IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Assessment of the Level of Trace Metals in Co mmonly Edible Vegetables and Fruits o f Baghdad City (Iraq) J.D. Salman, I.D. Sulaiman, S.S. Abd Al-Raziq Departme nt of Chemistry College of Education, Ibn Al-Haitham, Unive rsity of Baghdad Re ceived 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-samp les of fourteen varieties of vegetables and fruits, belonging to Beta vulgaris, Brassica rapa, Daucus carota, Allium cep a, Eurica sativa, M alva silvest ris, Coriandrum Sativum, Trigonella Foenum craecum, Anethum graveolens, Barassica oleracea, Phaseolus vulgaris, citrus reticulata, Py rus malus, and Punica granatum. Analysis for Cd,Pb, M n, Fe, Co, Ni, Cu and Zn were determined by flame atomic absorp tion sp ectrop hotometry . The results indicated that the M alva silvest ris recorded the highest concentrations of Cd and M n while Allium cep a showed the highest concentrations of Pb and Cu. But Eurica sativa, Anethum graveolens, p haseolus vulgaris and Daucus carota were observed the highest values of Fe, Co, Ni and Zn resp ectively. It can be noticed that the zinc has the highest values while the nickel recorded the lowest values in all st udied samples. Keywords : Trace metals, vegetables, fruits, Flame atomic absorp tion sp ectrometry Introduction The environment p ollution 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 p olluted environment in fruits and p lants is influenced by different factors and st op p ed through several mechanisms. Their p resence can have effects on different p hy siological p rocesses. Phot osy nthesis, resp iration, transp iration, cell membrane p ermeability . Using heavy metal contaminated vegetable p roducts in alimentation can have imp ortant 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, comp osition and intensity of atmosp heric deposition, including p recipitations, p hase of p lant vegetation [2]. Incidences of food contamination have become increasingly frequent in recent y ears raising question about their human health and economic consequences [3]. It is generally considered that heavy metals originate from two p rimary sources: natural inputs (e.g. p arent material weathering) and anthrop ogenic (e.g. metalliferous industries and mining vehicle exhaust, agronomic p ractices, etc.) [4]. Human health may thus be directly affected by ingesting fruits and vegetables. The effect becomes p ronounced due to imbalance of macro and micro-nutrients. The assessment of these nutrients in various raw foods dep ends on source, material and locality [5,6]. IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Different vegetable sp ecies accumulate different metals depending on environmental conditions, metal sp ecies, p lant available and forms of heavy metals. Studies have shown that up take and accumulation of metals by different p lant sp ecies depend on several factors and various researchers have st udied 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 p eriod 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 exp osed to various toxic metals. Heavy metals are easily accumulated in the edible p arts of leafy vegetables as compared to grain or fruit crop s [10]. Several st udies have been carried out to estimate the trace metal contents in vegetables. T he determination of metal content in vegetables is imp ortant from the view p oint of crop y ield technology , food nutrition and health impacts. In event of their excess p resence, these metals enter into the body and may disturb the normal functions of central nervous sy st em, liver lungs, heart, kidney and brain [11]. In the p resent work samples of vegetables and fruits were digested and analyzed by the method of flame atomic absorp tion sp ectrop hotometry to determine the concentrations of (Cd, Pb, M n, Fe, Co, Ni, Cu and Zn). The main aim of this st udy was to invest igate the level of trace metals in different varieties of vegetables and fruits, which are available in local market. In this st udy level of Cd, Pb, M n, Fe, Co, Ni, Cu and Zn are being reported for fourteen varieties of vegetables and fruits. Experime ntal S ample Preparation All the