DETERMINATION OF HEAVY METALS (CADMIUM, CHROMIUM, COPPER, LEAD AND NICKEL) IN SLIMMING TEAS BY USING ATOMIC ABSORPTION SPECTROSCOPY

ERINA ASMAWANI BT ABU BAKAR

BACHELOR OF SCIENCE (Hons.) CHEMISTRY FACULTY OF APPLIED SCIENCES UNIVERSITI TEKNOLOGI MARA NOVEMBER 2008

DETERMINATION OF HEAVY METALS (CADMIUM, CHROMIUM, COPPER, LEAD AND NICKEL) IN SLIMMING TEAS BY USING ATOMIC ABSORPTION SPECTROSCOPY

ERINA ASMAWANI BT ABU BAKAR

Final Year Project Report Submitted in Partial Fulfillment of the Requirements for the Degree of Bachelor of Science (Hons.) Chemistry in the Faculty of Applied Sciences Universiti Teknologi MARA

NOVEMBER 2008

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ACKNOWLEDGEMENTS Upon completion of this project, I would like to express my gratitude to many parties. My heartfelt thanks goes to my supervisor, Prof. Madya Zuraidah Abdullah Munir. Her guide, patience and word of wisdom has made it possible for me to complete this thesis. Her careful reviews, helpful suggestion and thoughtful critism also have been so important for the improvement and completion of this work. I also express my fond thanks to my parents and friends, whose words of encouragement and constant support that kept me going through difficult periods and tight deadlines. Beside that, I would like to thank Encik Adnan Bin Ismail, Encik Khairul, Encik Rosmi and Encik Mohd Kadim Bin Sarmean for their help in assisting me in doing the laboratory work. I would also express my thanks to the efforts of the previous researchers, book authors and the website authors for their endless effort in giving their best definition of understanding analytical chemistry. They have certainly eased the completion of this thesis. To all that are not mentioned here, I am deeply sorry and would do my very best to thank you.

Erina Asmawani Bt Abu Bakar

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TABLE OF CONTENTS Page ACKNOWLEDGEMENTS TABLE OF CONTENTS LIST OF TABLES LIST OF FIGURES LIST OF ABBREVIATIONS ABSTRACT ABSTRAK CHAPTER 1 INTRODUCTION 1.1 Background 1.2 Significance of study 1.3 Objectives of study iii iv vi vii viii x xi

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CHAPTER 2 LITERATURE REVIEW 2.1 Herbal tea 2.2 Previous study 2.3 The beneficial of minerals in tea 2.4 The negative effects of heavy metals in tea 2.5 The sources of heavy metals in tea CHAPTER 3 METHODOLOGY 3.1 Chemicals 3.2 Collection of sample 3.3 Treatment of sample 3.4 Preparation of standard solutions 3.5 Analysis of sample CHAPTER 4 RESULTS AND DISCUSSION CHAPTER 5 CONCLUSION AND RECOMMENDATIONS

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CITED REFERENCES APPENDICES CURRICULUM VITAE

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LIST OF TABLES Table 3.1 4.1 4.2 4.3 4.4 Caption Series of standard solutions that have been prepared for each element The wavelength for maximum absorption of metal Mean concentration (mg/L) of heavy metals in slimming tea samples Mean concentration (mg/kg) of heavy metals of the dry weight of slimming tea samples Fourteenth Schedule (Regulation 38) Maximum Permitted Proportion of Metal Contaminants in Specified Food Malaysia, 1985 Page 16 19 20 20

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LIST OF FIGURES Figure 1.1 2.1 3.1 3.2 3.1 3.2 4.1 4.2 Caption Common herbs in slimming tea preparations. CTC machine processing tea The general process flow of the sample treatment Flame atomic absorption spectroscopy (FAAS) Schematic diagram of FAAS Operation principle of FAAS Comparison of heavy metal content in slimming tea samples Heavy metals content in each sample from different countries Page 1 10 15 17 18 18 21 25

