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PUMS 99:1 UNIVERSITI MALAYSIA SARAH
BORANG PENGESAHAN STATUS TESIS
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I tnengaku membenarkan tesis (LPSI Smjanal Doktor Falsafah) ini di simpan di Perpustakaan Universiti Malaysia Sabah dengan syarat-syarat kegunaan seperti berikut:
1. Tesis adalah hakmilik Universiti Malaysia Sabah. 2. Perpustakaan Universiti Malaysia Sabah dibenarkan membuat salinan untuk tujuan pengajian sahaja. 3. Perpustakaan dibenarkan membuat salin an tesis ini sebagai bahan pertukaran antara institusi pengajian tinggi. 4. ** Sila tandakan ( / )
SULIT
TERHAD
7 I TIDAK TERHAD
~ (TANIrATANGAN PENULIS)
(Mengandungi maklumat yang berdarjah keselamatan atau kepentingan Malaysia seperti yang termaktub di dalam AKTA RAHSIA RASMI 1972)
(Mengandungi maklumat TERHAD yang telah ditentukakan oleh organisasifbadan di mana penyelidikan dijalankan)
DishhWllMelMJ CHEAL B AN
RY VUiI'9" ... A YSIA SABAH
A..lamat Tetap: g ~I./- I L-ot2.otJ~ ICfAf4fV ':)/:18/
____ 1 /tfVI J1 tV Ie r:. 11/ t:l, Rj
____ Ie E b M-I
6'700 D leu LI fIh /
rtCUikh: __ J-_' -.-:./_6_f"--,I_2-_o '_6 ___ _
A..1" AT AN: * Potong yang tidak berkenaan.
Nama Penyelia
Tarikh: --------------------------
* Jika tesis ini SULIT atau TERHAD, sila lampiran surat daripada pihak berkuasalorgansasi berkenaan dengan menyatakan sekali sebab dan tempoh tesis ini perlu dikelaskan sebagai SULIT danTERHAD.
* Tesis dimaksudkan sebagai tesis bagi Ijazah Doktor Falsafah dan Sarjana secara penyelidikan, atau disertasi bagi pengajian secara kerja kursus dan penyelidikan, atau Laporan Projek Sarjana Muda (LPSM).
DETERMINATION OF HEAVY METALS CONCENTRATION IN SQUIDS IN
KOTA KINABALU
GANESAN MENON AIL NEELAMEGAM
DISSERTATION SUBMITIED AS PARTIAL FULFILLMENT FOR THE DEGREE OF BACHELOR OF
FOOD SCIENCE WITH HONOURS
SCHOOL OF FOOD SCIENCE & NUTRITION UNIVERSm MALAYSIA SABAH
2010
DECLARATION
I hereby declare that the material in this dissertatton Is my own except for quotations, excerpts, equattons, summaries and references, which have been duly acknowledged.
20 May 2010 GANESAN MENON AIL NEELAMEGAM HN2006-4101
II
VERIFICATION
NAME GANESAN MENON AIL NEELAMEGAM
TmE DETERMINATION OF HEAVY METALS IN SQUIDS IN KOTA KINABAW
DEGREE: BACHELOR OF FOOD SCIENCE WITH HONOURS
DR. MOHO IQBAL HASHIM I SUPERVISOR
ASSOC. PROF DR. SHARIFUDIN MD. SHAARANI EXAMINER
DR. LEE JAU SHYA EXAMINER
ASSOC. PROF DR. MOHO ISMAIL ABDULLAH DEAN
MAY 2010
III
ACKNOWLEDGEMENT
This dissertation would not have been successfully written if not by the help and
support from everyone that involved directly as well as Indirectly of which is very
much appreciated and valued.
Arst of all, I would like to thank God for his blessings and for being with me all
the time especially in handling the difficult tasks which made me to complete my final
year project successfully with full of confidence.
My foremost thanks and wishes go to my supervisor, Or. Muhammad Iqbal
Hashimi. His Initial encouragement and support in this study and his continued kind
aSSistance, guidance and valuable supervision saw to the successful completion of my
dissertation. My sincere thanks to School of Food Sdence and Nutrition, Unlverlsitl
Malaysia Sabah which provided a very good learning opportunity for me during my
flnal year project.
I would like to forward my greatest appreciation to my beloved parents and all
other family members who have given me encouragement, moral support and
flnandal support all this while.
last but not least, I also would like to express my sincere thanks to all my
course mates and friends for their constant support, encouragement and helped In
accomplishing my dissertation. Thank you.
