Environment pollution hazard awareness is required for less industrialized countries which are faced with increasing periurban agriculture practice however. Lead (Pb) and Cadmium (Cd) were characterized around Abidjan city (Bingerville, Port-Bouët and Yopougon) in soil, perched ground water and vegetable crops (Hibiscus and sweet potato). Total amounts and speciations of metals were determined respectively. The sites were mainly differing with pH observed at Yopougon characterized by highest soil content of Pb (40 mg kg-1). In contrast with the low soil contents of metals, plant contaminations were observed in the root for Cd and Pb at Yopougon and Port-Bouët sites respectively with variance involving above and below ground organs as specific contamination of Hibiscus or sweet potato. Skeleton fractions as exchangeable (F1) and carbonate bound (F2) were characterizing these contaminations although additional fraction as oxide bound (F3) Cd and organic (F4) Pb were required respectively for effectiveness. The non-polluted perched groundwater pH, Eh, temperature and O2 concentration were likely concerned by these fractions availability beside that of residual fraction (F5) of Cd. Enhance isomorphic substitution of anionic Pb forms transforming F2 into F5 and the cationic substitutions between Cd and Pb were suggested for pollution management.
2. Ecotoxicity and vulnerability of Trace Metals in low industrialized environment
Guety et al. 002
In fact, Cd and Pb are considered as most ecotoxic
metals that exhibit adverse effects on all biological
processes of humans, animals, and plants characterized
by a great adverse potential to affect the environment
and the quality of food (Kabata-Pendias, 2011).
Results of several studies (Gadde and Laitien, 1974;
Forbes et al., 1976; Lamyet al., 1993) on Cd fixation by
soil organic matter (SOM) and Fe/Mn hydroxides lead to
some generalizations: (1) in all soil, Cd activity is strongly
affected by pH, (2) in acid soils, the SOM and
sesquioxides may largely control labile pool of Cd, (3) in
alkaline soil, precipitation of Cd compounds is likely
accounting for Cd equilibrium. Similarly, the stability of Pb
(PbOH
+
;Pb(OH)2;Pb(OH)3
-
, PbNO3
+
, PbCl
+
, PbCl2 ,
PbCl3
-
and organic forms) is relevant to soil pH among
other physicochemical properties (Nriaguet al, 1978;
Hem, 1985). Of course, the harmfulness characterizing
both metals is depending on their mobility which is
varying with their speciations in a given ecological
conditions (Kabata-Pendias and Sadurski, 2004).
There are many investigations about metal speciations in
developed countries (Shoberet al., 2007; Medved et al.,
2008; Mpunduet al., 2013) in contrast with pollutants
characterization studies elsewhere, especially in Africa
whereas increasing urbanization and industrialization
coupled with environment pollution are observed. Hence,
such knowledge is required for raising public awareness
of pollution and saving environment quality as well as
public health in urban zones.
Therefore, the actual study was initiated in peri-urban
agriculture areas of Abidjan (economic capital) in Côte
d’Ivoire to explore soil, water and plant contaminations by
Cd and Pb in relation with the characterization of the
speciations respectively.
MATERIAL AND METHODS
Description of studied sites
Abidjan is the economic capital of Côte d’Ivoire (West
Africa), on the shoreline of the Guinea Golf within
altitudes 5˚00 - 5˚30 N and longitudes 3˚50 - 4˚10 W. It
accounts for 10 districts and the major industrial activities
of the country. It is characterized by subequatorial climate
with annual average rainfall amount fluctuating between
1637 mm and 2048 mm irregularly distributed in time and
space scales as bimodal rainfall in pattern (Two rainy
seasons alternating with two dry seasons). Annual
averages air temperature and hygroscopic measurement
are recorded between 24˚C - 30˚C and 75% - 88%
respectively according to Guety et al. (2015). The soil is
sand clayed Ferralsols somewhere Acrisols developed on
tertiary and quaternary sand deposits. Actual survey was
conducted in vegetable cropping areas of Port-Bouët
(5˚25N - 3˚94W) and Yopougon (5˚35N - 4˚04 W)
characterized by higher industrial and commercial
activities contrasting with Bingerville (5˚31 N - 3˚87 W) as
control site with lower activities (figure 1).
Figure 1. Studied zones and sampling site localizations
Plants studied
Two vegetable species characterized by edible leaf as
local dietary habits (Kouakou, 2009) were concerned:
Hibiscus (Hibiscus sabdaroufa) locally named “Dah” and
sweet potato (Ipomoea batatas). While hibiscus is
matured about 2 -3 months of cropping duration sweet
potato does so in a longer period of 3 – 6 months
depending to the cultivars and the roots are also edible
as tubers. Both are characterized by shallow rhizosphere
(0 – 30 cm) receiving manual daily irrigation using
perched ground water of well (2 – 3 m in depth).
