Asian Journal of Agricultural Sciences 4(4): 291-297, 2012 ISSN: 2041-3890 © Maxwell Scientific Organization, 2012 Submitted: May 11, 2012 Accepted: May 29, 2012 Published: July 15, 2012 The Uptake of Lead by Maize Grown on Selected Agricultural Areas of Kaduna Metropolis, Nigeria S.S. Mohammed, M.B. Mohammed and N. Musa Department of Applied Science, College of Science and Technology, Kaduna Polytechnic, Kaduna, Nigeria Abstract: The research was carried out to determine the uptake of the metal by maize from soil samples of Kaduna, Nigeria. The lead concentrations of the maize and soil samples were determined using Flame Atomic Absorption Spectrometry (FAAS). The soil samples related to the maize were digested and extracted using different digestion and extraction reagents. The results indicated that the soil samples collected from various locations contain varying amounts of Lead and was distributed between residual, Oxide and carbonate/organic fractions. The result of the study also showed that in all the sample locations, the Pb contained in the soil was below the tolerable limit of 200 mg/kg and the ANOVA (p = 0.000<0.05) showed a significant difference in both the Lead concentrations across the various maize crops and across the various maize grown soils. Keywords: Atomic absorption spectrometry, kaduna metropolis, lead, maize, soil INTRODUCTION MATERIALS AND METHODS In many developing countries like Nigeria, soils are affected by mine waste disposal, acid deposition, sewage sludge and other anthropogenic and agricultural practices. Heavy metal contamination of arable soils through industrial and anthropogenic activities is a serious problem in Nigeria. The impact of contamination on the environment should be of scientific concern in order to minimize the threat of soil and groundwater contamination (Matos et al., 2001). Much research has been conducted on heavy metals contamination in soils from various anthropogenic sources such as industrial wastes (Adeniyi and Okediye, 2004; Yusuf, 2006), automobile emissions (Arowolo et al., 2000), mining activity (Kabala and Singh, 2001) and agricultural practice (Ayodele and Mohammed, 2011; Khairah et al., 2009). 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; Ayodele and Mohammed, 2011). Therefore the identification of chemical forms or phases of Pb in soil is necessary for estimating its biological availability, physico-chemical reactivity and transport in the environment and into the food chain (Yaman and Yusuf, 2002a). In this research, Pb concentration in maize and soil samples were extracted using the chemical reagents such as the mixture of HNO3/H2O2; Oxalic acid, Na2 EDTA and acetic acid. The relation between the maize and soil extracts lead contents was investigated. A flame atomic absorption spectrophotometer model 8010 Young Lin was used for the Pb determination. In the extraction procedures, 1.0 M oxalic acid, 0.05 M Na2EDTA and 1.0 M acetic acid were used. 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 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. 