British Journal of Pharmacology and Toxicology 3(2): 58-64, 2012 ISSN: 2044-2467

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British Journal of Pharmacology and Toxicology 3(2): 58-64, 2012
ISSN: 2044-2467
© Maxwell Scientific Organization, 2012
Submitted: January 21, 2012
Accepted: February 17, 2012
Published: April 25, 2012
Identification of Chemical Forms of Lead in Soil and Guinea Corn of Kaduna
Metropolis-Nigeria
1
1
S.S. Mohammed and 2J.T. Ayodele
Department of Applied Science, College of Science and Technology, Kaduna Polytechnic,
Kaduna, Nigeria
2
Department of Pure and Industrial Chemistry, Bayero University, Kano, Nigeria
Abstract: The identification of chemical forms of lead in agricultural samples is of interest for the evaluation
of its mobility, bioavailability and ecotoxicity. In this study, the lead concentrations of the guinea corn and soil
samples were determined using Flame Atomic Absorption Spectrometry (FAAS). The soil samples related to
the guinea corn 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 metal and was
distributed between residual, oxide and carbonate fractions. The result of the study also showed that in all the
samples locations, the Pb contain in the soil was below the tolerable limit of 200 mg/kg and the ANOVA (p
= 0.002<0.05) indicated a significant difference in the Pb concentrations across the various guinea corn
samples. Similarly, the ANOVA (p = 0.040<0.05) also indicated a significant difference in the Pb
concentrations across the various guinea corn grown soils.
Key words: Chemical forms, flame atomic absorption spectrometry, guinea corn, lead, soil
automobile emissions (Arowolo et al., 2000; Ma and Rao,
1997), Street dusts (Ayodele and Gaya, 1994) and
agricultural practice (Chlopecka et al., 1996; Gzyl, 1990;
Ayodele and Mohammed, 2011). The total heavy metal
content in the 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; Ayodele
and Mohanmmed, 2011). Therefore, the identification of
the chemical forms or phases of lead 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, 2002). In this research,
Lead concentration in Guinea corn and soil samples were
extracted using the chemical reagents such as the mixture
of HNO3 /H2 O2 , oxalic acid, Na2 EDTA and acetic acid.
The relation between the guinea corn and soil extracts
lead contents was investigated.
INTRODUCTION
Apart from natural weathering processes, the sources
of lead pollution are mining and smelting of the ores,
emissions from automobile exhaust and effluent from
storage battery industries use of glazed earthen waxcontainers, bad pipes and lead pigments (Hodel and
Chang, 2004). Organic lead, as tetraethyl and tetra methyl
lead is more acutely poisonous than inorganic lead. Lead
affects every organ system in the body. It is absorbed into
the body and distributed to the body, soft tissue and
bones. The central nervous system is the most vulnerable
to lead toxicity particularly in developing children
(Berthelson et al., 1995; Yaman et al., 2000). Heavy
metals and persistent organic pollutants are of concern
due to their potential harmful effects on human beings and
the environment. Studies have shown that the heavy
metals are potentially toxic to crops, animals and humans
when contaminated soils are used for crop production
(Xian, 1989). Heavy metals derived from anthropogenic
sources can strongly influence their speciation and
availability in the soil (Dutta et al., 1989). Heavy metals
from anthropogenic sources are also believed to be easily
accumulated in the top soil (Wang et al., 2003; Lu et al.,
2005). 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),
MATERIALS AND METHODS
A flame atomic absorption spectrophotometer model
8010 Young Lin was used for the Pb determination. In the
digestion and extraction procedures, concentrated nitric
Corresponding Author: S.S. Mohammed, Department of Applied Science, College of Science and Technology, Kaduna
Polytechnic, Kaduna, Nigeria
58
Br. J. Pharmacol. Toxicol., 3(2): 58-64, 2012
Fig. 1: Map of Kaduna metropolis showing the sampling sites
acid, hydrogen peroxide, 1.0 M oxalic acid, 0.05 M Na2
EDTA and 1.O M acetic acid were used.
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 guinea corn was thoroughly washed and allowed
to drain on a filter paper. Both the guinea corn 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.
