Environmental Monitoring and Assessment (2005) 105: 431–447

DOI: 10.1007/s10661-005-4440-0

c Springer 2005

A SURVEY OF TRACE METALS IN VEGETATION, SOIL AND LOWER

ANIMAL ALONG SOME SELECTED MAJOR ROADS
IN METROPOLITAN CITY OF LAGOS

O. R. AWOFOLU
Department of Chemistry, Faculty of Science, Lagos State University, Badagry Expressway Ojo,
Apapa, Lagos Nigeria
(e-mail: [email protected])

(Received 17 November 2003; accepted 19 August 2004)

Abstract. The concentration of trace metals (Cd, Cu, Pb and Zn) in a total of 144 samples of grass,
soil and lower animal (earthworm, Lybrodrilus violaceous) were collected and analysed for their
metallic content. Levels of cadmium ranged from 0.01–0.07 µg g−1 ; 0.01–0.12 µg g−1 and from
trace−0.05 µg g−1 dry weight for plant, soil and animal samples respectively. Mean concentration
of copper ranged 0.10–1.48 µg g−1 ; 0.10–2.90 µg g−1 and 0.01–0.08 µg g−1 for samples in
similar order as above. The levels of Pb varied from 0.01–0.14 µg g−1 ; 0.02–0.23 µg g−1 and
from trace−0.07 µg g−1 while that of Zn ranged from 0.19–1.80 µg g−1 ; 0.51–3.35 µg g−1 and
0.01–0.08 µg g−1 also in the same order of samples as mentioned above. Levels of metals in soil
samples were higher than the background levels with the exception of Zn but lower than European
Union (EU) limits. The results generally revealed the presence of metals in plant and animal samples
and metal dynamics up the food chain is highly possible. Acceptable recoveries of the spiking
experiment validate the experimental protocol.

Keywords: city, lower animal, soil, trace metals, vegetation

1. Introduction

Toxic effects of metals such as cadmium, lead, mercury etc. to man and wildlife
are well known. This category of metals is not required by man even in small
amounts (Tyler, 1981; Borgmann, 1983). However, metals such as copper and zinc
are classified as essential to life due to their involvement in certain physiological
processes. Elevated levels of these has however been found to be toxic (Spear, 1981).
Elevated levels of copper have been reported to cause brain damage in mammals
(DWAF, 1996b).
The presence of toxic heavy metals in the environment continues to generate a
lot of concern to environmental scientists, government agencies and health practi-
tioners. This is due to the health implications of their presence since they are non-
essential metals that are not required for any function either by plants or animals
(Greenland and Hayes, 1981), hence they are usually monitored for health purposes.

Present address: Department of Environmental Sciences, Faculty of Natural Sciences, Tshwane

