Research Journal of Applied Sciences, Engineering and Technology 3(3): 202-209, 2011 ISSN: 2040-7467 © Maxwell Scientific Organization, 2011 Received: January 16, 2011 Accepted: February 15, 2011 Published: March 30, 2011 Speciation of Nickel in Soils and Cereal 1 1 J.T. Ayodele and 2S.S. Mohammed Department of Pure and Applied Chemistry, Bayero University, Kano, Nigeria 2 Department of Applied Science, College of Science and Technology, Kaduna Polytechnic, Kaduna, Nigeria Abstract: The levels of trace elements in food and agricultural samples have been shown to influence human and plant metabolism. The study of heavy metal speciation is of interest for the evaluation of their mobility, bioavailability and ecotoxicity. In this study, the Nickel concentrations of the cereal and soil samples were determined using Flame Atomic Absorption Spectrometry (FAAS). The soil samples related to the cereal were digested and extracted using different digestion and extraction reagents. The results indicate that the soil samples collected from various locations, contain varying amounts of the metals, and it was distributed between Residual, Oxide and Carbonate fractions. The results of the study also showed that the lowest value of total Ni concentration in soil was in sampling point KC4 (2.93 mg/kg) and the highest value was in points ST6 and ST7 (105.37 mg/kg). In some of the sample locations, the Ni concentration was above the tolerable limit value of 50 mg/kg. The relationship between the cereal Ni and soil-extractable Ni concentrations was significant (p<0.05). Key words: Cereal, flame atomic absorption spectrometry, Nickel, soil, speciation surface or on inorganic cations exchange surfaces, watersoluble, and free-ion or chelated metal complexes in soil solution (Bennett, 1982). Much research has been conducted on heavy metals contamination in soils from various anthropogenic sources such as industrial wastes (Yusuf, 2006; Adeniyi and Okedeyi; 2004; Kakula and Osibanjo, 1988), automobile emissions (Arowolo et al., 2000; Ma and Rao, 1997), mining activity (Kabala and Singh, 2001; Ramos et al., 1994), street dusts (Ayodele and Gaya, 1994) and agricultural practice (Chlopecka et al., 1996; Gzyl, 1990). The total heavy metal content in soils provide a convenient means of expressing a measure of pollution, numerous reports have highlighted that such measures are deficient in predicting toxicity of metal pollutants (Yusuf, 2006). Heavy metals may be distributed among many components of the soil or sediment and may be associated with them in different ways (Harrison et al., 1981; Chlopecka et al., 1996; Kabala and Singh, 2001; Khairah et al., 2009). The nature of the association is referred to as speciation. The general approach for the soil speciation studies has been to separate the soil using different chemical reagents or solvents fractions and, by analyzing each fraction, to determine the amount of element combined or associated with each soil fraction or phase (Yaman et al., 2000). Therefore, the identification of the chemical form or phases of Nickel in soil is necessary for estimating its biological availability, physico-chemical reactivity and INTRODUCTION Nickel is a nutritionally trace metal for at least several animal species, micro-organisms and