American Chemical Science Journal

5(3): 238-246, 2015, Article no.ACSj.2015.023

ISSN: 2249-0205

SCIENCEDOMAIN international
www.sciencedomain.org

Speciation of Some Heavy Metals in Sediments of

the Pennington River, Bayelsa State, Nigeria
Leizou Kaywood Elijah1*, Horsfall Michael Junior2 and Spiff Ayebaemi Ibuteme2
1
Department of Chemical Sciences, Niger Delta University, Wilberforce Island, Nigeria.
2
Department of Pure and Applied Chemistry, University of Port Harcourt, P.O.Box 402, Port Harcourt,
Nigeria.

Authors’ contributions

This work was carried out in collaboration between all authors. Author LKE designed the study,
performed the statistical analysis, wrote the protocol, and wrote the first draft of the manuscript.
Author LKE the analyses of the study. Author LKE managed the literature searches. Edited and
proved by authors HMJ and SAI. All authors read and approved the final manuscript.

Article Information

DOI: 10.9734/ACSj/2015/14696
Editor(s):
(1) Nagatoshi Nishiwaki, School of Environmental Science and Engineering, Kochi University of Technology, Japan.
Reviewers:
(1) Anonymous, Egypt.
(2) Anonymous, Libya.
Complete Peer review History: http://www.sciencedomain.org/review-history.php?iid=862&id=16&aid=7311

th
Received 15 October 2015
Original Research Article Accepted 14th November 2014
th
Published 16 December 2014

ABSTRACT
The total heavy metal concentrations of some environmentally toxic metals in sediments of the
Pennington River System, Bayelsa state, Nigeria was examined. The concentrations of heavy
metals in each fraction were determined using a ANALYST 400 Perkin-Elmer AAS. The mean
concentrations (mg/kg) for the six metals in dry season sediment samples were: 0.14±0.17(As),
0.39±0.55(Co), 2.43±5.06(Cu), 26.82±22.19(Fe), 0.69±1.10(Pb), and 1.22±1.19(Zn), while the
mean metal concentrations (mg/kg) in wet season samples were:0.11±0.18(As),0.37±0.6(Co),
2.07±4.35(Cu), 26.65±24.79(Fe), 0.61±1.08(Pb), and 1.11±1.00(Zn) respectively. Speciation study
applying the five-stage sequential extraction scheme revealed that As, Co, and Pb in sediment
prevails mostly in exchangeable fraction. Cu and Zn were more prevalent in residual fraction, while
Fe was found more in residual and Fe/Mn-Oxide fractions. In an attempt to infer anthropogenic
input from natural input, comparison with sediment quality guideline (SQGs) and ecotoxicological
sense of heavy metal contamination was employed. The concentration of the studied heavy metals
in Pennington River System does not pose a threat to the sediment dwelling fauna and anyone who
consumes aquatic animals, particularly fish, from the Pennington River. According to SQGs, the
studied heavy metals of the Pennington River sediments were under the category of non-polluted.
_____________________________________________________________________________________________________

*Corresponding author: E-mail: pastorkayeleizou@yahoo.com;

