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    Journal of Basic and Applied Sciences Vol. 5, No. 2, 47-52, 2009 ISSN:1814-8085

    MARKET BASKET SURVEY OF SELECTED METALS IN FRUITS

    FROM KARACHI CITY (PAKISTAN)

    Erum Zahir*, Iftikhar Imam Naqvi and Sheikh Mohi Uddin

    Department of Chemistry, University of Karachi, Karachi-75270, Pakistan

    ABSTRACT

    Metals are essential for important biochemical and physiological functions and are necessary for maintaining health

    throughout life. In order to assess the impact of human activity on the food chain, monitoring of trace metals in a variety

    of fruits being sold in Karachis metropolis has been focus of this study. Trace levels of heavy metals such as Fe, Mn,

    Pb, Cu, Co, Ni, Cd, Cr and Zn were determined in 10 different varieties of fruits purchased from local market of Karachi

    city of Pakistan. The dried powdered samples were digested in 1: 3 mixtures of Perchloric acid (HClO 4)and Nitric acid

    (HNO3) and metal levels were analyzed by using atomic absorption spectrophotometer. The results were in the range of

    7.924-24.674 ug/g Fe, 0.531-7.571 ug/g Pb, 0.013-0.612 ug/g Mn, 0.543-3.234 ug/g Cu, 0.144-5.033 ug/g Ni, 0.173-

    0.299 ug/g Cd, 3.268-4.343 ug/g Cr, 0.138-21.409 ug/g Zn, 0.104-1.168 ug/g Co.

    Key words: Heavy metals, Atomic Absorption Spectrometry, Acid digestion, fruits.

    INTRODUCTION

    Fruits natural staple food of humans, contain substantial

    quantities of essential nutrients in a rational proportion. A

    generous intake of fruits in the diet enables a person to

    lead a healthy life. Fruits prevent all diseases and keep a

    person energetic and active all through his life even up to

    the ripe old age as in Table 1.

    Concentration levels of elements in plants and fruits are

    directly related to their interaction with all environmental,geological and biological systems (Bratter, P and Schrauel

    P., 1980). Ingestion of heavy metals through food can

    cause accumulation in organisms, producing serious

    health hazards such as injury to the kidney, symptoms of

    chronic toxicity, renal failure and liver damage (Abou-

    Arab et al., 1999; Sathawara et al., 2004)

    Table 1. Importance of Fruits in human Life

    Botanical name Common Name Importance

    Malus pumila Apple Rich in Iron, useful in acute and chronic dysentery among children, stomachdisorders, headache, heart disease, maintain blood pressure, dry hacking cough,

    removing kidney stone, mouth cleansing property and makes the body strong.

    Prunus armeniaca Apricot Rich in natural sugar, vitamin A, C and Calcium. Useful in treatment ofconstipation, anemia, skin diseases.

    Musa hybrids Banana Rich in Potassium, protein, vitamins. Useful in intestinal disorders, dysentery,arthritist and gout patients, anemia, kidney and liver disorders, tuberculosis,weight reduction. Paste of ripe banana gives relief of burns and wounds.

    Eugenia jambolana Jaman Rich in vitamin C, minerals, Proteins. Useful in diarrhea, dysentery, bleedingpiles, stimulate liver functions, effective for sterility and miscarriage.

    Citrus limon Lemon Rich in Citric acid and vitamin C. Useful as a food accessory, destroy toxins inbody, curing of gum diseases, catarrh, constipation, diarrhea, obesity, different

    haemorrhage, foot relaxation.

    Mangifera indica Mango Rich in vitamins, minerals. Useful in treatment of night blindness, loss ofweight, diadetes, seed are useful in diarrhea, throat infections, constipation, eye

    infections.

    Cyphomandra betacea Tomato Rich in calcium, phosphorus, vitamins. Useful in skin, diabetic patients,acidosis, eye diseases, obesity, liver, diarrhea,

    Manilkara zapota Chikoo Rich in water content, minerals and vitamins. Useful in inflammation duringurination, fever. It eliminates excessive bile in the body.

    Phoenix dactylifera Date Rich in vitamins, minerals. Useful in treatment of sore throat, fever, cystitis,edema, liver and abdominal disorders, plethora, asthma, thirst, hunger, loss ofbody weight, curing of pain, gastric troubles, enlarged liver and spleen.