plants, and therefore either deficiency or toxicity symptoms can occur when respectively, too little or too much Nickel is taken up (Bencko, 1983; Scott-Fordsmand, 1997). Nickel and Nickel compounds have many industrial and commercial uses, and the progress of industrialization has led to increased emission of pollutants into ecosystems. Although Nickel is vital for the function of many organisms, concentrations in some areas from both anthropogenic release and naturally varying levels may be toxic to living organisms (Diagomanolin et al., 2004). Inhalation exposure in occupational settings is a primary route for nickel-induced toxicity, and may cause toxic effects in the respiratory tract and immune system (Bennett, 1982). The general exposure to nickel mainly concerned oral intake, primarily through waste and food, as a contaminant in drinking water or as both a constituent and contaminant of food (Haber et al., 2000). Nickel is generally distributed uniformly through the soil profile but typically accumulates at the surface from disposition by industrial and agricultural activities. Nickel may present a major problem in land near towns, in industrial areas, or even in agricultural land receiving wastes such as sewage sludge. Nickel can exist in soils in several forms such as inorganic crystalline minerals or precipitates, complexes and absorbed on organic cations Corresponding Author: S.S. Mohammed, Department of Applied Science, College of Science and Technology, Kaduna Polytechnic, Kaduna, Nigeria 202 Res. J. Appl. Sci. Eng. Technol., 3(3): 202-209, 2011 Fig. 1a: Map of Nigeria showing Kaduna state Fig. 1b: Map of Kaduna state showing Kaduna metropolis Air flow rate (L/min) - 5.0 Shit width (nm) - 0.2 HCl current (mA) - 8.0 transport in the environment and into the food chain (Yaman and Yusuf, 2002). In this research, Ni concentrations in maize and soil samples were determined by Flame Atomic Absorption Spectrometry (FAAS). The soil samples were dissolved by using the chemical reagents such as the mixture of HNO3/H2O2, oxalic acid, Na2 EDTA and Acetic acid. The relation between the maize Ni contents and the Ni contents of the soil extracts was also investigated. In the digestion and extraction procedures, concentrated nitric acid, hydrogen peroxide, 1.0M oxalic acid, 0.05M Na2EDTA and 1.0M acetic acid were used. Stock solution of Ni (1000 mg/L) was prepared by dissolving Ni (NO3)2 in 1.0 mol/L nitric acid. MATERIALS AND METHODS Preparation of samples: The research covered seven agricultural sites in Kaduna, Nigeria. The sites are: Nasarawa (NS), Sabon Tasha (ST), Unguwar Muazu (UM), Tudun Wada (TW), Kakuri (KK), Mando (MD), Kabala (KB) west and Kachia (KC). The samples were collected during the harvest season (Oct-Nov., 2008, 2009 and 2010). The soil samples were collected from the different areas enumerated at a depth of about 10 cm A flame atomic absorption spectro-photometer model 8010 Young Lin was used for the Ni determination. The optimum conditions for FAAS are given as below: Wave length (nm) - 232 Acetylene flow rate (L/min) - 1.8 203 Res. J. Appl. Sci. Eng. Technol., 3(3): 202-209, 2011 Fig. 1c: Map of Kaduna Metropolis nitric acid was then added and centrifuged. 