N
ABSTRACT
DETERMINAnON OF HEAVY METALS CONCENTRAnON IN SQUIDS IN KOTA KlNABALU
The species of Loligo chinensis and Lol/go duvaucel/i from Kota K1nabalu were
sampled and analyzed for seven different heavy metals include Cd, Pb, Cu, Zn, Fe, Ni
and Mn by using two different methods; wet digestion method and dry ashing
method. The differences in heavy metals concentration among different squid species
were found not significant. The concentration of heavy metals in both squid species
may reflect their similar morphology and environmental factors. In this study, both
Loligo chinensis and LOl/go duvaucelli detected to accumulate similar amount of metal
In both methods although there is difference between the metal concentration values
obtained which is not significant except for lead in wet digestion method. Comparing
metal concentrations in squids among both methods used indicates that dry ashing
method is not suitable for detennination of metals with lower melting point The high
concentration of zinc in both species and both methods reflects that zinc is needed by
the squids as a nutrient and plays important roles In the growth of squids. Comparison
with the Malaysian Food Act 1983 and Food Regulation 1985 shows that cadmium and
lead surpass the maximum limit permitted in seafood; whereas for copper and zinc,
the amount is still not exceeding the current legislative limit for squid.
v
ABSTRAK
PENENTUAN KEPEKATAN LOGAN-LOGAN BERAT DAUN $OTONG Dr KOTA KINABALU
Spesls Loligo chlnensis dan LoIlgo dwaucelll darl Kota Klnabalu d/jadlkan sebagal
sampe/ dan dlkajl untuk tujuh jenls /ogam berat yang berbeza tennasuk at Q/, Pb,
Zn, Fe, NI dan Mn dengan menggunakan dua kaedah berbeza; penghadaman basah
dan pengabuan kerlng. Perbezaan kepekatan /ogam berat dl antara spes/s sotong
berbeza dldapatl bahawa bukan perbezaan bermakna. Kepekatan /ogam berat dl
da/am kedua-dua spesis sotong menggambarkan morfoiogl dan faktor persekltaran
yang seropa. Da/am kajlan In!, kedua-dua sampe/ Loligo chlnens/s dan Lollgo
dwaucel/l dlkesan mengumpu/kan kuantltllogam berat yang seropa da/am kedua-dua
kaedah yang dlgunakan walaupun terdapat perbezaan dlantara nllal kepekatan logam
yang dlperolehl yang bukan merupakan perbezaan bennakna kecua/l untuk logam
plumbum dalam kaedah penghadaman basah. Perbandlngan antara kepekatan logam
da/am safDng me/a/ul kedua-dua kaedah yang dlgunakan menggambarkan bahawa
pengabuan kering adalah tldak sesual untuk menentukan logam yang mempunyal
takat lebur yang rendah. Kuantltl /ogam zink yang tlnggi dalam kedua-dua spes/s
satang dan da/am kedua-dua kaedah menggambarkan bahawa zink dlper/ukan oIeh
satang sebagal nutrlen dan berperanan pentlng dalam pertumbuhan satong.
Perbandlngan yang dllakukan dengan Aida Makanan Malaysia 1983 dan Peraturan
Peraturan Makanan 1985 menunjukkan bahawa /ogam plumbum dan kMlmlum telah
meleblhl had makslmum yang dlbenarkan untuk makanan laut; manaka/a bagllogam
zlnk dan kuprom, kuantitlnya maslh di bawah had semasa yang dibenarkan untuk
satang.
