Journal of Environmental Treatment Techniques 2015, Volume 3, Issue 2, Pages: 118-125
118
Assessment of Heavy Metals in Borkena River in South Wollo
Ethiopia
Alemu Mengesha
1
and Omprakash Sahu
2
1- Department of Chemistry, NSC Wollo University (SW) Ethiopia
2- Department of Chemical Engineering, KIOT Wollo University (SW) Ethiopia
Received: 02/12/2014 Accepted: 06/03/2015 Published: 30/06/2015
Abstract
Trace elements concentration in Borkena River was investigated, as they can deteriorate water quality. Levels of Lead
(Pb) and Cadmium (Cd) in river water and industrial effluents taken from 3 industries found in Kombolcha were
determined by differential pulse anodic striping voltammetry. The river water down the site, where effluents join, had
significantly higher concentration of Pb and Cd than did the water above the drainage system. The concentration of Pb and
Cd in river water down the site where effluents join were found to be above the permissible limit values of WHO and
FAO. The highest contributor was KOSPI: BGI and Textile was the second and third interns of Pb content. The water
supply for domestic purpose and irrigation from the river down the site where the drainage system joins were note safe.
Keywords: Heavy metal analysis, Borkena River, Anodic Striping Voltammetry, Industrial Effluents
1 Introduction
1
Generally industrial or municipal wastes, containing
different chemicals, are disposed to water bodies such as
lakes, oceans and rivers as water is considered as
universal solvent [1]. The chemical contamination of
drinking water leads to health problems primarily
through chronic exposure, as it may persist for years
before detection [2]. In many countries the major
chemical pollutant of surface water comes from
industrial and municipal sewages as municipalities of
cities lacks sufficient waste treatment facilities [3].
Sometimes the corrosion of the urban water supply
system also contributes heavy metal contamination of
water [5]. The preservation and maintenance of natural
water resources is a burning issue. The quality of water
resources is deteriorating day by day due to continuous
discharge of municipal and industrial effluents. On the
other hand, the demand for safe water is increasing
continuously due to the increase in population, living
standard and industrialization [6]. The discharges from
many industrial wastes contain various organic and
inorganic water contaminants including higher level of
toxic heavy metals like Pb, Cd, Zn, Cu and others.
Among the various water bodies river water is the most
exposed for pollution due to the direct discharge of
municipal and industrial effluents to rivers. Under ground
water in the vicinity different drain systems also can be
polluted by toxic metals contamination from industrial,
domestic, mining and others waste discharges [3-5].
Among the various metal ions Pb, Cd and Hg are toxic at
all concentration level and have no known functions. The
metal ions of Cu, Zn, Co and Fe are required for
physiological and cellular activities but toxic above a
certain level [7, 8]. Toxic metals as they are non-
Correspondence author: Omprakash Sahu, Department
of Chemical Engineering, KIOT Wollo University (SW)
Ethiopia, Email:ops0121@gmail.com,
Tel: +251933520653.
degradable and bio-accumulative, cause tissue
degradation in nature [9, 10].
In literature different method has been suggested by
author as well some standard method are also available in
which Voltammetric is one of them. Voltammetric
method was first introduced by Heyrovsky in 1992, it
also known as Polarography. Polarography is a special
case of voltammetry referring to the current voltage
measurement acquired using a dropping mercury
electrode (DME) with a constant flow of mercury drops.
Voltammetry today represents a refined technique that
offers wide limits of detection and is used for trace
analysis [3]. Voltammetric techniques offer a number of
analytical advantages in environmental analysis [11, 12].
These includes, applicability to a wide range of
substances, high sensitivity with a linear concentration
range of analyse (10
-12
to 10
-1
M), tremendous number of
useful solvents and electrolyte, ease of automation, the
capability of determining more than one species at a
time, a well-developed theory which allows to reasonably
estimate the values of unknown parameters, and the ease
with which different potential wave forms can be
generated and small currents are measured. With
impactive impression toward the analyses pollution, it
was decided to dected the heavy metal in Broken River
by Voltammetric method. The river originates from Tosa
Mountain, which is located few kilometres from Dessie
town in South Wollo of Amhara region, Ethiopia, and
flows down to Kombolcha. Borkena River crosses the
plane of Kalu, Kemissie and finally joins to Awash River
in Afar region. Thousands of people are dependent on the
water of Borkena River and play vital role. The river is
used for irrigation, drinking and common household
purposes in the towns including Kombolcha, Harbu,
Dawa Chefa and Kemisie.