Soil, plant and water sampling
Multi-sites (Bingerville, Yopougon and Port-Bouët) survey
was conducted in 2013 in the district of Abidjan (5°18 N;
4°00 W; 10 asl) around the localities of Port-Bouët and
Yopougon characterized by higher industrial and
commercial activity intensities while prevailing agricultural
activity accounts for Bingerville.
In 600 m
2
of vegetables cultivated area in each of these
locations, 12 soil composite samples were randomly
taken in 0 – 20 cm and 20 – 40 cm depth using hand
augur respectively. Furthermore, a soil profile (120 cm
depth) was also sampled for each of the studied area.
Soil sampling was coupled with that of plant selecting one
plant between 4 soil samples’ positions. About 5 g of
matured plant organs as fresh leaf, stem and root were
taken from hibiscus and sweet potato respectively. Soil
and plant samples were kept in plastic package and
transported in icebox for laboratory analysis.
3. Ecotoxicity and vulnerability of Trace Metals in low industrialized environment
Int. J. Toxicol. Environ. Health 003
Groundwater was also collected from well for this
purpose.
Laboratory analysis
Soil samples were dried in room condition before being
ground and sieved (2mm). Soil pH were determined
using glass electrode in 1/2.5 ratio of soil/solution (water)
respectively. Soil electric conductivity (EC) measurement
was coupled with that of soil pH.Soil chemical extraction
of metal (Cd and Pb) was also done using a ground soil
sample (0.3 g) of 150 μm in size and aqua regia [3 mL de
HNO3 (65%; v/v) + 1 mL de HCl (37%; v/v)] as described
by Baize et al. (2005) and Laurent (2003). Three
measurements (Atomic Absorption Spectrometry) were
done for each analysis and the average was reported and
compared to the standard values (Table 1) defined by
Barneaud (2006) and Godin (2010).
Table 1. Maximum standard concentration of Cd and Pb in soil,
plant and water
Metal maximum standard
concentration
Cd Pb
Sol (mg kg
-1
) 0.7 60
Plant (mg kg
-1
) 1 8
Water (µm L
-1
) 5 10
The chemical fractionations of metals were assessed
following sequential extraction procedure based on
coupled methods of Tessier et al. (1979) and Ure (1990).
It was carried out progressively on initial weight of 1.0 g
of homogenized material using the following extractions
steps:
The step 1 was processed with 0.5 M magnesium
chloride adjusted to pH 7.0 with 10% ammonia solution in
room temperature of about 30˚C for determination of
metal exchangeable fraction (F1) from floated solution.
Then, the step 2 was applied to the residue adding 1 M
Sodium acetate adjusted to pH 5.0 with Acetic acid for
the determination of carbonate bounded fraction (F2)
concentration in subsequent floated solution. Similarly,
bounded fractions to Fe-Mn oxide (step 3) and organic
matter (step 4) were determined using 0.04 M
Hydroxylamine hydrochloride in 25% Acetic acid (F3) and
30% Hydrogen peroxide in 0.02 M Nitric acid (F4)
respectively. Then, residual/lithogenic fraction (F5) was
determined in step 5 using Acidic reaction (HNO3).
Plant material was washed in tap water to remove
adhered soil particles and subsequently shredded, oven
dried (60˚C), ground (1mm) for the use of 0.5 g of
sample. Plant samples were digested in 6 ml of each of
H202 and HNO3 during 3 hours at constant temperature of
95˚C in a Digi PREP. Flame atomic absorption
spectrometry was use for the determination of plant
concentrations of Cd and Pb.
Pre-cleaned polyethylene sampling bottles were
immersed about 10cm below the water surface as
encountered in the well used for crop irrigation. About
0.5L of the water samples were taken at each sampling
site. Samples were acidified with 10% HNO3, placed in an
ice bath and brought to the laboratory. The samples were
filtered through a 0.45μm micropore membrane filter and
kept at 4°C until analysis. The samples were analyzed
directly using inductively coupled plasma optical emission
spectrometry (ICP-OES) fixing 228.8 nm and 220.4 nm
as wave lengths for Cd and Pb respectively.
Statistical analysis
By descriptive analysis, the mean, maximum and
minimum values of soil of Cd and Pb as well as pH were
determined for a given site in 0 – 20 cm soil depth.
Similarly, mean values of Cd and Pb concentrations in
leave, stem and root were demined according to studied
sites. By analyze of variance (ANOVA), mean values of
perched ground water properties (T˚C, EC, Eh, pH, O2,
Pb and Cd) were also determined running the test of
Student-Newman-Keul. ANOVA was also done for
determination of soil contents of different fractions in Cd
and Pb in topsoil (0 – 40 cm) and subsoil (40 – 120 cm)
for a given site. Pearson correlation was done to
establish the relation soil total content of Cd and Pb
considering their concentrations in plant root, stem and
leaf. Similarly, both metal concentrations of different
speciations (F1, F2, F3, F4 and F5) were used for
Pearson correlation with plant organs equivalent
concentrations likewise for perched groundwater.