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 samples were collected from the different
areas enumerated at a depth of about 10 cm below the
surface (Yaman et al., 2005). The guinea corn samples
were collected at each of the locations. Guinea corn was
chosen for the purpose of the research study as it is the
Wet ashing of guinea corn: Five (5) g of oven dried
guinea corn samples was accurately weighed into an
evaporating dish and ashed at 480ºC in an ashing furnace
for 4 h.10 cm of a mixture of nitric acid-hydrogen
59
Br. J. Pharmacol. Toxicol., 3(2): 58-64, 2012
M ean of lead concentration in
guinea corn sam ple (m g/K g)
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 nitric acid was then added and centrifuged.
60 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.10 cm3 of a mixture of nitric acidhydrogen peroxide (2:1) was added to 5 g 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 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 Na2 EDTA (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. 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 60 cm3 water and
analysed for Pb using FAAS model 8010 Young Lin. A
blank digest was carried out in the same way.
6.00
5.00
4.00
3.00
2.00
1.00
K achia
S abon Tasha
U ngw an m uazu
Sites
Tudun w ada
K akuri
M ando
N asaraw a
K abala
w est
0.00
Fig. 2: Mean plot for lead concentration in guinea corn crops
(2000), Yaman and Bakirdere (2002) and Khairah et al.
(2009). Similar observations were made in the other
sampling locations. The concentration of the metal in soil
was highest at NS3 and least at KC3, KC4, KC6 and KC7.
In all the sampling locations, the Pb content in the soil
was below the tolerable limit of 200 mg/kg (Lindsay and
Norvell, 1978).
The ANOVA (p = 0.002<0.05) indicated a significant
difference in the Lead concentrations across the various
guinea corn soils. The real differences in Lead
concentrations can further be deduced by a post-hoc test
using the Duncan Multiple range test where means of
homogeneous subgroups are clearly displayed. Moreover,
the mean plots that follow depict the mean values of the
Lead concentrations across the various guinea corn crops.
The Duncan multiple range tests showed that Kachia,
Kakuri and Mando had the least Lead concentration while
Kabala west and Sabon Tasha had the highest lead
concentration as shown in Fig. 2.
RESULTS
Lead content in guinea corn and soils: The lead content
for the samples collected from the sampling locations is
shown in Table 1 to 8 The results of the Pb concentration
in guinea corn and soil varied from one location to
another. In the sampling sites Kabala (KB), the Pb
concentrations in guinea corn was higher than in the
corresponding soil. However, the sampling site, KB8
showed a higher concentration of the metal in the soil
than the corresponding guinea corn. This could be
attributed to agricultural activities, heavy traffic and other
anthropogenic activities at the sampling locations. Similar
results were reported by many investigators (Yaman and
Bakirdere, 2002; Yaman et al., 2000). The Pb
concentration at Nasarawa (NS) varied from one sampling
site to another NS1, NS2, NS4, NS7, NS8 showed higher
concentrations of the metal in guinea corn than the
corresponding soil samples, while NS3, NS5, NS6 showed
higher concentration of Pb in the soil than the
corresponding guinea corn. The variation in the metal
concentration could be attributed to the level of
agricultural and human activities in these locations. This
is in agreement with the results reported by Yaman et al.
Metal speciation: The distribution of Pb in the soil
samples collected from Kabala (KB), varied from one
sampling site to another. The metal existed in residual,
oxide and carbonate/organic phases.
The concentration of Pb bound to the residual
fraction (HNO3/H2O2) is highest in KB1, KB7 and KB8.
The residual fraction probably caused a release of the
metal into the soil solution, hence available for the plant
uptake. Thus, the metal is bioavailable and mobile in the
soil. Similar results were reported by Yaman et al. (2000),
Baranowski et al. (2002) and Yaman and Bakirdere
(2002).