60 cm³ water was added to the clear digest and was filtered. This was analysed for Ni using FAAS model 8010 Young Lin. A blank digest was carried out in the same way. below the surface (Yaman et al., 2005). The cereal samples were collected at each of the locations. Maize was chosen for the purpose of this research work as it is the staple food being produced and consumed in these areas. Kachia, a town situated about 130 km away from Kaduna was taken as a control Fig. 1(a, b, c). The cereal was thoroughly washed with water and allowed to drain on a filter paper. Both the cereal and soil samples were dried at 85ºC. All the analyses were carried out in the analytical laboratory of the department of Applied Science, College of Science and Technology, Kaduna Polytechnic, Kaduna - Nigeria Digestion and extraction of soil: Soil pH was measured (1:5, w/v) by digital pH meter. A modified Tessier et al. (1979) extraction method developed by Yaman et al. (2005) was used. 10 cm³ of a mixture of nitric acid-hydrogen peroxide (2+1) was added to 5g of soil sample and dried with occasional shaking on a hot plate and cooled. 4 cm³ of 1.5 mol/L nitric acid was added to the remainder, centrifuged and diluted to 60cm³ with water and filtered. The clear digest was analysed for Ni using FAAS model 8010 Young Lin. A blank digest was carried out in the same way. Soil extracts were obtained by shaking separately, 5 g of soil samples with 10 cm³ of 0.05 mol/L Na2EDTA (for carbonate and organically bound phases), 1.0 mol/L oxalic acid (for Wet ashing of cereal: Five (5) g of oven dried maize sample was accurately weighed into an evaporating dish and ashed at 480ºC in an ashing furnace for 4 h. 10 cm³ of a mixture of nitric acid-hydrogen peroxide (2+1) was added to the ashed sample and dried with occasional shaking on a hot plate and cooled, 4 cm³ of 1.5 mol/L 204 Res. J. Appl. Sci. Eng. Technol., 3(3): 202-209, 2011 Table 1: Results of Ni contents of maize and soil samples The results are mean values (mg/kg) ± standard deviation n = 3 Total metal conc Total metal conc in maize sample in soil sample Sample site maize HNO3/H2O2 metals samples (2+1) 5.85±2.9 5.85±2.9 KB1 KB2 38.05±17.8 14.63±2.9 KB3 58.54±29.3 17.56±2.9 KB4 5.85±2.9 8.78±2.9 KB5 29.27±2.9 17.56±2.9 KB6 35.12±2.9 20.49±5.9 KB7 32.20±2.9 20.49±5.9 KB8 38.05±2.9 22.44±6.1 Hot extraction ---------------------------------------------------------------EDTA Oxalic acid Acetic acid 0.05 M 1.0 M 1.0 M 2.93±0.0 14.63±2.9 26.34±2.9 8.78±2.9 11.71±2.9 14.63±2.9 8.78±2.9 14.63±5.9 17.56±5.9 6.15±3.0 17.56±5.9 26.34±5.9 11.71±2.9 14.63±5.9 17.56±2.9 14.63±2.9 17.56±2.9 17.56±5.9 11.71±2.9 17.56±5.9 17.56±2.9 14.63±2.9 17.56±5.9 20.49±5.9 Table 2: Results of Ni contents of maize and soil samples The results are mean values (mg/kg) ± standard deviation n = 3 Total metal conc. Total metal conc. in maize sample in soil sample Sample site maize HNO3/H2O2 metals samples (2+1) 11.71±5.9 11.71±2.9 NS1 NS2 29.27±2.9 11.71±2.9 NS3 43.90±2.9 14.63±5.9 NS4 14.63±5.9 11.71±2.9 NS5 32.20±2.9 14.63±2.9 NS6 38.05±2.9 17.56±2.9 NS7 11.71±2.9 11.71±5.9 NS8 32.20±2.9 14.63±2.9 Hot Extraction -------------------------------------------------------------------------EDTA Oxalic acid Acetic acid 0.05 M 1.0 M 1.0 M 14.63±2.9 43.90±2.9 26.34±2.9 11.71±5.9 23.41±2.9 17.56±5.9 11.71±5.9 36.10±19.5 17.56±2.9 