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LIST OF ABBREVIATIONS Al Ag As Ba Ca Cd Cr CTC Cu Co : : : : : : : : : : Aluminum Silver Arsenic Barium Calcium Cadmium Chromium Crush Tear Curl Copper Cobalt Flame Atomic Absorption Spectroscopy Iron Gram Gram per centimeter cube Hydrogen Peroxide Mercury Nitric Acid Potassium Molar

FAAS : Fe g : :

g/cm3 : H2O2 Hg HNO3 K M

:

:
:

: :

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Mg mL Mn

: : :

Magnesium Milliliter Manganese Milligram per kilogram Milligram per liter Lead Part per million Polyphenol oxidase Antimony Tin Zinc

mg/kg : mg/L : Pb ppm PPO Sb Sn Zn : : : : : :

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ABSTRACT DETERMINATION OF HEAVY METALS (CADMIUM, CHROMIUM, COPPER, LEAD AND NICKEL) IN SLIMMING TEAS BY USING ATOMIC ABSORPTION SPECTROSCOPY

Slimming tea is one of the many popular Asia herbal products. The presence of heavy metals in the slimming tea has received special attention because they are directly related to health. Six slimming teas from different brands and countries which were two slimming tea products from local, two from Indonesia and another two from China were used in this project. All samples were treated using acid digestion method and concentration of Cd, Cr, Cu, Pb and Ni were determined by using Atomic Absorption Spectroscopy. The result of analysis showed that the content of Cr in all slimming tea samples ranged between 4.900 and 31.350 mg/kg which the lowest content found in sample (X), a product from Malaysia and highest content of Cr was found in sample (3) which was product from China respectively. The levels of Cd in the slimming tea samples were between 2.500 and 3.850 mg/kg which the lowest level of Cd was found in sample (X) which product from Malaysia and highest from sample (Z) which is China product. The Cd value in all samples was higher than maximum permitted proportion of metal contaminants in specified food Malaysia, 1985 (regulation 38) which is 1.0 mg/kg. Analysis of Cu content in slimming tea samples indicated that the mean value of copper ranged between 2.150 and 18.600 mg/kg. The lowest value of Cu was found in sample (2) and the highest in sample (Y) and both of samples were from Indonesia. Ni in the slimming tea sample was in the range of 1.100 to 11.850 mg/kg. The lowest Ni content was found in sample (2) which product from Indonesia and highest in sample (Z) which is China product. For the Pb analysis, the absorbance measurements for all samples were too low which means that the Pb concentrations were non detectable

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ABSTRAK PENENTUAN TAHAP KEPEKATAN LOGAM BERAT ( KADMIUM, KROMIUM, KUPRUM, PLUMBUM DAN NIKEL) DI DALAM TEH MERAMPINGKAN BADAN DENGAN MENGGUNAKAN SPEKTROSKOPI PENYERAPAN ATOM Teh merampingkan badan adalah satu daripada pelbagai produk herba Asia. Kehadiran logam berat di dalam teh pengurusan badan telah menerima perhatian khas kerana ia berkait terus dengan kesihatan. Enam teh merampingkan badan dari jenama dan negara yang berbeza iaitu dua produk merampingkan badan dari tempatan, dua produk merampingkan badan dari Indonesia dan dua produk merampingkan badan dari China telah digunakan dalam projek ini. Kesemua sampel telah dirawat menggunakan kaedah pencernaan asid dan kepekatan Cd, Cr, Cu, Pb dan Ni telah ditentukan menggunakan spektroskopi penyerapan atom. Keputusan analisa menunjukkan kandungan Cr di dalam kesemua sampel teh dalam julat 4.900 dan 31.350 mg/kg yang mana kandungan paling rendah dijumpai di dalam sampel (X), produk dari Malaysia dan kandungan paling tinggi dijumpai di dalam sampel (3) iaitu produk dari China. Tahap nilai Cd di dalam kesemua sampel teh adalah di dalam julat antara 2.500 and 3.850 mg/kg yang mana tahap paling rendah dijumpai dalam sampel (X) iaitu produk dari Malaysia dan paling tinggi dari sampel (Z) iaitu produk dari China. Nilai Cd di dalam kesemua sampel adalah tinggi daripada tahap maksima yang dibenarkan oleh Peraturan- Peraturan Makanan Malaysia (1985) iaitu 1.0 mg/kg. Analisis kandungan Cu di dalam kesemua sampel teh menunjukkan nilai purata Cu di antara julat 2.150 and 18.600 mg/kg. Nilai Cu yang terendah dijumpai di dalam sampel (2) dan yang paling tinggi dijumpai di dalam sample (Y) dan kedua-dua sampel adalah dari Indonesia. Nilai Ni di dalam kesemua sampel teh di dalam julat antara 1.100 dan 11.850 mg/kg. Kandungan Ni paling rendah telah dijumpai di dalam sampel (2) iaitu produk dari Indonesia dan paling tinggi di dalam sample (Z) iaitu produk China. Untuk analisis Pb, sukatan penyerapan untuk kesemua sampel adalah terlalu rendah di mana purata kepekatan Pb tidak dapat dikesan.