VI
TABLES OF CONTENT
Page
TITLE I
DECLARATION II
VERIFICATION III
ACKNOWLEDGEMENT IV
ABSTRACT V
ABSTRAK VI
TABLES OF CONTENTS
UST OF TABLES XI
UST OF FIGURES XII
UST OF PHOTOGRAPHS XIV
UST OF SYMBOLS XV
UST OF APPENDIX XVI
CHAPTER 1: INTRODUCTION 1
1.1 Research Background 1
1.2 Objectives 5
1.3 Scope of Study 6
1.4 Previous studies 7
CHAPTER 2: UTERATURE REVIEW 9
2.1 Heavy metal cycle in the environment 10
2.2 Heavy metal pollution in aquatic ecosystem 10
2.3 Toxicity of heavy metals in the solution 12
2.4 Heavy metals in food 16
VII
2.5 Heavy metal as an essential minerai
2.6 Essential type of heavy metal
2.6.1 Copper
2.6.2 Zinc
2.6.3 Nickel
2.6.4 Iron
2.6.5 Manganese
2.7 Non-essential type of heavy metals
2.7.1 Lead
2.7.2 cadmium
2.8 Sample digestion for heavy metal detennination
2.8.1 Dry ashing
2.8.2 Wet Digestion
2.9 Squid
2.9.1 Squids In Sabah
2.10 FAAS Instrument
CHAPTER 3: METHODOLOGY
3.1 Sample Collection
3.2 Reagents
3.3 Apparatus
3.4 Material Preparation
3.5 Sample Preparation
3.5.1 Dry ashlng method
3.5.2 Wet digestion method
3.6 Preparation of Standard Solution
VIII
17
21
22
23
24
26
27
29
29
30
31
31
32
33
35
38
39
39
40
41
42
42
43
44
3.6.1 Standard solution for Manganese 45
3.6.2 Standard solution for Cadmium 45
3.6.3 Standard solution for Copper 46
3.6.4 Standard solution for Nickel 46
3.6.5 Standard solution for Lead 46
3.6.6 Standard solution for Zinc 47
3.6.7 Standard solution for Iron 47
3.7 Calibration and analysis using FMS 47
3.8 Water content 49
3.9 Statistical analysis 50
CHAPTER 4: RESULTS AND DISCUSSION 51
4.1 Water content 51
4.2 Calibration 51
4.3 Concentration of heavy metals 52
4.3.1 Comparison between squid species 53
4.3.2 Dry ashing method 54
4.3.3 Wet digestion method 56
4.4 Comparison between methods 60
4.4.1 Loligo chinensis 61
4.4.2 Loligo duvaucelli 63
4.5 Comparison of heavy metals concentration in squid 68 Samples with Malaysian Regulation
CHAPTERS: CONCLUSION 72
5.1 Recommendations 73
IX
REFERENCES
APPENDIX
x
74
82
UST OF TABLES
Page
Table 2.1 Oassification of metals 16
Table 2.2 The limit of heavy metal concentration In Food Act 20
Table 2.3 The limit of heavy metal concentration by USFDA 21
Table 3.1 The chemicals used with manufacturer and usage 40
Table 3.2 The apparatus used with brand and manufacturer 41
Table 3.3 Parameters for seven heavy metals before analysis 48
Table 4.1 Water content of LoIigo chinens/s and Loll9O duvaucelll 51
Table 4.2 Correlation coefficient of calibration graph for seven metals 52 analyzed
Table 4.3 Concentration of heavy metals In LoIi9O chinensis and Loi/go 53
duvaucelll by dry ashlng and wet digestion method
Table 4.4 Concentration order of heavy metals in each squid 68
samples by wet digestion method
Table 4.5 Concentration order of heavy metals In each squid samples by 68
dry ashlng method
Table 4.6 Maximum value that Is permissible by Malaysian Food Act 1983 69
and Food Regulation 1985
XI
UST OF FIGURES
Figure 2.1 Hydrology cyde of heavy metals in environment
Figure 2.2 Schematic presentations of metal reservoirs and their interaction in aquatic and terrestrial systems
Figure 2.3 Factors influendng toxicity of metals in solution
Figure 2.4 Morphology of squid
XII
Page
10
13
15
34
UST OF PHOTOGRAPHS
Photograph 2.1 Appearance of Lot/go chlnensis
Photograph 2.2 Appearance of Lo/igo duvaucelll
Photograph 3.1 Brownish smoke release from Erlenmeyer Rask
Photograph 3.2 Samples after dry ashing and wet digestion
XIV
Page
36
37
43
44
UST OF SYMBOLS
FAAS Flame Atomic Absorption Spectroscopy
Pb Lead
Cd cadmium
Cu Copper
Zn Zinc
Fe Iron
Ni Nickel
Mn Manganese
Kg Kilogram
9 Gram
J,lg/kg Microgram per kilogram
mg/kg Milligram per kilogram
J,lgg-l Microgram per gram
J,lg/mL Microgram per millimeter
nm Nanometer
% Percent
PPM Parts per million
FAO Food and Agricultural Organization
AOAC Association of Official Analytical Chemistry
H2SO4 Sulfuric Acid
HN03 Nitric Add
HO Hidrochloric add
XV
UST OF APPENDIX
Page
Appendix A Periodic Table 82
Appendix B calibration graph of copper 83
Appendix C calibration graph of zinc 84
Appendix 0 calibration graph of cadmium 85
Appendix E calibration graph of lead 86
Appendix F calibration graph of iron 87
Appendix G calibration graph of nickel 88
Appendix H calibration graph of manganese 89
Appendix I One way ANOVA 90
Appendix J Multiple Comparisons for cadmium 91
Appendix K Multiple COmparisons for lead 92
Appendix L Multiple Comparisons for copper 93
Appendix M Multiple Comparisons for zinc 94
Appendix N Multiple Comparisons for iron 95
Appendix 0 Multiple COmparisons for nickel 96
Appendix P Multiple Comparisons for manganese 97
AppendlxQ Standard solution for Nickel prepared before analysis 98
XVI
CHAPTER 1
INTRODUCTION
1.1 Research Background
Squids are the large and diverse group of marine cephalopods from the order
Teuthida. Squids live in all seas and they frequently swim In large groups called
shoals. Squids have soft body which are in elongated tubular shape, short compact
heads and two flns at the tail end. They also have chromatophores embedded In their
skin and the ability to expel Ink and rapidly change the colours and patterns of their
bodies, often to blend with their surroundings If threatened. Most of the squids range
in size from less than 30 centimetres to nearly 4S centimetres In length, including the
arms (Oarke, 1966).