14.63±2.9 46.83±2.9 29.27±2.9 14.63±5.9 26.34±2.9 20.49±5.9 17.56±5.9 29.27±2.9 23.41±2.9 23.41±2.9 11.71±5.9 35.12±2.9 14.63±5.9 29.27±2.9 23.41±2.9 pH 5.49 6.12 5.33 5.92 6.12 6.45 6.45 6.45 Table 3: Results of Ni contents of maize and soil samples The results are mean values (mg/kg) ± standard deviation n = 3 Total metal conc. Total metal conc. in maize sample in soil sample Sample site maize HNO3/H2O2 metals samples (2+1) MD1 8.78±2.9 23.41±2.9 MD2 32.20±2.9 8.78±2.9 MD3 35.12±2.4 11.71±2.4 MD4 14.63±2.9 29.27±2.9 MD5 35.12±2.9 35.12±2.9 MD6 35.08±2.9 17.56±2.9 MD7 35.12±2.9 17.56±2.9 MD8 32.20±2.9 8.78±2.9 Hot extraction -------------------------------------------------------------------------EDTA Oxalic acid Acetic acid 0.05 M 1.0 M 1.0 M 11.71±5.9 61.46±2.9 43.90±2.9 8.78±2.9 8.78±2.9 11.71±2.9 11.71±4.8 11.71±2.4 14.63±2.4 17.56±5.9 67.61±3.4 49.76±5.9 11.71±2.9 11.71±5.9 14.63±5.9 17.56±2.9 20.29±5.9 14.63±2.9 17.56±5.9 26.34±5.9 23.41±2.9 8.78±2.9 11.71±2.9 11.71±2.9 pH 4.15 4.45 4.56 4.35 4.26 4.75 4.75 4.75 oxide phases) and 1.0 mol/L acetic acid (for carbonate phases). The mixture was evaporated with occasional shaking on a hot plate. 4 cm³ of 1.5 mol/L nitric acid was added to the remainder and centrifuged. This is referred to as hot extraction. The digest was diluted to 60cm³ and analyzed for Ni using FAAS model 8010 Young Lin. A blank digest was carried out in the same way. pH 5.16 5.46 5.36 5.26 5.66 6.12 6.12 6.12 agricultural activities, soils from main roads and the various anthropogenic activities within the locations. This is in agreement with the result from other investigators (Kashem and Singh, 1998; Chamon et al., 2009; Hickey and Kittrick, 1984; Ana-Irina et al., 2008; Aydinalp and Marinova, 2003; Pei-Fang et al., 2008; Kashem et al., 2007; Khairah et al., 2004; Chamon et al., 2005). The lower Ni values obtained for some soil sites compared to other may be due to the lesser impact of anthropogenic sources of pollution in the locations. Similar findings were also observed by other investigators (Blom, 1986; Yusuf, 2007) reported a very drastic decrease in metal concentration away from the source point. The decreasing tendency with distance indicates the accumulation of metals by the anthropogenic activities within the locations. The pH of the soil samples from the various locations is acidic (Table 1-8). This could possibly increase the RESULTS AND DISCUSSION Total content of Ni in samples: The total content of Ni for the samples collected from the eight different agricultural locations at Kaduna, Nigeria are shown in Table 1 to 8. In general, the maize samples from KB, NS, MD, KK, UM, and KC had higher Ni concentrations than the corresponding soil samples. Maize sample obtained from site UM3 had the highest enrichment in Ni (107 mg/kg) compared to all the sites. This could be attributed to 205 Res. J. Appl. Sci. Eng. Technol., 3(3): 202-209, 2011 Table 4: Results of Ni contents of maize and soil samples The results are mean values (mg/kg) ± standard deviation n = 3 Total metal conc Total metal conc in maize sample in soil sample maize HNO3/H2O2 Sample site metals samples (2+1) KK1 5.85±2.9 5.85±2.9 KK2 29.27±2.9 5.85±2.9 KK3 35.12±2.9 8.78±2.9 KK4 11.71±2.9 11.71±2.9 KK5 32.20±2.9 32.20±2.9 KK6 35.12±2.9 11.71±2.9 