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Chapter II Review of the Previous Studies 15-25

2.2 Review of the Previous Studies 15

Joseph et al. [1] adopted instrumental neutron activation analysis (INAA) for the determination of various essential trace elements like Mg, Ca, Mn, K, Cr, Co and Zn and non-essential trace elements e.g., Al, Br, La, Yb, Rb, Ba, Eu and Sb in some Nigerian commercial milk and infant cereal formulas. The results showed that the samples analyzed contained adequate amounts of essential trace elements measured, with Mn being slightly deficient in all the samples. In addition, the results obtained for non- essential trace elements in most samples are within the recommended tolerable level. The concentrations of Ba and Sb are high in samples C1 of both the milk formulae.

Furthermore, the concentration of Sb is also found to be high in samples C2 of the cereal formula.

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Ayivor et al. [2] investigated a total of 16 imported baby cereals samples collected from various markets in the Greater Accra. Selected elemental Al, Br, Ca, Cl, K, Mg and Na contents were determined by INAA. The element that presented minor concentrations is Al. Its highest concentration was 11.04 ± 0.59 ppm in BFBN. Br was found in four of the 16 samples. Cl, Ca, Mg and Na were present in minor concentrations in most of the samples analyzed. The concentration of Cl ranged from 0.06-0.36% whereas Ca had concentrations ranging from 0.27-1.37 %. Na and K were found to range from 0.10 - 1.03%. This investigation had showed that the imported baby cereals on the Ghanaian market contain some important nutrients that appear to have a very positive effect on human health.

Karin et al. [3] assessed concentrations in intake of toxic and essential elements from formulas and foods. Concentrations of the essential elements Ca, Fe, Zn, Mn and Mo were significantly higher in most formulas than in breast milk. Daily intake of Mn from formula varies from ten up to several hundred times of the intake of the breast-fed infant levels that may be associated with adverse health effects. Drinking water used to mix powdered formula may add significantly to the concentrations in the ready-made products. Evaluation of potentially adverse effects of the elevated element concentrations in infant formulas and foods are warranted.

Committee on Toxicity of Chemicals (COT) in infant food [4] determined contaminants such as Pb, Cd, Sb, Ni and Sn resulting in the decrease of the intakes of essential elements like Cr, Cu, Se and Zn. Overall effect of this observation may potentially lead to nutritional deficiency to the babies of the area.

Shona et al. [5] analyzed milk and milk products that form a major part of a healthy diet.

Multi -elemental analysis of milk can determine whether milk is meeting the expected nutritional requirements or is lacking either due to regional soil deficiencies in the case of cow milk or poor diet in the case of breast milk. Alternatively, the analysis of trace elements that are toxic in nature can make people alert of the possible risk of contamination in milk. A good agreement between the determined and certified values for BCR-063 and baby formula and 108% and 94% recovery of iodine from the BCR- 063 and the baby formula respectively was observed.

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Ayala et al. [6] estimated contents of several elements such as Pb, Cd and As in food.

Presence of these elements may cause a health problem when toxic limits are exceeded.

Particularly, children are very sensitive to food pollution. The elemental composition of major (Al, Ca, K) and trace elements (Mn, Fe, Zn, Cu, Br, Sr, Pb, Cr, Ni) as well as C and O from matrix were measured. However the samples had exceeded official standards of Pb concentrations.

Gintare et al. [7] has found maximum concentration of Pb in Iceberg lettuce (0.5042±0.0148 mg/kg). Maximum concentration of Cd was found in squid (0.8669±0.3561 mg/kg). The analysis had revealed that the supplier and the foodstuff are statistically not significant (p>0.005) for the concentration of Cd and Pb. Concentrations were measured by atomic absorption method (AAM) using an atomic absorption spectrometer.

