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International Journal of Food Nutrition and Safety, 2015, 6(2): 67-73 International Journal of Food Nutrition and Safety ISSN: 2165-896X Florida, USA Journal homepage: www.ModernScientificPress.com/Journals/IJFNS.aspx Article Evaluation of Some Heavy Metals in Food Crops of Lead Polluted Sites of Zamfara State, Nigeria Yahaya, M.Y.1*, Umar, R.A.1, Wasagu, R.S.U.1 and Gwandu, H.A.2 1 Department of Biochemistry, Faculty of Science, Usmanu Danfodiyo University, Sokoto, Sokoto State, Nigeria. 2 Department of Crop Science, Faculty of Agriculture, Usmanu Danfodiyo University, Sokoto, Sokoto State, Nigeria * Author to whom correspondence should be addressed; e-mail: [email protected] Article history: Received 15 May 2015, Received in revised form 26 June 2015, Accepted 10 July 2015, Published 15 July 2015. Abstract: Lead pollution has become an important public health issue nationwide especially in the Northern part of Nigeria, where some of the populace in the rural areas indulge in mining and smelting. The Level of heavy metals (Pb, Cd, Hg, Ni, Co) in three cereals collected from Dareta, Bagega and Abare villages of Anka L.G.A, Zamfara State were determined using atomic absorption spectrometer (AAS). Maize from Bagega (0.003±0.019 mg/g) has the highest Pb content and is significantly (P<0.05) higher than that from Dareta (0.050± 0.003 mg/g) and control (0.003±0.000 mg/g). Cadmium level is highest in maize grains from Dareta (0.005 ± 0.001 mg/g), compared to maize from the other two villages sampled. Nickel is highest in sorghum from Dareta (0.073±0.018 mg/g) and is significantly (P<0.05) higher than that from Abare (0.001±0.000 mg/g) and Bagega (0.072 ± 0.015 mg/g). Cobalt is highest in rice from Bagega (0.012± 0.003 mg/g) while mercury is highest in maize from the control site (0.124±0.007 mg/g), and is significantly (P<0.05) higher than that from Dareta (not detected). The concentration of all these metals was found to be above the WHO safe limits. This could be attributed to mining activities, organic and inorganic fertilizers application and acidification of the soil. Continued intake of these cereals may result in accumulation of the metals in the tissues of the villagers which may have a biochemical and toxicological implication. Keywords: Heavy metals, cereals, levels, Zamfara, lead poisoning. Copyright © 2015 by Modern Scientific Press Company, Florida, USA Int. J. Food Nutr. Saf. 2015, 6(2): 67-73 68 1. Introduction In the recent years, the rate at which humans are exposed to heavy metals poisoning has become an increasing concern due to the health risks they tend to pose. Exposure can be agricultural, commercial or industrial. Cereals can absorb these metals from the soil or dust containing them (SEPA, 1993). The 2009 lead poisoning disaster in some parts of Zamfara State, Nigeria was the largest in magnitude in the history of man. It involved more than one hundred and ninety nine (199) villages with a death toll of four hundred (400) (Anonymous, 2010). Rice, maize and sorghum were used to determine the levels of some heavy metals from Zamfara State. These three cereals were chosen as they belong in the thirty (30) most consumed crops in the world (Reddy, 2012) and also in our area of study. The elements of interest in this research are lead, cadmium, nickel, cobalt and mercury. Lead taken internally in any of its forms is highly toxic; the effects usually felt after it has accumulated in the body over a period of time (Guidotti and Ragain, 2007). Effects of lead exposure in humans include, abdominal pain, peripheral neuropathy and behavioral changes such as increased aggression with symptoms like anemia, colic, palsy, body weakness, constipation, and often paralysis of the ankles and wrists (Guidotti and Ragain, 2007). Buildup of cadmium levels in water, air, and soil has been occurring particularly in industrial areas. Acute exposure to cadmium fumes may cause flu like symptoms including chills, fever, and muscle ache sometimes referred to as "the cadmium blues." Symptoms may show after a week in the absence of respiratory damage (Shannon et al., 1998). More severe exposures can cause tracheobronchitis, pneumonitis, and pulmonary edema. Symptoms of inflammation may start hours after the exposure and include cough, dryness and irritation of the nose and throat, headache, dizziness, body weakness, fever, chills, and chest pain (Shannon et al., 1998). Exposure to cobalt can be through food since high levels are found in fish, nuts, green leafy vegetables and fresh cereals and most of the cobalt ingested is inorganic in nature (Barceloux, 1999). However, cobalt (as sulphate) is included in some