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CHAPTER 1 INTRODUCTION

1.1

Background Slimming tea is one of the many popular Asian herbal products. Slimming teas are herbal teas, marketed for their slimming properties; contain laxatives or diuretics or a combination of both. A laxative is defined as any medicines that either stimulates bowel movements or soften the stools for emptying while diuretic is used to rid the body of excess water through an increased rate of urination. Besides tea, common herbs used in these local and imported preparations are the laxatives senna, cascara, buckhton or rhubarb root and the diuretics uva ursi, mallow or licorice root. Many cases reported nowadays are about toxic heavy metals in Asian herbal products (Ernst, 2005).

(a) Senna leaves (b) Cascara (c) Uva Ursi Figure 1.1 Common herbs in slimming tea preparations.

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Heavy metals are metallic elements that have density greater than 5 g/cm3 and can be hazardous at elevated concentration. Heavy metals are dangerous because they tend to bioaccumulate. Bioaccumulation means an increase in the concentration of a chemical in a biological organism over time, compared to the chemical's concentration in the environment. Compounds are accumulated in living things any time they are taken up and stored faster than they are metabolized or excreted. Heavy metals can not be degraded or destroyed. They can enter our bodies to a small extent via food, drinking water and air. As trace metals, some heavy metals give undesirable effect and some heavy metals give a negative effect. Death can occur from metal poisoning but is dependent upon the dose. Usually people inhale or ingest small amounts of metals which build up in the body slowly interfering with function and slowly causing illness which may ultimately end in death.

In this study, heavy metals in slimming tea were detected by using flame atomic absorption spectroscopy. Flame atomic absorption is a very common technique for detecting metals and metalloids in environmental samples. It is very reliable and simple to use.

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1.2

Significance of study

Nowadays people are obsessed to slimming down their body. They want fast result and easiest method. They take slimming tea. Slimming tea has been reported ensure rapid weight loss. But many cases have been reported about toxic heavy metals in herbal products especially products from Asia. The intake of food contaminated by heavy metal is harmful to human health and several countries have imposed food laws to restrict the presence of heavy metal in food and beverages. From this study, heavy metal contents in six slimming tea products were determined. Knowledge of the heavy metal contents enable us to compare to the allowable limits. Besides that, by comparing the heavy metal contents in the samples, it can help consumers to choose which products are safe to use and which product must be avoided.

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1.3

Objectives of study In this study, five heavy metals were detected and the concentrations of these heavy metals were determined. The objectives of the project include to: 1. Determine cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and lead (Pb) in slimming tea samples which were two products from Malaysia, two products from Indonesia and another two products from China by using flame atomic absorption spectroscopy. 2. Compare heavy metal contents in slimming tea samples from local products with those from other countries.