 Leizou et al.; ACSj, 5(3): 238-246, 2015; Article no.ACSj.2015.023
Keywords: Speciation; Pennington River System; Sediment.
1. INTRODUCTION
Speciation helps in the identifications and
quantification of the defined geochemical
fractions, forms or phases in which an element
exists in the environment [1,2]. Speciation in
sediment compartment is a significant step to
understand the potential environmental risk,
distribution, mobility and bioavailability of
pollutants. Determining the total content of heavy
metals in the sediments may be useful for the
characterization of pollution intensity, however,
speciation of heavy metals with selective
extracting agents gives further information about
the fundamental reactions that govern the
behaviour of metals in sediment and helps to
assess the environmental impact of
contaminated soil and sediment [3,4,5].
Sequential extraction procedure is used to
partition heavy metals in soil and sediments in
order to assess the forms of heavy metals in
contaminated soils and sediments. It provides
information on potential mobility as well as
bioavailability and plant uptake of heavy metals
[6,7]. It also determine the bioavailability of the
metal in soil and sediment to other biota within
the aquatic ecosystem. Metals dissolved in soil
solution, surface and interstitial waters and those
adsorbed on the sediment by cation exchange
processes are usually readily available to aquatic
and benthic organisms as well as to plants.
Metals strongly bound to the sediments and
complexes with other chemical compounds are
of less concern as they most likely unavailable to
the biota [8]. Sediments contaminated with
metals may act as a secondary pollution source
for aquatic ecosystem, and study of metal
concentration in sediment is useful for the
estimation of pollution trends [5]. Study on the
geochemistry of river sediment in the Pennington
River system has not been undertaken by
previous workers. The river is under tidal
influence and receives effluent from several
sources and oil production activities take place
off-shore of the environment. In addition, there is
uncontrolled domestic sewage disposal; fishing,
marine boats are very common of the
Pennington River system and anecdotal
information suggests that the river receives
effluents off-shore where oil production activities
take place. This study was carried out to check
the speciation of heavy metals (arsenic, cobalt,
copper, iron, lead, and zinc) in the surface
sediments from Pennington River system,
Bayelsa State, Nigeria.
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2. MATERIALS AND METHODS
2.1 Study Area
The Pennington River is a natural river
geographically located in Bayelsa state, Niger
Delta region, Nigeria (Fig. 1). The river lies
between the coordinates of latitude 04o15’’ North
and latitude 05o23’’South and longitude 05o22”
West and 06o45” East. Pennington River is a
distributary and it also flows into the Atlantic
Ocean (Bight of Benin).
2.1 Reagents Used and Their Sources
The reagents and chemicals used are of
analytical grade. The reagents used are HNO3
(Riedel-deHaën, Germany), 30% hydrogen
peroxide, H2O2and 70% perchloric
acid,HClO4British Drug House (BDH) Chemicals
Ltd, Poole, England. Solutions were prepared
using doubly distilled water. All glass wares used
(conical flask, measuring cylinder, volumetric
flask, and watch glass) were washed with liquid
detergent and rinsed thrice followed by oven
drying.
2.3 Sampling and Pre-treatment of
Sediment Samples
In this study, sediment samples were collected
from four stations located along the Pennington
River system. Details of these sites are given in
Table 1. Sediments were sampled using a
bottom grab sampler (Hydro-Bios) and then
immediately transferred into plastic bags and
refrigerated. In order to get a representative
sample for each station, several sub-samples
were collected and mixed together. The sediment
samples were analyzed for total metal [9] and
metal speciation [10].
2.4 Determination of Metal Speciation in
Sediment
For the heavy metal speciation in sediment a
five-stage sequential extraction procedure was
employed in this study. This sequential extraction
was based on the principles of [10,11]. This
extraction procedure defines the following five
metal speciation regular forms: exchangeable,
carbonate-bound, Fe/Mn-oxide bound, organic
matter/sulfide bound and residual fraction
(Table 2).
 Leizou et al.; ACSj, 5(3): 238-246, 2015; Article no.ACSj.2015.023
Table 1. Sites, description of activities and
details
Sites Description of Details
activities
A Fishing, marine boats Upstream
B Fishing, marine boats Middle reach
C Fishing, marine boats Down stream
D Fishing, marine boats Mouth
Stage1. Exchangeable fraction: 1g of sediment +
16ml of MgCl2 at pH = 7 were extracted at room
temperature for 1hour. The mixture of extraction
solution and sediment were shaken carefully
throughout extraction.
Stage 2.Carbonate bound: Residue of fraction 1
+ 16ml of 1M Sodium acetate/acetic acid buffer
at pH=5 for 5hours at room temperature.
Continuous shaking was maintained throughout
the period.
Stage 3. Fe/Mn-Oxide bound: Residue from
fraction 2 + 20 ml of 0.4M NH2OH.HCl (13.9g
NH2OH.HCl dissolved in 500mlof distilled water)
in 25 %(v/v) acetic acid at a temperature of 96ºC
in water bath for 6 hrs.
Stage 4. Organic matter/sulfide bound: Residue
from fraction 3 + 3 ml of 0.02M HNO3 + 5ml of
30% ( v/v) hydrogen peroxide, which has been
adjusted to pH= 2.Mixture was heated to 85ºC in
water bath for 2hours, with occasional shaking
and allowed to cool down. Then + 3 ml of 30%
H2O2 adjusted to pH=2 with HNO3. Mixture
heated again at 85ºC for 3hours with occasional
Table 2. Summary of sequential Extraction Scheme Used
Fraction Extractant
F1 1g of sediment sample +16ml of
1M MgCl2, pH=7
F2 16ml of CH3COONa/CH3COOH
buffer, pH=5
F3 20ml of 0.4M NH2OH. HCl in 25%
CH3COOH
F4 1.3ml of 0.02M HNO3+5ml of 30%
H2O2,pH=2 with HNO3
2.3ml of 30% H2O2, pH = 2 withHNO3
3. 5ml of 3.2M NH4OAc in 20%
HNO3 followed by dilution to 20ml with
de-ionized water
F5 5ml HNO3+ 10ml HF +10ml HClO4
*Tessier et al. (1979); **Abu-Kukati,2001 ***RT = room temperature
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shaking and allowed to cool down. Lastly + 5ml
of 3.2M ammonium acetate in 20% (v/v) HNO3,
followed by dilution to a final volume of 20ml with
de-ionized water.
Stage 5. Residual or inert fraction: Residue from
fraction 4 was oven dried at 105ºC. Digestion
was carried out with a mixture of 5ml conc.
(HNO3, 70% W/W) + 10 ml, of hydrofluoric acid
(HF, 40%, W/W) + 10 ml of perchloric acid
(HClO4, 60% w/w in Teflon beaker.
2.5 Instrumentation and Statistical
Analysis of Data
In this study, raw data was used in calculating
the correlation coefficient using Microsoft Excel
2010. Both descriptive and inferential statistical
analyses were used to interpret the data in this
study. Pearson correlation analysis was also
carried out. The heavy metal concentrations in
each fraction were determined by using an
ANALYST 400 Perkin-Elmer AAS.
3. RESULTS AND DISCUSSION
The results of the metal speciation in sediment
samples in dry season (January, 2011),wet
season(September, 2011) of the Pennington
River are presented in Table 3. The percentages
of the heavy metals in the fractions are
represented graphically in Figs. 2-7 for dry and
wet season.
Time(h) Temp. ºC Designation
1 RT Exchangeable
5 RT Carbonate bound
6 96 Fe/Mn-oxide
bound
2 85 Organic matter
bound
3 85
Residual
 Leizou et al.; ACSj, 5(3): 238-246, 2015; Article no.ACSj.2015.023