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 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. Ten cm³ of a mixture of nitric acid-hydrogen peroxide Corresponding Author: S.S. Mohammed, Department of Applied Science, College of Science and Technology, Kaduna Polytechnic, Kaduna, Nigeria 291 Asian J. Agric. Sci., 4(4): 291-297, 2012 Fig. 1: Map of Kaduna metropolis showing the sampling sites 292 Asian J. Agric. Sci., 4(4): 291-297, 2012 (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 nitric acid was then added and centrifuged. Sixty cm³ water was added to the clear digest and was filtered. This was analysed for Pb using FAAS model 8010 Young Lin. A blank digest was carried out in the same way. 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. Ten cm³ of a mixture of nitric acid-hydrogen peroxide (2+1) was added to 5 g of soil sample and dried with occasional shaking on a hot plate and cooled. Four cm³ of 1.5 mol/L nitric acid was added to the remainder, centrifuged and diluted to 60 cm³ with water and filtered. The clear digest was analysed for Pb 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 oxide phases) and 1.0 mol/L acetic acid (for carbonate phases). The mixture was evaporated with occasional shaking on a hot plate. Four 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 60 cm³ and analyzed for Pb using FAAS model 8010 Young Lin. A blank digest was carried out in the same way. RESULTS Lead content in maize and soils: The lead content for the samples from the different sampling locations is shown in Table 1-8. The results from the sampling locations indicate higher concentrations of the metal in maize than the corresponding soil. The concentration of the metal in KK is higher in soil than the corresponding maize sample. This is in agreement with the results by other investigators who observed similar variations (Yaman et al., 2000; Yaman and Bakirdere, 2002b; Wieczorek et al., 2005; Ana-Irina et al., 2008). The concentration of the metal in soil was highest in MD5, MD6, MD8, KK5 and KK6. In all the sampling locations, the Pb content in the soil was below the tolerance limit of 200 mg/kg (Lindsay and Norvell, 1978). The ANOVA (p = 0.000<0.05) showed a significant difference in the Lead concentrations across the various maize samples. The differences in Lead concentrations can further be deduced by a post-hoc test using the Duncan Multiple range test where the means of homogeneous subgroups are clearly displayed. Moreover, the mean plots that follow depict the mean values of the Lead concentrations across the various maize crops. The Duncan multiple range tests indicated that Sabon Tasha and Kachia had the least Lead concentration in maize crops. While Mando and Nasarawa had the highest Lead concentration as depicted in Fig. 2. Metal speciation: The Pb distribution in the soil samples collected from the sampling locations, varied from one site to other. The metal exists in the forms; residual, oxide, Fe-Mn oxide and carbonate/organic. The concentration of the metal bound to residual fraction is highest in KB, KK , TW and UM . Therefore, Pb is said to be residual species, bioavailable, mobile and available for plant uptake in these locations (Yaman et al., 2000; Baranowski et al., 2002; Yaman and Bakirdere, 2002b). The concentration of Pb bound to carbonate/organic fraction is highest in NS