contamination in the vegetables carried higher health risk indexes (Balkhair and

Ashraf, 2016)

Eastern Nigeria

During a population health risk assessment on the consumption of heavy-metal-contaminated

food crops and fruits in Owerri, Imo State, it was reported that the concentration of lead,

cadmium, and nickel exceeded the maximum allowable concentrations for agricultural soil as

recommended by the European Union (Orisakwe et al., 2012). Levels of lead, cadmium, and

nickel in food crops were highest in Oryza sativa, Glycine max, and Pentabacta microfila

respectively. The highest levels of lead, cadmium, and nickel in fruits were detected in

Canarium schweinfurthii, Citrus reticulata, and Ananas comosus, respectively (Orisakwe et

al.,

2012). It is therefore important to note that local foodstuffs commonly consumed in eastern

Nigeria may contribute to the burden of heavy metal, and this is of public health importance.

This is alluded to by the fact that heavy metals were found in rice samples in Enugu State at

levels above the WHO maximum permissible limit. Hazard quotients and total hazard index

for lead and cadmium in these studies were greater than 1 (Ihedioha et al., 2016). Lead levels

21
in spices such as Prosopis africana, Xylopia aethiopica, Piper gineense, Monodora myristica,

and Capsicum frutescens in Awka, Ebonyi State, were 8 to 30 times higher than the

WHO/FAO permissible limit. This implies that spices consumed in this region may add to the

burden of lead (Asomugha et al., 2014).

The Niger Delta Region

The Niger Delta, comprised of nine states greatly endowed with abundant natural resources,

gives rise to increased industrial activities (Orisakwe et al., 2012). Environmental degradation

of the oil-rich region has caused wanton destruction and continuous harm to the physical,

social, and economic health of its people. Petroleum refineries produce a wide variety of air

and water pollutants and hazardous solid wastes (Worghu, 2000). Studies on the concentration

of trace metals in crops harvested in some oil exploration sites in Rivers State revealed that

the mean concentration of lead was 1.1mg/kg in cocoyam and 9.1mg/kg in okro (Hart et al.,

2005). This result reflects a higher concentration of heavy metals in crops from the

industrialized locations, with green vegetables having the highest uptake than other crops.

These findings call for concern, particularly as heavy metals bioaccumulate and pose a serious

health risk to man and animals. The concentration of zinc, cadmium, lead, iron, copper,

chromium, cobalt, and manganese were relatively higher than those from non oil-producing

areas, of which the concentration of lead was significantly higher in cassava and plantain from

these areas than in non-oil exploration areas (Alum et al., 2014). Heavy metal concentrations

in food crops grown around Etelebou oil flow station in Bayelsa State had higher

concentrations of iron, zinc, chromium, copper, and lead than the control values gradually

accumulating over time. Of particular interest was the accumulation of lead in cassava and

plantain. These findings are indicative of potential health hazards faced by the indigenous

22
population who feed on these crops. Therefore, there is a need to closely monitor the great

danger posed by the bioaccumulation of these heavy metals on the health of the population in

this region (Nkwocha et al., 2011).

2.3 SOIL–PLANT METAL TRANSFER AND HEALTH RISK ASSESSMENT

INDICES

Indices of soil–plant metal transfer and health risks have been proposed to describe the

translocation of heavy metals in soil and plant systems (plant uptake factors) and to assess the

extent of risk from the dietary intake of vegetables and other food crops (Yang et al., 2018).

This section discusses the different indices used to determine the ecotoxicological effects and

health risks from the intake of contaminated food crops.

2.3.1 Soil–plant transfer indices

(a) Bio-concentration factor

Although the enrichment factor (EF) was initially proposed to quantify the soil–plant transfer

of heavy metals, other terms, such as BCF and the plant uptake factor, are also widely used in

environmental biogeochemistry (Khan et al., 2010; Brioschi et al., 2013; Chang et al., 2014;

Yang et al., 2018). The BCF is an important parameter for the soil–plant transfer of hazardous

contaminants such as heavy metals. Several studies have demonstrated that the highest BCF

values are found in leafy vegetables, followed by tuberous ones, whereas the lowest values are

found in horticulture crops and fruits (Yang et al., 2018). Transfer factor (TF)/metal transfer

factor (MTF) are similar terms used in place of BCF in documented literatures (Rashed, 2010;

Khan et al., 2013). In some case studies using the TF, food crops and medicinal plants were

found to affected by heavy metals in the atmosphere, which has serious human health

23
implications (Jarup, 2003; Cui et al., 2004; Chary et al., 2008; Cao et al., 2010; Street, 2012;

Amaya et al., 2013; Sahoo and Kim, 2013; Gall et al., 2015; Kohzadi et al., 2018).

BCF = Concentration in crop/vegetable

Concentration in soil

(b) Pollution load index (PLI)

The PLI can be used to assess the extent of heavy metal pollution (Rasheed, 2010). PLI = (CF

x CF x CF3 x - - - - - CFn)1/n where C is the concentration of a metal in soil divided by its

background or baseline value (concentration in unpolluted soil/control/reference) to obtain

CF.

The PLI is scored using a scale from 1 to 6: 0 = none, 1 = none to medium, 2 = moderate,

3 = moderate to strong, 4 = strongly polluted, 5 = strong to very strong, and 6 = very strong

(Rasheed, 2010).

(c) Diverse health risk assessment indices

The transfer of contaminants from food crops to humans has also been widely studied in terms

of health risk (Khan et al., 2008b; Zhuang et al., 2009; Gall et al., 2015; El-Kady and

AbdelWahhab, 2018) using indices such as the HRI, hazard index (HI), hazard quotient (HQ),

DIM, and daily dietary index (DDI).