    Azadirachta indica Neem Rich in vitamins, minerals. Useful as antiseptic, antimicrobials, treatment ofurinary disorders, diarrhea, fever, bronchitis, skin diseases, burns, hypertensions,

    cancer, digestive and blood disorders and cosmetic products.

    * Corresponding Author: Email: [email protected]

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    J. basic appl. sci.48

    The poorest urban farmers are prone to toxic metal load as

    they are most likely to use high risk sites and undeveloped

    land (Sawio, 1999). Studies have shown that urban soils

    can receive large inputs of trace metals from different

    anthropogenic sources but especially from automobile

    emissions, waste dumping sites and contamination of

    ground water from excessive use of chemical pesticides

    and fertilizers in agriculture (Nabulo et al., 2006).Human health may be directly affected by ingestion fruits

    and vegetables, if enhanced amount of macro-

    micronutrients are present in such edible (Disipio et al.,

    1999). Increasing knowledge about the potentially

    deleterious effects of heavy metals on environmental and

    human health has prompted closer examination of the

    presence and behavior of such elements in agriculture

    ecosystems. Heavy metals occur in many fertilizers and in

    some pesticides, purposefully included as micro

    nutritional or bicidal components, present as naturally

    occurring contaminants, or introduced when waste

    materials are used to formulate fertilizer products. Heavy

    metals may be of particular concern in tree fruit

    production because of the importance of foliar spray,

    which deposits fertilizer and pesticide residue directly on

    to fruits. Current issues concerning heavy metal and

    nutrient management include natural cadmium

    enrichment in phosphorous fertilizer, anthropogenic

    heavy metal contamination of zinc fertilizer and copper

    contamination of soil resulting from historical pesticide

    application (ISHS, 2001).

    It is well known that an excess or deficiency of trace

    metals present in the human body can cause harmful

    effects. For example an excess of Cu in the body cause

    Wilsons disease while a deficiency of Zn is responsible

    for retarded body growth (Olivaries et al., 1996).

    This study is aimed to present a data of trace levels of

    metals in different types of fruits available for the

    consumption to the inhabitants of Karachi from various

    sources and this data will help to provide the status of

    heavy metals pollution in Pakistan and also to assure food

    safety and to protect the end user from food that might

    affect their health.

    MATERIALS AND METHODS

    The selection of fruits based on criteria regarding their

    consumption and availability. The composite samples offruits were collected from the several local market of

    Karachi city- Pakistan.

    All fruit samples were washed thoroughly and separately.

    Running tap water was employed to remove dust and

    adhered particles. The samples were later rinsed thrice

    with deionized water and subsequently dried in oven at

    60-80C. After drying and cooling, about 2 g of each

    dried sample was weighed accurately in cleaned and dried

    50ml beaker and digested in 10 ml of 1:3 mixture of

    concentrated 65% HClO4 : HNO3 (Merck) using a

    hotplate, till clear solution was obtained. Digested

    samples were cooled at room temperature. These were

    then acidified with 10 ml of 1:1 mixture of HCl:H2O and

    filtered through 0.45 micron filter paper and the volume

    was made up to 50ml with distilled water (AOAC 2000).

    The digested samples were transferred to cleaned driedplastic bottles for chemical analysis by using Atomic

    Absorption Spectrometry (Perkin Elmer AAnalyst 700).

    Table 2. Standard operating conditions for the analysis of

    heavy metals using Atomic Absorption Spectrometry.

    MetalsWavelength

    (nm)

    Lamp

    Current

    (mA)

    Flame

    Slit

    Width

    (mm)

    Fe 248.3 30

    Air-Acetylene

    0.2

    Pb 283.3 12 0.7

    Mn 279.5 30 0.2

    Cu 324.8 30 0.7Co 240.7 30 0.2

    Ni 232.0 30 0.2

    Zn 213.9 20 0.7

    Cd 228.8 6 0.7

    Cr 357.9 30 0.7

    Standard solutions of heavy metals were provided by

    Merck (Darmstadt, Germany). The standards were

    prepared from the individual 1000 mg/l standards

    (Merck), in 0.1 N HNO3. Working standards were

    prepared from the previous stock solutions. Quality

    assurance (QA) and quality control (QC) procedures were

    strictly followed throughout the present study. The levelof accuracy and QC for the determination of heavy metal

    concentrations was comprised of measurements of natural

    matrix Certified Reference Material (CRM) and the

    measurements of duplicates for each batch of samples.

