Chemical Speciation & Bioavailability

ISSN: 0954-2299 (Print) 2047-6523 (Online) Journal homepage: http://www.tandfonline.com/loi/tcsb20

Screening and speciation of heavy metal

contaminated soil from an automobile spare-parts
market

E. U. Asagba, F. E. Okieimen & J. Osokpor

To cite this article: E. U. Asagba, F. E. Okieimen & J. Osokpor (2007) Screening and speciation
of heavy metal contaminated soil from an automobile spare-parts market, Chemical Speciation &
Bioavailability, 19:1, 9-15, DOI: 10.3184/095422907X198022

To link to this article: http://dx.doi.org/10.3184/095422907X198022

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Chemical Speciation and Bioavailability (2007), 19(1) 9

Screening and speciation of heavy metal contaminated

soil from an automobile spare-parts market
E.U. Asagbaa *, F.E. Okieimena and J. Osokporb
a
Department of Chemistry and bDepartment of Geology, University of Benin, Benin City, Nigeria

ABSTRACT
The contributions of automobile spare-parts market activities to heavy metals burden and the forms in
which some of these metals exist in the soil environment were assessed. Total values of 150.0 mgykg
lead, 98.7 mgykg copper, 5.0 mgykg cadmium, 250.3 mgykg manganese, and 14.0 mgykg nickel were
obtained on screening the soil in an automobile spare-parts market. Only lead, cadmium and copper
were above threshold values and were consequently speciated. Upon speciating, 6.2% lead, 25.7%
copper and 52.0% cadmium were potentially bioavailable.

Keywords: heavy metals, screening, contamination, speciation, environmental significance

INTRODUCTION tion; phytoremediation; development of predictive

The activities in an automobile spare-parts market
ranging from dismantling of vehicles, solid wastes
generation and disposal, spray-painting, scrapping of
old vehicles, combustion of fossil fuels, incineration
of metalliferous and non-metalliferous wastes, use
and disposal of petroleum and petroleum by-
products may represent important sources of heavy
metal contamination in the environment.
The use of the total levels of metals in assessing
the potential impact of heavy metal contaminated
sites is oftentimes not satisfactory. This is because
the environmental signicance or otherwise of a
contaminant is dependent on its chemical form.
Hence, it is essential in the assessment of the level
of contamination to speciate the soil. The process of
separating soils, sediments and soil components into
operationally dened fractions in the assessment of
contamination is called speciation.
The study of the speciation of contaminants in the
environment is essential for understanding release
mechanisms, spatial resolution, chemical transfor-
mations, toxicity, bioavailability, and ultimate
impacts of contaminants on human health; mechan-
isms of microbial transformations, e.g. bioremedia-
models; effective remediation and waste manage-
ment strategies; and risks assessment (Sparks, 2003).
Heavy metals are partitioned into ve operation-
ally dened fractions based on the use of a sequence
of reagents of increasing reactivity in the extraction
process. Though several batch and sequential extrac-
tion schemes exist for assessing the various species
of metals in soils (Gupta and Chen, 1975; McLaren
and Crawford, 1973; Stover et al., 1976; Tessier
et al., 1979; Welte et al., 1983; Chao, 1984;
Clevenger, 1990; Shuman, 1985; Rauret et al.,
1989; Oviasogie and Ukpebor, 2003), the usefulness
or otherwise of these extraction schemes is depen-
dent to a large extent on the nal use of the data
acquired.
Depending on extraction conditions, interference
from other element and various components of the
soil, variations between results obtained by different
extraction schemes may be signicant. Earlier
workers (Ramos et al., 1994; Lo and Yang, 1998)
have identied three possible sources of variation;
the limited selectivity of extractants; redistribution
of metals during the extraction process; and, the
failure of the extraction process at high metal
concentrations.