Stahl et al. [8] found that oral intake of foodstuffs would appear to be the most important source of aluminum. Consequently, the joint FAO/WHO Expert Committee on Food Additives reduced the provisional tolerable weekly intake value for aluminum from 7 mg kg-1 body weight/week to 1 mg/kg body weight/week. Analysis of aluminum content of a number of foods and food products was therefore undertaken in order to evaluate the nutritional intake of aluminum.

Judith et al. [9] proposed an infant formula. Like breast milk, the formula was designed to deliver fluid for hydration; protein to provide amino acid building blocks for growth;

carbohydrates to fuel the muscles, brain, and other organs; concentrated calories of fat for energy; and various vitamins and minerals. The three main categories of infant formula are differentiated by the type of protein they contain: cow's milk-based, soy protein-based and hydrolyzed or amino acid formulas in which the proteins have been predigested.

Chocolate and milk chocolate samples collected from the Austrian market were analyzed by Manfred Sage [10] for nutrient, essential and non-essential elements including the non-metals B, Si, S, and I. The cocoa contents ranged from 20-100%. Among the non- wanted trace elements Ni was found high, Cd largely ranged below 0.20 mg/kg but a few samples contained higher Cd reaching 0.90 mg/kg which was contrary to previous

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studies of the same samples. Contrary to other sweets, consumption of 100 g of chocolate satisfies the recommended daily intake for Cr-Cu-Fe and 300 g for Mg and Zn, which is particularly important for the adequate trace element supply of children and vegans.

Tsdale et al. [11] showed high variability in the concentrations of elements in the fresh fruits, vegetables, herbs, and processed foods. The overall average concentrations of Ca (1501 μg/g), Mg (186.5 μg/g), Fe (55.8 μg/g), Zn (22.2 μg/g), Pb (10.2 μg/g), Cu (5.8 μg/g), Cr (>0.1µg/g), Cd (>0.1µg/g) and Ni (>0.04µg/g) were obtained in the samples.

The elemental concentrations were generally poorly correlated in the food samples.

However, a strong inter-element association between Cu and Fe concentration and a weak association between Ca and Fe were found. A survey questionnaire was administered to 396 participants in the Greensboro metropolis to evaluate the food consumption pattern and a daily/weekly dietary estimate intake of vegetables, fruits, herbs and processed foods.

Kalantari et al. [12] studied contamination of baby food supplements such as Mamana and Ghoncheh, which are widely used in Iranian markets. In this study 14 samples of Mamana and 15 samples of Ghoncheh were investigated for aflatoxin B1, B2, and G1.

According to the CB method, extraction was carried out and aflatoxins B1, B2 and G1 were identified and measured. The results of this study showed that 2 of 15 samples of Mamana and 2 of 14 samples of Ghoncheh were contaminated with aflatoxin B1 and B2.

(< 2ppb).

Salah et al. [13] have studied fifty random milk powder samples which were collected from different outlets in Dakahlia Governorate of Egypt to determine heavy metals and trace elements as Pb, Cd, Al, Fe, Se and Mn. The average concentration of Pb, Cd, Al, Fe, Mn and Se in examined milk powder samples were 0.791; 0.322; 1.57; 20.41; 0.497 and 0.014 ppm, respectively. The calculated daily intake of Pb, Cd, Al, Fe, Mn and Se from consumption of 200 ml reconstituted milk powder per day were 158.5, 64.4, 313.4, 4082, 99.4 and 2.8 µg, respectively, which contributed about 31.64, 92.0, 26.12, 85.04, 1.99 and 3.5% from the acceptable daily intake of these elements, respectively.

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The European Food Safety Authority (EFSA) [14] received a request from the European Commission for a scientific opinion on perchlorate in food. A total 11675 samples were instigated mainly for fruits, vegetables, and fruit and vegetable products. The EFSA Panel on Contaminants in the Food Chain (CONTAM Panel) performed estimates of both chronic and „short-term‟ exposure considering the available dataset, and data from the literature on the levels of perchlorate in fruit juices, alcoholic beverages, milk, infant formulae and breast milk. They established a tolerable daily intake of 0.3 µg/kg body weight per day, based on the inhibition of thyroid iodine uptake in healthy adults.