The main objective of this study is to investigate the
pollution potential of industrial effluents on the river by
considering the targeted toxic metal pollution status of
the river and point sources of the effluents.
Journal web link: http://www.jett.dormaj.com
J. Environ. Treat. Tech.
ISSN: 2309-1185
Journal of Environmental Treatment Techniques 2015, Volume 3, Issue 2, Pages: 118-125
119
2 Material and methods
2.1 Material
2.1.1 Chemicals
Nitrate salts of Pb
2+
and Cd
2+
(Blulux), concentrated
HNO
3
(LOBA), NaOH (Blulux), sodium acetate
(Blulux), acetic acid (Blulux ) and distilled water were
used through the experiment.
2.1.2 Apparatus
Voltammetric determination of Cd
2+
and Pb
2+
was
performed with BAS 100B, electrochemical analyzer
connected with Dell computer. Three-electrode
electrochemical system consisting of a glassy carbon
working electrode (radius =1.5 mm), a platinum wire as
counter electrode and an Ag/AgCl reference electrode
were used. The glassy carbon electrode was polished
with alumina (0.05 μM) and rinsed with distilled water
after each run. To measure the pH of solutions a Jenway
digital model 3305 pH meter with a combination of glass
electrode were used. Plastic bottles (HDPE), filter paper,
electrochemical glass cell were used in the experiment.
2.2 Methods
2.2.1 Preparations of Standard Solutions
(a) Lead (Pb): A 0.1599 g of Pb(NO
3
)
2
was dissolved
in 200 mL of distilled water; 10 mL of
concentrated HNO
3
was added and the solution was
diluted to the mark of 500 mL volumetric flask.
(b) Cadmium (Cd): A 0.2744 g of Cd (NO3)2.4H2O
was dissolved in 200 mL of distilled water, 10 mL
of concentrated HNO
3
was added and the solution
was diluted to the mark of 0.5 L volumetric flask.
The prepared stock solutions were containing 200
mg/L of the targeted metal ions. Standard solutions
were prepared by series of dilutions of the stock
solutions daily.
(c) Acetate Buffer: A 0.1 M acetate butter (pH = 4.5)
was prepared by dissolving 8.2 g of sodium acetate
in 0.8 mL of distilled water and by adding 5.75 mL
of acetic acid ( CH
3
COOH). The pH of the buffer
solution was adjusted by adding drops of
concentrated HNO
3
or NaOH. The HNO
3
was also
used to acidify the sample which prevents
adsorption of the metal ions on the wall of the
container. Distilled water was used to prepare
solutions and to clean equipments.
2.2.2 Sampling
From five sites, a total of seventeen composite
samples were collected in clean high density
polyethylene (HDPE) bottles within a week. Seven
industrial effluent samples were collected from the outlet
of the tankers of KOSPI, BGI and Textile factories
according to the schedule of discharge for a week. In
order to study the net contamination potential of the
industrial wastes at Kombolcha on the river, two sets of
samples (five bottles for each) were collected from sites;
i) Borkena Before the drain system of Effluents join the
river (BOBE); ii) Borkena After the drain system of
effluents join the river (BOAE). During sampling, the
bottles were first filled and rinsed three times with the
sample before collecting some for analysis and a grab
sample at each site was collected within 12 hours of a
day with 30 minutes intervals. Besides, tap water sample
from physical chemistry research laboratory of Bahir Dar
University was probed for the toxic metals ions of Pb and
Cd.
2.2.3 Sample Preparation
The samples were filtered through 0.45 μm
membrane filter into a beaker and acidified by adding
concentrated HNO
3
to the pH of 2. The acidified filtrate
was cooled in a refrigerator until analysis to avoid
variation in composition [13- 17]. Substantial
concentrations of organic materials in samples hinder the
electro chemical analysis of metal ions by forming stable
complexes with metal and by adsorbing on the electrode
surface. To avoid the interference acid digestion of the
samples was used. A 50 mL of the acidified sample and
10 mL of concentrated nitric acid in an Erlenmeyer flask
was heated on a hot plate for 2 hours. The light-colored
solution was cooled and filtered into 50 mL volumetric
flask and diluted to the mark. These digested samples
were preserved in refrigerator for analysis.