The concentration of the metal bound to carbonate
fraction (CH3COOH) is highest in KB2, KB3, KB4 and
KB6. Hence the metal is said to be carbonate species and
available for plant uptake (Yaman et al., 2000; Yaman
60
Br. J. Pharmacol. Toxicol., 3(2): 58-64, 2012
Table 1: Results of Pb concentrations in G/Corn and soil samples at Kabala, Results of mean values (mg/kg)±STD DEV (n = 3)
Hot extraction
-----------------------------------------------------------------------------------------------Metal conc in G/Corn
Metal conc in soil sample
EDTA
Oxalic acid
Acetic acid
HNO3/H2O2 (2+1)
0.05 M
1.0 M
1.0 M
Sample site
pH
sample HNO3/H2O2 (2+1)
4.45
2.51±0. 2
2.23±0.1
ND
ND
ND
KB1
4.60
2.65±0.1
ND
2.38±0.1
ND
3.44±0.1
KB2
5.45
10.85±2.2
ND
ND
4.26±0.7
19.53±3.1
KB3
4.45
9.70±1.8
2.12±0.7
2.28±0.7
1.33±0.5
10.88±2.0
KB4
KB5
5.15
1.92±0.6
1.64±0.7
0.94±0.6
2.12±0.8
1.62±0.7
5.25
3.62±1.1
3.07±1.0
0.41±0.1
0.30±0.1
5.30±1.3
KB6
4.55
7.81±1.6
7.14±1.4
6.64±1.3
6.47±1.3
4.74±1.0
KB7
4.55
0.41±0.2
4.18±1.2
2.50±0.9
ND
ND
KB8
Table 2: Results of Pb concentrations in G/Corn and soil samples at Nasarawa, Results of mean values (mg/kg)±STD DEV (n = 3)
Hot extraction
-----------------------------------------------------------------------------------------------Metal conc in G/Corn
Metal conc in soil sample
EDTA
Oxalic acid
Acetic acid
HNO3/H2O2 (2+1)
0.05 M
1.0 M
1.0 M
Sample site
pH
sample HNO3/H2O2 (2+1)
NS1
4.50
3.91±0.2
0.56±0.1
ND
8.37±2.2
7.53±2.0
NS2
5.50
4.57±0.1
4.11±0.7
ND
8.28±2.1
7.22±1.1
NS3
5.45
7.39±2.4
60.25±9.7
1.39±0.4
ND
ND
NS4
5.45
1.75±0.6
1.39±0.4
2.95±0.8
1.67±0.7
1.25±0.3
NS5
5.25
1.39±0.2
1.70±0.6
1.22±0.1
1.59±0.8
0.72±0.1
NS6
5.35
0.05±0.0
3.07±1.0
0.36±0.1
1.39±0.4
2.50±0.8
NS7
5.15
5.97±1.3
5.19±1.1
3.85±1.0
ND
4.60±1.2
NS8
4.45
0.11±0.1
ND
ND
ND
ND
Table 3: Results of Pb concentrations in G/Corn and soil samples at Mando, Results of mean values (mg/kg)±STD DEV (n = 3)
Hot extraction
-----------------------------------------------------------------------------------------------Metal conc in G/Corn
Metal conc in soil sample
EDTA
Oxalic acid
Acetic acid
HNO3/H2O2 (2+1)
0.05 M
1.0 M
1.0 M
Sample site
pH
sample HNO3/H2O2 (2+1)
MD1
4.46
ND
1.95±0.4
ND
ND
1.67±0.1
MD2
ND
2.12±0.4
1.92±0.1
ND
ND
MD3
5.25
ND
0.11±0.1
26.76±4.0
ND
ND
MD4
4.47
10.60±2.1
1.92±0.8
1.78±0.6
2.37±0.4
7.57±1.1
MD5
5.35
2.17±0.8
1.55±0.7
2.51±0.9
0.89±0.6
5.19±1.7
MD6
5.20
0.02±0.0
0.22±0.3
2.83±0.6
0.17±0.2
3.91±1.5
MD7
4.55
5.05±1.1
6.05±1.3
2.32±0.9
3.99±1.1
3.76±1.0
MD8
4.55
ND
0.09±0.2
ND
ND
ND
Table 4: Results of Pb concentrations in G/Corn and soil samples at Kakuri, Results of mean values (mg/kg)±STD DEV (n = 3)
Hot extraction
-----------------------------------------------------------------------------------------------Metal conc in G/Corn
Metal conc in soil sample
EDTA
Oxalic acid
Acetic acid
HNO3/H2O2 (2+1)
0.05 M
1.0 M
1.0 M
Sample site
pH
sample HNO3/H2O2 (2+1)
KK1
4.45
ND
ND
ND
ND
2.23±0.01
KK2
4.45
ND
ND
ND
13.06±3.2
2.18±0.1
KK3
4.50
1.67±0.7
3.01±0.9
6.16±2.1
ND
ND
KK4
5.15
2.09±0.7
2.70±0.9
2.48±0.9
1.67±0.5
1.92±0.8
KK5
4.34
2.59±0.8
1.47±0.5
1.64±0.6
1.33±0.4
10.60±2.1
KK6
5.15
3.91±1.1
6.69±1.7
0.50±0.1
0.16±0.1
2.23±0.6
KK7
4.50
3.91±1.1
6.69±1.7
0.50±0.1
0.16±0.1
2.23±0.6
KK8
4.50
ND
1.36±0.2
0.24±0.1
ND
0.11±0.1
Similar trends were observed in NS, MD, TW, KK,
ST, UM and KC. The HNO3/H2O2, EDTA, CH3COOH
and (COOH)2 extractables Pb are considered as available
Pb in these locations.
