IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Assessment of the Level of Trace Metals in Commonly Edible Vegetables and Fruits of Baghdad City (Iraq) J.D. Salman, I.D. Sulaiman, S.S. Abd Al-Raziq Department of Chemistry College of Education, Ibn Al-Haitham, University of Baghdad Received in : 28 November 2010 Accepted in :12 April 2011 Abstract A study was carried out to determine the concentrations of trace metals in vegetables and fruits, which are locally available in the markets of Baghdad-samples of fourteen varieties of vegetables and fruits, belonging to Beta vulgaris, Brassica rapa, Daucus carota, Allium cepa, Eurica sativa, Malva silvestris, Coriandrum Sativum, Trigonella Foenum craecum, Anethum graveolens, Barassica oleracea, Phaseolus vulgaris, citrus reticulata, Pyrus malus, and Punica granatum. Analysis for Cd,Pb, Mn, Fe, Co, Ni, Cu and Zn were determined by flame atomic absorption spectrophotometry. The results indicated that the Malva silvestris recorded the highest concentrations of Cd and Mn while Allium cepa showed the highest concentrations of Pb and Cu. But Eurica sativa, Anethum graveolens, phaseolus vulgaris and Daucus carota were observed the highest values of Fe, Co, Ni and Zn respectively. It can be noticed that the zinc has the highest values while the nickel recorded the lowest values in all studied samples. Keywords : Trace metals, vegetables, fruits, Flame atomic absorption spectrometry Introduction The environment pollution with heavy metals is due mainly to the activity of humans. High quantities of these metals can be toxic for all organisms. The entry of heavy metals from the polluted environment in fruits and plants is influenced by different factors and stopped through several mechanisms. Their presence can have effects on different physiological processes. Photosynthesis, respiration, transpiration, cell membrane permeability . Using heavy metal contaminated vegetable products in alimentation can have important effects on short or long terms[1]. Absorp tion and accumulation of heavy metals in vegetables and fruits are influenced by many factors, including: concentration of heavy metals in soil, composition and intensity of atmospheric deposition, including precipitations, phase of plant vegetation [2]. Incidences of food contamination have become increasingly frequent in recent years raising question about their human health and economic consequences [3]. It is generally considered that heavy metals originate from two primary sources: natural inputs (e.g. parent material weathering) and anthropogenic (e.g. metalliferous industries and mining vehicle exhaust, agronomic practices, etc.) [4]. Human health may thus be directly affected by ingesting fruits and vegetables. The effect becomes pronounced due to imbalance of macro and micro-nutrients. The assessment of these nutrients in various raw foods depends on source, material and locality [5,6]. IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Different vegetable species accumulate different metals depending on environmental conditions, metal species, plant available and forms of heavy metals. Studies have shown that up take and accumulation of metals by different plant species depend on several factors and various researchers have studied them [7,8]. There is a growing concenrn about human intake of toxic trace elements such as cadmium, chromium and lead, which even at low doses over along period of time can lead to malfunction of organs and cause chronic toxicity [9]. Food and water are the main sources of our essential metals these are also the media through which we are exposed to various toxic metals. Heavy metals are easily accumulated in the edible parts of leafy vegetables as compared to grain or fruit crops [10]. Several studies have been carried out to estimate the trace metal contents in vegetables. The determination of metal content in vegetables is important from the view point of crop yield technology, food nutrition and health impacts. In event of their excess presence, these metals enter into the body and may disturb the normal functions of central nervous system, liver lungs, heart, kidney and brain [11]. In the present work samples of vegetables and