Statistical package of SAS (version 9) was used for these
analysis considering α = 0.05. Studied sites (Bingerville
(1), Port-Bouët (2) and Yopougon (3)) were discriminated
by Cd and Pbspeciations (F1, F2, F3, F4 and F5) using
SPSS 16 package.
RESULTS
Soil and groundwater characteristics in studied sites
There is clearness of variation in soil acidity across the
studied sites (Table 2) of which, Yopougon site is
outstanding with highest mean value of pH (8.6) while,
the others (Bingerville and Port-Bouët) are characterized
by values ranging in acidic to neutral pH.
However, soil content of Cd is often missing (0 mg kg
-1
)
indifferently to sites and highest mean values account for
Port-Bouët (1.5 mg kg
-1
) and Yopougon (1.4 mg kg
-1
)
sites contrasting with the lowest value recorded in the soil
of Bingerville (0.56 mg kg
-1
) as the control site. In turn,
4. Ecotoxicity and vulnerability of Trace Metals in low industrialized environment
Guety et al. 004
Table 2. Ranges of soil (0 – 20 cm) contents of totals Cd and Pb as well as the pH according to
studied sites
Site
Bingerville Port-Bouët Yopougon
Cd (mg kg
-1
) Maximum 2.0 4.9 5.7
Mean 0.56 1.5 1.4
Minimum 0 0 0
Pb (mg kg
-1
) Maximum 62.7 56.1 57.2
Mean 21.0 33.6 40.0
Minimum 11.6 12.6 20.7
pH Maximum 5.8 7.1 8.7
Mean 5.6 7.0 8.6
Minimum 5.1 5.6 7.6
P (mg kg
-1
) Maximum 21.70 28.42 44.16
Mean 12.72 18.79 19.76
Minimum 4.06 4.48 6.67
CEC (cmol kg
-1
) Maximum 2.01 3.33 28.21
Mean 1.59 2.02 13.28
Minimum 0.88 1.53 3.94
Ca (cmol kg
-1
) Maximum 0.33 0.89 11.96
Mean 0.26 0.39 4.68
Minimum 0.14 0.12 0.89
Clay (%) Maximum 5 2 12
Mean 3 2 10.80
Minimum 2 1.5 10.65
MO (g kg
-1
) Maximum 22.5 21.25 15.51
Mean 20.35 17.05 12.22
Minimum 19.32 14.07 7.3
Number of sample = 24
there is always Pb content in soil wherever with minimum
values ranging between 11.6 mg kg
-1
and 20.7 mg kg
-1
for a maximum reaching 62.7 mg kg
-1
especially at
Bingerville site which is also characterized by lowest
mean value however. Mean value of soil content of Pb is
almost twice higher for Yopougon site as compared to
that of Bingerville which is 1/3 lower than the value
observed for Port-Bouët site.
No significant difference accounts for sites referring to
ground water concentration of Pb and EC, however. In
turn, significant lowest values of temperature (27˚3C),
oxygen concentration (2.03 mg L
-1
), redox potential (-7.03
mV) are determined for the ground water at Yopougon
entirely contrasting with Bingerville site (control site). The
ground water at Port-Bouët site is particularly
characterized by highest value of temperature (30˚C).
Except for Yopougon, no concentration of Cd is
determined in groundwater.
Site specific metal fractions in soils
Figures 2 and 3 are showing the discrimination of studied
sites in the basis of soil profile (0 – 120 cm) contents of
Cd (variance: F1= 99, 6 %; F2= 0, 4 %) and Pb (variance:
F1= 87, 7 %; F2= 12, 3 %) speciations as site
characteristics respectively.
There is no influence of lithogenic fraction of Cd as site
characteristic while Bingerville and Yopougon sites are
diametrically opposed according to Cd speciations with
exchangeable (F1), Ca-bound (F2) and oxide bound (F3)
fractions positively characterizing Yopougon site (Figure
2). Furthermore, there is no influence of oxide-bound
fraction in Port-Bouët site characteristics as observed for
Cd while organic fraction accounts for negatively
although with limited influence for all the studied sites.
Roughly, similar picture is observed for sites
characterization by Pb speciations in soils (Figure 3) with
no influence of oxide bound fraction (F3). In addition, no
significant influence of lithogenic fraction (F5) is observed
like for Ca-bounded form (F2) of Pb. These bounded
fractions were positively characterizing Bingerville site in
opposition with Port-Bouët site more relative to the
exchangeable and organic fractions of Pb as
characteristic.
By analysis of soil total contentment of the most
significant Pb and Cd speciations (F1, F2, F4 and F5)
according to the functions 1 of Figures 2 and 3
respectively, soil contents of Cd and Pb as total of F1 and
F2 fractions are showing opposite scenarios in site
difference according to soil depths (Table 5): significant
difference is observed for Cd (F1+F2) in topsoil while no
significant difference accounts for Pb (F1+F2) entirely
5. Ecotoxicity and vulnerability of Trace Metals in low industrialized environment
Int. J. Toxicol. Environ. Health 005
Figure 2. Sites (1: Port-Bouët; 2: Bingerville; 3:
Yopougon) discrimination according to cadmium
speciations
Figure 3. Sites (1: Port-Bouët; 2: Bingerville; 3:
Yopougon) discrimination according to Lead speciations
contrasting with the measurement in the subsoil.