Amongst the vulnerable subpopulations potentially acute effects of perchlorate have been suggested for fetuses and infants.

Taborsky et al. [15] determined the contaminants in milk and milk products. Certified reference materials for the determination of contaminating chemical elements, organochlorine pesticides, polychlorinated biphenyls, dibenzodioxins, dibenzofurans, and aflatoxin M1 were presented. Properties of these reference materials and possibilities for their use were discussed together with the maximum tolerances of contaminants in milk and milk products. The basic information about the producers and distributors of the reference materials in this area is provided.

Bamidele et al. [16] determined proximate compositions of moisture, protein, ash, fat, crude fiber and carbohydrate and the levels of 37 elements e.g., P, Ca, Cu, Mg, Mn, Na, K, Zn, Pb, Bi, Sn, Ti, Si, Tl, Sb, Ba, Se, Sr, S, Ag, Cd, Mo, Ni, Al, As, Be, Co, Cr, Sc, V, W, Zr, B, Ce, Li, Te and U in 13 brands infant formulae samples obtained from 3 developing (Nigeria, South Africa and Venezuela) and 5 developed (USA, France, Italy, Denmark and Germany) countries. In addition, the daily intakes of the elements from formulae from developing and developed countries were estimated and compared. The results suggested that the estimated daily intake from infant formulae obtained from developing countries compare well with those from the developed countries and are within statutory safe limits.

Melisa et al. [17] determined the contents of 3 toxic trace elements (arsenic, cadmium and lead) in commercial gluten-free cereal bars marketed in Argentina by ICP-MS and assessed the dietary intake of the 3 toxic elements compared with reference values. The results obtained indicated that the highest total concentration of arsenic is provided by

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the gluten-free cereal bars with green apple pomace (28.2 µg/kg) and the levels of cadmium were lower than 10 µg/kg or even below MDL in all samples. The lead contents in all bars with honey samples were exceptionally higher than in the other samples (levels greater than130µg/kg). The intake of available gluten-free cereal bars are generally safe for consumers, but particular attention should be paid to monitor the content of arsenic and lead gluten-free cereal bars to ensure the quality of the product.

Baidoo et al. [18] determined the concentrations of heavy metals and found them to be As< 0.06 and < 0.04, Hg < 0.04 and < 0.04 and Cd < 0.08 and < 0.04 respectively for the seeds and the fruit. The average concentration of trace elements in the seed were: Al (11.50 µg/g), Ba (17.3 µg/g), Br (2.45 µg/g), Co (0.07 µg/g), Cu (28.6 µg/g) and Fe (>42 µg/g) for dried pulp fruit.

Khalifa et al. [19] analyzed various essential elements (Ca, Na, Mg, Fe, Cu and Zn) and non-essential elements (Al, As, Cd, Hg, Pb, Sb and Sn) in 56 samples, collected from different areas of Riyadh, Saudi Arabia. Mercury was not detected in any of the samples whereas Pb and Cd were detected in almost all the samples. Sb and Sn were found in the range of 0.04 and 0.054 ppm respectively. Rusks and biscuits type of food showed a little higher concentration of some elements. Daily intake of elements was calculated on the basis of information specified by the manufacturers of different branded formulae and baby food on the containers.

Mohammed [20] determined the levels of essential and toxic elements. Particle Induced X-ray Emission (PIXE) analysis was used as a complementary technique for the determination of P, Cr, Ni, Fe, Zn, and Cd that could not be determined by short irradiation INAA. The concentrations of .Na, Mg, Al, P, Cl, K, Ca, V, Cr, Mn, Fe, Cu, Zn, Br, and I were determined in food samples using a combination of both techniques.

