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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
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
i
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
ii
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.
iii
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
iv
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
v
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
vi
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
vii
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
viii
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
ix
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
x
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
xi
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
xii
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.
1
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.
2
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.
3
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
4
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).
5
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).
6
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.
7
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)
8
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).
9
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
10
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