The pH of the soil samples from all the locations is
acidic. The bioavailability of lead from soil decreases
with increasing pH (Moraghan and Mascani, 1991; Morel,
1997). The acidity of the soils increases the solubility and
and Bakirdere, 2002; Khairah et al., 2009; Takac et al.,
2009).
The concentration of the metal bound to oxide
fraction (COOH)2 is highest in KB5. Hence, Pb is said to
be oxide species and available in this site for plant uptake.
Similar results were reported by other investigators
(Yaman et al., 2000; Feng et al., 2009 ; Urunmatsoma et
al., 2010).
61
Br. J. Pharmacol. Toxicol., 3(2): 58-64, 2012
Table 5: Results of Pb concentrations in G/Corn and soil samples at T/Wada, Results of mean values (mg/kg)±STD DEV (n = 3)
Hot extraction
-----------------------------------------------------------------------------------------------Metal conc in G/Corn
Metal conc in soil sample
EDTA
Oxalic acid
Acetic acid
Sample site
pH
sample HNO3/H2O2 (2+1)
HNO3/H2O2 (2+1)
0.05 M
1.0 M
1.0 M
TW1
4.60
ND
0.56±0.1
ND
ND
6.14±2.0
TW2
5.15
ND
10.60±2.1
2.64±0.8
6.03±2.2
ND
TW3
4.50
16.63±3.0
ND
48.27±5.0
63.00±5.7
ND
TW4
5.10
2.37±0.8
0.92±0.4
1.67±0.7
2.48±0.9
1.73±0.7
TW5
4.55
2.23±0.7
0.89±0.4
2.67±0.9
1.44±0.6
9.20±2.5
TW6
4.50
4.74±1.5
0.69±0.4
0.25±0.3
3.91±1.1
0.47±0.3
TW7
4.55
3.26±1.0
6.50±.3
5.74±1.2
4.54±1.0
2.37±0.7
TW8
4.15
ND
ND
0.36±0.1
ND
0.05±0.1
Table 6: Results of Pb concentrations in G/Corn and soil samples at S/Tasha, Results of mean values (mg/kg)±STD DEV (n = 3)
Hot extraction
-----------------------------------------------------------------------------------------------Metal conc in G/Corn
Metal conc in soil sample
EDTA
Oxalic acid
Acetic acid
Sample site
pH
sample HNO3/H2O2 (2+1)
HNO3/H2O2 (2+1)
0.05 M
1.0 M
1.0 M
ST1
5.10
0.84±0.1
ND
ND
ND
ND
ST2
4.50
8.28±2.5
1.06±0.8
ND
ND
ND
ST3
5.45
11.71±2.1
ND
36.44±4.8
ND
7.24±1.4
ST4
4.50
2.42±0.8
1.42±0.68.6
5±2.1
1.14±0.3
1.67±0.5
ST5
4.45
1.50±0.6
2.73±0.9
0.47±0.3
1.31±0.5
2.59±0.8
ST6
5.15
6.42±1.4
0.44±0.3
5.85±1.3
3.38±1.1
2.50±0.9
ST7
5.10
6.00±1.4
3.51±1.1
1.86±0.7
4.41±1.4
3.48±1.0
ST8
4.10
ND
ND
ND
ND
ND
Table 7: Results of Pb concentrations in G/Corn and soil samples at U/Muazu, Results of mean values (mg/kg)±STD DEV (n = 3)
Hot extraction
-----------------------------------------------------------------------------------------------Metal conc in G/Corn
Metal conc in soil sample
EDTA
Oxalic acid
Acetic acid
Sample site
pH
sample HNO3/H2O2 (2+1)
HNO3/H2O2 (2+1)
0.05 M
1.0 M
1.0 M
UM1
5.05
2.51±0.8
ND
ND
ND
ND
UM2
5.50
2.45±0.4
ND
ND
ND
ND
UM3
5.25
10.07±2.0
27.06±4.1
ND
Nil
1.70±0.4
UM4
4.45
11.16±2.3