Moreover, highest content of a given metal is associated
to lowest content of the second (e.g. highest topsoil
content of Cd is associated to the lowest amount of Pb in
subsoil at Yopougon site). Highest content of Pb (8.42
mg kg
-1
) is observed for Port-Bouët as total of F1+F4
fractions also outstanding with 1.85 mg kg
-1
as F1+F2
fractions of Pb. No significant difference between sites is
observed for total content of F2 + F5 fractions
indifferently to studied metal.
Topsoil contents of Pb and Cd as total of F1+F2 fractions
(Figures 4 and 5) are often greater than that of the
subsoil and the amounts of both metals are contrasting
according to the sites. Highest amount of Pb accounts for
Bingerville as control site, however (Figure 5).
However, no significant difference is observed between
the mean values of topsoil contents of Pb speciations
according sites respectively (Table 6) but, soil content of
Pb-F2 (CaO-bound) at Bingerville site is twice greater
(2.10 mg kg
-1
) than that of Port-Bouët site (1.42 mg kg
-1
)
which is also threes greater compared with that of Pb-F2
(0.4 mg kg
-1
) at Yopougon. In turn, topsoil content of Pb-
F5 (residual fraction) at Bingerville site is twice and
threes greater than that of Port-Bouët (4.53 mg kg
-1
) and
Bingerville (3.66 mg kg
-1
).
In contrast, significant differences are observed between
the mean values of subsoil contents of Pb-F1 and Pb-F2
according to sites. Highest values of both Pbs peciations
are observed at Port-Bouët while lowest accounts for
Yopougon site studiously. This trend is contrasting with
6. Ecotoxicity and vulnerability of Trace Metals in low industrialized environment
Guety et al. 006
Figure 4: Mean value of Cd as total of F1+F2 fraction in soil
depths according to sites
Figure 5. Mean value of Cd as total of F1+F2 fraction in soil depths
according to sites
that of Cd speciation’s, which are significantly highest for
F1 and F5 in both top and subsoil at Yopougon beside
similar observation in the topsoil for F2. Of these results
(Table 6), no significant difference accounts for Pb
speciation contents in topsoil between the sites studied
as much as for Cd-F1, Cd-F2 and Cd-F5 while such of
difference is characterizing the subsoil content of F1 for
Pb and Cd respectively.
Metal concentrations in plant and groundwater
Figures 6 and 7 are showing the concentrations of Cd
(Figure 6) and Pb (Figure 7) in plant organs (leaf, stem
and root) according to studied sites respectively.
Less than 6 mg kg
-1
as Cd concentrations account for
above ground organs (leaf and stem) indifferently to sites
except for Port-Bouët which is characterized by leaf
concentration of Cd recorded over 0.7 mg kg
-1
and about
0.65 mg kg
-1
for the stem (Figure 6). In turn, greater
amount of Cd concentrations are observed in the root
especially at Yopougon site where the concentration is
brushing 0.85 mg kg
-1
. However, Cd concentration is
likely decreasing when from the leaf to the root
throughout stem at Port-Bouët site while studious
increasing is observed at Bingerville site. Lowest
concentration of Cd is noticed for the stem collected at
Yopougon.
The concentration of Pb is also increasing from above
ground biomass (leaf and tem) to root at Yopougon site
(Figure 7) remaining lower than 6 mg kg
-1
and contrasting
with the irregular trend observed at Port-Bouët in highest
range of 8.5 mg kg
-1
to 10 mg kg
-1
.
7. Ecotoxicity and vulnerability of Trace Metals in low industrialized environment
Int. J. Toxicol. Environ. Health 007
Figure 6: Cadmium (Cd) concentrations in crop leaf, stem and root in studied areas
(Barres are representing standard deviation)
Figure 7. Lead (Pd) concentrations in crop leaf, stem and root in studied areas
(Barres are representing standard deviation)
Moderate range (6 – 8 mg kg
-1
) of fluctuation is
characterizing Pb concentrations in plant organs at
Bingerville. Roughly, Port-Bouët site is outstanding with
highest concentration of Pb indifferently to the plant
organs.
This trend is consistent with that of Pb concentrations in
sweet potato and Hibiscus across sites (Table 7). But,
highest accumulation of Pb (10.5 mg kg
-1
) accounts for
stem of sweet potato at Port-Bouët as observed for stem
and/or root of Hibiscus as genotype difference of Pb
mobilization in plant according to environments (sites).
Lowest values of Pb concentrations are characterizing
Yopougon site indifferently to plant and their organs
respectively. In turn, highest concentrations of Cd are
observed in there for roots of sweet potato and Hibiscus.