The concentrations of elements in both foods were in the range of the elemental levels reported in the literature. However, concentrations of P which was an indicator of the anti-nutrition compound phyticacid, were found to be high. Rice from two regions reported to be the major cultivators of rice in Tanzania (Mbeya and Morogoro) showed similar elemental mean concentration levels.

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Emumejaye [21] determined the concentration of 40K in samples of powdered milk consumed in Delta State and also made a brief discussion of radioactivity transference from the environment to mankind. Ten samples of milk were collected and analyzed for radioactivity concentration. The results obtained for the milk sample were compared with World Health Organization (WHO) standard to ensure its safety to human consumption and were found to be lower than the permissible limits.

Rogan et al. [22] focused on the heavy metal contamination of the paddy soils and rice from Kocani Field (eastern Macedonia). Very high concentrations of As, Cd, Cu, Pb and Zn were found in the paddy soils (47.6, 6.4, 99, 983 and 1,245 μg/g) and the rice (0.53, 0.31, 5.8, 0.5 and 67 μg/g) in the western part of Kocani Field close to the Zletovska River which drains the mining facilities of the Pb–Zn mine in Zletovo. In terms of health risk, the observed highest concentrations of these elements in the rice could have an effect on human health and should be the subject of further investigations.

Choudhury et al. [23] analysed 31 elements by INAA using 5-minute and 6-hour thermal neutron irradiation followed by high-resolution γ-ray spectrometry. Heavy toxic metals e.g., Cd, Ni and Pb determined by atomic absorption spectrometry were found below permissible limits. Most elements in different brands vary in a narrow range. Ginger is particularly enriched in Ca, Fe, Mg and Mn whereas black pepper is enriched in Cr, Se, P and Zn. Cu/Zn shows linear relationship (r = 0.92) with Cu whereas Fe and Mn exhibit inverse correlation (r = –0.89) in different brands. Hydro distillation of pipali yielded an essential oil whereby 10 organic constituents were identified by GC-MS.

Tasneem et al. [24] analyzed TEs by electrothermal atomic absorption spectrometer, prior to microwave induced acid digestion. The validity of methodology was tested by simultaneously analyzing certified reference material and standard addition method. It was observed that ISF contains higher concentration of understudy toxic analysts as compared to IMF. All the three TEs, Al, Cd and Pb were detected in different branded infant formulae, in the range of (1070–2170), (10.5–34.4), and (28.7–119) μg/kg, respectively. The estimated intakes of TEs as μg/kg/week for infants (>1 year) through milk formulae are well below the recommended tolerable levels of these elements.

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The Radiation Monitoring Group, Office of Atoms for Peace (OAP) in cooperation with the Food and Drug Administration (FDA) [25] monitored the foodstuffs imported from Japan especially the Fukushima and nearby areas. The measurements were mainly conducted using gamma spectroscopy systems in order to analyze the radioactive concentration of I, Cs, and Cs fission products. In total 442 samples were analyzed after the nuclear accident. The samples were contaminated with fission isotopes in the ranges of 0.63-15.25 Bq/kg, 1.45-44.70 Bq/kg, and 0.45-51.10 Bq/kg for I, Cs, and Cs fission products respectively.

Calabrese et al. [26] carried out an investigation on the farmers in the Chernobyl accident areas and observed that the milk of their cows was contaminated with cesium- 137 above the limit of 300 Bq per liter imposed by Swedish authorities. Moreover, the cesium-137 limit for meat was accepted there as it was 600 Bq/kg, which, from a health physics point of view, is meaningless, as consumption of 1 kg of such a meat would correspond to a dose of 0.0078 mSv.

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References

[1] Joseph, E., Nasiru1, R., Ahmed Y.A., “Trace Elements Pattern in Some Nigerian Commercial Infant Milk and Infant Cereal Formulas”, Annals of Biological Research, 2 (2), 351-360, (2011).