3.1 Metal Speciation in Sediments Concentration (range, mean ± standard

The data shows that, concentration (mg/kg) of
arsenic in sediments ranged from 0.12 - 0.19
with mean value of 0.14±0.17 during the dry
season while it ranged from 0.08 -
0.12(0.11±0.18) in wet season. A comparative
analysis between arsenic levels in Pennington
River and average shale as reported in Table 4
shows that, values of arsenic in this study were
low. The result agreed with concentration of
arsenic in natural environment [12].
The concentration of cobalt ranged between 0.36
– 0.42 mg/kg with an average of 0.39 ± 0.55
mg/kg during the dryseason while it ranged from
0.36 – 0.39 mg/kg in wet season with an average
of 0.37±0.60 mg/kg. The levels were also lower
when compared with levels in natural
environment [12].
deviation, mg/kg) for copper was 0.56 - 6.15,
(2.43±5.06) in dry season and 0.92-3.74,
(2.07±4.35). The levels were also low when
compared to levels in natural environment [12].
The values (mg/kg) for iron (range, mean ± std)
in dry and wet seasons were (14.60 45.08, 26.82
±22.19) and (15.40-32.39, 26.65±24.79)
respectively. The levels of iron were lower when
compared to levels in natural environment [12].
The concentration of Pb ranged from 0.57 – 0.87
mg/kg with a mean (0.69±1.10) mg/kg during the
dry season while it ranged from 0.51–0.72 mg/kg
in wet season with a mean of 0.61±1.08 mg/kg.
The levels were also low when compared to
levels in natural environment [12].