2.2.4 Procedures
In a typical differential pulse anodic striping
voltammetry, 10 mL of a 0.1 M acetate buffer and 10 mL
of sample were transferred to a clean cell. After the
operating parameters of DPASV have been adjusted the
solution was sprayed with nitrogen for 5 min. The
operating parameters are given in Table 1.
Table 1: Operating parameter of Voltammetry
S.No
Parameters
Description
1
Mode
Differential Pulse
2
Calibration
Standard Addition
3
Purge Time
180s
4
Deposition Time
300s
5
Quite Time
30s
6
Depositions Potential
-1V
7
Pulse Amplitude
50mV
8
Pulse Width
50ms
9
Initial Potential
-1V
10
Finial Potential
-0.2V
11
Sweep Rate
15mV/s
The metal ions of Pb and Cd were deposited by
reduction at - 1.0 V on a bare glassy carbon electrode
surface. The deposited metals were oxidized by scanning
the potential of the electrode from -1.0 to - 0.2 V using
differential pulse model.
The voltammogram of the sample were recorded and
the procedure was repeated after addition of standard
solution of the targeted metal ions. The quantification
and determination of sensitivity for Pb (II) and Cd (II)
were accomplished by standard addition to the sample.
The peak currents of each metal in the sample, and after
standard addition were recorded for calibration and
quantification. This method was preferred as the
sensitivity of differential pulse striping voltammetry
analysis varies between samples of different ionic
strength [5, 10, 18].
The activity coefficient and the diffusion current
constant of metal ions vary with the matrix of the
solution. As the rates of diffusion and the activity
coefficients of the analyses vary with composition of the
sample, the signal produced by a given analyse changes
as the matrix changes. The sensitivity, the magnitude of
peak current produced per 1pp, of metal ion in standard
and samples of different composition can vary
substantially [13, 19-20]. A basic issue that must be
considered for all calibration procedures is the matrix
effects on the analyse signal. The advantage of standard
addition method in both qualitative and quantitative
analysis is that all measurements, (E½, ip), are made in
Journal of Environmental Treatment Techniques 2015, Volume 3, Issue 2, Pages: 118-125
120
the same matrix [19]. Hence, as the calibration curves,
as well as, the sensitivity of analyses is strongly affected
by the matrix of the solution standard addition method is
preferred over the method of calibration using standard
solution alone [18, 19].
3 Results and Discussion
3.1 Mechanism of Voltammetric
The common characteristics of all Voltammetric
techniques is the application of a potential (E) to an
electrode and monitoring of current for chemical
analysis. In voltammetry method the potential is varied
or the current is recorded over a period of time (t). Thus
the current response is used to qualitatively and
quantitatively characterize the electro-active species. The
current (i) is plotted as a function of an applied potential
wave form. The magnitude of the peak current (ip) is
proportional to the concentration of the analysis. In each
Voltammetric waves, the current increases at the
reduction or oxidation potential of the analysis. The
measure of the peak currents forms the basis of
quantitative analysis. The maximum current is
proportional to concentration and the rate of diffusion of
analyses from the solution to the electrode surface. The
potential at which the diffusion current reaches half of
the limiting values is known as the half-wave potential
(E
1/2
).It is characteristic of the particular electro- active
species involved and used for qualitative analysis of
metal ions [18,19]. Half wave potential (E
1/2
) for
reduction of metal ions can be expressed by equation (1)
1
2
,
ln ln
2
M
O
D
om
RT
L
D nF
RT
E E KC
nF
Where; Eo is the standard reduction potential, n is
number of electrons, D
M
is diffusion coefficient of
oxidized specie, D
O
is diffusion coefficient of reduced
specie. When current is generated because of reduction
or oxidation reaction at the WE, a counter reaction takes
place at the CE. The analyses in the bulk diffuse to the
surface of the WE and undergo reduction or oxidation
reaction. The current generated due to this reaction
provides chemical information about the analyse. The
fundamental principles and applications of the various
types of Voltammetric techniques are derived from the
same electrochemical theory [21]
3.2 Analysis of Industrial Effluent Samples
3.2.1 Textile Effluent Samples
Three samples collected on different days at the point
source of textile effluent site were probed for Pb (II) and
Cd (II). Only Pb was found at detectable concentration.
