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Determination of Heavy Metals in Fruits from a Farm and Town Markets Najwa binti Md. Salleh (16788) Bachelor of Science with Honours (Resource Chemistry) 2009 Faculty of Resource Science and Technology

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Page 1: Najwa binti Md. Salleh (16788) - ir.unimas.my of heavy metals in fruits from a farm and... · kepada bahagian seperti isi, kulit dan biji. Kajian logam berat adalah Zn, Cu, Ni, Fe,

Determination of Heavy Metals in Fruits from a Farm and Town Markets

Najwa binti Md. Salleh (16788)

Bachelor of Science with Honours

(Resource Chemistry)

2009

Faculty of Resource Science and Technology

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Determination of Heavy Metals in Fruits from a Farm

and Town Markets

Najwa binti Md. Salleh

This project is submitted in partial fulfillment of the requirements for the Degree of Bachelor of

Science with Honours (Chemistry Department)

Resource Chemistry

Department of Chemistry

Faculty of Resource Science and Technology

Universiti Malaysia Sarawak

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DECLARATION

No portion of the work referred to in this dissertation has been submitted in support of an

application for another degree or qualification at this or other university or institution of higher

learning.

Najwa binti Md. Salleh

16788

Resource Chemistry

Department of Chemistry

Faculty of Resource Science and Technology

University Malaysia Sarawak

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ACKNOWLEDGEMENTS

The final year project had been very tough and challenging task. Firstly, Alhamdulillah, I

have successfully finished the project. Thanks to ALLAH the most gracious and merciful. Very

big thanks to my supervisor, Dr Harwant Singh for his help, support, advice and motivation. My

thanks also go to my supportive friends and course mate who contribute upon completion of my

project.

My appreciation also awarded to Mr. Send and Tuan Haji Karni, our lab assistants, for

their guidance and advice during lab session. Lastly, my gratefulness and affection goes to my

parents who give priceless support and motivation to me during completion of my project. Thank

you so much for the contributions.

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Table of Contents

ACKNOWLEDGEMENT…………………………………………………………. ii

TABLE OF CONTENTS…………………………………………………............... iii

LIST OF APPENDICES…………………………………………………………… vi

LIST OF ABBREVIATIONS.................................................................................... vii

LIST OF TABLES..................................................................................................... viii

LIST OF FIGURES................................................................................................... ix

ABSTRACT............................................................................................................... xii

CHAPTER 1: INTRODUCTION……………………………………………..…... 1

1.1 Background……………………………………………………….…….. 1

1.2 Objectives………………………………………………………….….... 1

1.3 Statement of problem…………………………………………………... 2

CHAPTER 2: LITERATURE REVIEW……………………………………….…. 3

2.1 Fruit……………………………………….……………………..……… 3

2.1.1 Definition of Fruits………………………………………….... 3

2.1.2 Different Type of Fruits…………………………………….... 3

2.2 The Heavy Metals…………………….……………………………….... 9

2.2.1 Pollution by Heavy Metals………………………...…………. 10

2.3 The Soil………………………………………………………..………... 10

2.3.1 Soil pH……………………………………………………..…. 11

2.3.2 Organic Matter……………………………………………....... 12

2.3.3 Cation Exchange Capacity………………………………….... 13

2.4 Heavy metals in fruits…………………………………………………... 14

2.5 Sources of Heavy Metals in Plants……………………………………... 15

2.5 Soil – Plant Relationships and Heavy Metals Uptake…………..……… 15

2.5.1 The soil-plant system…………………………………………. 15

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2.5.2 Plant Uptake of Heavy Metals……………………………...... 16