Moreover, there is higher concentration of Cd in the root
of sweet potato at Bingerville site (control site) when
compared with that of Port-Bouët while reverse scenario
accounts for Hibiscus.
Overall, there is significant negative correlation between
Pb concentration in the root and total soil contents of Cd
(-0.47) and Pb (-0.48) respectively, all top medium (Table
8). But, these correlations are contrasting with the
positive correlations observed for Cd concentration in the
8. Ecotoxicity and vulnerability of Trace Metals in low industrialized environment
Guety et al. 008
Table 3. mean values of soil contents of totals Cd and Pb as well as the pH according to studied
sites
a and b are indicating mean values with significant difference in column for α=0.05
Table 4. Characteristics of perched groundwater as determined in the studied sites
T˚C EC
(ms cm
-1
)
O2
(mg L
-1
)
Eh
(mV)
pH Pb
(mg L
-1
)
Cd
(mg L
-1
)
Bingerville 28.7ab 0.08a 5.90a 72.90a 5.7c 0.12a ----
Port-Bouët 30.8a 0.65a 4.90ab 23.52b 6.5b 0.44a ----
Yopougon 27.3b 0.45a 2.03b -7.03c 7.2a 0.31a 0.03
GM
P> F
29.4
0.01
0.46
0.101
4.44
0.06
28.22
0.001
6.5
0.0001
0.33
0.44
----
----
a and b are indicating mean values with significant difference; ----: Missing data
Table 5. Mean values of topsoil and subsoil contents of combined F1+F2, F1+F4 as Cd and F1+F2,
F1+F4 and F2+F5 as Pb in Topsoil and Subsoil according to studied sites
Topsoil
Site
Cd-F1+F2
(mg kg
-1
)
Pb-F1+F2
(mg kg
-1
)
Cd-F1+F4
(mg kg
-1
)
Pb-F1+F4
(mg kg
-1
)
Pb-F2+F5
(mg kg
-1
)
Bingerville
0,06a 1,11b 0,09ab 3,90a 4,32a
Port-Bouët
0,21a 1,85a 0,03b 7,50a 11,67a
Yopougon
0,58a 0,29c 0,24a 4,62a 23,36a
P> F
Mean (mg kg
-1
)
0.04
0.30
0,02
0,93
0,04
0,14
0,32
4,90
0,47
13,40
Subsoil
Site
Cd-F1+F2
(mg kg
-1
)
Pb-F1+F2
(mg kg
-1
)
Cd-F1+F4
(mg kg
-1
)
Pb-F1+F4
(mg kg
-1
)
Pb-F2+F5 (mg
kg
-1
)
Bingerville
0,11c 2,70a 0,12b 4,73b 5,77a
Port-Bouët
0,28b 2,83a 0,16b 8,42a 5,95a
Yopougon
1,90a 0,58a 1,01a 6,96ab 9,82a
P> F
Mean (mg kg
-1
)
0,001
0,54
0,39
2,33
0,01
0,31
0,03
6,65
0,10
6,65
a, b and c are indicating mean values with significant difference in column for α=0.05
root. Meanwhile, consistent negative correlations are
observed for Cd and Pb concentrations in the stem with
limited significant for Pb concentration however,
especially for soil content of Pb. No significant correlation
is observed for Cd concentration in leaf as referring to
soil contents of Cd and Pb while leaf accumulation of Pb
can decrease with the increasing of both metal contents
in soil according to the negative correlation significantly
observed respectively.
However, soil content of Cd can be released as F2 and
F5 fractions with increasing of groundwater pH according
to the significant positive correlations observed
respectively while, negative correlations with these Cd
fractions account for groundwater redox potential (Eh).