and ST. The metal is said to be organically bound. Thus, bioavailable, mobile and available for plant Table 1: Results of Pb concentrations in maize and soil samples at Kabala Hot extraction ----------------------------------------------------------------------------------------------------------------Metal conc in Metal conc in soil sample HNO3 maize sample Sample site pH EDTA 0.05 M Oxalic acid 1.0 M Acetic acid 1.0 M HNO3/H2O2(2+1) H2O2 (2+1) KB1 KB2 KB3 KB4 KB5 KB6 KB7 KB8 5.16 5.46 5.36 5.26 5.66 6.12 6.12 6.12 4.05±0.9 4.05±0.9 38.33±1.7 36.67±3.3 38.33±1.7 40.00±1.7 40.00±1.7 40.00±1.7 3.33±1.7 3.33±1.7 25.00±1.7 31.11±3.5 26.67±1.7 28.50±3.1 26.67±3.3 28.33±1.7 3.33±1.7 3.33±1.7 23.33±3.3 6.67±1.7 25.00±3.3 26.67±3.3 26.67±1.7 26.67±1.7 Results of mean values (mg/kg) ±standard deviation (n = 3) 293 6.67±1.7 6.67±1.7 31.67±1.7 5.00±1.7 30.00±1.7 33.33±1.7 31.83±3.6 31.67±3.3 11.67±1.7 11.67±1.7 25.00±1.7 6.67±3.3 25.00±1.7 26.67±1.7 26.67±3.3 28.33±3.3 Asian J. Agric. Sci., 4(4): 291-297, 2012 Table 2: Results of Pb concentrations in maize and soil samples at Nasarawa Hot extraction ---------------------------------------------------------------------------------------------------------------Metal conc in Metal conc in soil sample HNO3 maize sample Sample site pH EDTA 0.05 M Oxalic acid 1.0 M Acetic acid 1.0 M HNO3/H2O2(2+1) H2O2 (2+1) NS1 5.49 5.00±1.7 5.00±1.7 6.67±1.7 21.67±1.7 13.33±1.7 NS2 6.12 58.33±3.3 51.67±1.7 91.67±3.3 71.67±3.3 51.67±3.3 NS3 5.33 60.00±3.3 53.33±1.7 91.67±3.3 74.44±3.5 53.33±1.7 NS4 5.92 40.00±1.7 31.67±3.3 6.67±1.7 5.00±3.3 6.67±1.7 NS5 6.12 60.00±1.7 53.33±1.7 93.33±1.7 73.33±1.7 53.33±1.7 NS6 6.45 61.67±3.3 53.33±1.7 95.00±3.3 75.00±1.7 55.00±3.3 NS7 6.45 60.00±1.7 55.00±3.3 93.33±3.3 75.00±1.7 53.33±1.7 NS1 5.49 5.00±1.7 5.00±1.7 6.67±1.7 21.67±1.7 13.33±1.7 Results of mean values (mg/kg) ±standard deviation (n = 3) Table 3: Results of Pb concentrations in maize and soil samples at Mando Hot extraction ---------------------------------------------------------------------------------------------------------------Metal conc in Metal conc in soil sample HNO3 maize sample Sample site pH EDTA 0.05 M Oxalic acid 1.0 M Acetic acid 1.0 M HNO3/H2O2(2+1) H2O2 (2+1) MD1 4.15 3.33±1.6 10.00±1.6 5.00±1.4 31.67±1.6 21.67±1.6 MD2 4.45 60.00±1.7 58.33±3.3 50.00±16.7 73.33±3.3 55.00±3.3 4.56 58.33±3.3 56.67±1.7 51.67±1.7 73.33±1.7 56.67±1.7 MD3 4.35 11.67±1.7 21.67±1.7 11.67±3.3 41.67±3.3 31.67±3.3 MD4 4.26 61.67±1.7 61.67±1.7 51.67±1.7 75.00±1.7 56.67±1.7 MD5 4.75 63.33±1.7 61.67±1.7 53.33±1.7 76.67±3.3 66.67±3.3 MD6 4.75 63.33±3.3 61.11±3.5 53.33±1.7 76.83±1.9 58.33±3.3 MD7 4.75 63.33±1.7 61.67±1.7 53.33±1.7 76.67±1.7 58.33±1.7 MD8 Results of mean values (mg/kg) ±standard deviation (n = 3) Table 4: Results of Pb concentrations in maize and soil samples at Kakuri Hot extraction -------------------------------------------------------------------------------------------------------------Metal conc in Metal conc in soil sample HNO3 maize sample HNO3/H2O2(2+1) H2O2 (2+1) Sample site pH EDTA 0.05 M Oxalic acid 1.0 M Acetic acid 1.0 M 5.08 2.50±1.7 2.50±1.7 6.25±1.7 15.00±1.7 10.00±7.3 KK1 KK2 4.98 56.67±3.3 58.33±3.3 46.67±3.3 43.33±1.7 46.67±1.7 5.14 58.33±1.7 