In Fig. 1 the DPAS voltammogram for Pb obtained from
standard addition in the textile sample. The net current of
Pb (II) value in the sample was 12.75 μA and the
reduction potential was observed at - 0. 44 V. The peak
current was increasing proportionally with the
concentration of Pb in standard addition.
The successive addition of standard solution did not
bring significant potential peak shifts or any other
changes to the voltammogram, except an increase in peak
currents. The peaks of Pb (II) were reasonably symmetric
with narrow bas widths. The calibration curve of the peak
current as a function of Pb (II) concentrations in solution
during standard addition was linear with correlation
coefficient (R) = 0.993 as shown in Fig. 2. From the
intercept of this line with concentration axis at zero
current signals, the concentration of Pb (II) in the sample
can be calculated.
Fig.1: Differential pulse anodic striping voltammogram for textile
effluent sample spiked with standard Pb (II) solution: a) 10 mL of acetate
buffer + 10 mL of sample, b) a +100 µL of 10 mg/L standard Pb solution,
c) a + 150 µL of 10 mg/L standard Pb solution, d) a + 200 µL of 10 mg/L
standard Pb solution, e) a + 250 µL of 10 mg/L standard Pb solution.
Fig.2: Plot of peak current as a function of concentration for Pb (II)
obtained by standard addition method in textile sample.
In the three samples from the same site similar peak
currents and average Pb (II) concentrations were
obtained. The average Pb (II) concentration determined
from the intercept and R value of the calibration plot was
134 ± 3 μg /L.
3.2.2 BGI Effluent Samples
Based on the waste disposal schedule, after the waste
has been passed the treatment system three effluent
samples were collected at a point source of BGI. These
different samples were analyzed for detection of Pb (II)
and Cd (II) by differential pulse anodic stripping
Voltammetry. From the three samples only Pb (II) was
found. In Fig. 3 the DPAS voltammogram of Pb in three
BGI effluent samples. The voltammogram of each
sample were broad with different peak currents as
indicated in the figure. The reduction potential of Pb (II)
was observed at - 0. 42 V and the average peak current
was 23 μA. The magnitude of the peak currents of
sample two was higher than that of sample three and
sample one. But the sensitivity for Pb (II) in each sample
was identical.
Based on their peak currents, sample two has the
highest Pb (II) concentration and sample one has the
least. The average concentration of Pb (II) calculated
from the sensitivity determined by single standard
addition method and from the peak currents of each
sample was found to be 241± 5 μg /L. The sensitivity of
the technique for Pb in these samples was 95.2 nAL/μg
and current produced by 1 μg/L of Pb in the solution. To
determine the sensitivity a single standard addition
-0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
e
d
c
b
a
Current (mA)
Potential (V) vs. Ag/AgCl
y = 0.0923x + 11.625
R² = 0.9955
0
5
10
15
20
25
30
35
40
-200 -100 0 100 200 300
Current (µA)
Concentration (µg/L)
Journal of Environmental Treatment Techniques 2015, Volume 3, Issue 2, Pages: 118-125
121
method was used: the current produced before and after
spiking with 10 mg/L of Pb solution were recorded and
the proportion was set from the change in concentration
and current produced. The plot of peak current for
function of concentration shown in Fig. 4.
Fig.3:Differential pulse anodic stripping voltammograms for three BGI
effluentsamples in 0.1 M acetate buffer at pH = 4.5; a) sample 1 b)
sample 3 c) sample 2
Fig.4: Plot of peak current as a function of concentration for Pb (II)
obtained by standard addition method in BGI sample.
In the three samples from the same site similar peak
currents and average Pb (II) concentrations were
obtained. The average Pb (II) concentration determined
from the intercept and R value of the calibration plot was
241 ± 5 μg /L.
3.2.3 KOSPI Effluent Samples
A bottle of composite sample from the point source
was analyzed for determination of Pb (II) and Cd (II).