collected samples of various vegetables and fruits were separately washed with tap water and double distilled water to remove airborne p ollutants. All the sample were then oven-dried in a hot air at 70-80C for 24h, to remove all moist ure. Dried samples were p owdered using a p estle 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-p ure or analytical reagent (A.R) grade(GBC 933). Dist illed and deionized water was used for dilution and p reparation of reagents and st andards. The p urity of the dist illed water used for the p reparation of all reagents and calibration standards. Heavy metals analyses were carried out using GBC 933 p lus, Flam At omic Absorp tion Sp ectrop hotometer. Results and Discussion The concentrations of Cd, Pb, M n, Fe, Co, Ni, Cu and Zn analy sed 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 p resence in the human environment comes from anthrop ogenic activities [1]. Figure (1) shows that the concentrations of cadmium was higher in all samples st udied than the recommendable maximium limits for 0.05 mg/ml excep t Allium cep a was recorded 0.03 mg/ml. The highest values were found in M alva silvestris for 0.83 mg/ml. Lead accumulates in the Skeleton, esp ecially in bone narrow. It is aneurotoxin and causes behavioural abnormalities, retarding intelligence and mental development Figure (2) p resents the concentrations of lead in samp les studied it can be noticed that the concentrations IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 of lead was lower than their maximum limit values 0.5 mg/ml excep t Allium cepa and citrus reticulate was recorded (1.83, 0.62) mg/ml resp ectively. The trace metal like M n and Fe are considered as essential element for normal life p rocesses [12] Figure (3) clearly the concentrations of manganese in the vegetables and fruits st udied 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 cataly st and is p resent 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 t he lowest values 0.16 mg/ml. Cobalt is a p oisonous non essential heavy metal when ingested in large amount it is excreted through the urinary sy st em [14]. Figure (5) the concentrations of cobalt in the vegetables and fruits st udied 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 cep a while Phaseolus vulgaris and Eurica sativa the highest values 0.09 mg/ml. It was observed in Figure (6) that the fruits st udied recorded the values range between (0.04-0.05) mg/ml. The high level of these element has a low toxicity to man [15]. Cop p er is an essential element widely distributed and alway s p resent in food animals livers which are the major contributor t o dietary exp osure to copp er. It is necessary for normal biological activities of amino-oxides and ty rosine enzy me-concentrations of copp er shows in Figure (7) that the samples st udied were recorded in the range between (0.07-3.80) mg/ml. A daily dietary intake of (2-3) mg of copp er is recommended for human adults [13]. Continous ingestion of cop p er from food induces chronic copp er poisoning in man. Zinc is p resent in the body as a co-factor for enzy mes such as orginase and diaminase. It takes p arts in the sy nthesis of DNA-p roteins and in sulin. It is essential for the normal functioning of the cell including p rotein sy nthesis, carbohy drate metabolism cell-growt h and cell division. Figure (8) that the concentrations of zinc in these vegetables and fruits st udied was found to be (0.42-21.60) mg/ml, a normal body contains (1.4-2.3) gm of zinc and it is p resent in all body cells. In view of this the estimated concentrations of metals in vegetables and fruit st udies under invest igation do not cause health hazards for consumers. It can be noticed that t he concentrations of metal in vegetables and fruits st udied was found lower than the recommendable maximum limits excep t cadmium. The elements in the samp les studied altogether Zn > Fe > M n > Cu > Co > Pb > Cd > Ni Consump tion of fruits or vegetables contaminated with heavy metals by humans could lead to changes in health of the inhabitants of p olluted 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, t hat the range of relative standard deviation percentage and max r elative error percentage for each element is shown in table (4) . Re ferences 1- Alina, Soceanu, (2009) "Presence of heavy metals in fruits from p runus genera" Ovidius University Annals of Chemistry , 20(1): 108-110. IBN AL- HAITHAM J. FOR PURE & APPL. S CI. 