KK7 32.20±2.9 11.71±2.9 KK8 35.12±2.9 11.71±5.9 Hot extraction -------------------------------------------------------------------------EDTA Oxalic acid Acetic acid 0.05 M 1.0 M 1.0 M 17.56±2.9 46.83±2.9 20.49±2.9 20.49±5.9 29.27±2.9 40.98±5.9 20.49±5.9 35.12±2.9 43.90±2.9 23.41±2.9 52.68±2.9 26.34±2.9 23.41±2.9 29.27±2.9 43.90±5.9 26.34±5.9 35.12±5.9 46.83±2.9 26.34±5.9 35.12±2.9 43.90±2.9 26.34±5.9 32.20±2.9 46.83±5.9 pH 5.08 4.98 5.14 5.14 5.18 5.58 5.08 4.98 Table 5: Tesults of Ni Contents of Maize and Soil Samples The results are mean values (mg/kg) ± standard deviation n = 3 Total metal conc Total metal conc in maize sample in soil sample maize HNO3/H2O2 Sample site metals samples (2+1) TW1 8.78±2.9 9.76±3.4 TW2 67.32±5.9 73.00 ±2.9 TW3 73.00 ±2.9 102.44±2.9 TW 4 70.24±2.9 76.10±2.9 TW 5 14.63±2.9 14.63±5.9 TW 6 70.24±2.9 70.24±2.9 TW 7 73.17±2.9 79.02±2.9 TW 8 73.17±5.9 76.10±2.9 Hot extraction ----------------------------------------------------------------------EDTA Oxalic acid Acetic acid 0.05 M 1.0 M 1.0 M 23.41±2.9 52.68±2.9 46.83±2.9 87.80±29.3 90.73±2.9 79.02±5.9 102.44±2.9 110.93±3.4 93.66±5.9 90.73±2.9 93.66±2.9 81.95±5.9 23.41±2.9 29.27±2.9 88.78±4.5 90.73±2.9 93.66±2.9 83.90±6.1 93.66±2.9 96.59±5.9 84.88±5.9 93.66±2.9 93.66±5.9 84.88±5.9 pH 5.07 5.12 5.25 5.27 5.17 5.49 5.49 5.49 Table 6: Results of Ni Contents of Maize and Soil Samples The results are mean values (mg/kg) ± standard deviation n = 3 Total metal conc Total metal conc in maize sample in soil sample maize HNO3/H2O2 Sample site metals samples (2+1) ST1 8.78±0.0 9.76±2.9 ST2 93.66±5.9 99.51±2.9 ST3 96.59±2.9 99.51±5.9 ST4 8.78±2.9 29.27±2.9 ST5 70.24±2.9 70.24±2.9 ST6 99.51±2.9 105.37±5.9 ST7 100.49±4.5 105.37±2.9 ST8 96.59±5.9 102.44±2.9 Hot extraction ------------------------------------------------------------------------EDTA Oxalic acid Acetic acid 0.05 M 1.0 M 1.0 M 23.41±2.9 52.68±2.9 46.83±2.9 90.73±2.9 93.66±2.9 81.95±2.9 90.73± 2.9 96.59±5.9 84.88±2.9 29.27±2.9 49.76±2.9 35.12±2.9 90.73±2.9 93.66±2.9 83.90±6.1 96.59±5.9 99.51±2.9 87.80±5.9 93.66±2.9 99.51±5.9 84.88±2.9 93.66±2.9 96.59±2.9 87.80±2.9 pH 5.14 5.20 5.24 5.82 5.25 6.10 6.10 6.10 Table 7: Results of Ni contents of Maize and soil samples The results are mean values (mg/kg) ± standard deviation n = 3 Total metal conc Total metal conc in maize sample in soil sample maize HNO3/H2O2 Sample site metals samples (2+1) UM1 5.85± 2.9 14.63±2.9 UM2 99.51±2.9 90.73±2.9 UM3 107.32±4.5 93.66±2.9 UM4 17.56±2.9 26.34±5.9 UM5 102.44±2.9 93.66±2.9 UM6 105.37±2.9 93.66±2.9 UM7 105.37±2.9 93.66±2.9 UM8 99.51±2.9 93.66±2.9 Hot extraction ------------------------------------------------------------------------EDTA Oxalic acid Acetic acid 0.05 M 1.0 M 1.0 M 17.56±2.9 52.68±2.9 30.24±4.5 93.66±5.9 81.95±5.9 81.95±2.9 93.66±5.9 81.95±2.9 84.88±5.9 29.27±2.9 64.39±2.9 40.98±2.9 96.59±2.9 84.88±2.9 84.88±5.9 99.51±2.9 87.80±5.9 87.80±2.9 99.51±5.9 84.88±5.9 87.80±5.9 96.59±2.9 84.88±5.9 84.88±5.9 pH 4.01 4.10 4.22 4.74 4.11 4.54 4.54 4.54 solubility and mobility of the metal in the soils. Such increase in solubility of the metal is likely to lead to increased availability of the metal for plant uptake, and it might cause Ni toxicity. The results indicate that appreciable soil acidification has taken place in the vicinity