CHAPTER 3: METHODOLOGY AND MATERIALS………….………………. 18

3.1 Sampling Location…………………………………………….………... 18

3.2 Sample Preparation………………………………………….………….. 19

3.2.1 Tissues Selection……………………………………………… 19

3.3 Preparation of Plant Tissues………………………………….…………. 20

3.3.1 Decontamination……………………………………………… 20

3.3.2 Oven Drying………………………………………………….. 20

3.3.3 Particle Size Particle………………………………………….. 20

3.3.4 Storage………………………………………………………... 20

3.4 Sample Digestion……………………………………………………….. 21

3.5 Analysis of Samples……………………………………………………. 22

3.5.1 Determination of Heavy Metal in Fruits……………………… 22

3.6 Dilution Factor………………………………………………………….. 23

3.7 Statistical Analysis……………………………………………………… 23

CHAPTER 4: RESULTS………………………………………………………….. 24

4.1 Concentration of Heavy Metals in Fruits………………………………. 24

CHAPTER 5: DISCUSSION……………………………………………………… 29

5.1 Heavy Metals in Individual Fruits……………………………………… 29

5.1.1 Fruits from a Farm at Kampung Bunga, Serian, Sarawak……. 29

5.1.2 Fruits from a Town Market, Tarat, Sarawak…………………. 33

5.1.3 Fruits from a Town Market, Serian, Sarawak………………... 35

5.2 Comparison of Similar Part of Various Fruits………………………….. 38

5.2.1 Fruits from a Farm at Kampung Bunga, Serian, Sarawak……. 38

5.2.2 Fruits from a Town Market, Tarat and Serian, Sarawak……… 43

5.3 Comparison of Heavy Metals in Fruits between different Locations….. 47

5.3.1 Banana………………………………………………………... 48

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5.3.2 Pineapple……………………………………………………… 50

5.3.3 Starfruit……………………………………………………….. 53

5.3.4 Papaya………………………………………………………… 56

5.3.5 Lime…………………………………………………………... 61

5.4 Comparison of Heavy Metals in Present Fruits with Food Act (1983)… 63

5.4.1 Fruits from a Farm at Kampung Bunga, Serian, Sarawak……. 63

5.4.2 Fruits from a Town Market, Tarat and Serian, Sarawak……… 66

CHAPTER 6: CONCLUSIONS AND RECOMMENDATION…………………. 68

CHAPTER 7: REFERENCES..…………………………………………………… 69

CHAPTER 8: APPENDICES……………………………………………………... 73

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LIST OF APPENDICES

APPENDIX A: Raw data from AAS (ppm)

APPENDIX B: Results above detection limit

APPENDIX C: Results of heavy metal concentration (mg/kg)

APPENDIX D: Result from Two-Way ANOVA

APPENDIX E: Results from Post-Hoc test

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LIST OF ABBREVIATIONS

AAS - Atomic Absorption Spectroscopy

cm3 - Cubic Centimeter

°C - degree Celsius

FAO - Food and Agriculture Organization

g - gram

HNO3 - Nitric Acid

kg - kilogram

mg - milligram

ml - milliliter

mm - millimeter

WHO - World Health Organization

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List of Tables and Figures

Tables

Table 1: Some common non-seasonal fruits…………...…………………………… 3

Table 2: The chart about the nutrients contain in banana…………………………... 4

Table 3: The chart of nutrients in papaya…………………………………………… 5

Table 4: The chart of nutrients in pineapple…………………………………..……. 7

Table 5: The nutrients in one pound of lime………………………………………... 8

Table 6: The nutrition that contain in “star fruit”…………………………………... 9

Table 7: Parts of the fruits………………………………………………………….. 19

Table 8: Fruits from a Farm at Kampung Bunga, Serian, Sarawak………………… 24

a) Flesh…………………………………………………………………….... 24

b) Skin………………………………………………………………………. 25

c) Seed……………………………………………………………………… 25

Table 9: Fruits from a Town Market, Tarat, Sarawak……………………………… 26

a) Flesh……………………………………………………………………... 26

b) Skin………………………………………………………………………. 26

Table 10: Fruits from a Town Market, Serian, Sarawak……………………………. 27

a) Flesh…………………………………………………………………….... 27

b) Skin………………………………………………………………………. 27

c) Seed……………………………………………………………………… . 28

Table 11: Comparison between the concentration of heavy metals and

Food Acts (1983)…………………………………………………………. 64

Table 12: Comparison between the concentration of heavy metals and

Food Acts (1983)…………………………………………………………. 64

Table 13: Comparison between the concentration of heavy metals and

Food Acts (1983)…………………………………………………………. 65

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Table 14: Comparison between the concentration of heavy metals and