The DPAS voltammogram for KOSPI waste water
sample obtained from standard addition technique is
shown in Fig. 5. Both Pb (II) and Cd (II) were detected in
this sample. The Cd striping peaks in the sample, and
after spiked with standard solution, were symmetric with
narrow bas widths. The peak current increases rapidly
during each spike. However, the Pb stripping peaks were
asymmetric with slow increment of peak current as it can
be seen in the voltammogram.
Though the sensitivities were different, the peak
currents of both Pb and Cd were increased proportionally
with the solution concentration. Fig.6 and Fig.7 show the
standard addition curves of peak current versus
concentration of Cd (II) and Pb (II), respectively.
Fig.5:Differntial pulse anodic stripping voltammogram for KOSPI waste
water sample spiked with the standared solution of Cd (II) and Pb (II)
(10 mg/L each) : a) 10 mL of acetate buffer + 10 mL of sample, b) a +
100 µL of 10 mg /L standard solution, c) a + 200 µL of 10 mg/L standard
solution, d) a + 250 µL of 10 mg/L standard solution.
Fig. 6: Plot of peak current as a function of concentration for Cd
obtained by standard addition method in KOSPI sample.
Good linearity of peak current and concentration of
the standard added was observed for Cd (II). The
concentration of Cd in the sample was calculated from
the magnitude of intercept on the negative X-axis and
from the linear regression correlation coefficient (R =
0.998). The quotient of the intercept and R value gives
the concentration.
Fig 7: Plot of peak current as a function of concentration for Pb
obtained by standard addition method in KOSPI sample.
The linearity of the response and added concentration
of Pb (II) was observed with regression coefficient of
0.999. In the calibration, the sensitivity of voltammetry
for Pb and Cd were 8.95 nA L/μg and 107.5 nAL/μg,
respectively. In this sample the Pb sensitivity was much
less than that of Cd. From the intercepts and correlation
coefficients of the two calibration graphs the
concentrations of Pb and Cd in KOSPI sample were
determined to be 514.4 ± 4 and 251 ± 5 μg /L,
respectively.
-0.6 -0.5 -0.4 -0.3 -0.2
-0.02
-0.01
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
a
b
c
Current (mA)
Potential (V) vs. Ag/AgCl
y = 0.0923x + 11.625
R² = 0.9955
0
5
10
15
20
25
30
35
40
-200 -100 0 100 200 300
Current (µA)
Concentration (µg/L)
-1.0 -0.8 -0.6 -0.4 -0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
d
c
b
a
Current (mA)
Potential (V) vs. Ag/AgCl
y = 1.0509x + 263.76
R² = 0.9974
0
100
200
300
400
500
600
-300 -200 -100 0 100 200 300
Current (µA)
Concentration (µg /L)
251
y = 0.0093x + 4.7207
R² = 0.999
0
1
2
3
4
5
6
7
8
-600 -400 -200 0 200 400
Current (µA)
Concentration (µg /L)
514
Journal of Environmental Treatment Techniques 2015, Volume 3, Issue 2, Pages: 118-125
122
3.3 The Borkena River Water Samples
The level of Pb and Cd were also measured in ten
water samples of Borkena River. In order to see the net
impact of the industrial wastes at Kombolcha two
locations in the river were chosen on the basis of the
reach of the industrial effluents into the river.
3.3.1 Borkena River before effluents joins the river
(BOBE)
A total of five water samples from BOBE, were
analyzed by DPASV. In these samples well-defined
stripping peaks for Pb and Cd were observed. Fig. 8
shows the DPAS voltammogram for Borkena River
water sample at the site before the industrial drain
systems join the river. The peaks for both metals in the
sample, as well after spiking, were symmetric with
narrow bas width. The reduction potentials for Pb (II)
and Cd (II) were observed at - 0.41 V and -0.56V with a
corresponding maximum net current values of 0.47 and
0.8 μA.
Fig.8: Differential pulse anodic stripping voltammogram for Pb and Cd
in water sample of Borkena River, at the site before the efflents mix
(BOBE), spiked with standard Pb (II) and Cd (II) solution : a) 10 mL
of acetate buffer + 10 mL of sample, b) a + 100 µL of 1 mg/L standard
Pb and Cd solution, c) a + 150 µL of 1 mg/L standard Pb and Cd
solution.