multi-constituent licensed medicines, at a maximum daily dose of 0.25 mg. Occupational exposure to cobalt occurs usually through inhalation (“Cobalt”). Nickel is present in a number of enzymes in both plants and microorganisms and in humans it influences iron absorption and metabolism (Lenntech, 2011). Humans may be exposed to its pollution through breathing, drinking water, eating food (especially large quantities of vegetables) (Lenntech, 2011) or smoking cigarettes (“Nickel”). Mercury, a free-flowing liquid at room temperature (Henderson, 2000) known as ‘liquid silver’ occurs in deposits mostly as cinnabar. This metal is highly toxic by ingestion or inhalation of the dust. Mercury poisoning can occur from exposure to any of its form through inhalation of mercury vapor or ingestion, which is mostly by eating seafood (“Mercury”). Copyright © 2015 by Modern Scientific Press Company, Florida, USA Int. J. Food Nutr. Saf. 2015, 6(2): 67-73 69 2. Materials and Methods 2.1. Collection and Preparation of Samples Twenty seven composite samples were collected from three local (Bagega, Dareta and Abare) villages in Zamfara State while the control was taken from Kaduna State. The representative samples were further pulverized into small pieces using mortar and pestle. The semi-fine powdered form was then stored in plastic bags before they were subjected to dry ashing and dissolution in preparation for further analysis. 2.2. Chemicals All chemicals and solvents were collected form the Department of Biochemistry, Usmanu Danfodiyo University, Sokoto. 2.3. Dry Ashing 2.0g from each representative sample was placed inside a marked crucible and then placed into a furnace (Lenton, UK) with a fixed temperature of 6000C. It was left to be fully burned, that is turned into ash matter which took 3hrs. 2.4. Elemental Analysis The heavy metals lead, cadmium, nickel, cobalt and mercury were detected using the fast sequential atomic absorption spectrophotometer (Varian-AA240-FS model, US) using four (4) lamps with optimized determination time that sorts the elements in the standard and digested samples by wavelength and flame type. 2.4. Statistical Analysis The data were expressed in mean±standard error (SE) and analyzed using Graph Pad Instat Software, Sandiego USA) application. One-way ANOVA and Turkey’s multiple comparisons were carried out to test for any significant differences between the means. 3. Results and Discussion Upon completion of the analysis, the final results were computed and presented in table 1 below. Levels of heavy metals in maize, rice and sorghum obtained from lead polluted areas in Anka LGA, where estimated using Atomic absorption spectrometer (AAS). Pb concentration in maize samples were higher (table 1 above) than the Food and Agriculture Organization/ World Health Copyright © 2015 by Modern Scientific Press Company, Florida, USA Int. J. Food Nutr. Saf. 2015, 6(2): 67-73 70 Organization (FAO/WHO) 1986 codex (0.0003mg/g) and also far above previous values reported by Choi (2011) who reported the maximum level of lead to be 6ppm (0.006mg/g). Going by Choi’s work (2011), all other grains apart from those collected from Bagega and Dareta have lead levels that were within allowable limits. These levels were observed to be significantly (P<0.05) higher than the control and this can be explained by the absence of mining activities in the control area. Table 1: Heavy Metal Content of Cereals from Bagega, Dareta, Abare villages and Control in mg/g. Pb BAGEGA (mg/g) 0.081±0.019a DARETA (mg/g) ABARE (mg/g) CONTROL (mg/g) 0.050±0.003a 0.003/±0.000b 0.003±0.000b Cd 0.001±0.001a 0.005±0.001b BDL a- BDL a Ni 0.055±0.006a 0.060±0.010a BDL b BDL b Co 0.008±0.008 0.006±0.003 0.001±0.000 0.001±0.000 Hg 0.043±0.043 BDL a 0.000±0.013 0.124±0.007b Pb 0.036±0.011 0.042±0.031 0.005±0.000 0.003±0.000 Cd 0.002±0.000a 0.003±0.007a BDL b BDL b Ni 0.056±0.007a 0.063±0.006a 0.001±0.000b 0.001±0.000b Co 0.012±0.003 0.002±0.002 0.001±0.000 0.006±0.006 Hg 0.031±0.031 BDL BDL 0.060±0.005 Pb 0.028±0.008 0.017±0.017 0.004±0.000 0.002±0.000 Cd 0.003±0.001 0.004±0.002a BDL b BDL b Ni 0.072±0.015a 0.073±0.018a 0.001±0.000b BDL b Co 0.009±0.005 0.002±0.002 0.001±0.000 BDL Hg BDL a BDL a BDL a 0.080±0.001b SAMPLE MAIZE RICE SORGHUM BDL=Below detection limit; Values are mean±SE; P<0.05) Values with different superscript across the row differ significantly Low blood level of lead may be problematic over a long period as it exerts its toxicity mainly through the inhibition of heme synthesis whereby it competes with Fe 2+ at the site of porphyrin Copyright © 2015 by Modern Scientific Press Company, Florida, USA Int. J. Food Nutr. Saf. 2015, 6(2): 67-73 71 biosynthesis (hemoglobin)(Goldberg, 1968). This