Food Acts (1983)…………………………………………………………. 66

Table 15: Comparison between the concentration of heavy metals and

Food Acts (1983)…………………………………………………………. 66

Table 16: Comparison between the concentration of heavy metals and

Food Acts (1983)…………………………………………………………. 67

Figures

Figure 1: Banana (Musa paradisiacal)……………………………………………… 4

Figure 2: Papaya (Carica papaya)…………………………………………………. 5

Figure 3: Pineapple (Ananas comosus)…………………………………………….. 6

Figure 4: Lime (Persian Lime)…………………………………………………….. 7

Figure 5: Carambola (Averrhoa carambola)………………………………………. 8

Figure 6: The soil-plant system……………………………………………………. 16

Figure 7: Sampling Locations………..……………………………………………... 18

Figure 8: Flow Chart for Wet-Digestion…..……………………………………….. 22

Figure 9: Heavy Metals in Individual Fruits from a Farm at Kampung Bunga,

Serian, Sarawak…...................................................................................... 29

Figure 9a: The concentration of heavy metals in banana……..……………. 29

Figure 9b: The concentration of heavy metals in pineapple……..…………. 30

Figure 9c: The concentration of heavy metals in starfruit………..………… 30

Figure 9d: The concentration of heavy metals in papaya…………..………. 31

Figure 12e: The concentration of heavy metals in lime…………………….. 31

Figure 10: Heavy Metals in Individual Fruits from a Town Market at Tarat,

Sarawak………………………………………………………………… 33

Figure 10a: The concentration of heavy metals in banana…………………. 33

Figure 10b: The concentration of heavy metals in pineapple………………. 34

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Figure 11: Heavy Metals in Individual Fruits from a Town Market at Serian,

Sarawak………………………………………………………..………... 35

Figure 11a: The concentration of heavy metals in starfruit………………… 35

Figure 11b: The concentration of heavy metals in papaya…………………. 36

Figure 11c: The concentration of heavy metals in lime. …………………… 36

Figure 12: Comparison between the Similar Parts of Various Fruits from a Farm at

Farm at Kampung Bunga, Serian, Sarawak……………………………... 37

Figure 12a: The concentration of heavy metals in flesh……………………. 37

Figure 12b: The concentration of heavy metals in skin…………………….. 38

Figure 12c: The concentration of heavy metals in seed. …………………… 39

Figure 13: Comparison between the Similar Parts of Various Fruits from a Town

Market at Tarat and Serian, Sarawak……………………………………. 43

Figure 13a: The concentration of heavy metals in flesh……………………. 43

Figure 13b: The concentration of heavy metals in skin…………………….. 45

Figure 13c: The concentration of heavy metals in seed. …………………… 47

Figure 14: Comparison of Heavy Metals in Similar Fruits between different Sources:

Banana…………………………………………………………………... 48

Figure 14a: The concentration of heavy metals in banana flesh…………… 48

Figure 14b: The concentration of heavy metals in banana skin……………. 49

Figure 15: Comparison of Heavy Metals in Similar Fruits between different Sources:

Pineapple………………………………………………………………… 51

Figure 15a: The concentration of heavy metals in pineapple flesh………… 51

Figure 15b: The concentration of heavy metals in pineapple skin…………. 52

Figure 16: Comparison of Heavy Metals in Similar Fruits between different Sources:

Starfruit………………………………………………………………….. 54

Figure 16a: The concentration of heavy metals in starfruit flesh…………... 54

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Figure 16b: The concentration of heavy metals in starfruit skin…………… 55