of the locations. Similar results were also reported by many authors (Baranowski et al., 2002; Kashem and Singh, 1998; Chamon et al., 2005). Metal speciation: The distribution of Ni in the soil samples collected from Kabala showed that the metal exists in three forms; the residual, oxide and carbonate phases (Table 1). The concentration of the metal bound to carbonate (CH3COOH) is higher than in the oxide [(COOH)2], EDTA or residual (HNO3/H2O2) except in KB6, KB7 and KB8, where its concentration is higher in residual fraction than the other two fractions. This shows 206 Res. J. Appl. Sci. Eng. Technol., 3(3): 202-209, 2011 Table 8: Results of Ni Contents of Maize and Soil Samples The results are mean values (mg/kg) ± standard deviation n = 3 Total metal conc Total metal conc in maize sample in soil sample maize HNO3/H2O2 Sample site metals samples (2+1) KC1 14.63± 2.9 73.17±5.9 KC 2 17.56±5.9 5.85±0.0 KC 3 17.56±2.9 5.85±2.9 KC 4 17.56±2.9 2.93±0.0 KC 5 49.76±2.9 38.05±2.9 KC 6 46.83±2.9 49.76±2.9 KC 7 49.76±5.4 43.90±5.9 Hot extraction ------------------------------------------------------------------------EDTA Oxalic acid Acetic acid 0.05 M 1.0 M 1.0 M 5.85±2.9 5.85±2.9 73.17±2.9 5.85±2.9 11.71±2.9 8.78±2.9 5.85±2.9 5.85±2.9 5.85±2.9 11.71±2.9 14.63±5.9 20.49±2.9 43.90±2.9 46.83±2.9 40.98±2.9 46.83±5.9 46.83±2.9 40.98±2.9 46.83±2.9 40.98±5.9 40.98±2.9 Table 9: Correlation Matrix for maize and different Ni extractable species in soil EDTA Oxalic acid Acetic acid Components Maize sample HNO3/H2O2 (a) Maize sample 1 0.743* 0.566 - 0.197 - 0.807 1 0.951** 0.314 - 0.718* HNO3/H2O2 EDTA 1 0.405 - 0.621 Oxalic acid 1 0.355 Acetic acid 1 - 0.474 pH 1 (b) Maize sample 1 0.625 -0.441 - 0.020 - 0.747* 1 -0.037 - 0.068 - 0.397 HNO3/H2O2 EDTA 1 - 0.559 0.841** Oxalic acid 1 - 0.139 Acetic acid 1 0.323 pH 1 (c) Maize Sample 1 -0.367 -0.044 - 0.918** - 0.883** 1 0.398 0.493 0.524 HNO3/H2O2 EDTA 1 0.432 0.504 Oxalic Acid 1 0.995** Acetic Acid 1 - 0.509 PH 1 (d) Maize sample 1 0.284 0.586 - 0.857** 0.995** 1 0.321 - 0.334 0.310 HNO3/H2O2 EDTA 1 - 0.282 0.645 Oxalic acid 1 - 0.855** Acetic acid 1 0.216 pH 1 (e) Maize sample 1 0.962** 0.994** 0.939** 0.605 1 0.982** 0.959** 0.632 HNO3/H2O2 EDTA 1 0.967** 0.581 Oxalic acid 1 0.401 Acetic acid 1 0.489 pH 1 (f) Maize sample 1 0.991** 0.998** 0.999** 0.985** 1 0.996** 0.984** 0.955** HNO3/H2O2 EDTA 1 0.995** 0.976** Oxalic acid 1 0.990** Acetic acid 1 0.203 pH 1 (g) Maize sample 1 0.995** 0.993** 0.959** 0.992** 1 0.999** 0.978** 0.998** HNO3/H2O2 EDTA 1 0.982** 0.999** Oxalic acid 1 0.986** Acetic acid 1 0.075 pH 1 *: Correlation is significant at the 0.05 level (2-tailed); **: Correlation is significant at the 0.01 level (2-tailed) 207 pH 6.16 6.24 6.15 6.08 6.07 6.14 6.01 pH 0.372 0.878** 0.917** 0.557 - 0.287 0.261 0.578 - 0.660 0.693 - 0.632 0.224 - 0.526 0.199 0.186 0.337 0.035 0.656 0.532 0.616 0.526 0.223 0.285 0.250 0.233 - 0.040 0.021 0.044 0.195 Res. J. Appl. Sci. Eng. Technol., 3(3): 202-209, 2011 Table 9: Continued Components Maize sample HNO3/H2O2 EDTA Oxalic acid Acetic acid (h) Maize sample 1 0.284 0.586 - 0.857** 0.995** 1 0.321 - 0.334 0.310 HNO3/H2O2 EDTA 1 - 0.282 0.645 Oxalic acid 1 - 0.855** Acetic acid 1 0.216 pH 1 *: Correlation is significant at the 0.05 level (2-tailed); **: Correlation