fruits were digested and analyzed by the method of flame atomic absorption spectrophotometry to determine the concentrations of (Cd, Pb, M n, Fe, Co, Ni, Cu and Zn). The main aim of this study was to investigate the level of trace metals in different varieties of vegetables and fruits, which are available in local market. In this study level of Cd, Pb, M n, Fe, Co, Ni, Cu and Zn are being reported for fourteen varieties of vegetables and fruits. Experimental Sample Preparation All the collected samples of various vegetables and fruits were separately washed with tap water and double distilled water to remove airborne pollutants. All the sample were then oven-dried in a hot air at 70-80C for 24h, to remove all moisture. Dried samples were powdered using a pestle and mortar and sieved through muslin cloth. (0.1 gram) of each sample was weighed using sensitive balance (0.1 mg sensitive). The digestion carried out by adding (2 ml) of concentrated nitric acid (70%), heating for one hour, cooling and dilution to (25 ml) in a volumetric flask using double distilled water. All reagents were ultra-pure or analytical reagent (A.R) grade(GBC 933). Distilled and deionized water was used for dilution and preparation of reagents and standards. The purity of the distilled water used for the preparation of all reagents and calibration standards. Heavy metals analyses were carried out using GBC 933 plus, Flam Atomic Absorption Spectrophotometer. Results and Discussion The concentrations of Cd, Pb, Mn, Fe, Co, Ni, Cu and Zn analysed in fourteen varities of vegetables and fruits are given in Table 1, 2 and 3. Cadmium is a toxic element, this metal causes adverse health effects in humans and their presence in the human environment comes from anthropogenic activities [1]. Figure (1) shows that the concentrations of cadmium was higher in all samples studied than the recommendable maximium limits for 0.05 mg/ml except Allium cepa was recorded 0.03 mg/ml. The highest values were found in Malva silvestris for 0.83 mg/ml. Lead accumulates in the Skeleton, especially in bone narrow. It is aneurotoxin and causes behavioural abnormalities, retarding intelligence and mental development Figure (2) presents the concentrations of lead in samples studied it can be noticed that the concentrations IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 of lead was lower than their maximum limit values 0.5 mg/ml except Allium cepa and citrus reticulate was recorded (1.83, 0.62) mg/ml respectively. The trace metal like Mn and Fe are considered as essential element for normal life processes [12] Figure (3) clearly the concentrations of manganese in the vegetables and fruits studied it was found to be in the range between (0.02-1.60) mg/ml. A daily dietary intake (2.5- 5) mg of manganese by human contributes to the well being of the cells [13], these values indicate that the concentrations of manganese were lowest that the recommendable maximum limit. Iron is an important element in human body metabolism which acts as a catalyst and is present in greater amount than any other trace element. The Figure (4) shows the highest values of iron in Eurica sative 2.54 mg/ml while recorded Beta vulgaris the lowest values 0.16 mg/ml. Cobalt is a poisonous non essential heavy metal when ingested in large amount it is excreted through the urinary system [14]. Figure (5) the concentrations of cobalt in the vegetables and fruits studied was range between (0.11-1.37) mg/ml. It can be noticed that the highest values of cobalt in Anethum graveolens. Nickel recorded values range between (0.02-0.09) mg/ml, the low values were 0.02 mg/ml in Daucus carota and Allium cepa while Phaseolus vulgaris and Eurica sativa the highest values 0.09 mg/ml. It was observed in Figure (6) that the fruits studied recorded the values range between (0.04-0.05) mg/ml. The high level of these element has a low toxicity to man [15]. Copper is an essential element widely distributed and always present in food animals livers which are the major contributor to dietary exposure to copper. It is necessary for normal biological activities of amino-oxides and tyrosine enzyme-concentrations of copper shows in Figure (7) that the samples studied were recorded