University of Technology, Pretoria, South Africa.
432 O. R. AWOFOLU

Trace metals have been referred to as common pollutants, which are widely
distributed in the environment with sources mainly from the weathering of minerals
and soils (Merian, 1991; O’ Neil, 1993). However, level of these metals in the envi-
ronment has increased tremendously in the past decades as a result of human inputs
and activities. Motor vehicles introduce quite a number of toxic chemicals into the
environment among which are Cd, Pb, Zn and Cu that are increasingly detected in
vegetation and soil (Fatoki and Hill, 1994; Dudka et al., 1996) and in lower animals
along major roads since organisms inhabiting contaminated soils are known to
take up heavy metals (Marinussen et al., 1997; Nuorteva and Elberg, 1999).
Some studies have also reported the transfer of trace metals from contaminated
soil to plants and from plants to livestock (Oskarson et al., 1992) with the sub-
sequent transfer through the food chain up to man. It is not uncommon to find
ruminants feeding on grasses and birds that feed on insects and earthworms along
these roads. High concentration of metals like Cd and Pb in the environment may
lead to accumulation, becoming toxic to plants and animals with possible danger
to human health. Sources of these metals also include atmospheric deposition from
industrial emission, refuse incineration and dumping of various wastes such as used
batteries, metal scraps etc. directly along the roads.
Cadmium is one of the most toxic elements with reported carcinogenic effects
in human (Goering et al., 1994). It accumulates mainly in the kidney and liver and
high concentration has been found to lead to chronic kidney dysfunction. It induces
cell injury and death by interfering with calcium regulation in biological systems. It
has also been implicated as an endocrine disrupter. Apart from the health problems
it poses, the metal, together with other elements form a toxic “soup” that often
acts synergistically. That is, the effect of a single element is often multiplied by the
presence of other elements.
United States Environmental Protection Agency classified lead as being poten-
tially hazardous and toxic to most form of life (USEPA, 1986). It has been found to
be responsible for quite a number of ailments in human such as chronic neurological
disorder especially in foetus and children. This eventually results in behavioural
and attitude changes with progressive retardation. Lead has been found to be bio-
accumulated by benthic bacteria, plants and other aquatic biota (DWAF, 1996b).
The ubiquity of this metal in the environment could be traced to a wide increase
in industrial activities and the continual use of leaded petrol in many developing
nations. Leaded petrol is still in use in Nigeria. It has been pointed out that Africa’s
contribution to global lead pollution has increased from just 5% in 1980s to 20%
in 1996 (Nriagu, 1978, 1979, 1989; Anon, 1996). Other inputs of lead into the
environment include wastes from used lead batteries, atmospheric deposition from
automotive and industrial emissions.
Copper is among some heavy metals that are essential to life but could be
toxic at elevated levels. It is toxic at low concentration in water and is known
to cause brain damage in mammals (DWAF, 1996a). Elevated levels of these has
however been found to be toxic (Spear, 1981). Toxicity of copper in plants as a
 A SURVEY OF TRACE METALS IN VEGETATION, SOIL AND LOWER ANIMAL 433

result of high level in sewage treated agricultural soil has been reported (Baryla
et al., 2000). Contribution to copper environmental burden could be by atmospheric
deposition from metal industries and power plants that are burning fossil fuels (Kral
et al., 1992). The interest in determination of copper lies between the threshold of
essentiality and toxicity.
Although, Zn has been found to have low toxicity to man but prolonged con-
sumption of large doses can result in some health complications such as fatigue,
dizziness, and neutropenia (Hess and Schmid, 2002). Some literatures have also
revealed that zinc could be toxic to some aquatic organisms such as fish (Alabaster
and Lloyd, 1980).
This study reports the level of trace metals (Cd, Pb, Zn and Cu) in vegetation,
soil and lower animal (earthworm, Lybrodrilus violaceous) along some major and
minor roads in metropolitan city of Lagos. This is with a view of examining the
accumulation of metals by plants through contaminated soil and in earthworm as a
result of their feeding on leaf crumbs and particles within the vicinity.

2. Materials and Methods

2.1. SAMPLES AND SAMPLING PROTOCOL

Samples were collected from 12 major and minor roads in Lagos metropolis once in
the months of May, July, September and November of 2002. Tens of thousands of ve-
hicles are known to pass through the major roads in Lagos per day especially during
working days (Akeredolu, 1989). The map of sampling sites is as shown in Figure 1
while the major and minor roads are indicated in Figure 2a. Approximate varied dis-
tances of sampling sites from roads were between 4 m and 10 m. Surface soil samples
were collected randomly from each site with the aid of clean stainless steel spoon,
washed with soap and rinsed with distilled water after each sampling. Soil samples
were placed in transparent polyethylene bags, labelled and taken to the laboratory
for treatment and analysis. The common grass was chosen as the plant sample.
This is a wild plant that grows widely as the common name implies. These
were also randomly taken from the vicinity of the sampled area where soil were
collected, placed in large paper bag, labelled and also taken to the laboratory for
treatment and analysis. The invertebrate (Lybrodrilus violaceous) were collected
by digging into the soil within the same vicinity where plant and soil samples were
taken using clean forceps into plastic container, labelled and taken to the laboratory
for treatment and analysis.