Figure 17: Comparison of Heavy Metals in Similar Fruits between different Sources:

Papaya…………………………………………………………………… 57

Figure 17a: The concentration of heavy metals in papaya flesh……………. 57

Figure 17b: The concentration of heavy metals in papaya skin…………….. 59

Figure 17c: The concentration of heavy metals in papaya seed……………. 60

Figure 18: Comparison of Heavy Metals in Similar Fruits between different Sources:

Lime……………………………………………………………………... 61

Figure 18a: The concentration of heavy metals in lime flesh………………. 61

Figure 18b: The concentration of heavy metals in lime skin……………….. 62

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Determination of Heavy Metals in Fruits

Najwa binti Md. Salleh

Resource Chemistry

Faculty of Resource Science and Technology

Universiti Malaysia Sarawak (UNIMAS)

ABSTRACT

The environmental study, carried out in the Serian and Tarat which located in the Kuching area, Sarawak.

The objectives of the study were to determine the type of heavy metals that contain in fruits, banana (Musa

paradisiacal), pineapple (Ananas comosus), starfruit (Averrhoa carambola), papaya (Carica papaya), and lime

(Persian Lime) and to determine the concentration of heavy metals in different types of fruit. The fruits also were

divided into part such as flesh, skin and seed. Heavy metals studied were Zn, Cu, Ni, Fe, Co, Cd, Mg and Pb. The

concentrations of heavy metals were determined using Atomic Absorption Spectroscopy (AAS) (Model Perkin –

Elmer 3110). The results of the study showed that the level of Mg content in all parts were higher concentration

compare to others elements. Cd and Pb were not detected in all parts of fruits. However the concentrations of heavy

metals studied in these fruits were still below the maximum level allowed by the Food Act (1983) except the Zn that

most of the samples were exceed the permissible limit of Food Act (1983).

Keywords: Heavy metal, fruits, AAS.

ABSTRAK

Dalam kajian persekitaran, yang telah dijalankan di sekitar Serian dan Tarat yang terletak di kawasan

Kuching, Sarawak. Objektif bagi kajian ini adalah untuk menentukan jenis kandungan logam berat yang terdapat di

dalam buah-buahan seperti pisang (Musa paradisiacal), nanas (Ananas comosus), belimbing (Averrhoa

carambola), betik (Carica papaya), dan limau nipis (Persian Lime) dan ia turut bertujuan untuk menentukan

kepekatan kandungan logam berat di dalam setiap buah-buahan yang berbeza. Buah-buahan tersebut dibahagikan

kepada bahagian seperti isi, kulit dan biji. Kajian logam berat adalah Zn, Cu, Ni, Fe, Co, Cd, Mg dan Pb.

Kepekatan logam berat di dalam buah-buahan ditentukan dengan menggunakan Atomic Absorption Spectroscopy

(AAS) (Model Perkin – Elmer 3110). Keputusan menunjukkan bahawa kandungan Mg di dalam semua bahagian

buah-buahan adalah tinggi berbanding dengan logam berat yang lain. Cd dan Pb tidak dapat dikesan di dalam

semua sampel. Walaubagaimanapun, kandungan logam berat di dalam buah-buahan masih di bawah tahap

maksimum yang dibenarkan oleh Akta Makanan (1983) kecuali Zn yang kandungan kepekatannya adalah melebihi

had yang dibenarkan di dalam semua sampel.

Kata Kunci: Logam berat, buah-buahan, AAS.

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Chapter 1

Introduction

1.1 Background

The past few decades have generated consciousness of more diverse environmental

pollution issues. One of the issues is the presence of heavy metals in the soil from pesticides,

insecticides and herbicides deposited onto soils and vegetation. The heavy metals that

contaminate the soils are taken up and transported to other parts of plants like fruits. Humans

are exposes to these heavy metals through the food chain because food is essential for

humans. Humans must take food as their daily diet for the nutrition which included fruits.