    NIST standard 1573 (Tomato leaves) was used for the

    evaluation of procedures. Percentage recoveries ranged

    between 92.3% and 113% with % RSDs for the mean

    recoveries below 8.7% for CRM 1573, whereas the

    percent relative standard deviation (%RSD) for duplicate

    samples analyzed was less than 9%. Two- way ANOVA

    were carried out for statistical analysis with the program

    SPSS 10.0 for windows.

    RESULTS AND DISCUSSION

    Fruits are important source of nutrients and offer

    advantages over dietary supplements, because of low cost

    and wide availability. In daily diet fruits have been

    strongly associated with reduced risk for some forms of

    cancer, heart disease, stroke and other chronic ailments

    (Goldberg, 2003). Climatic conditions, particularly

    temperature and light intensity, have an especially strong

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    Zahir et al. 49

    effect on the nutritional quality of fruits and vegetables

    oxidation (Mozafar, 1994). Although antioxidant capacity

    varies greatly among fruits and vegetables it is better to

    consume a variety of commodities rather than limiting

    consumption to a few with the highest antioxidant

    capacity (Kalt, 2002).

    Soil type, the rootstock used for fruit trees, mulching,irrigation, fertilization and other cultural practices

    influence the water and nutrient supply to the plants,

    which can affect the composition and quality attributes

    (appearance, texture, taste and aroma) of the harvested

    plant parts (Goldman et al., 1999).

    Pakistan has all the natural flavors, usually considered

    ideal for the production of good quality of fruits like

    fertile soil, temperature variation and other climatic

    condition. Pakistani fruits are being demanded in almost

    all over the world. Presently Pakistan is exporting fruits to

    USA, Europe, Middle East, India, Srilanka and many

    other countries.

    The present work is focused on establishing trace

    elemental levels in different types of fruit samples in

    order to find ecological and environmental relationship

    between trace elements. Our result shows Table 3 that the

    data are quite divergent and no regular pattern of metal

    content is observed. Fe concentration is higher as

    compared to the other metals in fruit samples. It was

    found highest in Apple that is 24.67ug/g. The maximum

    iron ion level permitted for food is 15mg kg1

    according

    to (Turkish Food Codex Anonymous Regulation 2002).

    Iron is an important component of hemoglobin and intake

    of iron in human body from fruits is very good to health.Among various samples, Banana shows lesser

    concentration 1.650 ug/g while in the other samples the

    concentration of iron is in between 7.92-16.517 ug/g. In

    other studies the concentration of iron was reported as

    35.6 mg/kg for raw foodstuff (Waheed et al., 2003).

    Cadmium is readily available for uptake by plants as there

    is a clear association between cadmium concentration in

    soil and the plants grown on the soil (Elinder et al.,

    1996).The guideline value for cadmium in soil from plant

    uptake is 1 mg/ kg dry soil weight (DEFRA, 2002). In the

    present study the concentration of cadmium in fruits has

    been found within the range of 0.1726-0.2995 ug/g. It is

    the least in apple among all. Cadmium concentrations

    were within the advisory interval (0.5-5 mg/kg) (Danish,

    2000). Cobalt is lowest in Jaman i.e 0.104 ug/g and

    highest in Banana 1.168 ug/g.