Fig. 1. Map of study area showing sampling sites

Table 3. Seasonal variation of total mean concentrations (mg/kg) in sediment of

Pennington River

Dry Season Wet Season

Metals Range Mean±std Range Mean±std
As 0.12-0.19 0.14±0.17 0.08-0.12 0.11±0.18
Co 0.36-0.42 0.39±0.35 0.36-0.39 0.37±0.60
Cu 0.56-6.15 2.43±5.06 0.92-3.74 2.07±4.35
Fe 14.60-45.08 26.82±22.19 15.40-32.39 26.65±24.79
Pb 0.57-0.87 0.69±1.10 0.51-0.72 0.61±1.08
Zn 1.15-1.28 1.22±1.19 0.88-1.32 1.11±1.00

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 Leizou et al.; ACSj, 5(3): 238-246, 2015; Article no.ACSj.2015.023

Zinc levels in Pennington River sediment
samples were 1.15-1.28,(1.22±1.19) mg/kg) in
dry season and 0.88–1.32, (1.11±1.00) mg/kg for
wet season. The result obtained in this study for
zinc concentrations agreed with those reported
by [13,14] from Diobu River in Port Harcourt,
which are of the same geographical Niger Delta
region with similar sources of contaminant input.
3.2 Statistical Evaluation of Data
To find an internal structure not accessible at first
glance of the results in Table 3, statistical
multivariate methods were used to study the data
by considering the sediments as objects and the
determined parameters as variables, by building
a Pearson’s correlation matrix (PCM) and the
data presented in Table 5. The PCM analysis
provided a means of statistically ascertaining the
association/correlation of one parameter with
another. PCM analysis reveals a positive
correlation between the metal ions in both
seasons; this could indicate a common source
for all the metals, however, very few of the
metals are significantly correlated with each
other. This behavior could indicate non-point
source.
The six heavy metals investigated in sediment
samples of the Pennington River system in
Bayelsa state, Nigeria was investigated in both
dry and wet seasons and results are presented in
(Figs. 2-7) as percent fraction of metal species in
the five geochemical phases.
an occurrence of the highest arsenic percentage
in exchangeable and carbonate fractions in both
dry season and wet seasons. The least percent
of arsenic appeared in the Fe/Mn-Oxide and
residual fractions. This is an indication that
arsenic was biologically available in the river
being investigated.
Speciation pattern of cobalt in both seasons is
presented in Fig. 3. The figure shows that cobalt
had highest accumulation in exchangeable
fraction in both dry and wet seasons. It was
however low in all the other immobilized
fractions. This is an indication that cobalt was
biologically available in the river being
investigated.
Speciation pattern of copper in both seasons is
presented in Fig. 4. The figure shows that copper
had highest accumulation in residual fraction in
both dry and wet seasons. It was however low in
all the other easily mobilized fractions. This
shows that there is little or no danger of copper
bioavailability in the study area.
Fig. 5 shows the speciation pattern of Fe. The
lowest value of iron in the fractions was obtained
in exchangeable fraction. The other geochemical
fractions that contain low percent of iron are
carbonate and organic respectively. The highest
value was obtained in the residual fraction in
both seasons. This shows that iron cannot be
remobilized in the study area.

Speciation patterns for arsenic in dry and wet

seasons are shown in Fig. 2. The results indicate

Table 4. Comparison of heavy metal concentration with some river

Heavy metals(mg/kg)
Rivers As Co Cu Fe Pb Zn
Genesse, USA 18 40 47
Toyohira, Japan 22 24 152
Lagos Lagoon 0.60 19.39 0.45 0.73
Average Shale 13 19 45 4.10 20 95
This study 0.13 0.38 2.25 26.74 0.65 1.27

Table 5. Correlation coefficient matrix of mean heavy metal concentrations in dry and wet
seasons of Pennington River

Dry Season Wet Season

As Co Cu Fe Pb Zn As Co Cu Fe Pb Zn
As 1 As 1
Co 3.20 1 Co 0.75 1
Cu 0.37 0.90 1 Cu 0.74 0.99 1
Fe 0.19 0.87 0.82 1 Fe 0.85 0.76 0.75 1
Pb 0.45 0.88 0.92 0.61 1 Pb 0.75 0.99 0.98 0.85 1
Zn 0.28 0.16 0.48 0.52 0.12 1 Zn 0.90 0.61 0.60 0.54 0.55 1