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CHAPTER 2 LITERATURE REVIEW 2.1 Herbal tea A variety by themselves, herbal tea is completely different from the other varieties of tea. Not being tea in the true sense, herbal tea is simply fresh herb containing medicinal properties. By infusing a teaspoon of these fresh herbs like mint, tutlsi, ginger, jasmine and many others into hot water, their medicinal properties seep into the water giving the drinkers the desired effect, which could be laxative, curative, refreshing, sedative or antacid in nature. Herbal tea is referred to in various ways. Among its nicknames are as sleeping tea, slimming tea, dieters' tea, cholesterol lowering tea , depending upon their specific medicinal effect. Most herbal tea contain tea (Camellia sinensis) which was mixed with the herbs. Camellia sinensis is the tea plant, the plant species whose leaves and leaf buds are used to produce tea. It is of the genus Camellia , a genus of flowering plants in the family Theaceae. White tea, green tea, oolong and black tea are all harvested from this species, but are processed differently to attain different levels of oxidation.

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2.2

Previous study Bagel et al (2005) reported the daily mineral intake by consuming herbal teas for a 70 kg person per day are 500 mg Ca, 300 mg Mg, 15 mg Fe, 5 mg Al, 2.8 mg Mn, 15 mg Zn, 2.5 mg Cu, 1.6 mg Sr, 1.1 mg Ba, 0.025 mg Ni, 0.05-0.2mg Cr, 0.04 mg Co, 0.415 mg Pb and 0.057 mg Cd. This shows that the amounts of heavy metals are presence in herbal tea. Most of slimming tea products consists of tea (Camellia sinensis) which is either green tea or black tea. Ansari et al (2007) stated that tea (Camellia sinensis) is the most popular beverage in the world and contains several essential nutrients, which are beneficial for human health. The contamination of tea leaves by heavy metals may pose a serious threat to human, because they are not biodegradable and remain in environment and pass to food chain. The concentration of heavy metals of Cd, Pb, Ni, and Al and macro elements of Fe, Zn, Cu and Mn were determined by atomic absorption spectrometry on 30 samples of black tea cultivated in Iran and compared with the results for 30 samples of imported black tea in 2006. The results of analysis showed that the mean level of Al was 699.2172.7 mg/kg for Iranian and 388.398.3 mg/kg for imported black tea. However, the values for Cd, Pb, and Ni were nondetectable. The most abundant nutritive metal was manganese with 155.2-214.2 mg/kg and 96.7-332.9 mg/kg in Iranian and imported black tea, respectively.

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Seenivasan et al (2007) have done a research about heavy metal content of black teas from South India. A total of one hundred black tea samples, collected from the tea growing regions of Valparai and Nilgiris in Tamil Nadu, Vandiperiyar, Wayanad and Munnar in Kerala and Karnataka state were analyzed for heavy metals. Cu, Cr, Ni, Cd and Pb in tea samples were analyzed using atomic absorption spectrophotometer equipped with flame and graphite furnace. Air-acetylene flame was used for determination of metal content. The mean values for the results of analysis of tea samples in mg /kg, were 24.07 for Cu, 4.76 for Cr, 2.53 for Ni, 0.14 for Cd and 0.81 for Pb in tea. There were wide variations in the heavy metal contents of black teas collected from different regions of South India. The results indicated that the contents of Cu, Cr, Ni, Cd and Pb in tea were different for the different agro climatic regions. Xie et al (1998) reported that the average Pb level in Chinese black tea samples is higher than Pb level in South India black tea samples. 2.3 The beneficial of minerals in tea Herbal teas contain beneficial minerals such as Ca, Na and K. Ca is the main component of bone and teeth and its function in cell membranes, in muscles, by regulation of endo and exoenzymes and has great importance in regulation of blood pressure (Kili & Kse, 2001).