    The concentration of lead was found maximum in Chikoo

    Table 3. Concentration (g/g dry wt) Standard deviation of Heavy metals in Fruits

    Fruit Samples Fe Pb Mn Cu Ni Cd Cr Zn Co

    Apple 24.676

    1.261

    1.818

    0.205

    0.019

    0.008

    0.543

    0.035

    0.971

    0.183

    0.173

    0.069

    3.930

    0.270

    21.496

    1.733

    0.407

    0.053

    Apricot 14.086

    0.166

    1.597

    0.995

    0.037

    0.005

    1.420

    0.090

    1.119

    0.220

    0.246

    0.038

    3.975

    0.462

    1.543

    0.542

    1.049

    0.203

    Banana 16.508

    2.177

    3.152

    0.665

    0.037

    0.002

    1.606

    0.250

    1.316

    0.635

    0.262

    0.032

    4.343

    0.326

    0.785

    0.124

    1.168

    0.559

    Chikoo 14.544

    1.655

    7.571

    2.417

    0.064

    0.005

    3.145

    0.100

    1.099

    0.368

    0.280

    0.061

    4.304

    0.125

    28.227

    3.007

    0.272

    0.026

    Date 16.517

    2.950

    2.291

    0.699

    0.045

    0.003

    0.644

    0.049

    1.818

    0.103

    0.194

    0.036

    4.180

    0.382

    49.586

    9.063

    0.141

    0.091

    Jaman 9.120

    3.251

    2.928

    0.886

    0.021

    0.001

    2.772

    0.455

    0.597

    0.280

    0.278

    0.017

    3.931

    0.280

    0.138

    0.006

    0.104

    0.091

    Lemon 16.366

    6.843

    1.961

    0.164

    0.612

    0.065

    2.947

    0.042

    0.975

    0.102

    0.292

    0.070

    3.973

    0.893

    0.032

    0.005

    0.364

    0.048

    Mango 9.563

    4.394

    1.914

    0.932

    0.050

    0.028

    3.234

    0.279

    5.033

    1.723

    0.275

    0.025

    4.095

    0.194

    0.668

    0.066

    0.871

    0.201

    Neem 9.962

    1.178

    1.554

    0.027

    0.013

    0.002

    1.829

    0.308

    0.645

    0.195

    0.299

    0.068

    3.268

    0.062

    10.845

    1.543

    0.388

    0.051

    Tomato 7.924

    0.680

    0.531

    0.092

    0.049

    0.008

    3.122

    0.080

    0.144

    0.061

    0.245

    0.034

    2.864

    0.032

    12.345

    0.784

    0.340

    0.014

    Minimum 7.924 0.531 0.013 0.543 0.144 0.173 2.864 0.032 0.104

    Maximum 24.676 7.571 0.612 3.234 5.033 0.299 4.343 49.586 1.168

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    J. basic appl. sci.50

    7.571 ug/g and minimum in tomato 0.531 ug/g. WHO has

    established a provisional tolerable weekly intake for lead

    of 0.025 mg kg1

    of body weight (WHO, 1993). As lead is

    not being translocated readily in plants, it could be

    suggested that Pb found in different samples originated

    from atmospheric deposition. This may also be due to the

    vehicular lead emission could be likely source of lead

    pollution in areas close to agricultural fiels. On contrary,in all fruit samples, the uptake and accumulation of Mn is

    relatively lower 0.019-0.612 ug/g. The US National

    Academy of Sciences recommended 2.55 mg per day

    manganese (National Academy of Science, 1980) and, the

    WHO recommended 29 mg per day for an adult (WHO,

    1994).

    Zinc is an essential metal for proper body functions. The

    concentration of zinc is highest in date 49.586 ug/g and

    minimum is in lemon. The maximum tolerable daily

    intake of Zn is 0.31 mg kg1

    (FAO/WHO, 1982). Our

    values for Zn (II) ion in understudy apricot samples were

    above the WHOs values. Chromium is important for

    glucose tolerance in human body. The maximum

    concentration of Cr is 4.343 and minimum was 2.864

    ug/g. The Food and Nutrition Board of the NAS/NRC

    states that a safe, adequate intake of chromium for an

    adult is 50200 ug/day (Gupta, 2006). Copper plays a

    critical role in a variety of biochemical processes. The

    lowest concentration 0.543 was found in apple and the

    highest concentration is in mango 3.234 ug/g.

    Trees are long-lived organisms, which can take up trace

    elements from the soil, water or air, and retain them for a

    long time. Trace metals may enter the human body

    through consumption of food plants grown in

    contaminated soil. Cu is in the range of 0.543- 3.234 ug/gand the highest concentration of Ni is in mango 5.033

    ug/g and lower in tomato 0.144 ug/g that is within the

    reported normal range of 0.10-5.00 mg/kg (Kabata-

    Pendias et al., 1992). Exposure of consumers and related

    health risks are usually expressed as provisional tolerable

    daily intake (PTDI), a reference value established by Joint

    FAO/WHO (1999). The FAO/WHO who has set a limit

    for heavy metal intake based on body weight for an

    average adult (60 kg body weight). PTDI for Pb, Cd, Cu,and Zn are 214 g, 60 g, 3 mg and 60 mg, respectively

    (Joint FAO/WHO Expert Committee on Food Additives,

    1999).