The reduction potential of Cd (II) in these samples
shift from the expected value, (-0. 59 V) by a 0.03 V. But
because of the complex formation and variation in
activity coefficient, the reduction potential of metal ion
can vary over one volt depending on the matrix of the
solution [5, 12]. Besides as the surface coverage and
adsorption of a metal deposit on the electrode change, the
reduction potential of a given metal ion can vary with
concentration. The most important advantage of
electrochemical techniques to assure a given analyse at
the observed potential is standard addition method [12].
As the analysis was done in the same matrix and from the
increment of peak current with standard Cd addition, it is
an obvious logic that the given analyse is Cd. The
standard addition peak currents for both Pb (II) and Cd
(II) were increased proportional to concentration. The
linear relation of the peak currents and concentrations of
added Pb (II) and Cd (II) are shown in Fig.9 and Fig.10
respectively.
The plot of peak currents against concentration of Pb
(II) added was linear with regression correlation
coefficient of 0.998.
Good linearity of peak current and concentration of
Cd (II) was observed with correlation coefficient of
regression 0.999. The concentration of each metal was
calculated from the intercept on the negative x axis and
from the correlation coefficients. The concentrations of
Pb and Cd are 21.7 and 3.95μg/L, respectively. The
calibration curves of peak current as a function of
concentration for each metal were linear with correlation
coefficient R= 0.999.
Fig. 9: Plot of peak current as a function of concentration for Pb
obtained by standard addition method in BOBE sample.
Fig. 10: Calibration plot of peak current as a function of
concentration for Cd obtained by standard addition method in BOBE
sample.
3.3.2 Borkena River after the effluents joins the river
(BRAE)
Five water samples of Borkena River at the junction
point of the river and the industrial effluent drain system
were analyzed. Fig.11 shows the DPAS voltammogram
of Pb and Cd in BOBE and BOAE samples
-0.8 -0.6 -0.4 -0.2
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
b
a
Current (mA)
Potential (V)
Fig. 11: Differential pulse anodic stripping voltammogram for Pb and Cd
in water sample of Borkena River at two differen sites a) BOAE b)
BOBE
As it can be seen from the figure, the potentials of Cd
and Pb in BOBE and BOAE samples show shift from
each other. This is due to variation of the matrix of
solutions in the two sets of samples. Though it is not
possible to know the exact composition, the BOAE
samples should contain several complexing agents
disposed with industries wastes. However, both the
-0.8 -0.6 -0.4 -0.2
0.01
0.02
0.03
0.04
0.05
0.06
0.07
c
b
a
Current (mA)
Potential(V) vs. Ag/AgCl
y = 0.0202x + 0.4296
R² = 0.9989
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
-30 -20 -10 0 10 20 30
Current (µA)
Concentration (µg /L)
21.7
y = 0.215x + 0.8497
R² = 0.9991
0
1
2
3
4
5
6
-10 -5 0 5 10 15 20 25
Current (µA)
Concentration (µg /L)
Journal of Environmental Treatment Techniques 2015, Volume 3, Issue 2, Pages: 118-125
123
relative and the absolute reduction potential shifts
observed are insignificant as compared with the
maximum potential shift suggested from variation of
matrix and concentrations [5,12 and 19]. Thereby it is
logical to see that the reduction potential of a given metal
ion in BOAE samples to be hgigher than in that of
BOBE. Besides the potential, it is clearly indicated from
the voltammograms that the peak currents of Pb and Cd
in Borkena River after the effluent join the river are
higher than that of BOBE samples. Based on the peak
currents of oxidation, concentrations of each metal in
BOBE and BOAE samples were determined to be 21.7 ±
2 and 333.5 ±4 μg /L for Pb and 3.95 ± 1 and 231.5 ± 4
μg /L for Cd in the respective order.
3.4 Tap water Sample
The tap water sample was also collected from
Bhirdar University for examine the heavy metal. The
study is shown in Fig.12.
Fig. 12: Differential pulse anodic stripping voltammogram for Pb
and Cd in sample of BDU tap water ; a) peak of Pb and b) peak of
Cd.