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 Leizou et al.; ACSj, 5(3): 238-246, 2015; Article no.ACSj.2015.023

In Fig. 6, lead accumulated most in the
exchangeable fraction in both seasons followed
by the other fractions. This is an indication that
lead was biologically available in the river being
investigated.
In Fig. 7, zinc accumulated most in the residual
fraction in both seasons followed by the other
fractions. This means that zinc will not be
released easily to the water layers and so will be
less bio-available to the organisms in the study
area.
Assessment of sediment pollution based on
SQGs and ecotoxicological sense of heavy metal
contamination Sediments were classified as non-
polluted, moderately polluted and heavily
polluted based on SQGs of USEPA [15].
According to SQGs, the heavy metals studied in
sediments of the Pennington River were under
the category of non-polluted in both dry and wet
seasons [16,15]. The ecotoxicological sense of
heavy metal contamination in sediments was
determined using sediment quality guidelines
developed for marine and estuarine ecosystem
[17,18,19,20]. These effects are as follow: a) The
effect range low (ERL) / effect range median
(ERM) b) The threshold effect level (TEL) /
probable effectlevel (PEL).The heavy metals
studied in sediments of the Pennington River do
not exceed TEL values which can lead to
adverse impact on the sediments dwelling fauna
(Table 6). The guideline thereby proving that the
Pennington River is uncontaminated with (As,
Co, Cu, Fe, Pb and Zn).

Table 6. Concentration of heavy metals in Pennington River and its comparison with SQDs

Element SQGs non- SQGs moderately SQGs heavily TEL(mg/kg) This

polluted(mg/kg) polluted(mg/kg) polluted(mg/kg) study(mg/kg)
As 5.9 0.13
Co 0.38
Cu ˂25 25-50 ˃50 18.70 2.25
Fe 26.74
Pb ˂40 40.60 ˃60 30.20 0.65
Zn ˂90 90-200 ˃90 124.00 1.17

Dry Season As Wet Season As

70 70
Speciation(%)
Speciation(%)

60 60
50 50
40 40
30 30
20 20
10 10
0 0

Geochemical Fractions Geochemical Fractions

Fig. 2. Dry and wet seasons speciation pattern of arsenic

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 Leizou et al.; ACSj, 5(3): 238-246, 2015; Article no.ACSj.2015.023

Dry Season Co Wet Season Co

100 100
Speciation(%)

80 80

Speciation(%)
60 60
40 40
20 20
0 0

Geochemical Fractions Geochemical Fractions

Fig. 3. Dry and wet seasons speciation pattern of cobalt

Dry Season Cu Wet Season Cu

100 100
Speciation(%)
Speciation(%)

80 80
60 60
40 40
20 20
0 0

Geochemical Fractions Geochemical Fractions

Fig. 4. Dry and wet seasons speciation pattern of copper

Dry Season Fe Wet Season Fe

40 60
Speciation(%)

Speciation(%)

30 50
40
20 30
10 20
10
0 0

Geochemical Fractions Geochemical Fractions

Fig. 5. Dry and wet seasons speciation pattern of iron

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 Leizou et al.; ACSj, 5(3): 238-246, 2015; Article no.ACSj.2015.023

Dry Season Pb Wet Season Pb

Speciation(%)
Speciation(%)
100 70
80 60
50
60 40
40 30
20
20 10
0 0

Geochemical Fractions Geochemical Fractions

Fig. 6. Dry and wet seasons speciation pattern of lead

Dry Season Zn Wet Season Zn

Speciation(%)
Speciation9%0

60 50
50 40
40 30
30
20 20
10 10
0 0

Geochemical Fractions Geochemical Fractions

Fig. 7. Dry and wet seasons speciation pattern of zinc

4. CONCLUSION COMPETING INTERESTS

Speciation is a powerful and versatile technique Authors have declared that no competing
for predicting the degree of contamination risk of interests exist.
a river system. In this present study, all heavy
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_________________________________________________________________________________
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