(d) Potential ecological risk index (RI)

This parameter reflects the sum of the risk factors for all hazardous heavy metals in a soil

sample and the biotic responses (Chabukdhara et al., 2016).

24
 (e) Incremental lifetime cancer risk (ILCR)

The ILCR was proposed by Liu et al. (2013) to assess the carcinogenic potential of metallic

contaminants in the environment.

ILCR = CDI × CSF

where CDI is the chronic daily intake of a chemical carcinogen (mg/kg), and CSF is the

cancer slope factor.

Studies have reported on the assessment of the health risks of metals in food crops.

Zhuang and co-workers (Zhuang et al., 2009), considered this for consumption of vegetables

and rice South China. Mahmood (Mahmood and Malik, 2014) carried out health risk on

vegetables using DIM and THQ. In Romania Banat County, THQ exceeded the safe levels for

parsley, lettuce, and cabbage. This was done for male and female adults, and the result showed

that THQ for a female was higher than that for men (Harmanescu et al., 2011). Contrary to the

aforementioned studies THQ was used to study health risk in vegetables and fruits in

Bangladesh where the result showed that no health risks (Harmanescu et al., 2011). Odukoya

et al., (2017) used ILCR on his study in south-west Nigeria

25
 CHAPTER THREE

METHODOLOGY

3.1. RESEARCH DESIGN

The study will focus on analyzing vegetable and fruit samples for heavy metals from selected

farmlands in Iseyin, using the result to calculate the DIM, THQ and ILCR indices and hence

assess the potential health risk.

3.2. SAMPLING SITE

Iseyin is a town located in the Nigerian state of Oyo. It is approximately 100 km (62 mi) north

of Ibadan. The city was estimated to have a population of 236,000, per a United Nations 2005

estimate, which increased to 302,990 in 2011 (NPC, 2011), and has a total land mass of 1,419

km2 (548 sq mi) (Adewuyi et al., 2018). Iseyin is centrally located and accessible via road

networks from Ibadan, Oyo, Abeokuta, and Ogbomoso. There are expanses of land which can

be used for industrial, agricultural and institutional purposes in and around the city. Iseyin is

part of the Oke-Ogun referred to as the “food basket’’ of Nigeria.

Because of sustainable annual rainfall in the area, the major agricultural activities are farming,

hunting, fishing, and food processing, among others. Iseyin produces virtually all farm

produces such as yam, maize, cassava, plantain among many others.

3.3 SAMPLES

Non-leafy vegetables: tomatoes, cucumber, lettuce and Leafy vegetables: dandelion greens,

amaranths, Jute and spinach.

26
3.4 SAMPLE COLLECTION AND PRETREATMENT

Five grams of samples will be randomly collected from six farmlands in Iseyin by randomized

design. 5 g of samples will also obtained from a farm land about 400 km from the major town,

with no surrounding industrial activities and irrigation done using clean tap water. The

vegetable samples will be washed with tap water to remove the soil particles adhered to the

surface of the vegetables then rinsed with distilled water. The water on the surface of the

leaves will be removed with blotting papers, samples will be cut into pieces and dried in an

oven at 100˚C until a constant weight will be achieved after which their midribs were

removed. The dried samples will be ground, sieved through 2 mm pore size sieve, and then

stored at room temperature. Arrowroots will be pilled, crushed, and dried in the oven at 100˚C

before being pulverized and stored in polythene zip-bags.

3.5 SAMPLE PREPARATION AND ACID DIGESTION

3.5.1 Acid Digestion of Samples

The procedure according to (Gerondi and Arruda, 2012) will be employed. Exactly 1.0 g of

each sample will be weighed and placed in 500mL Kjeldahl digestion flask followed by 10

mL of 68% concentrated nitric (V) acid. The mixture will be heated gently in the digestion

block until brown fumes disappeared, it will then be allowed to cool for 15 minutes. To the

mixture, 5mL of 70% perchloric acid will be added and heated until the solution turned clear

and white fumes seen. The resulting mixture will be left to cool and then filtered using

Whatman No. 42 filter paper. Then 5mL of the filtrate will be put into 50mL volumetric flask

and topped to the mark with distilled water. The final solution will be transferred into the acid

cleaned plastic bottle, sealed, and stored in a deep freezer. Three replicate digestions will then

be performed.
27
3.6 ATOMIC ABSORPTION SPECTROSCOPY (AAS) ANALYSIS

3.6.1 Chemicals and Reagents

The chemicals and reagents will be of analytical grade (99.99% purity) manufactured by

Sigma Aldrich Company. These were ; manganese metal wire, magnesium metal strip,

chromium metal strip, iron metal fillings, zinc metal granules, copper strips, aluminium wire,

lead metal, 70% perchloric acid, 68% concentrated nitric (V) acid, 6% nitric (V) acid and 10%

nitric (V) acid.

3.6.2 Preparation of Standard Solutions

Standard solutions of elements (1000 mg/L) will be prepared using metals (manganese metal

wire, magnesium metal strip, chromium metal strip, iron metal fillings, zinc metal granules,

copper strips, aluminium wire, lead metal) of analytical grade (99.9% pure) and concentrated

acids (Crouch et al., 2014).

3.6.3 Instrumentation

The operating parameters for the AAS (Shimadzu AA-6300) equipment will be set according

to the manufacturer’s specifications. The Air-C2H2 flame will be used to analyze all the

metals.

The detection limit will be set at ≤0.01000 ppm, repeatability ≤ 2.00%, and stability ≤ 6.0%

(Crouch et al., 2014).

3.6. STATISTICAL ANALYSIS

Data will be analyzed using SPSS software version 26 for parameters as mean, standard

deviation, one-way ANOVA (at 95% confidence level).

28
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