2.2. S AMPLE PRE - TREATMENT

Plant samples were properly rinsed with tap water and then with distilled water to
remove any attached soil particles, cut into smaller portions and then placed in large
434 O. R. AWOFOLU

Figure 1. Map of Nigeria (top right with Lagos State as indicated) and location map of area showing
sampling sites (S1–S12).

clean crucible where they are oven dried at 100 ◦ C for about 48 h. The dried plant
samples were grinded into fine particles using clean acid washed mortar and pestle.
Determination of plant metallic content was based on the fine grinded sample.
Soil sample from each site was homogenised and air-dried a circulating air in the
oven at 30 ◦ C overnight and then passed through a 2 mm sieve. All metallic determi-
nations from soil samples were based on the fine particles obtained. The earthworms
were also properly rinsed with tap water and then distilled water so as to remove
any attached soil particles on their bodies. They were then dried in the oven at about
100 ◦ C overnight. The dried samples were carefully grinded without sieving.

2.3. I NSTRUMENTATION

Quantitation of metallic content of digested samples was carried out with the Atomic
absorption spectrophotometer Pye-Unicam 939 model equipped with a deuterium
background corrector and powered by the solar software. The operational conditions
employed in the instrumentation are presented in Table I.

3. Chemicals

All chemicals used were of analytical grades and metal standard solutions were
prepared from (1000 mg/L) stock solutions of the metals. Glassware were properly
 A SURVEY OF TRACE METALS IN VEGETATION, SOIL AND LOWER ANIMAL 435

(a)

(b)
Figure 2. (a) Box and whiskers plot of Cd conc. in plant vs. sampling sites. ∗ S1: Lagos State University,
Badagry Expressway, Ojo Lagos, † S2: Isheri-Iba Road, Lagos, † S3: Apapa-Oyingbo Road, Lagos,
∗
S4: Tin Can Island Expressway, Lagos, ∗ S5: Oshodi Expressway, Oshodi Lagos, † S6: Adeniyi Jones
Avenue, Ikeja, Lagos, † S7: Ijora Course-Way, Ijora Lagos, † S8: Moshood Abiola Way, Iganmu Lagos,
†
S9: Nnamdi Azikiwe Road, Lagos Island, Lagos, † S10: C.M.S road, Lagos Island, Lagos, † S11:
Broad Street, Lagos Island, Lagos, ∗ S12: Obafemi Awolowo Road, Ikoyi Lagos (∗ Major road, † Minor
road). (b) Box and whiskers plot of Cd conc. in soil vs. sampling sites. (c) Box and whiskers plot of
Cd conc. in lower animal vs. sampling sites.
(Continued on next page)
436 O. R. AWOFOLU

(c)
Figure 2. (Continued )

washed with liquid soap, rinsed with water, soaked in dilute nitric acid overnight
and then rinsed thoroughly with distilled water before use. Working standards was
prepared from the stock solutions of each metal and calibration standards were
prepared from the working standards. Good linearity of all calibration curves was
obtained and used in the quantitative analysis.

3.1. Q UALITY ASSURANCE

3.1.1. Vegetation
0.5-g of pre-digested plant samples was weighed into 100 mL beaker, spiked with
metal standards (0.5 ppm of Cd and Pb and 5.0 ppm of Zn and Cu standards).

TABLE I
Instrumental conditions and parameters employed in elemental analyses

Lamp current (mA) Flow rate

Lamp λ Slit automatic
Element Min-max Operational (nm) width (nm) Gas mixture (L/min)

Cd 3–7.5 7 228.8 0.5 Air/acetylene 1.0–1.2

Cu 5–10 8 324.8 0.5 Air/acetylene 0.8–1.1
Pb 10 10 217.0 0.5 Air/acetylene 0.9–1.2
Zn 4–10 8 319.9 0.5 Air/acetylene 0.9–1.2
 A SURVEY OF TRACE METALS IN VEGETATION, SOIL AND LOWER ANIMAL 437

A mixture of 5 mL of concentrated HNO3 and 2 mL of HClO4 were added and this

was digested on low heat using hot plate until the content was about 2 mL. The
digest was allowed to cool, filter into 50 mL standard flask using 0.45 µm Millipore
filter kit (Millipore Corp. Bedford MA). The beaker was rinsed with small portions
of double distilled water and then filtered into the flask. Triplicate digestion of each
sample was carried out together with blank digest without the plant sample.

3.1.2. Lower Animal

The same procedure described above for the analysis of plant samples was evaluated
and applied to that of animal samples.