effect results in porphyria, a medical condition caused by the body’s failure to metabolize porphyrin. Cadmium in cereals according to the Food and Agriculture Organization/ World Health Organization (FAO/WHO) codex is 0.0002mg/g. Going by this, the detected values in this work present unsafe concentrations. Apart from the crops from Abare and the rice and sorghum grains from the control site, all other grains contained cadmium far above the safe limit, this discovery can be due to the remediation exercise that was carried out not long before this research. But previous work by Afshar et al., (1995) on Amol rice (a variety in Iran) reported lower values of cadmium compared to this work. The values reported of (0.00009mg/g) were lower than the WHO values (0.0002mg/g). Cadmium is relatively poorly absorbed into the body, but once absorbed, is slowly excreted like other metals, and accumulates in the kidney causing renal damage (“Cadmium”). The mechanism by which cadmium exerts its toxicity involves increasing oxidative stress due to it being a catalyst in the formation of reactive oxygen species, further increasing lipid peroxidation (oxidative degradation of lipids) (ATSDR, 2013). Bagega and Dareta heavy metal (nickel) content was higher than the reported levels in yam powder of lead and cadmium (Mei et al., 2013). However, the nickel content of Abare grains were similar to the earlier report (Mei et al., 2013). Other values for nickel were reported between the ranges of 0.00052-0.00814mg/g in maize sample (Mei et al., 2013). The above range was lower than the ones in this work in the grains collected from Bagega and Dareta respectively. Remarkably, the nickel content in all the grains are higher than the standard limit of 0.0004mg/g set by the Organization for Safety and Health Administration (OSHA, 2008). Foodstuffs naturally contain small amounts of nickel and its intake increases when people consume large quantities of vegetables from polluted soils since plants are known to accumulate nickel (Lenntech, 2011). Nickel exposure is associated with oxidative damage to DNA bases, inhibition of DNA repair enzymes (DNA polymerases ε, polymerase δ and DNA ligase which puts the final touch) and increase in reactive oxygen species by reduction and oxidation of metal ions (Fe2+/Fe3+). The mercury levels found in our samples are higher than those reported by the National Food Safety Standard on Contaminants in Food (2010), which presented a value of 0.00002mg/g Hg in grains. Mercury toxicity is mediated by inhibition of human thioredoxin system (Carvalho et al., 2008). Mercury can naturally be found deposited in soil, plants, rocks and tend to be much higher in seafood. Therefore, the levels could have been absorbed by the plants from the water or transferred through the air or dust (“Mercury”). The levels of cobalt recorded in this work are higher than the standard limit set by OSHA (0.000042mg/g). Cobalt has been reported to be essential to both humans and animals (“Cobalt”). It is Copyright © 2015 by Modern Scientific Press Company, Florida, USA Int. J. Food Nutr. Saf. 2015, 6(2): 67-73 72 a key constituent of cobalamin, also known as vitamin B12, which is the primary biological reservoir of cobalt as an "ultra trace" element (“Cobalt”). Cobalt is an essential element in life required in minute amounts (“Cobalt”). After nickel and chromium, cobalt is a major cause of contact dermatitis (“Cobalt”). Fortunately, the body system has glutathione as its primary detoxification mechanism and as such is responsible for the removal of these toxic metals from the body. 4. Conclusion The study established the presence of some heavy metals in the cereals from the area of study. Although the cereals may have absorbed the metals either from the mining sites through dust or were exposed to through soil and water as a result of acidification, which increases the heavy metal level in the soil. Another factor could have been through the application of in-organic fertilizers during farming. If the residents continue taking these cereals, their blood will eventually contain high levels of these metals. References China to move residents from lead smelter base-report. Reuters Dec 07-2009. Accessed 06-11-12. (http://www.reuters.com/article/rbcsindustrymaterialutilitiesnews) Gusau. Microsoft Student 2009. DVD. Redmond, WA: Microsoft Corporation, 2009c. Cadmium. Microsoft Student 2009. DVD. 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United States, Agency for Toxic Substances and Disease Registry: Cadmium Toxicity: How does Cadmium induce pathogenic changes. Atlanta, Georgia. ATSDR Publications, 2 Dec 10, 2013. Copyright © 2015 by Modern Scientific Press Company, Florida, USA