*To whom correspondence should be addressed: E-mail: egba73@yahoo.com doi: 10.3184/095422907X198022

www.scilet.com
10 Screening and speciation of heavy metal contaminated soil from an automobile spare-parts market
Table 1 Some physicochemical properties of the soil samples
Sample no: pH %Sand %Silt
1 5.4 75.4 5.4
2 5.8 79.4 3.4
3 5.8 77.4 5.4
Mean 5.4 77.4 4.7
Despite the limitations that may be associated with
the selectivity of some of the extractants, these
schemes are useful in examining the association of
trace metals with various components of soils and
also in obtaining useful information on heavy metal
distribution in soils.
The objectives of this study were to: (i) determine
the degree of soil contamination by lead, cadium,
copper, nickel and manganese, from the activities of
automobile spare-parts market; (ii) determine the
various metal fractions of the contaminated soil;
and (iii) determine the physicochemical properties
of the soil. The data obtained from this study would
allow the evaluation of the contribution of automo-
bile spare-parts market activities to heavy metal
contamination and the selection of appropriate soil
and waste management practices to limit the mobi-
lity of heavy metals to sources of potable water
supply.
MATERIAL AND METHODS
Study area
The study area is an automobile spare-parts market
in the metropolitan city of Benin. It is located on
longitude 5
.45 0 N and latitude 5
.04 0 E. The market
has operated for over 10 years. It covers an approx-
imate area of 150,000 m2. An access road made of
asphalt links the market to other parts of the city.
The rainfall pattern in this region is characteristic of
the rainforest zone with a mean annual rainfall of
1,898.0 mm and two distinguishing peaks in the
months of July (3313.0 mm) and September
(3621.0 mm) (Iyamu et al., 2004). Three composite
samples were collected at various locations and
sampling done in the month of August. The soil
type is paleodult with a sandy loam texture and a
slightly acidic nature. Some physicochemical prop-
erties of the soil are given in Table 1.
Soil sampling, preparation and analysis
Seven composite samples were collected each from
three different locations at the topsoil depth of 0
10 cm using a plastic trowel. The samples were
%Clay %TOC CEC (cmolykg)
19.2 2.8 1.0
17.2 3.3 1.1
17.2 3.0 1.1
17.9 3.0 1.1
mixed thoroughly to make three replicate samples.
The samples were air-dried at room temperature and
sieved. Particles with diameter less than 2 mm were
kept for further analysis.
The physicochemical properties of the samples
were determined according to standard methods.
Soil pH was determined in water according to the
method of Folsom et al. (1981). Twenty grams of
soil were weighed into a 100 mL beaker and 20 mL
of distilled water was then added. The soilywater
mixture (ratio 1 : 1) was stirred with a glass rod
intermittently for 30 minutes.
The pH meter was calibrated using buffer solu-
tions of pH 4 and 7. The meter was set with the
appropriate controls to pH 7.0.The electrodes were
rinsed and subsequently immersed into the soil/water
mixture. The pH was recorded as pH (H2O).
Total organic carbon was determined by the
Walkley-Black rapid oxidation method (Nelson and
Sommer, 1982), with a correction factor of 1.33 to
account for the incomplete oxidation of recalcitrant
organic compounds. One gram of the soil was
weighed into a 250 mL Erlenmeyer ask; 10 mL
1 N K2Cr2O7 solution was added into the ask and
swirled gently to wet the sample thoroughly. This
was followed with 20 mL concentrated H2SO4 and
the whole mixture was allowed to cool. 100 mL of
de-ionized water was added followed by few drops
of the Ferroin indicator and the mixture was titrated
with 0.5 N FeSO4 solution to a wine-red endpoint. A
blank determination was also performed.
Particle size analysis was by the method of Day
(1965). De-ionised water (100 mL) was added to
50 g of soil in a 250 mL beaker. This was followed
by l0 mL concentrated H2O2. The content of the
beaker was heated on a heating mantle until frothing
stopped. The mixture was cooled and transferred into
a 100 mL shaking bottles and 20 mL 10% sodium
hexametaphosphate solution was added. The mixture
was shaken in a mechanical shaker for 1 hour.
The suspension was later transferred to 1 L sedi-
mentation cylinder and brought to mark with water.
A plunger was used to agitate the suspension. The
hydrometer was then lowered into the suspension
 E.U. Asagba, F.E. Okieimen and J. Osokpor
and its reading was taken after 40 s. The temperature
was noted. The rst reading, R1, gave the percent
clay and silt.
The suspension was allowed to stand. After 2
hours, the hydrometer and temperature readings
were again taken. This second reading, R2, gave
the percent clay.
The cation exchange capacity was by the buffered
a mmonium acetate method of Thomas (1982).