3.1.3. Soil
5-g of the pre-digested soil samples was placed in 100 mL beaker and spiked
with metal standards as described above. 3 mL of 30% H2 O2 was added following
a previously described procedure by Sharidah (1999). This was left to stand for
60 min until the vigorous reaction ceased. 75 mL of 0.5 M solution of HCl was
added and the content heated gently at low heat on the hot plate for about two hours.
The digest was then filtered into 50 mL standard flask.
Triplicate digestion of each sample together with blank was also carried out.
This method has been widely applied and recognised as very informative in envi-
ronmental metallic investigations where metal fractions associated with carbonate,
sulfides, soluble salts organic matter held, Fe-Mn oxide are removed.

3.2. ANALYSIS OF ENVIRONMENTAL SAMPLES

Trace metals were determined in the plant, soil and animal samples following the
procedure described for each of the sample above.

3.3. S TATISTICAL ANALYSIS

The results of the metal obtained in the food samples were subjected to statistical
evaluation using the Pearson Correlation Coefficient statistical functions on the
Microsoft Excel. It is a dimensionless index, which ranges from −1.0 to 1.0 and
also reflects the extent of a linear relationship between two data sets. The r-value
of the regression line is given as:
n( X Y ) − ( X )(Y )
r=

[n X 2 − ( X )2 ][n Y 2 − ( Y )2 ]

4. Results and Discussion

The operational parameters on the atomic absorption spectrometer for the analysed
metals are presented in Table I. Results of the recoveries of spiked plant, soil and
438 O. R. AWOFOLU

TABLE II
a
Mean% recoveries (±S.D.) of trace metals from spiked samples

Metals Plant Soil Animal

Pb 92.4 ± 0.004 88.9 ± 0.003 90.7 ± 0.005

Cd 87.8 ± 0.002 93.6 ± 0.004 96.2 ± 0.003
Cu 96.2 ± 0.002 95.5 ± 0.005 91.8 ± 0.004
Zn 90.8 ± 0.004 94.1 ± 0.002 97.3 ± 0.004
a
Average of three replicate analyses.

animal samples are as shown in Table II. Percentage recoveries obtained for metals
under investigation (Cd, Pb, Zn and Cu) varied between 87.8 ± 0.002–96.2 ± 0.002;
88.9 ± 0.003–95.5 ± 0.005 and 90.7 ± 0.005–97.3 ± 0.004 for the vegetation, soil
and animal samples respectively. Acceptable recoveries were obtained in all cases,
which validate the experimental protocol.
Results of the analyses of trace metals in a total of 144 samples of plant, soil and
lower animal for all periods of sampling at the 12 sites are presented in Figures 2–5.
The mean concentration of cadmium ranged from 0.01 µg g−1 (S1)–0.07 µg g−1
(S7); 0.01 µg g−1 (S3)–0.12 µg g−1 (S7, S8) and trace (S2, S5, S9 and S12)–0.05
µg g−1 (S7) for plant, soil and animal samples respectively (Figure 2a–2c). Highest
concentration of 0.12 µg g−1 cadmium was obtained from soil sample while the
lowest was trace in animal sample.
This value is much higher than trace amount obtained as background value from
“uncontaminated” residential area within the premises of Lagos State University
Ojo, Nigeria (Adeniyi and Afolabi, 2002). It is also lower than 1–3 µg g−1 limit
given by the European Union (EU) Council Directive 86/278/EEC, lower than
the background level of 0.9 µg g−1 by Purves (1985) and 0.18 µg g−1 obtained
in analysed soil from the vicinity of an industrial area (Singh and Abdulkashem,
1999). Generally, levels of cadmium obtained in soil were higher at some sites than
those from plants and animal samples. This was not unexpected since soil has been
described as ready sink or reservoir of pollutants including trace metals where they
concentrate according to the level of pollution (Becker et al., 2001; Onyari et al.,
2003).
Cadmium was detected in over 70% of analysed samples, which indicate the
ubiquity of this toxic metal in the environment. Possible dynamics of the metal
was also revealed by its detection in earthworms that inhabits the soil. Apart from
natural source, other probable sources of Cd are wastes from Ni-Cd based batteries.
Perhaps, the largest source of cadmium release to the general environment is from
the burning of fossil fuels (coal, oil, etc.) and from the incineration of municipal
waste materials.
Although, levels of Cd obtained in soil were lower than the EU limit and the
background value given by Purves (1985), detection of the metal in plant and lower
 A SURVEY OF TRACE METALS IN VEGETATION, SOIL AND LOWER ANIMAL 439