60.00±1.7 48.33±3.3 45.00±3.3 48.33±1.7 KK3 5.14 11.67±1.7 21.67±1.7 11.67±3.3 41.67±3.3 31.67±3.3 KK4 KK5 4.34 61.67±1.7 61.67±1.7 51.67±1.7 75.00±1.7 56.67±1.7 5.15 63.33±1.7 61.67±1.7 53.33±1.7 76.67±3.3 66.67±3.3 KK6 4.5 63.33±3.3 61.11±3.5 53.33±1.7 76.83±0.0 58.33±3.3 KK7 KK8 4.5 26.09±0.7 26.83±0.7 22.36±1.5 20.87±0.7 21.61±1.5 Results of mean values (mg/kg) ±standard deviation (n = 3) Table 5: Results of Pb concentrations in maize and soil samples at T/wada Hot extraction -------------------------------------------------------------------------------------------------------------Metal conc in Metal conc in soil sample HNO3 maize sample HNO3/H2O2(2+1) H2O2 (2+1) Sample site pH EDTA 0.05 M Oxalic acid 1.0 M Acetic acid 1.0 M TW1 5.07 3.33±1.7 3.33±1.7 8.33±1.7 20.00±1.7 13.33±7.3 TW2 5.12 50.00±16.7 18.33±1.7 13.33±3.3 6.67±3.3 TW3 5.25 53.33±1.7 20.00±1.7 15.00±1.7 6.67±3.3 10.00±1.7 TW4 5.27 18.33±1.7 15.00±1.7 13.33±1.7 11.67±1.7 13.33±1.7 TW5 5.17 51.67±1.7 51.67±1.7 15.00±1.7 8.33±1.7 10.00±3.3 TW6 5.49 53.33±1.7 21.67±1.7 16.67±1.7 10.00±1.7 11.67±3.3 TW7 5.49 51.67±1.7 21.67±1.7 16.67±1.7 8.33±1.7 11.67±1.7 5.49 51.67±1.7 21.67±1.7 TW8 Results of mean values (mg/kg) ±standard deviation (n = 3) 15.00±3.3 10.00±1.7 11.67±1.7 294 8.33±3.3 Asian J. Agric. Sci., 4(4): 291-297, 2012 Table 6: Results of Pb concentrations in maize and soil samples at S/tasha Hot extraction -------------------------------------------------------------------------------------------------------------Metal conc in Metal conc in soil sample HNO3 maize sample HNO3/H2O2(2+1) H2O2 (2+1) Sample site pH EDTA 0.05 M Oxalic acid 1.0 M Acetic acid 1.0 M ST1 5.14 5.00±1.7 5.00±1.7 10.00±1.7 20.00±1.7 11.67±1.7 ST2 5.20 15.00±3.3 11.67±3.3 13.33±3.3 10.00±1.7 10.00±3.3 ST3 5.25 15.00±3.3 13.33±3.3 11.67±3.3 10.00±3.3 10.00±1.7 ST4 5.82 20.00±1.7 16.67±1.7 15.00±3.3 13.33±1.7 15.00±1.7 ST5 5.25 16.67±1.7 13.33±3.3 15.00±1.7 11.67±1.7 11.67±3.3 6.10 16.67±1.7 15.00±1.7 16.67±3.3 13.33±3.3 13.33±1.7 ST6 ST7 6.10 16.67±1.7 15.00±3.3 16.67±1.7 13.33±1.7 11.67±3.3 ST8 6.10 15.00±3.3 13.33±3.3 15.00±1.7 11.67±3.3 11.67±1.7 Results of mean values (mg/kg) ±standard deviation (n = 3) Table 7: Results of Pb concentrations in maize and soil samples at U/muazu Hot extraction -------------------------------------------------------------------------------------------------------------Metal conc in Metal conc in soil sample HNO3 maize sample HNO3/H2O2(2+1) H2O2 (2+1) Sample site pH EDTA 0.05 M Oxalic acid 1.0 M Acetic acid 1.0 M UM1 4.01 3.33±1.7 6.67±1.7 8.33±1.7 13.33±1.7 13.35±1.6 UM2 4.10 53.33±1.7 11.67±3.3 10.00±1.7 8.33±3.3 10.00±3.3 UM3 4.22 55.00±3.3 13.33±1.7 11.67±3.3 10.00±1.7 11.67±3.3 UM4 5.82 18.33±1.7 16.67±1.7 13.33±3.3 15.00±3.3 13.33±3.3 UM5 4.11 55.00±1.7 13.33±1.7 11.67±3.3 10.00±3.3 8.33±3.3 UM6 4.54 56.67±3.3 15.00±3.3 13.33±3.3 11.67±1.7 13.33±1.7 UM7 4.54 55.00±1.7 15.00±1.7 13.33±1.7 10.00±1.7 13.33±1.7 4.54 55.00±1.7 15.00±1.7 UM8 Results of mean values (mg/kg) ±standard deviation (n = 3) 11.67±3.3 10.00±1.7 13.33±1.7 Table 8: Results of Pb concentrations in maize and soil samples at Kachia Sample site KC1 KC2 KC3 KC4 KC5 KC6 KC7 KC1 pH 6.16 6.24 6.15 6.08 6.07 6.14 6.01 6.16 Metal conc in