Cd (mg kg
-1
) Pb (mg kg
-1
) pH
Bingerville 0.65b 15.25c 5.6c
Port-Bouët 0.5b 29.97b 6.8b
Yopougon 2.33a 49.15a 8.6a
P> F 0.0001 0.0001 0.0001
9. Ecotoxicity and vulnerability of Trace Metals in low industrialized environment
Int. J. Toxicol. Environ. Health 009
Table 6. Mean values of Pb and Cd speciations (F1, F2, F3, F4 and F5) in soils according to studied sites (Bingerville, Port-Bouët and Yopougon)
Content of Pb
Topsoil Subsoil
F1 F2 F3 F4 F5 F1 F2 F3 F4 F5
Bingerville
0.60a 2.10a 4.18a 4.13a 3.66a Bingerville 0.55a 0.56b 4.34a 3.34a 3.76a
Port-Bouët
1.41a 1.42a 6.69a 7.01a 4.53a Port-Bouët 0.65a 1.20a 6.91a 6.85a 10.47a
Yopougon
0.18a 0.40a 3.89a 6.78a 9.42a Yopougon 0.08b 0.21b 12.77a 4.54a 23.15a
P> F 0.46 0.14 0.07 0.08 0.07 0.02 0.02 0.26 0.34 0.46
Content of Cd
Topsoil Subsoil
F1 F2 F3 F4 F5 F1 F2 F3 F4 F5
Bingerville
0.02c 0.09b 0.20a 0.10a 0.12b Bingerville 0.03b 0.03a 0.22a 0.06a 0.14b
Port-Bouët
0.12b 0.15b 0.29a 0.03a 0.26b Port-Bouët 0.01b 0.20a 0.79a 0.02a 0.73ab
Yopougon
0.89a 1.01a 0.21a 0.12a 1.27a Yopougon 0.18a 0.40a 2.09a 0.05a 1.88a
P> F 0.001 0.001 0.15 0.43 0.03 0.03 0.05 0.54 0.06 0.03
Table 7: Mean values of Pb and Cd concentrations in leaf, stem and root of sweet potato and Hibiscus according to sites respectively
Pb concentration (mg kg
-1
)
Sweet potato Hibiscus
Bingerville Port-Bouët Yopougon Bingerville Port-Bouët Yopougon
Leaf 6.17cB 9.72bA 2.92bC 6.91bB 8.81bA 3.10cC
Stem 6.41bB 10.50aA 5.01aC 6.17bB 9.42aA 5.52bC
Root 7.80aB 9.60bA 5.81aC 8.42aB 9.71aA 6.12aC
P> F <0.001 <0.001 <0.001 <0.001 <0.001 <0.001
Cd concentration (mg kg
-1
)
Leaf 0.52cB 0.81aA 0.57bC 0.46cC 0.64aA 0.48Bb
Stem 0.64bB 0.72bA 0.41cC 0.53bB 0.60aA 0.47bC
Root 0.72aB 0.65cC 0.94aA 0.61aC 0.66aB 0.77aA
P> F <0.001 <0.001 <0.001 <0.001 <0.001 <0.001
a, b and c are indicating mean values with significant difference in column for α=0.05; A, B and C are indicating mean values with significant difference in line for α=0.05
10. Ecotoxicity and vulnerability of Trace Metals in low industrialized environment
Guety et al. 010
Table 8. Pearson correlation coefficient (R) and probability (P) observed for soil total contents of Cd and Pb according to
corresponding concentrations in crop leave, stem and root indifferently to sites
Soil [Cd] Soil [Pb]
Leaf [Pb] R -0.47 -0.48
P 0.003 0.002
Stem [Pb] R -0.29 -0.15
P 0.076 0.366
Root [Pb] R -0.34 -0.37
P 0.041 0.023
Leaf [Cd] R -0.18 0.08
P 0.272 0.623
Stem [Cd] R -0.41 -0.44
P 0.011 0.006
Root [Cd] R 0.41 0.56
P 0.013 0.0003
Table 9. Pearson correlation coefficient (R) and probability (P) of Cd and Pb fractions (F1, F2, F3, F4 and F5)
according to perched ground water properties
Cd fraction
F1 F2 F3 F4 F5
pH R 0.44 0.64 0.52 -0.18 0.82
P 0.200 0.044 0.112 0.609 0.003
T˚C R -0.54 -0.50 -0.23 -0.56 -0.45
P 0.101 0.139 0.508 0.086 0.186
Eh R -0.39 -0.59 -0.49 0.22 -0.77
P 0.257 0.069 0.143 0.530 0.008
O2 R -0.37 -0.53 -0.34 0.29 -0.68
P 0.284 0.107 0.324 0.413 0.028
EC R 0.104 0.10 -0.13 -0.34 -0.11
P 0.772 0.760 0.716 0.329 0.759
Pb fraction
F1 F2 F3 F4 F5
pH R -0.37 -0.31 0.54 0.34 0.63
P 0.341 0.382 0.101 0.326 0.047
T˚C R 0.35 0.54 -0.168 0.27 -0.29
P 0.307 0.105 0.641 0.450 0.405
Eh R 0.29 0.25 -0.53 -0.37 -0.60
P 0.419 0.490 0.114 0.287 0.062
O2 R 0.53 0.73 -0.48 -0.31 -0.44
P 0.104 0.013 0.153 0.377 0.196
EC R -0.14 0.21 -0.12 0.51 -0.10
P 0.697 0.552 0.726 0.127 0.771
The increase of oxygen amount in groundwater can
induce the reduction of soil content of Cd-F5 likewise for
Cd-F4 as illustrated by the correlation values observed
for groundwater temperature (Table 9).
Except for residual fraction of Pb (F5) which has
contrasting correlations with groundwater pH (0.63) and
Eh (-0.60) respectively beside the high positive
correlation (0.73) between Ca-bound fraction (F2) and
groundwater concentration of O2, there is limited relations
between soil content of Pb and the studied characteristics
of groundwater (Table 9). Furthermore, no influence of
these characteristics are noticed for F1 (exchangeable)
and F3 (oxide-bound) fractions indifferently to studied
metals and no relationship is observed for EC whatever
the metal and relevant fractions.