The rapid growth of fruit processing now makes it possible for humans to consume a

wider variety of fruits. Fruit a good source of vitamin, minerals and antioxidants. Fruits also

consist of the largest part of water that is around 75-95%. Other constituents of fruits include

celluloses, fibers, pectin, and tannins. However, heavy metal contents in fruits and the soil in

which these fruits were grown have been reported (Mazurek et al., 1995). The high

concentration of heavy metals in food can effect human health such as, lead (Pb) causes

chronic damage to the nervous system in humans; mercury causes damage to the brain and the

central nervous system while the copper (Cu) causes anemia, liver and kidney damage.

1.2 Objectives

1. To determine the types of heavy metals present in selected fruits.

2. To determine the concentration of heavy metals in different types of fruit.

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1.3 Statement of Problem

This study was carried out on different types of fruits to evaluate their quality based on

the content of heavy metals. Samples of five fruits, namely, papaya, banana, star fruit,

pineapple and lime were taken from different farmlands and purchased from local markets.

The criteria for the selecting of the local fruits analyzed were that they were not seasonal

fruits.

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Chapter 2

Literature Review

2.1 Fruits

2.1.1 Definition of Fruits

Fruits can be defined in many ways depending on the context. In botany, a fruit is a

reproductive structure of an angiosperm which develops from the ovary and accessory tissue,

which surrounds and protects the seed. The seed-bearing part of a plant, often edible, colorful

and fragrant, is produced from a floral ovary after fertilization.

2.1.2 Different Type of Fruits

Table 1 lists some common fruits that are non seasonal fruits and are described below.

Table 1: Some common non-seasonal fruits

Binomial Name Specific Name Family

Banana Musa paradisiaca Musaceae

Papaya Carica papaya Caricaceae

Pineapple Ananas comosus Bromeliaceae

Lime Persian Lime Citrus

Carambola (Star fruit) Averrhoa carambola Averrhoa

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a) Banana (Musa paradisiacal)

Bananas come prepackaged in their own yellow jackets and are available for harvest

throughout the year (George, 2001) as shown in Figure 1. Bananas are a very good source of

vitamins B6, potassium, dietary fiber, and manganese. Table 2 shows the nutrients present in

bananas.

Figure 1: Banana (Musa paradisiacal)

Table 2: The chart about the nutrients contain in banana (Mateljan, 2001).

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b) Papaya (Carica papaya)

Papayas are spherical or pear-shaped in orange color with either yellow or pink hues

as shown in figure 2. The inner cavity of the papaya is black, round seed encased in

gelatinous-like substance. The papaya is an excellent source of vitamin C and very good

source of folate and potassium. It also contains of dietary fiber, vitamin E, vitamin A and

vitamin K (Ashram, 2000). Table 3 shows the nutrients present in papayas.

Figure 2: Papaya (Carica papaya)

Table 3: The chart of nutrients in papaya (Mateljan, 2001).

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c) Pineapple (Ananas comosus)

Pineapples have a wide cylindrical shape, a scaly green, brown or yellow skin and a

regal crown of spiny, blue-green leaves and fibrous yellow flesh as shown in Figure 3. The

area closer to the base of the fruit has more sugar content and therefore a sweeter taste and

more tender texture. Pineapples have exceptional juiciness and a vibrant tropical flavor that

balances the tastes of sweet and tart (Khassandra, 2007).

Figure 3: Pineapple (Ananas comosus)

Pineapple is an excellent source of vitamin C and manganese. It is also a good source

of carbohydrates, sugar, soluble and insoluble fiber, sodium, vitamins, minerals, fatty acids

and amino acids. Table 4 show the nutrients present in pineapples.

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Figure 4: The chart of nutrients in pineapple (Mateljan, 2001).

d) Lime (Persian Lime)

Limes, as shown in Figure 4, are green in color and heavy for their size are the most

desirable commercially due to their extremely acidity. When it full ripe, yellow lime does not

have a high acid content. Limes are very high in vitamin C, are a good source of vitamin B1,

and are rich in potassium. A drink of lime juice and whey is a perfect cooler for the brain and

nervous system. Limes can be used to treat brain fever, or human retarded (Anonymous,

1998). Table 5 shows the nutrients in one pound of lime.