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 p articulate matter", Environmental solution,94:325-335. 3- M usaiger , 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 analy ses and Gls to identify p ollutants and their sp atial p att erns in urban soils in Galway ,Ireland , Enviromental p ollution 142:501- 511 5- Wiersma, D.; Van Goor, B.J. and Vander Veen, N.G. (1986) "Cadmium, Lead, M ercury and Arsenic concentrations in crops and corresp onding 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- M ido, Y.and Satake, M . (2003) “Chemicals in the environment. In Toxic M etals” (M .S. Sethi, and S.A. lqbal, eds), p p .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 p lants 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 foodst uffs in JAIPUR EJEAFChe,Electronic Journal of Environment al ,Agricultural and food chemist ry 8 (2): 96-101. 10- M apanda, F.; M angway ana, E.N.; Ny amangara, J.and Giller, K.E. (2005) "The effects of long-term irrigation using water on heavy metal contents of soils under vegetables. Agriculture, Ecosy st em and Environment, 107:151-156. 11- Huheey, J.E.; Keiter, E.A. and Keiter, R.L. (2000) “Inorganic chemist ry ”, 4 th Ed., Pearson Education Inc., USA, p .889. 12- Gulfrz, M .; Ahmed, T. and Afz al, H. (2001) "concentration level of heavy and trace metals in the fish and relevant water from Rawal and M angla dam". Bio.sci.(5): 414, 105-109. 13- Dara, SS. (1993)"Environmental chemist ry and p ollution control. First edition, Published by S. Chand and Company Ltd., New Delhi, India, p p .184-205. 14- Salman,J.D. and Faisel,M .Z.(2000),Study of the concentration of Totalsusp ended p articulates and some heavy metals in the city of Baghdad , Ibn- Al-Haitham J.For p ureand Ap p l.Sci.13(1):60-68 15- Salman ,J.D.(2001) determination of trace elements in some vegetables by Flame atomic absorp tion sp ectrometry , Ibn- Al-Haitham J.For p ureand Ap p l.Sci.14(1):66-72 Table (1): Concentrations of trace me tals i n root vegetables (mg/ml) by FAAS No Samp le M etal Cd Pb M n 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 cep a 0.03 1.84 0.75 0.98 0.70 0.02 3.80 2.90 IBN AL- HAITHAM J. FOR PURE & APPL. S CI. 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 T rigonella F oenum 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 me tals i n frui t (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 rel ative error for each metal in all samples M etal % RSD % M ax RE Cd 2.15 – 19.37 0.048 Pb 3.14 – 15.39 0.243 M n 0.62 – 12.40 0.037 Fe 1.85 – 10.65 ــــــــ ــــ ـ Co 6.75 – 15.02 ــــــــ 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. S CI. VOL. 24 (2) 2011 Fig. (1): Concentration of Fig. (2): Concentration of Cadmium in samples studie d lead in samples studied Fig. (3): Concentration of Fig. (4): Concentration of manganese in samples studied iron in samples studie d Fig. (5): Concentration of Fig. (6): Concentration of cobalt in samples studie d 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. S CI. VOL. 24 (2) 2011 Fig.(7): Concentration of Fig. (8): Concentration of copper in samples studie d 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 جامعة بغداد، كلیة التربیة ابن الهیثم ،قسم الكیمیاء 2010تشرین الثاني 28: استلم البحث في 2011نیسان 12: قبل البحث في الخالصة الخضـروات والفواكـه جمعـت مـن االسـواق المحلیـة لمدینــة تتضـمن الدراسـة تقـدیر تراكیـز بعـض العناصـر النـزرة فـي ــًا متنوعـــاعشـــر ةبغـــداد تضـــمنت اربعـــ والبصـــل االخضــــر ،والجـــزر ،والشـــلغم ،الشـــونذر(مــــن الخضـــروات والفواكـــه انموذجـ 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 ار قـد ســجل اعلـى التراكیــز لعنصـري الكــادمیوم والمنغنیـز بینمــا اظهـر البصــل االخضــر یــتشـیر النتــائج الـى ان الخ امــا الكركیــر والشــبنت والفاصــولیا الخضــراء والجــزر فقــد لــوحظ اعلــى التراكیـــز . اعلــى التراكیــز لعنصــري الرصــاص والنحــاس 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