DISCUSSION
Cadmium pollution hazards
According to Heinrichs et al. (1980),worldwide average
concentration of cadmium in the lithosphere is 0.098 mg
kg
-1
and mean values in soils of most industrialized
countries (e.g. United States of America) are depending
to soil types and the sites ranging below 1.5 mg kg
-1
however (Burau et al., 1973; Lund et aI., 1981; Logan
and Miller, 1983 ; Holmgren et al., 1993). In contrast with
the industrialization level of Côte d’Ivoire (Cherniwchan,
2012), this value is close to the mean values of Cd
observed in the top soils at Port-Bouët (1.5 mg kg
-1
) and
Yopougon (1.4 mg kg
-1
) sites and maximum values
11. Ecotoxicity and vulnerability of Trace Metals in low industrialized environment
Int. J. Toxicol. Environ. Health 011
recorded across sites were ranging between 2 mg kg
-1
and 5.7 mg kg
-1
(Table 2) over the threshold level of 0.7
mg Cd kg
-1
(Alloway, 1990) This is a major output of the
current study as an awareness pointing out the poor
control of urbanization source of pollution early gusted by
Innes and Haron (2000) as a guilty behavior in rapid
industrialization regions.
Beside the microbial transformation of soil total Cd
(Czaban and Wróblewska, 2005), soil solution
characteristics as pH, Eh, temperature and concentration
of O2, may have significantly contributed to Cd
speciations occurrence in soil: Residual fraction of Cd
(F5) in soil was roughly predominant in both topsoil (0.40
mg kg
-1
) and subsoil (0.95 mg kg
-1
) across the studied
sites while CaO3-bound (0.30 mg kg
-1
) and oxide-bound
(1.08 mg kg
-1
) fractions did so in topsoil and subsoil
respectively. Yopougon site was outstanding with highest
residual and exchangeable fractions of Cd (Table 5).
Likewise, for Cd concentration in root indifferently to
studied plants (Figure 6, Table 6). Caution should be paid
to sweet potato, which was characterized by 0.94 mg kg
-1
of Cd in tuber closely to the critical level of 1 mg kg
-1
(Godin, 2010). Difference in soil pH and crop ability of
low weight organic acid secretion in soil (Krishnamuri et
al., 1997; Mann and Ritchie, 1993) may have contributed
to this when referring to Cd speciations in soils as the
combination of F1, F2 and F3 characterizing Yopougon
site contrasting with Port-Bouët site in spite of almost
similar total amount of Cd. Moreover, the concentration of
Cd in the plant root was likely increasing with that of soil
content of total Cd (Table 7). Therefore, harmfulness of
Cd in Yopougon site for sweet potato was due to the total
proportion of F1, F2 and F3 while F4 accounted for Port-
Bouët site instead of F3 with limited potential of
contamination.
These analyze reveal potential interactions between Cd
speciations as synergism or antagonism mechanisms as
topic for further study in order to deepen knowledge.
Contrast in lead pollution hazards
Yet the peri-urban agriculture production of Abidjan was
deemed contaminated by Pb (Guety et al., 2015), the soil
contents of total Pb were heterogeneous across sites and
highest amount was observed at Yopougon (40 mg kg
-1
)
followed by that of Port-Bouët (33.6 mg kg
-1
) though
below the threshold level of 60 mg kg
-1
(Alloway, 1990).
Moreover, similar low concentrations of Pb (< 10 mg L
-1
)
(Fageria et al, 2010) were characterizing the groundwater
which was likely concerned by carbonate and residual
bound fractions enrichment in soil when increasing its pH
and O2 concentration (Table 9). Indeed, trace metals do
not exist in soluble forms for a long time in waters (Dossis
and Warren, 1980): they are present mainly as
suspended colloids or fixed by organic and mineral
substances. Consequently, the contamination of plant as
observed according to the high concentrations (> 8 mg
kg
-1
) of Pb in leaf, stem and root respectively at
Yopougon site (Figure 7) was likely relevant to the total
amount of F1 and F4 in topsoil as well as that of F1+F2 in
subsoil (Table 5) instead of single effects apart,
especially in topsoil (Table 5). Base on the negative
correlations observed between Pb concentrations in plant
organs (leaf, stem and root) and that of soil respectively
(Table 9), we assume the reduction of the concentrations
of these harmful fractions of Pb, probably by
transformation to residual fraction (F5) when soil total
content of Pb increased. This assertion is supported by
Figure 2 pointing out the most important fractions of Pb
as F1, F2, F4 and F5 across sites and carbonate bound
fraction (F2) coupled with the residual form (F5) were
opposed to Port-Bouët site characteristics of Pb (F1 and
F4) illustrating most sensitivity of F2 to be transform into
F5 hence, reducing Pb harmfulness. Such transformation
was reported as buffer mechanism controlling the
migration and fixation of Pb as well as the bioavailability
(Bolan et al., 2003) involving phosphorus availability in
the soil, and resulting in pyromorphite formation (Cao et
al., 2002; Scheckel and Ryan, 2004). Of course, available
soil P may be higher in Port-Bouët compared to that of
the other sites because of the prevailing neutral pH (Koné
et al., 2011; 2014). Thought agricultural practice involving
the application of chicken manure may be concerned by
increasing of both P and Pb amounts in soil as specially
in yopougon (Amadji et al., 2013). Hence, there is
opportunity of Pb self-control of harmfulness in soil
neutral pH condition somewhat differing with the case
described by Cotter-Howells and Caporn, (1996) relative
to mineral phosphate effect in Pb polluted soil.