Figure 4: Lime (Persian Lime)

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Table 5: The nutrients in one pound of lime. (Anonymous, 1998)

Calories 107 Iron 2.3 mg

Protein 2.8 g Vitamin A 50 I.U.

Fat 0.8 g Thiamine 0.10 mg

Carbohydrates 42.4 g Riboflavin 0.08 mg

Calcium 126 mg Niacin 0.7 mg

Phosphorus 69 mg Ascorbic acid 94 mg

e) Carambola (Averrhoa carambola)

The carambola or Malayans may refer to it as belimbing batu, belimbing besi,

belimbing pessegi, belimbing sayur, or as “star fruit” is orange-yellow skin and juicy, crisp

and yellow flesh when fully ripe. It is shown in Figure 5. When we cut in cross-section, we

can see the form of a star. It contains vitamin, water and some energy.

Figure 5: Carambola (Averrhoa carambola)

In the Table 3 below, it show the nutrition facts when take the “star fruit’ per 100

gram of edible portion (Morton, 1987).

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Table 6: The nutrition fact present in “star fruit” (Morton, 1987).

Food Value per 100 g of Edible Portion

Calories 35.7

Moisture 89.0-91.0 g

Protein 0.38 g

Fat 0.08 g

Carbohydrates 9.38 g

Fiber 0.80-0.90 g

Ash 0.26-0.40 g

Calcium 4.4-6.O mg

Phosphorus 15.5-21.0 mg

Iron 0.32-1.65 mg

Carotene 0.003-0.552 mg

Thiamine 0.03-0.038 mg

Riboflavin 0.019-0.03 mg

Niacin 0.294-0.38 mg

Ascorbic Acid 26.0-53.1 mg

2.2 Heavy Metals

According to Alloway (1990) the term ‘heavy metals’, although not easily defined, is

widely recognized and used. It is a member of a group of elements that exhibit metallic

properties, which include the transition metals, some metalloids, lanthanides, and actinides.

Heavy metals or trace metals are those with atomic weights from 63.546 to 200.590 and have

a density greater than five.

According to the U.S. Agency for Toxic Substances and Disease Registry, the heavy

metals were present in toxic waste sites. They are highly toxic and can cause damaging effects

even at very low concentrations. They tend to accumulate in the food chain and in the body

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and can be stored in soft (e.g., kidney) and hard tissues (e.g., bone). Being metals, they often

exist in a positively-charged form and can bind on to negatively-charged organic molecules to

form complexes.

2.2.1 Pollution by Heavy Metals

The definition given by Alloway (1990), state that pollution is the introduction by man

into environment of substances or energy liable to cause hazards to human health, harm to

living resources and ecological system, damage the structures or amenity, or interference with

legitimate uses of the environment. Pollution is applied only to the situation where toxicity

has occurred.

Heavy metals are mobile and can easily be taken up by plants in the environment.

Plants have shown to have great ability to accumulate metals from the environment (Khairiah

et al., 2004). The toxic heavy metals entering the ecosystem may lead to geoaccumulation,

bioaccumulation and biomagnification (Chandrappa and Lokeshwari, 2006). These metals

may reach and contaminate plants, vegetables, fruits and canned foods through air, water, and

soil during cultivation (Husain et al., 1995; Ozores et al., 1997; Geert et al., 1989) also during

industrial processing and packaging (Tsoumbaris et al., 1994).

2.3 The Soil

The soil is a key component of terrestrial ecosystems, both natural and agricultural,

being essential for the growth of plants and the degradation and recycling of dead biomass. It

is a complex heterogeneous medium comprising mineral and organic solids, aqueous and

gaseous components (Alloway, 1990). This heterogeneous mixture of mineral and organic