10.88±2.1
1.14±0.4
1.98±0.6
2.23±0.8
UM5
5.60
1.86±0.8
1.61±6.0
1.50±0.3
1.39±0.5
2.31±0.9
UM6
5.60
1.95±0.8
1.95±0.8
3.62±1.3
0.36±0.2
5.30±1.4
UM7
5.60
3.82±1.1
3.40±1.1
5.86±1.5
1.83±0.7
2.09±0.8
UM8
5.65
ND
0.08±0.0
ND
2.23±0.7
ND
Table 8: Results of Pb concentrations in G/Corn and soil samples at Kachia, Results of mean values (mg/kg)±STD DEV (n = 3)
Hot extraction
-----------------------------------------------------------------------------------------------Metal conc in G/Corn
Metal conc in soil sample
EDTA
Oxalic acid
Acetic acid
Sample site
pH
sample HNO3/H2O2 (2+1)
HNO3/H2O2 (2+1)
0.05 M
1.0 M
1.0 M
KC 1
4.55
0.12±0.1
0.02±0.0
0.03±0.0
0.13±0.1
0.01±0.0
KC 2
4.55
0.01±0.0
0.03±0.0
ND
ND
0.01±0.0
KC 3
5.15
ND
0.01±0.0
0.01±0.0
0.16±0.1
ND
KC 4
4.50
0.03±0.0
0.01±0.0
0.01±0.0
0.12±0.0
0.01±0.0
KC 5
4.55
0.13±0.0
0.12±0.0
0.02±0.0
0.37±0.1
ND
KC 6
5.10
0.03±0.0
0.01±0.0
0.03±0.0
0.13±0.0
0.01±0.0
KC 7
5.15
0.01±0.0
0.01±0.0
0.02±0.0
0.13±0.0
ND
using the Duncan Multiple range test where means of
homogeneous subgroups are clearly displayed. Moreover,
the mean plots that follow depict the mean values of Lead
concentrations across the various guinea corn grown soils.
The Duncan multiple range tests showed that Kachia
had the least Lead concentration in their soils while the
highest Lead concentration in soil was Ungwan Muazu
and Nasarawa as depicted in Fig. 3.
mobility of the metal in the soils. Such increase in
solubility of the metal could lead to increased availability
of the metal for plant uptake (Baranowski et al., 2002;
Takac et al., 2009).
The ANOVA (p = 0.04 < 0.05) indicated a significant
difference in the Lead concentrations across the various
guinea corn grown soils. The differences in Lead
concentrations can further be deduced by a post-hoc test
62
Mean of lead concentration in
guinea corn sample (mg/Kg)
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10.00
8.00
6.00
4.00
2.00
Sites
Kachia
Ungwan muazu
Sabon Tasha
Tudun wada
Kakuri
Mando
Nasarawa
Kabala
west
0.00
Fig. 3: Mean plot for lead concentration in guinea corn grown
soil
CONCLUSION
Total trace metal composition of soil is of little
importance in determining its uptake by plants and
consequently, in contaminating the food chain since the
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.
ACKNOWLEDGMENT
The authors show great appreciation to Kaduna
Polytechnic, Nigeria for providing facilities to analyze the
samples and to Nasiru Musa, Kabiru Shehu, Yusuf AbdulRaheem, for the help in sample collection, metal and
statistical analyses.
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