Endeavors of Pb and Cd pollution managements
The self-control of Pb harmfulness in agricultural system
may be relevant to anionic forms of Pb (e.g. Pb(OH)3
-
,
PbCl3
-
, Pb(CO3)2
2-
) because of P forms (H2PO4
–
and
HPO4
2 –
) in soil solution hence, excluding the other forms
of Pb (e.g. PbOH
+
; Pb(OH)2;, PbNO3
+
, PbCl
+
, PbCl2).
Therefore, this strategy of Pb pollution management
advocated by some experts including Melamed et al.
(2003) may have partial efficacy.
In turn, exchangeable form and carbonate bound fraction
are constituting the skeleton forms required for Cd and
Pb harmfulness in the studied ecology even though their
effective pollution ability further involve oxide bound
fraction for Cd and organic form for Pb respectively with
contrast across sites (Figures 2, 3, 4 and 5): Increasing of
skeleton fractions of Cd (F1+F2) amount in soil was
associated with the reduction of that of Pb across sites
(Figures 4 and 5) likely consecutive to isomorphic
substitution between Cd
2+
and Pb
2+
. In the light of this
analysis, polluted soil amendment with inorganic or
synthetic material enriched in bivalent cations (e.g. Ca
2+
,
Mg
2+
even Al
3+
, Fe
3+
, Si
4+
) may have potential to fixed
(immobilize) both Cd
2+
and Pb
2+
, hence reducing their
12. Ecotoxicity and vulnerability of Trace Metals in low industrialized environment
Guety et al. 012
bioavailability as F1 and F2 when, the residual form
amounts will increase. Bentonite properties can be
explored for this purpose referring to the successful test
conducted by Schütz et al. (2013) for trace metals
immobilization. Furthermore, the nitrification of bentonite
has improved this potential by dividing the basic
montmorillonite layers, providing more space for
adsorption of cadmium cations and leads (Galamboš et
al., 2010).
Success of such attempt strategy can be expected in the
studied ecology as spontaneously occurring according to
figures 2 and 3: Negative influence of Cd oxide bound
fraction was observed for the characteristics of Port-
Bouët site saved from Cd pollution in spite of the amount
of soil total Cd (1.5 mg kg
-1
) somewhat greater than
elsewhere. Almost similar scenario was observed for
Yopougon site with the turnover of Pb residual fraction
consecutively to carbonate bound fraction transformation
resulting limited pollution of soil Pb in spite of the greatest
amount of soil Pb (40 mg kg
-1
).
However, change in trace metal forms can be observed
over time, including the release of more bioavailable
fractions as observed for soil Cd according to soil pH
(Mann and Ritchie, 1993). Because this eventuality, one
might explore phytoremediation options which may be
effective for the studied crops when considering Cd and
Pb concentrations in non edible organs: Highest
concentrations of Cd were observed for the stem and leaf
of sweet potato attesting safety of the tuber for
consumption and the removal of 1.58 mg Cd kg
-1
from the
soil at Port-Bouët. In the same manner, higher
concentrations Pb were observed in the root and stem of
Hibiscus at Yopougon and Port-Bouët as remediation
aptitude of this species characterized by edible leaf.
CONCLUSION
There is stray impulse of Cd pollution at Yopougon site,
especially for below ground organ of tuber crop as sweet
potato and the harmfulness was most related to
combined effect of exchangeable, carbonate bound and
oxide bound fractions. In turn, Pb pollution was observed
at Port-Bouët in leaf, stem and root indifferently to crop
and the most harmful fractions included also the
exchangeable and organic forms beside carbonate bound
fraction which may be transform into residual bound
fraction as buffer mechanism of soil Pb decontamination
as self-control which may be limited to anionic forms
however. Specific remediation potential of studied crops
was recommended for sustaining peri-urban agro
systems around Abidjan city.
ACKNOWLEDGEMENTS
We are particularly grateful to Dr Brahima Koné as
mentor of this study. NAN Georges Marcellin is not
forgotten for its financial support. The authors
acknowledged the contributions of Dr. C. Juan Pedro
Hernández Touset, Marta Eliane Doumer, Dr. R.W.
Gaikwad, Patricks Otomo and Yu Li for donating their
time, critical evaluation, constructive comments, and
invaluable assistance toward the improvement of this
very manuscript.
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