(a)

(b)
Figure 3. (a) Box and whiskers plot of Zn conc. in plants vs. sampling sites. (b) Box and whiskers
plot of Zn conc. in soil vs. sampling sites. (c) Box and whiskers plot of Zn conc. in lower animal vs.
sampling sites
(Continued on next page)
440 O. R. AWOFOLU

(c)
Figure 3. (Continued )

animal samples calls for sustained monitoring. Ruminants that wander and graze
along roadsides feed on these grasses while birds and domestic fowls feed on
insects and earthworms. Transfer of metals across the food chain and accumulation
are most probable with resultant health problems especially in animals that occupy
the upper echelons of food chain.
The mean concentration of copper in analysed samples ranged from 0.10 µg
g −1 (S1)–1.48 µg g−1 (S7); 0.10 µg g−1 (S1)–2.90 µg g−1 (S7) and 0.01 µg
g−1 (S4) – 0.08 µg g−1 (S6, S11) in plants, soil and the lower animal respec-
tively (Figure 3a–3c). 2.90 µg g−1 was obtained as the highest concentration of
copper in soil with an incremental trend of soil > plants > animal. This con-
centration is much higher than 0.19 µg g−1 of Cu in soil from background “un-
contaminated” soil (Adeniyi and Afolabi, 2002) but lower than 50–140 µg g−1
limit given by EU Council Directive 86/278/EEC and 16.6 µg g−1 as background
concentration in normal uncontaminated soil (Purves, 1985). It is also lower than
the upper range value of 2.8–18.9 µg g−1 obtained in a similar study (Fatoki,
2000).
Thus, concern of possible accumulation and toxicity of this metal in ruminants
grazing on vegetation along these roads and of birds feeding on earthworms is
alleviated. The levels detected in this study are probably from natural sources with
insignificant contribution from environmental pollution.
The concentration ranges of lead obtained in samples were 0.01 µg g−1 (S4, S6)–
0.14 µg g−1 (S7); 0.02 µg g−1 (S12)–0.23 µg g−1 (S8) and trace (S8)–0.07 µg g−1
 A SURVEY OF TRACE METALS IN VEGETATION, SOIL AND LOWER ANIMAL 441

(S4) for plant, soil and animal samples respectively (Figure 4a–4c). 0.23 µg g−1
was obtained as the highest concentration of Pb from soil in this study. This follow
similar trend observed in Cd and Cu with higher concentrations detected in soil than
in plant an animal samples. This value is higher than 0.14 µg g−1 as background

(a)

(b)
Figure 4. (a) Box and whiskers plot of Cu conc. in plants vs. sampling sites. (b) Box and whiskers
plot of Cu conc. in soil vs. sampling sites. (c) Box and whiskers plot of Cu conc. in lower animal vs.
sampling sites.
(Continued on next page)
442 O. R. AWOFOLU

(c)
Figure 4. (Continued )

level of Pb in soil from “uncontaminated area” (Adeniyi and Afolabi, 2002) but
much lower than the EU limit of 50–300 µg g−1 (Council Directive 86/278/EEC),
12–20 and 32 µg g−1 as background levels in normal uncontaminated soil given
by Singh and Steinnes (1994) and Purves (1985) respectively. The value is also
lower also than 17–99 µg g−1 range obtained by Singh and Abulkashem (1999) in
a similar survey.
Possible contribution to soil metallic burden from environmental sources such
as vehicular exhaust is quite evident when concentrations from control area are
considered. Levels of Pb obtained in soil might be lower than the EU limit, detection
of the metal in plant and animal samples revealed the possibility of further passages
into the food chain. Lead is a very toxic metal and potentially hazardous to most
forms of life (USEPA, 1986).
Nationally estimated consumption of leaded fuel in Nigeria was 20 million litres
of petrol per day and it was predicted that about 15,000 kg of lead is emitted into
the environment by burning through this source (Agbo, 1997). Hence, automobile
exhausts were believed to account for more than 80% of the air pollution in some
urban centres especially in Lagos, the commercial nerve centre of the country. The
level of lead in Nigeria’s super grade gasoline is 600–800 mg per litre (Osibanjo
and Ajayi, 1989; Shy, 1990), which is much higher than permissible levels in some
pollution conscious countries.
The concentration of zinc from analysed samples ranged from 0.19 µg g−1
(S12)–1.80 µg g−1 (S3); 0.51 µg g−1 (S12)–3.35 µg g−1 (S7) and 0.01 µg g−1
(S2, S8 and S11)–0.08 µg g−1 (S5) for plant, soil and animal samples respectively
 A SURVEY OF TRACE METALS IN VEGETATION, SOIL AND LOWER ANIMAL 443