maize sample HNO3/H2O2(2+1) 18.33±1.7 30.00±3.3 30.00±3.3 30.00±10.2 25.00±1.7 17.44±21.6 26.67±1.7 18.33±1.7 Hot extraction -------------------------------------------------------------------------------------------------------------Metal conc in soil sample HNO3 H2O2 (2+1) EDTA 0.05 M Oxalic acid 1.0 M Acetic acid 1.0 M 13.33±1.7 26.67±1.7 28.33±3.3 28.33±5.6 11.67±1.7 14.73±19.5 6.67±1.7 13.33±1.7 11.67±1.7 35.00±1.7 25.00±3.3 25.00±9.8 6.67±1.7 16.71±20.1 5.00±1.7 11.67±1.7 15.00±3.3 35.00±1.7 36.67±1.7 36.67±5.3 3.33±1.7 13.99±18.0 5.00±3.3 15.00±3.3 11.67±3.3 26.67±1.7 26.67±3.3 26.67±7.7 5.00±1.7 13.99±18.2 5.00±1.7 11.67±3.3 Results of mean values (mg/kg) ±standard deviation (n = 3) uptake Similar results were reported by other workers working under similar conditions (Yaman et al., 2000; Takac et al., 2009). The metal concentration bound to oxide fraction is highest in KB, MD, KK and KC. Thus, is said to be oxide species and available for plant uptake in these locations. Similar results were observed by several authors working in similar situations (Yaman et al., 2000; Feng et al., 2009). The Pb concentration associated with Fe-Mn oxide fraction is highest in MD and ST. The metal is said to be Fe-Mn oxide species, bioavailable, mobile and available for plant uptake in these sampling locations (Urunmatsoma et al., 2010). The pH of the soil samples from all the locations is acidic. This could be attributed to heavy traffic anthropogenic and agricultural activities on the sampling sites (Yusuf, 2007; Chamon et al., 2009; Khairah et al., 2009). The bioavailability of lead decreases with increasing pH (Moraghan and Mascani, 1991; Morel, 1997). 295 Me an of le ad concentration in maize sample (mg/K g) Asian J. Agric. Sci., 4(4): 291-297, 2012 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. 60.00 50.00 40.00 30.00 20.00 Ka ch ia Ka ba la we st Na s ar aw a Ma nd o Ka ku ri Tu du nw ada Sa bo n ta s Un ha gw an mu az u 10.00 Sites Fig. 2: Mean plot for lead concentration in maize crops Mean of lead concentr a tion in soil sample (mg/K g) 50.00 ACKNOWLEDGMENT The authors show great appreciation to Kaduna Polytechnic, Nigeria for providing facilities to analyze the samples and to Kabiru Shehu and Yusuf Abdul Raheem, for the help in sample collection, metal and statistical analyses. REFERENCES 40.00 30.00 20.00 Ka ch i a Sab on t as ha Un gw an mu az u ri nw a da Ka ku Tu du Ka ba la w est Na sa r aw a Ma n do 10.00 Sites Fig. 3: Mean plot for lead concentration in maize grown soil The ANOVA (p = 0.000<0.05) indicated a significant difference in the Lead concentrations across the various maize soils. The real differences of Lead concentrations in maize soils can further be analyzed by a post-hoc test using the Duncan Multiple range test where the means of homogeneous subgroups are displayed. Moreover, the mean plots clearly depict the mean values of the Lead concentrations across the various maize soils. The Duncan multiple range tests showed that Sabon Tasha and Ungwan Muazu had the least Lead concentration in maize soils. While kakuri, Nasarawa and Mando had the highest Lead concentration in soil as depicted in Fig. 3. 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