There are 30 families and approximately 460 species of squid collectively
include cuttlefish known to exist in oceans around the world (Sugiyama et al., 1989).
In Malaysia common squids are known with local name as 'Sotong biasa', 'Sotong
cumlt' or 'Cumlt-cumit' and its scientific name Is Loligo spp (ISSCAAP, 2004). Squids
are consumed as one of the main seafood CUisine among all categories of people
around the wood. Calamari is a famous Mediterranean cuisine in which squids are
butter-coated and deep fried. In Malaysian CUisine, squid Is used In stir-fries, rice, and
noodle dishes. In some parts of South East Asian countries, the squids are dried and
shredded and eaten as seasoned snacks.
Nowadays, health-conscious about heavy metals content in seafoods has
increased significantly. Trace elements and metals are continuously released In the
aquatic environment via natural and anthropogenic Influx. The determination of these
analytes in squid has interest because of the importance of many of these elements to
human health. This interest arises from two areas of concem, nutritional and
toxicological. Nutritional because trace metals such as ca, Fe, Mg, Zn, Cu, Co and AI
are necessary for maintenance of optimum health and toxicological since certain
metals such as Pb, Cd, As and Hg are detrimental to optimum health. Furthermore, it
is an important aspect of environmental analysis because seafood is used as
bloindicator organisms to assess bioavailability contaminant concentrations in coastal
waters. Molluscs have long been known to naturally accumulate metals to high
concentrations. Although metals in gastropod and bivalve molluscs have been the
subject of considerable research, metal metabolism in cephalopod molluscs have been
relatively poorly investigated. In addition, cephalopods are quantitatively important in
many food webs. Cephalopods have been reported to accumulate metals including Cu,
Zn and Cd to concentrations far exceeding that of surrounding seawater (Stephen and
Julian, 2002).
The term 'heavy metals' can be refer as a group of metallic elements with
atomic weights greater than 40 and are characterized by similar electronic distribution
in their extemal shell. These include alkali earth metals (e.g., caldum, magnesium),
alkali metals (e.g., sodium, potaSSium), lanthanides and actinides (e.g., uranium). It Is
also known as trace metal. In aquatic system, the heavy metals of greatest concem
are copper, zinc, cadmium, mercury and lead. These elements are toxic to organisms
above speciflc threshold concentration but many of them (e.g., copper and zinc) are
essential for metabolism at lower concentrations. Toxic heavy are usually present at
2
low concentration in aquatic ecosystem, but deposits of anthropogenic origin have
raised the heavy metal concentration, creating environmental problems in coastal
zones, lakes and rivers (Iyenger et a/., 1998).
In Malaysia, rapid Industrial development Is undergoing and there have been
inddences of toxic pollution from industry. Metal contamination In the aquatic
environment arises from industrial processes (e.g., mining, smelting, finishing and
plating of metals, paint and dye manufacture) and from pipes and tanks in domestic
systems, discharging a variety of toxic metals such as cadmium, copper, zinc and lead
into the environment (Moore and Ramamoorthy, 1984). In the aquatic environment,
the concentration, transport, transformation, and disposition of a chemical or material
are primarily controlled by the following:
• The physical and chemical properties of the compound
• The physical, chemical and biological properties of the eoosystem
• The sources and rates of input of the chemical into the environment.
Pollution by heavy metals in coastal environment has become a global phenomenon
because of its tOxidty, persistence for several decades in the aquatic environment,
bloaccumulatlon and biomagniflcatlons In the food chain (Valls and Lorenzo, 2002).
Nowadays, squids are an important seafood resource for human consumption.