    In other studies, the results showed that the concentration

    of metals in various food stuff ranged between 0.04-8.88

    Cu, 3.07-126.0 Fe, 0.19-22.8 Zn, 0.15-1.16Cd and Pb has

    been in the range of 0.11-2.04 mg/kg (Waheed et al.,

    2003). Our results also follow the same pattern.

    In other studies different spices, dry fruits and plant nuts

    commonly consumed in Pakistan were assayed for the

    heavy metals cadmium, lead, copper, zinc, iron and

    manganese by the potentiometric stripping analysis and

    atomic absorption spectrophotometry. The results

    revealed wide variation in heavy metal content among

    different biological materials. Spices generally exhibited

    higher value for trace metals specially lead (6.69.2

    g/g), cadmium (0.651.34 g/g), iron (142.3285.0

    g/g) and zinc (64.265.8 g/g). Dry fruits contained

    relatively lesser amounts of heavy metals than plant nuts.

    Almonds contained higher levels of lead (1.02 g/g) and

    cadmium (0.24 g/g) than other nuts and dry fruits (Sattar

    et al. 1989). The above study showed much higher

    amount of metals than in our study. Comparison details of

    metal content in fruits of our study and other studies are

    shown in Table 4.

    Table 4. Levels of metals in fruits in previously published results from other parts of the world.

    Fruitsample

    Fe Pb Mn Cu Ni Cd Cr Zn Co Ref

    Apple 121.15 23.48 8.75 3.00 47.43 8.39 8.75 35.88 25.40 India a

    Yeshwantpur

    market 2008Banana 190.99 7.46 417.39 14.19 8.90 13.36 88.32 45.64 185.90

    Chikoo 134.87 29.86 11.59 12.32 4.32 9.44 50.10 23.90 n.d

    Lemon 43.99 58.70 11.05 6.76 37.94 9.09 227.50 22.19 8.70

    Mango 75.16 67.20 11.59 6.34 n.d 16.9 37.36 18.29 6.23

    JamanDate 0.44-

    7.94---- 0.10-

    0.510.11-0.65

    --- 0.05-0.74

    0.02-1.45

    0.22-2.02

    0.06-0.11

    Egypt b 2000

    Tomato --- 0.26 --- 1.83 --- 0.01 ---- 7.69 --- Egypt c 2006

    Apricot 76.8-80.1

    2.36-2.50

    7.10-7.53

    2.25-2.42

    3.41-3.66

    0.19-0.22

    .0162-

    .016911.7-12.0

    --- Turkey d 2009

    a Mahdavian ,SE and Somashekar, RK 2008, b Mohamed, AE 2000, c Radwan, MA and Salama, AK 2006d Saracoglu, S et al. 2009

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    Zahir et al. 51

    This variation of metal concentrations in the different

    fruits samples may be related to variation in texture,

    structure, chemical and mineral composition of soil.

    Statistical analysis (P > 0.05, ANOVA) does not signify

    meaningful differences between the metal concentrations

    pertaining to different fruits.

    Morphology of leaves and fruits influence the dustdeposition and hence different patterns were observed for

    elemental concentrations in plant tissues and their fruits.

    The bioaccumulation of trace elements in the leaves and

    fruits of the trees is the combined result of the uptake

    processes via the roots from the soil, which is then

    transported to the leaves and translocated to the fruits,

    land through shoots.

    CONCLUSION

    In conclusion, the results represent that the fruits of

    Pakistan contained the metal content within the safe limits

    (WHO, 1997). As the human health is directly affected byingestion of fruits and vegetables. The distribution of

    toxic elements in nature, their concentration and

    migration via from atmosphere, aqueous and soil affect

    the human activities. Biomonitoring of trace elements in

    the fleshy fruits should be continued because these are the

    main source of food for human.

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