25 mL 1 N NH4Oac was added to 5 g of soil in a
50 mL centrifuge tube. This was shaken for about
30 min in a mechanical shaker and separation was
effected by centrifuging at 2,000 rpm for 10 min.The
supernatant was decanted into a 50 mL volumetric
ask. The process was repeated and the 50 mL
solution was made up to the mark with the 1 N
NH4OAc solution.
The concentrations of K and Na in the 1 N
NH4OAc extract were determined by Flame photo-
metry while those of Mg2 and Ca2 were obtained
using atomic absorption spectrophotometry (Buck
Scientic).
Total metal concentration was determined by the
method of Tyler and Olsson (2001). Two grams of
soil were digested by microwave oven technique in
closed Teon tubes at 172
C for 2 h, using 20 mL of
HNO3 (1 : 2). The sample was ltered through a
Whatman 42 lter paper into a 100 mL volumetric
ask and made up to the mark with distilled water
and stored for heavy metal analysis.
Sequential extraction
One gram of soil was used in the sequential extrac-
tion process. The method adopted was that of Lo and
Yang (1998) with slight modication.
Soluble fractionyspecies:
The soluble fraction was obtained by extracting with
10 mL of water for 16 h in a mechanical shaker.
After each extraction process, liquid-solid separation
was effected by centrifuging the mixture at
1,500 rpm for 15 minutes. The supernatant was
decanted into a plastic sample bottle for metal
analysis while the residue was carried through the
whole analysis.
Exchangeable fractionyspecies:
10 mL of 1 M MgCl2 was added to the residue and
this was agitated for 10 h in a mechanical shaker.
11
Carbonate fractionyspecies:
8 mL of 1 M NaOAc was added to the residue and
this was adjusted to pH 5.0 with HOAc. The mixture
was agitated for 5 h.
FeyMn bound fractionyspecies:
20 mL of 0.04 M NH2OH.HCl in 25 mL HOAc was
added and the mixture was heated in a thermostated
water bath to 96 + 3
C with occasional agitation in a
mechanical shaker for 6 h.
Organically bound fractionyspecies:
3 mL of 0.02 M HNO3 and 5 mL of 30% H2O2 (pH
2.0) were added to the residue, and the mixture was
heated in a waterbath to 85 + 2
C for 2 h with
occasional agitation. An additional 3 ml of 30%
H2O2 was added and the mixture was heated for 3 h.
Residual fractionyspecies:
The residue from the extraction process was trans-
ferred to a Teon tube and digested with 5 mL HF
and 10 mL HClO4 until the residue dissolved.
After each successive extraction phase, the residue
was washed with 8 mL of water.
All reagents used were analytical grade (BDH or
Sigma). All glass and plastic wares were acid-
washed. The water used for the extraction process
and preparation of reagents was double distilled in
an all-glass distillation unit.
Standard solutions (BDH or Sigma) of the various
metals ranging from 2.0 100 ppm were used to
calibrate the ame photometer and the atomic
absorption spectrophotometer. Procedural blank
samples were subjected to similar extraction
method using the same amounts of reagents.
The analyses were carried in triplicates and the
results (not shown) showed no signicant differences
between determinations.
Heavy metal levels in the blank determinations
were below the detection limits of the Atomic
absorption spectrophotometer.
Heavy metal analysis was performed using
Atomic Absorption Spectrophotometer (Buck
Scientic).
The entire sequential scheme is schematically
shown in Figure 1.
RESULTS AND DISCUSSION
The results of the physicochemical analysis of the
soil samples are given in Table 1. From the results of
12 Screening and speciation of heavy metal contaminated soil from an automobile spare-parts market
F2
Exchangeable
Figure 1 Sequential extraction scheme.
the analysis, the samples were predominantly sandy
loam soils with a moderately acidic pH value
ranging from 5.4 to 5.9. The cation exchange
capacity of the soil was 1.1 cmolykg and the total
organic carbon content ranged from 2.8 to 3.3% with
a mean value of 3.0%. This value of TOC (%) is high
for the weathered soils (ultisols) of the Benin plains.
This may be due to the introduction of hydrocarbons
from spent oils and other petroleum waste.
The results of the total metal determination are
shown in Table 2. From the results, the values of
150.0 mgykg lead, 98.7 mgykg copper, and
5.0 mgykg cadmium were above the stated values
of 19.0 mgykg lead, 50.0 mgykg copper, and
0.1 mgykg cadmium for uncontaminated soil.
(Sparks, 2003). However, the values of
250.3 mgykg manganese and 14.0 mgykg nickel
were below the stated values of 950.0 mgykg manga-
nese and 80.0 mgykg nickel.
Only the forms of lead, copper and cadmium were
assessed because their concentrations were of
environmental signicance. The results of the
sequential extraction are given in Table 2. The
results were further expressed as percentage distribu-
 E.U. Asagba, F.E. Okieimen and J. Osokpor 13