in the range between (0.07-3.80) mg/ml. A daily dietary intake of (2-3) mg of copper is recommended for human adults [13]. Continous ingestion of copper from food induces chronic copper poisoning in man. Zinc is present in the body as a co-factor for enzymes such as orginase and diaminase. It takes parts in the synthesis of DNA-proteins and in sulin. It is essential for the normal functioning of the cell including protein synthesis, carbohydrate metabolism cell-growth and cell division. Figure (8) that the concentrations of zinc in these vegetables and fruits studied was found to be (0.42-21.60) mg/ml, a normal body contains (1.4-2.3) gm of zinc and it is present in all body cells. In view of this the estimated concentrations of metals in vegetables and fruit studies under investigation do not cause health hazards for consumers. It can be noticed that the concentrations of metal in vegetables and fruits studied was found lower than the recommendable maximum limits except cadmium. The elements in the samples studied altogether Zn > Fe > Mn > Cu > Co > Pb > Cd > Ni Consumption of fruits or vegetables contaminated with heavy metals by humans could lead to changes in health of the inhabitants of polluted areas and contribute to the emergence of various chronic diseases. Accuracy and Precision The accuracy and precision of the results were also evaluated by analysing each sample was found, that the range of relative standard deviation percentage and max relative error percentage for each element is shown in table (4) . References 1- Alina, Soceanu, (2009) "Presence of heavy metals in fruits from prunus genera" Ovidius University Annals of Chemistry, 20(1): 108-110. IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 2- Vontsa, D.; Grimanis, A.and Samara, C. (1996)"Trace elements in vegetables grown in industrial areas in relation to soil and air particulate matter", Environmental solution,94:325-335. 3- Musaiger , A.O.; Al-Jedah J.H. and Souza, R.D. (2008) Occurrence of contaminats in foods commonly consumed in Bahrain ,"Food control " 19 :854 4- Zhang, C . (2006) Using multivariate analyses and Gls to identify pollutants and their spatial patterns in urban soils in Galway ,Ireland , Enviromental pollution 142:501- 511 5- Wiersma, D.; Van Goor, B.J. and Vander Veen, N.G. (1986) "Cadmium, Lead, Mercury and Arsenic concentrations in crops and corresponding soils in the Netherlands", J. Agric. Food Chem. 34:1067-1074. 6- Takacs, S. and Tatar, A. (1997) "Trace elements in the environment and in human organs, Environ. Res. 42:312-320. 7- Mido, Y.and Satake, M. (2003) “Chemicals in the environment. In Toxic Metals” (M.S. Sethi, and S.A. lqbal, eds), pp.45-68. Discovery Publishing House, New Delhi,. 8- Bingham, T.F.; Page, A.I.; Hahler, R.J. and Ganje, T.J. Growth. (1975) “Cadmium accumulation of plants grown on soil treated with cadmium enriched sewage sludge”. J. Environ. Qual. 4:207-210 9- Kumar, A.; Sharma, I.K.; Alka Sharma, Sarita varshney and Verma, P.S, (2009) "Heavy metals contamination of vegetable foodstuffs in JAIPUR EJEAFChe,Electronic Journal of Environment al ,Agricultural and food chemistry 8 (2): 96-101. 10- Mapanda, F.; Mangwayana, E.N.; Nyamangara, J.and Giller, K.E. (2005) "The effects of long-term irrigation using water on heavy metal contents of soils under vegetables. Agriculture, Ecosystem and Environment, 107:151-156. 11- Huheey, J.E.; Keiter, E.A. and Keiter, R.L. (2000) “Inorganic chemistry”, 4 th Ed., Pearson Education Inc., USA, p .889. 12- Gulfrz, M.; Ahmed, T. and Afzal, H. (2001) "concentration level of heavy and trace metals in the fish and relevant water from Rawal and Mangla dam". Bio.sci.(5): 414, 105-109. 13- Dara, SS. (1993)"Environmental chemistry and pollution control. First edition, Published by S. Chand and Company Ltd., New Delhi, India, pp.184-205. 14- Salman,J.D. and Faisel,M.Z.(2000),Study of the concentration of Totalsuspended particulates and some heavy metals in the city of Baghdad , Ibn- Al-Haitham J.For pureand Appl.Sci.13(1):60-68 15- Salman ,J.D.