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Na and K are of great importance for many regulation systems in the body. Na is excreted in sweat by the body. Besides tea, fruits, vegetables and coffee are good sources of K and Na. The minimum daily intake of Na and K are 2.4 g and 3.5 g (Baysal, 2002).

Stagg et al (1975) emphasized the therapeutic action of tea. Tea is an important source of manganese (Mn) and potassium (K) which could be beneficial for hypertensive patients. 2.4 The negative effects of heavy metals in tea Besides minerals, herbal teas also containing several heavy metals such as Al, Mn, Zn, Cu, Cr, Co, Cd and Pb. Heavy metals such as copper (Cu) is essential to maintain metabolism of the human body but at higher concentration they can lead to poisoning. It can cause kidney and liver damage. Nickel (Ni) is also needed in small amount to produce red blood cells but at higher concentration it becomes mildly toxic. It can cause heart and liver damage. Cadmium (Cd) is associated with renal dysfunction and it may also produce bone defects such as osteoporosis.

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Beside copper (Cu), chromium (Cr) can be can accumulated in kidney and liver and can cause severe damage to those systems. In addition, this metal can also damage the circulatory and nerve tissue. High levels of lead (Pb) may result in toxic biochemical effects in humans which in turn cause problems in the synthesis of haemoglobin, effects on the kidneys, gastrointestinal tract, joints and reproductive system and acute or chronic damage to the nervous system and also can cause mental retardation.

2.5

The sources of heavy metals in tea The main sources of heavy metals in plants are their growth media, nutrients, agro inputs and soil. Other sources may include pesticides and fertilizers. Elevated heavy metal levels cause damage to plants such as delayed flowering, lower chlorophyll content and reduction in the number and quality of shoots (Setia et al, 1989). Seenivasan et al (2007) stated that Cu is one of the native metals found in tea, central to polyphenol oxidase enzyme. Polyphenol oxidase (PPO) enzymes catalyse the o-hydroxylation of monophenols (phenol molecules in which the benzene ring contains a single hydroxyl substituent) to o-diphenols (phenol molecules containing two hydroxyl substituents). They can also further catalyse

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the oxidation of o-diphenols to produce o-quinones. It is the rapid polymerisation of o-quinones to produce black, brown or red pigments (polyphenols) that is the cause of fruit browning. The used of copper fungicides cause the presence of undesirable levels of Cu content and also increase the accumulation of Pb and Cd in black tea. Cr is considered as a local contaminant and comes mainly through the crush tearcurl (CTC) rollers during the manufacturing of black tea. CTC machine is shown in Figure 2.1.

Figure 2.1 CTC machine processing tea. Franklin et al (2005) reported that potassic fertilizers contained 2.7 to 16 mg/kg Ni as impurity while commercial phosphatic fertilizers contained 19 to 24 mg/kg Ni. It is clearly evident that Ni mainly comes through the foliar and soil application of low quality fertilizers and micro nutrients. They also

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reported 4.9 to 5.5 mg/kg of Cd in phosphatic fertilizers and 11.8 to 50.9 mg/kg in zinc sources. It appears that contaminated phosphatic and zinc fertilizers were the sources of Cd in tea. Michie et al (1977) and Tsushida et al, (1977) reported that tea soils are acidic and this condition favours solubility of heavy metals. Tea bushes adjacent to heavy traffic gets exposure to Pb and Cd through fallout from automobile exhaust and dust.

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CHAPTER 3 METHODOLOGY 3.1 Chemicals The list of chemicals used were: Standard stock solutions (1000 ppm) of Cd, Cu, Cr, Pb and Ni 6.0 M HNO3 30% Hydrogen Peroxide (H2O2)

3.2

Collection of sample Six slimming tea products of different brands were used in this project. Two of the tea products were from local, two from Indonesia and another two from China. Four slimming tea products which were two from Malaysia and two from Indonesia were purchased from the local retail outlets. Another two slimming tea products which are from China were purchased from local Chinese medicine shop.

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