Table 2 Concentration of Total and various forms of the heavy metals (mgykg)
Fractions Pb (mean SE) Cu(mean SE) Cd(mean SE) Mn(mean SE) Nickel(mean SE)
Total 150.0
51.3 98.7
19.2 5.0
2.1 250.3
49.4 14.0
6.1
Soluble 1.4
0.8 3.6
3.4 0.2
0.1 NR NR
Ex 0.8
0.7 6.9
6.9 0.7
0.6 NR NR
Carb 6.9
6.3 13.7
4.8 1.7
0.5 NR NR
Ox 43.0
13.7 20.9
8.4 1.2
0.3 NR NR
Red 30.3
10.6 24.2
9.9 0.7
0.3 NR NR
Res 63.6
58.9 24.6
6.6 0.5
0.3 NR NR

NR, not required.

tion of metals in each fraction and these are
presented in Table 3.
The highest concentrations of lead and copper
were in the residual fraction while cadmium was
mainly concentrated in the carbonate fraction. The
high levels of lead and copper in the residual fraction
may be due to the presence of acid resistant mineral
and organic materials. Furthermore, because of the
predominantly sandy nature of the soil, the metals
may have co-precipitated with various silicate
species consequent to their adsorption into the
mineral lattice (Manceau et al., 1996; Manceau
et al., 1999). Previous workers (Adano et al., 1995;
Chlopecka et al., 1996) have also reported the
presence of cadmium, lead and copper in the residual
fraction.
Carbonates have been implicated as immobilizing
most heavy metals by providing an adsorbing or
nucleating surface and by buffering the soil pH
(Dudley et al., 1991). Lo and Yang (1998) reported
the concentration of some heavy metals in the
carbonate fraction. In this present work, 4.7% Pb,
14.6% Cu and 34.0% Cd appears to be bound in this
fraction. According to Ramos et al. (1994), seques-
tration of heavy metals by carbonates is an important
mechanism in the mobility and availability of heavy
metals in the environment.
However, as pointed out by various workers
(Doner and Lynn, 1989; Lambert et al., 1997),
carbonates are only stable in soils with high pH
values. Considering the relatively low pH of the soil,
i.e. 5.7, it is unlikely that carbonates are present. It
may therefore be concluded that the acidic
NaOAcyHOAc solution may have dissolved metals
bound to other soil components. Lo and Yang (1998)
have also reported the dissolution of non-corre-
sponding phases by the same solution. According
to Ostergren et al. (1999), the dissolution of non-
target phases is one of the drawbacks of most
sequential schemes.
Heavy metals interact with organic matter through
various mechanisms, which affect their bioavail-
ability. A large proportion of the metals are bound
to organic carbon. 29.4% Pb, 22.3% Cu and 24.0%
Cd are found in this fraction. In a recent work by
Jaradat et al. (2006), 13% Pb, 44% Cu and 13% Cd
were bound to the organic fraction of soils collected
around a scrap yard of discarded vehicles. In an
earlier work by Levy et al. (1992), the complexation
of humic acids with some heavy metals followed the
sequence: Cu4Pb4Cd. In this current study, the
sequence Pb4Cd4Cu is somewhat different. This
might be due to the differences in humic acids
compositions from different locations and also the
modication of humic acid-metal interactions by
other soil components.
Iron and manganese oxides have been implicated
in the sequestration of heavy metals in the environ-
ment (Nachtegaal and Sparks, 2004). Copper has the
highest amount in this fraction (25.8%), while lead
and cadmium made up 20.7% and 14.0%, respec-
tively. Recently, Jaradat et al. (2006) reported the
sequestration of 450% Pb, 25% Cu and 440% Cd
by the reducible fraction. In an earlier study, Levy