(2001) determination of trace elements in some vegetables by Flame atomic absorption spectrometry , Ibn- Al-Haitham J.For pureand Appl.Sci.14(1):66-72 Table (1): Concentrations of trace metals in root vegetables (mg/ml) by FAAS No Sample Metal Cd Pb Mn Fe Co Ni Cu Zn 1 Beta vulgaris 0.19 0.08 0.59 0.16 0.18 0.05 0.37 0.95 2 Brassica rapa 0.13 0.15 0.02 0.36 0.14 0.05 0.25 1.10 3 Daucus carota 0.55 0.16 0.40 0.24 0.11 0.02 0.41 21.60 4 Allium cepa 0.03 1.84 0.75 0.98 0.70 0.02 3.80 2.90 IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Table (2): Concentrations of trace metals in leave vegetables (mg/ml) by FAAS No Sample Metal Cd Pb Mn Fe Co Ni Cu Zn 5 Eurica sativa 0.45 0.40 1.30 2.54 0.20 0.09 0.50 0.80 6 Malva silvestris 0.83 0.37 1.60 1.50 0.49 0.05 0.81 2.45 7 Coriandrum sativum 0.35 0.10 0.77 1.80 0.24 0.06 0.44 3.10 8 Trigonella Foenum craecum 0.61 0.30 1.31 1.73 0.37 0.07 0.42 0.50 9 Anethum graveolens 0.24 0.17 0.41 1.07 1.37 0.05 0.07 0.66 10 Barassica oleracea 0.23 0.12 0.48 0.49 0.18 0.03 0.17 0.42 11 Phaseolus vulgaris 0.33 0.05 0.86 0.28 0.34 0.09 0.67 10.80 Table (3): Concentrations of trace metals in fruit (mg/ml) by FAAS No Sample Metal Cd Pb Mn Fe Co Ni Cu Zn 12 Citrus reticulate 0.06 0.62 0.13 0.24 0.32 0.05 0.12 0.80 13 Pyrus malus 0.31 0.41 0.15 0.64 0.20 0.04 0.34 1.49 14 Punica granatum 0.49 0.26 0.12 0.43 0.35 0.04 0.24 0.73 Table (4): The range of relative standard deviation and max relative error for each metal in all samples Metal % RSD % Max RE Cd 2.15 – 19.37 0.048 Pb 3.14 – 15.39 0.243 Mn 0.62 – 12.40 0.037 Fe 1.85 – 10.65 ـــــ ـــ ــــ ـ Co 6.75 – 15.02 ـــــ ـــ ــــ ـ Ni 1.78 – 19.04 0.284 Cu 0.78 – 8.82 ـــــــ ــــ ـ Zn 1.80 – 5.27 0.041 IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Fig. (1): Concentration of Fig. (2): Concentration of Cadmium in samples studied lead in samples studied Fig. (3): Concentration of Fig. (4): Concentration of manganese in samples studied iron in samples studied Fig. (5): Concentration of Fig. (6): Concentration of cobalt in samples studied nickel in samples studied 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 2 3 4 5 6 7 8 9 10 11 12 13 14 C a d m iu m ( m g /m l) 0 0. 2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 1 2 3 4 5 6 7 8 9 10 11 12 13 14 L e a d ( m g /m l) 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 1 2 3 4 5 6 7 8 9 10 11 12 13 14 M a n g a n e s e ( m g /m l) 0 0. 2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Ir o n ( m g /m l) 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1 2 3 4 5 6 7 8 9 10 11 12 13 14 C o b a lt ( m g /m l) 0 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 11 12 13 14 N ic k e l ( m g /m l) x 1 0 -2 IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Fig.(7): Concentration of Fig. (8): Concentration of copper in samples studied zinc in samples studied 0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2 3.6 4 1 2 3 4 5 6 7 8 9 10 11 12 13 14 C o p p e r (m g /m l) 0 2 4 6 8 10 12 14 16 18 20 22 24 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Z in c ( m g /m l) 2011) 2( 24المجلد مجلة ابن الھیثم للعلوم الصرفة والتطبیقیة )العراق(تقییم مستوى العناصر النزرة في الخضروات والفواكھ في مدینة بغداد جاسم داود سلمان، انتظار داود سلیمان، ساهرة صادق عبد الرزاق د، كلیة التربیة ابن الهیثم ،قسم الكیمیاء جامعة بغدا 2010تشرین الثاني 28: استلم البحث في 2011نیسان 12: قبل البحث في الخالصة ة تقـدیر تراكیـز بعـض العناصـر النـزرة فـي الخضـروات والفواكـه جمعـت مـن االسـواق المحلیـة لمدینــة تتضـمن الدراسـ ــر ةبغـــداد تضـــمنت اربعـــ ــًا متنوعـــاعشـ ــر ،والجـــزر ،والشـــلغم ،الشـــونذر(مــــن الخضـــروات والفواكـــه انموذجـ والبصـــل االخضــ حللـت عناصــر .والرمـان ،والتفـاح ،والاللنكـي ،والفاصــولیا الخضـراء ،واللهانـة ،والشـبنت ،والحلبـة ،والكزبـرة ،والخیـار ،والكركیـر، .مطیافیة االمتصاص الذري اللهبي عمالالكادمیوم والرصاص والمنغنیز والحدید والكوبلت والنیكل والنحاس والزنك باست ـادمیوم والمنغنیـز بینمــا اظهـر البصــل االخضــر یــتشـیر النتــائج الـى ان الخ ار قـد ســجل اعلـى التراكیــز لعنصـري الكـ ــز . اعلــى التراكیــز لعنصــري الرصــاص والنحــاس ـا الكركیــر والشــبنت والفاصــولیا الخضــراء والجــزر فقــد لــوحظ اعلــى التراكیـ امـ وجـد مـن خـالل هـذه الدراسـة ان عنصـر الزنـك قـد سـجل اعلـى التراكیـز . لعناصـر الحدیـد والكوبلـت والنیكـل والزنـك علـى التـوالي .في حین سجل النیكل اوطأ التراكیز في النماذج المدروسة العناصر النزرة ،الفواكه ،الخضر ،جهاز طیف األمتصاص الذري اللهبي : الكلمات المفتاحیة