[2] Ayivor, J.E., Debrah, S., Forson, A., Nuviadenu, C., Buah, K. A., Denutsui, D.,

“Trace Elements in Some Imported Commercial Infant Cereal Formulas on the Ghanaian Market by INAA”, Der Pharma Chemica, 3 (5), 94-100, (2011).

[3] Karin, L., Brita, P., Margaretha G., Marie V., “High concentrations of essential and toxic elements in infant formula and infant foods – A matter of concern”, Food Chemistry, 3(2), 34-39, (2011).

[4] Cot Statement on a Survey of Metals in Infant Food, “Committee on Toxicity of Chemicals in Food, Consumer Products and the Environment”, (2003).

[5] Shona, M.D., Julian, D., Willis, Lothar, R., “The Determination of Major and Trace Elements in Milk using ICP-Q-MS”, Thermo Scientific, Germany, 10(1), 56-61, (2014).

[6] Ayala, D., Ruvalcaba-Sil, J.L., “External PIXE-RBS Analysis of Bottling Baby Food”, PIXE 10th Int. Conference, 939, 1- 3, (2004).

[7] Gintarė, G., Dovile, L., Egle C., “Cd and Pb concentrations in the main groups of foodstuff” 9th Int. Conference on Environmental Engineering, May, (2014).

[8] Thorsten, S., Hasan T., Hubertus, B., “Aluminium content of selected foods and food products”, Envi. Sci. Europe, 23(37), 76-80, (2011).

[9] Judith, C., Thalheimer, “Recommended Uses of Common Infant Formulas”, 26(12), 32-40, (2014).

[10] Manfred, S., “Chocolate and Cocoa Products as a Source of Essential Elements in Nutrition”, J., Nutr. Food Sci., 2(1), 1-5, (2012).

[11] Tsdale, F., Mehari, LaVana, G., A‟ja, L., Duncan, Sayo O. F., “Trace and Macro Elements Concentrations in Selected Fresh Fruits, Vegetables, Herbs, and Processed Foods in North Carolina USA”, J. Envi. Prot., 6, 573-583, (2015).

[12] Kalantari, H., Kalantari, GH., Nazari, K. Z., “Evaluation of Aflatoxins Contamination in Baby Food Supplements (Mamana & Ghoncheh)”, J.Natural Pharmaceutical Products, 6(1): 42-50,(2011).

[13] Salah, F. A. A. E., Esmat, I. A., Mohamed, A. B., “Heavy metals residues and trace elements in milk powder marketed in Dakahlia Governorate”, Int. Food. Res. J., 20(4), 1807-1812, (2013).

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[14] European Food Safety Authority (EFSA), “Scientific opinion on the risks to public health related to the presence of perchlorate in food, in particular fruits and vegetables, on contaminants in the food chain (Contam)”, EFSA Journal, 12(10), 3869-3883, (2014).

[15] Taborsky, T., Hejtmankova, A., Dolejskovaj, J., “Reference materials for the determination of contaminants in milk and milk products”, Czech J. Food Sci., 21, 111–

120, (2003).

[16] Bamidele, Olu-Owolabi, S.O., Fakayode, K.O., Adebowale, P.C., Onianwa,

“Proximate and elemental composition and their estimated daily intake in infant formulae from developed and developing countries: A comparative analysis”, J. Food, Agriculture & Environment, 5 (2), 40-44, (2007).

[17] Melisa, J. H., Roxana, N. V., Sonia C. S., Eduardo J. M., Roberto G. P., “Toxic Trace Element Contents in Gluten-free Cereal Bars Marketed in Argentina”, Int. J.

Celiac Disease, 3(1), 12-16, (2015).

[18] Isaac, K. B., John J. F., Linda, O. P., Apori, N., Jude B. S., Nicholas S. O., Robert, E. Q., “Major, Minor and Trace Element Analysis of Baobab Fruit and Seed by Instrumental Neutron Activation Analysis Technique”, Food and Nutrition Sciences, 4, 772-778, (2013).

