best fruit 2013( procedure )890
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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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