(a)

(b)
Figure 5. (a) Box and whiskers plot of Pb conc. in plants vs. sampling sites. (b) Box and whiskers
plot of Pb conc. in soil vs. sampling sites. (c) Box and whiskers plot of Pb conc. in lower animal vs.
sampling sites.
(Continued on next page)
444 O. R. AWOFOLU

(c)
Figure 5. (Continued )

(Figure 5a–5c). 3.35 µg g−1 of zinc in soil was obtained as the highest concentration.
Similar metallic incremental concentration trend was also observed with zinc in
relation to analysed samples (soil > plant > animal).
The highest value of Zn in soil obtained in this study is lower than reported
value of 4.75–16.16 µg g−1 in “uncontaminated” soil in another area of the country
(Alexander and Pasquini, 2004) and the EU limit of 150–300 µg g−1 (Council
Directive 86/278/EEC). Also, concentration ranges of Zn in soil and plant ob-
tained in this study were lower than 0.6–119.5 µg g−1 and 7.0–134.8 µg g−1
ranges respectively reported in a similar study (Fatoki, 2000) and also lower than
53–477 µg g−1 range in analysed soil samples from industrial sites reported by
Singh and Abulkashem (1999).
Apart from the natural source of zinc in the environment, significant contribu-
tions are likely to come from additives containing zinc in lubricating oils and tyres
(Smith et al., 1975). Waste cans of lubricating oil could be found along major roads
and in sewers in the metropolis.
Relationship between the analysed metals and the samples at some sites were
reflected by the Pearson Correlation Coefficient derived from paired test. Approx-
imate correlation (r = 0.90) was found between the amounts of Cd obtained in
plant and animal, while no correlation exist (r = 0.71) between animal and soil
and (r = 0.85) between plant and soil at S1. Good correlation in the amount of Zn
was established between plant and soil (r = 0.95) and (r = 0.97) between plant
 A SURVEY OF TRACE METALS IN VEGETATION, SOIL AND LOWER ANIMAL 445

and animal while excellent correlation was obtained (r = 0.99) between soil and
animal and at S12.
Approximate correlation of 0.92 was also found in the amount of Pb between
plant and animal while there was no correlation (r = 0.86 and 0.64) between soil
and animal and between plant and soil respectively at S4. Significant correlation of
0.94 and 0.95 were obtained between plant and soil and plant and animal with no
correlation (r = 0.82) obtained between soil and animal respectively at S10 for Cu.
All these correlations indicate similar sources of metals in the analysed samples at
their respective sites.
Paucity of data on similar studies and limit values in the country for trace metals
in samples necessitate reference to values in other countries and organisations.
Hence, data from this study might contribute and also fill this gap. Although,
levels of the analysed metals obtained in soil were lower than the EU limits and
some reported background levels, regular monitoring is essential as a result of the
detection of metals such as Cd and Pb in plant and lower animal. This is important
because ruminants roaming around do feed on these grasses and accumulation in
their bodies is highly probable. The metal could subsequently be passed onto man
with the consumption of the ruminant.

5. Conclusion

Results obtained in this study generally revealed the presence of analysed metals
in plants from contaminated soils along roads in Lagos metropolis. Most probable
sources of these metals are from motor vehicles, wastes from petroleum products
such as lubricating oil that are dumped along these roads and from industrial emis-
sions via atmospheric deposition. Sustained monitoring is essential especially with
the detection of toxic metals such as Cd and Pb in grass and animal samples since
ruminants wandering along these roads feed on the grasses while birds and domes-
tic fowls feed on the earthworms and insects. Possible transfer of these metals up
the food chain is highly probable.

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