[19] Khalifa, A. S., Dilshad, A., “Determination of key elements by ICP-OES in commercially available infant formulae and baby foods in Saudi Arabia”, African Journal of Food Science, 4(7), 464 - 468, (2010).

[20] Mohammed, N. K., “Nuclear Techniques Applied to Biological Samples from Tanzania to Monitor the Nutritional Status of Children”, A Ph. D. thesis, University of Surrey, (2008).

[21] Emumejaye, K., “Determination of potassium – 40 (40K) concentration in some powdered milk samples consumed in Delta State, Nigeria”, IOSR J. App. Phy., 2(3), 08- 12, (2012).

[22] Rogan, N., Serafimovski, T., Dolenec, M., Tasev, G., Dolenec, T., “Heavy metal contamination of paddy soils and rice (Oryza sativa L.) from Kocani Field (Macedonia)”, Environ Geochem. Health, 31(4), 439-451, (2009).

[23] Choudhury, R. P., Kumar, A., Reddy, A. V. R., Garg, A.N., “Thermal neutron activation analysis of essential and trace elements and organic constituents in Trikatu:

An Ayurvedic formulation”, Journal of Radioanalytical and Nuclear Chemistry, 274(2), 411–419, (2007).

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[24] Tasneem, G., Kazi, N. J., Jameel, A., Baig, H., Afridi, G.A., Kandhro, M., Arain, M. K., Jamali, A., Shah, Q., “Determination of toxic elements in infant formulae by using electrothermal atomic absorption spectrometer”, Food and Chemical Toxicology, 47(7), 1425–1429, (2009).

[25] Itthipoonthanakorn, T., Krisanangkura, P., Udomsomporn, S., “The study on radioactive contamination in foodstuffs imported from Japan after the Fukushima accident”, J. of Radio-analytical & Nuclear Chemistry, 297(3), 419-422, (2013).

[26] Calabrese, E.J., Baldwin, L.A., “Toxicology rethinks its central belief”, Nature, 421(13), 691-692, (2003).

[27] Abdulaziz, A., El-Taher, A., “A Study on Transfer Factors of Radionuclides from Soil to Plant”, Life Science Journal, 2, 532-539, (2013).

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Chapter III

Theoretical Aspects Related to the Work

3.1 Theoretical Aspects of Neutron Activation Analysis

Neutron Activation Analysis (NAA) [1] method is a quantitative and qualitative method, based on the nuclear reaction between neutrons and target nuclei. It is a useful method for the simultaneous determination of major, minor and trace elements of geological, environmental, biological samples in ppb to ppm range without or with chemical separation [2]. In this elemental analysis method, radioactivity is measured from the energy of the activated elements in the sample irradiated by neutron beam. This NAA method has an excellent beauty to analyze all elements in the sample at once without any destruction. NAA method has the desirable feature of detection sensitivities for a large number of elements; each of which is identified via the energies of the gamma-ray photons of its neutron-induced radioisotope and corresponding half-life. It also has a high degree of accuracy and an excellent measurement precession [3].

3.2 Theory of Neutron Activation Analysis

Neutron activation is initiated through irradiation of a nucleus with neutrons to produce a radioactive species, usually referred to as a radionuclide. The number of radionuclides produced depends on the number of target nuclei. The number of neutrons depend on the factor called the cross section which defines the probability of activation occurring. If the activation product is radioactive, it will decay with a characteristic half-life. The nucleus has a certain finite life-time (10-13 - 10-15 seconds) during which it remains in a highly excited state (Fig. 3.1) due to the high binding energy and kinetic energy of the neutron in the nucleus. The energy of the neutrons bombarding the nucleus will dictate the type of interaction that occurs and consequently the nature of the activation product.

De-excitation of the compound nucleus occurs in different ways and is independent of the compound nucleus formation processes, the emitted gamma is called a prompt gamma, since it is emitted immediately after activation [4].