Table 3 Percentage distributions of lead, cadmium and copper (%)

Fractions Lead Cadmium Copper
Soluble 1.0 4.0 3.8
Exchangeable 0.5 14.0 7.3
Carbonate 4.7 34.0 14.6
Oxidizable 29.4 24.0 22.3
Reducible 20.7 14.0 25.8
Residual 43.6 26.2 10.0
14 Screening and speciation of heavy metal contaminated soil from an automobile spare-parts market
et al. (1992) reported the association of lead,
cadmium and copper in the reducible fraction.
The selectivity sequence of the metals,
Cu4Pb4Cd is consistent with the selectivity
sequence of absorption or co-precipitation on either
iron gel or goethite (Sparks, 2003). The fact that iron
(ii) and iron (iii) precipitate as hydroxides at
pH42.0, while manganese (ii) precipitates at a
pH48.6 strengthens further the conclusion that
iron rather than manganese species may be the
main species responsible for the sequestration of
the heavy metals at the prevailing soil pH, i.e. 5.7.
Iron (ii) and (iii) species have been indicated to
scavenge metals from soil solution that would
normally not precipitate considering both thermo-
dynamic and redox factors (Scheidegger and Sparks,
1996; Scheidegger et al., 1998).
Once formed, the entrapment of other cations
within the crystal lattice of iron and manganese
oxide species could be an important mechanism for
sequestering metals in soil and water environments
such that they are less mobile and bioavailable
(Sparks, 2001). However, heavy metals retained in
this form may be a long-term source of contamina-
tion since they could be released if there are changes
in the redox status of the soil (Wassay et al., 2001).
The exchangeable fraction of the cadmium made
up about 14.0%, which is the highest in this fraction
while copper and lead were 7.3% and 0.5%, respec-
tively. The various concentration trends of the heavy
metals under study are consistent with previous
observations (Li et al., 2001; Li and Thornton,
2001; Jaradat et al., 2006). This fraction is especially
important because of the high mobility of metals
from this fraction to the aqueous phase.
The aqueous phase or soluble fraction consists of
metal species found in the soil solution. Majority of
solutes in the soil solution are ions, which occur
either as free hydrated ions or as various complexes
with organic or inorganic ligands (Sparks, 2003).
The metals found in this fraction comprise a small
fraction of the total metals in the soil with 1.4 mgykg
lead (1.0%), 7.3 mgykg copper (3.8%), and
0.2 mgykg cadmium (4.0%). The metals in this
fraction are the most labile form and may conse-
quently be leached into surface water sources.
The potentially availableybioavailable metals
comprise those that can be accessed by man
through ingestion and are usually considered as
being of anthropogenic origin. They may be approx-
imately related to metals in the soluble
exchangeable carbonate fractions. In this
present study, 9.0 mgykg of lead, 24.1 mgykg of
copper and 2.6 mgykg of cadmium were found to
be potentially bioavailable. The relative bioavail-
ability of the heavy metals in the contaminated soil
followed the trend: Cd4Pb4Cu.
CONCLUSION
The screening of an automobile spare-parts market
revealed the presence of elevated concentrations of
lead, cadmium and copper. On speciating, the resi-
dual fraction contained the highest concentrations of
lead and copper while the highest value of cadmium
(0.7 mgykg) was found in the carbonate fraction. The
values for the potentially available and bioavailable
fractions of lead, cadmium and copper were higher
than the values stated by Sparks (2003) for unconta-
minated soil.
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