Food pollution are caused by heavy metal pollution which they can exist naturally and
also through anthropogenic. The contamination of heavy metals In squids will cause
an effect on human body and will cause disease and death. Marine organisms
accumulate most trace elements to concentration of many times higher than those
3
present In seawater. The toxldty of the heavy metal can be seen In some issues. The
best known example of deaths attributable to contaminants Ingested in seafood is the
so-called Mlnamata disease caused by mercury released from the Chlsso Corporation
plant, which was first reported in Japan In 1956 (Pradyumna, 2005). Other trace
metals also have been the cause of environmental poisoning outbreaks. An unusual
disease, known as "Itai-ital" disease broke out In the Jlntsu River basin In Japan (louiS
et aI., 1996). The symptoms of the disease Indude yellow discoloration of the teeth,
loss of the sense of smell, a reduction In red blood cell numbers, lumbar and leg pains
and skeletal bones. It is now believe that the primary cause of the ltal-ltai syndrome
was the discharge of cadmium-rich effluents from zinc mine to the river and watering
system.
4
1.2 Objectives
The main objectives of this research are : -
1) To determine and compare the level of heavy metal concentration; lead (Pb),
nickel (Ni), cadmium (Cd), copper (Cu), Iron (Fe), Manganese (Mn) and zinc
(Zn) In Loligo chlnensis and Lotigo duvaucelli and compare two sample
preparation methods; dry-ashing method and wet digestion method.
2) To compare the level of lead, nickel, cadmium, copper, iron, manganese and
zinc in squids sample with Malaysian Food Act 1983 and Food Regulation 1985.
5
1.3 Smpe of study
Major scope of this study is to determine the amount of heavy metals; lead (Pb),
nickel (Ni), cadmium (Cd), copper (Cu), chromium (Cr),and zinc (Zn) in two type squid
sample that has been collected which are Lol/go chinensis and Lol/go duvaucel/ from
Kota Kinabalu, Sabah. This study also carried out to determine whether squids caught
in sea areas of Kota Klnabalu are safe for consumption based on maximum level of
metals concentration allowed in Malaysian Food Act 1983 and Food Regulation 1985.
This study use Flame Atomic Absorption Spectrometry (FAAS) to detect the
concentration level in squid sample. Two types of different sample preparation
methods are used in this study, dry ashing method and wet digestion method. These
two sample preparation methods are widely used In the determination process of
heavy metals in food. So this study will determine which sample preparation methods
are more suitable for detection of lead (Pb), nickel (Ni), cadmium (Cd), copper (Cu),
chromium (Cr), and zinc (Zn) in seafood especially squids.
6
1.4 Previous study on detennination of heavy metals In squids
For many years, there are widely studies about the heavy metals in the squids using
many different variables. However, the species and location of squids that had been
researched is limited. The first widely documented Instance of public health Impact
resulting from aquatic contamination by heavy metals occurred at Minamata Bay In
Japan, commencing in 1953 (louis, 1996).
A study conducted on heavy metals In squids in Tanjung Karang, Selangor
shows that Lollgo edu/is contains zinc at highest concentration followed by iron and
copper (Tuldmat, 2006). The order of heavy metal concentration from highest to
lowest Is Zn > Fe > Cu > Ni > Pb > Cd. The study also reveals that heavy metal
content in squids at T Is lower than the permitted maximum limit by Food Regulation
1985.
Another study conducted on heavy metals In seafoods in Kuala Kemaman,
Terengganu shows that Lol/go ch/nensis contains zinc at highest concentration
followed by copper and iron (Tuldmat, 2002). The order of heavy metal concentration
from highest to lowest is Zn > CU > Fe > Cd > Pb > NI. The study also reveals that
heavy metal content In squids at Kuala Kemaman is lower than the permitted
maximum limit by Food Regulation 1985.
There are also wortdwide researchers studied about heavy metal concentration
in squids from various species. Prafulla (2001), studied about concentration of heavy
metals in the sqUid, LoI/go duvaucell and Doryteuthls slbogae caught from the
Southwest Coast of India. The mean values (highest at the three stations) of highly
hazardous metals In the muscle of the two species, were: Hg < 0.05, 0.07; Cd is 0.55,
7
0.89; Pb is 0.99, 0.89; Cr is 0.72, < 0.45 and Ni is 0.45, 0.19 ppm, all within the
international safety limits. However, elevated levels of some of the metals, particular1y
Cd, Zn and Cu were sometimes observed. The study also shows that The metal levels
In the squids varied greatly between the species and In the same species (L
duvaucell) from different regions. The present study shows that the average
concentrations of all metals are significantly lower in of both the squids from all the
regions and are far below the legal limits. They do not seem to cause any health
hazard by consuming the edible parts of squids.
8
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