is significant at the 0.01 level (2-tailed) pH 0.199 0.186 0.337 0.035 different forms have different mobilities, bioavailabilities and potential environmental contamination potential. The results on heavy metal speciation in the study indicated that the soil samples collected from various areas contain varying amounts of the metal. The metal was distributed between residual, oxide and carbonate fractions. An increase of the metal concentration in some areas suggests that heavy use of agrochemical materials for planting activities could cause increase in the content of heavy metals in the soil. that Ni in soils occurs in the carbonate, oxide and residual fractions with highest concentration coming from the carbonate fraction (KB1, KB4). Similar results were also reported by many authors (Yaman and Bakirdere, 2002; Hickey and Kittrick, 1984; Sposito et al., 1982). The Nickel concentration in the soil from Nasarawa (NS), showed that the metal exists also in three forms; that is residual, oxide and carbonate. The predominance of the oxide fraction in these areas is in agreement with the results reported by Hickey and Kittrick (1984) and Sposito et al. (1982). The carbonate fraction is the highest in NS7. This is in agreement with the result from other investigators (Yaman and Bakirdere, 2002). Similar observations were made in the other agricultural locations with respect to nickel concentration in soil fractions. In case of total Ni concentration in the soil, the lowest value was in point KC4 and the highest was in the sampling points ST6 and ST7. In some of these sampling locations, the Nickel concentration is above the tolerable limit value of 50 mg/kg (Baralkiewicz and Siepak, 1999). The highest concentration of Ni and the metals in the areas is not only a problem with respect to plant nutrition and the food chain, they may constitute a direct health hazards as well. The highest concentration of total and extractable Ni could be attributed to agricultural processes, heavy traffic and other anthropogenic activities within the locations (Kashem and Singh, 1998). HNO3/H2O2 extractable, EDTA extractable, CH3COOH extractable and (COOH)2 extractable Ni have been considered as available Ni (Lindsay and Norvell, 1978). These Ni species should measure available concentration of Ni in the soil samples of the agricultural locations. The results of correlation calculations (Table 9) shows that the HNO3/H2O2, EDTA, (COOH)2 and CH3COOH3 extractable and total Ni content in maize positively and significantly correlate with each other at 0.05 and 0.01 levels. Hence it could be deduced that the various reagents used were efficient for the extraction of this metal from the soil at these levels. ACKNOWLEDGMENT The authors show great appreciation to Kaduna Polytechnic, Nigeria for providing facilities to analyze the samples and to Nasiru Musa, Kabiru Shehu, Dr. A.O. Lawal, Yusuf Abdul-raheem, Sarkiyayi Shehu and Nuruddeen for the help in sample collection, metal and statistical analyses. REFERENCES Adeniyi, A.A. and O.O. Okediye, 2004. Assessing the speciation pattern of lead and zinc in surface water collected from Abegede Creek, Ijora, Lagos. Pak. J. Sci. Ind. Res., 47: 430-434. Ana-Irina, S., O. Vasile, J. 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