The sensitivity for Pb and Cd determined by standard
addition method were found to be 21.7 nAL/μg and
202.4 nAL/μg, respectively. The calculated
concentrations for each metal were 21.7 ± 0.5 μg /L for
Pb and 4.1 ± 0.2 μg /L for Cd. The net currents of Pb and
Cd found in the sample were 0.5 μA and 0.83 μA
respectively. The concentration of Pb is greater than that
of Cd unlike their peak current values. This is due to the
sensitivity of the technique, that is, the magnitude of the
current produced per 1 μg/L of each metal was lower for
Pb than for Cd and hence the ratio of the peak current to
the sensitivity (concentration) was greater for Pb.
3.5 Comparatively Study
Eighteen different samples were analyzed by
differential pulse anodic stripping voltammetry. Seven
waste effluent samples from three industries, ten river
water samples, and one tap water sample were probed for
Pb and Cd. The mean Pb and Cd contents of all samples
were successfully determined. Both metal ions were
found in KOSPI waste sample, in Borkena River water
samples collected at two sites, before and after the
effluents mix with the river and in tap water sample of
Bihar Dar University. Only Pb was found in BGI and
textile samples. The results of the experiments are
summarized in Table 2.
Table 2: Concentration of heavy metal in different sample and limits
S.No
Type
Sample
Pb (
g/L)
Cd(
g/L)
1
Effluents
Textile
134±3
Not dected
2
BGI
241±5
Not dected
3
KOSPI
514.4±4
251±5
4
River Water
BOBE
21.7
3.95
5
BOAE
333.5
230.5
6
Drinking Water
Tap Water
23
4.1
7
Permissible Limits
WHO (Drinking)
50
10
8
FAO (Irrigation)
500
100
It is evident from the results that the concentrations
of each toxic metal ion vary significantly in different
drains depending on the nature of waste effluents. As it
can be seen from Table 2 the highest concentration of
both toxic metals, Pb and Cd, were released from
KOSPI. Only Pb was found in BGI and Textile waste
effluents. The least polluted effluent both in quality and
quantity discharges out from textile.
The Borkena river water samples which were
collected at two sites, (before and after industrial drain
system joins the river) showed substantial difference in
their Pb and Cd content. The concentrations of each
metal ion in the river at the site just after the junction
point of the drain system were found much higher than
the other site.
It is apparent from the result that huge amount of
toxic metal ions are released from various industrial
drains at Kombolcha to Borkena River. The
concentrations of metal ions determined in three
industrial effluents are graphically compared in Fig. 13.
Fig.13: Comparatively study of heavy metal different industry
The sources of chemical contaminants of
environmental matrixes occur when chemicals are used
in industries and disposed with wastes. Agricultural
-0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3
0.0004
0.0006
0.0008
0.0010
0.0012
0.0014
0.0016
0.0018
0.0020
0.0022
b
a
Current (mA)
Potential (V) vs. Ag/AgCl
Journal of Environmental Treatment Techniques 2015, Volume 3, Issue 2, Pages: 118-125
124
activities, such as use of excessive amount of fertilizers,
pesticide and contaminated water for irrigation causes
contamination of crops. Thus the Pb and Cd
contamination of BOAE by industrial wastes at
Kombolcha should come from their applicability in the
nearby industries. Generally it is recognized that;
cadmium is used in metal plating, coating, pigments
stabilizer, and painting. Lead is used in painting dying,
and welding activities. Thereby the possible sources of
the contaminant Pb and Cd in KOSPI are wastes from
painting, plating, stabilizing and welding activities of the
steel products. In textile wastes from the use of dyes for
textile products is the most supposed source. For BGI,
the by-product of brewing crops, which have been
harvested by application of fertilizers, pesticide and use
of contaminated irrigation water, is the suspected source.
Trace metals can be absorbed by roots of plants and can
exist in adsorbed or complex forms with organic
compound. As toxic level of Pb and Cd in drinking water
or food results in profound disturbance to the normal
biochemical and neurological process by crossing the cell
membrane, the Borkena River water just as it reaches
Kombolcha is dangerous to people and to any aquatic life
[22-25].
4 Conclusions
The investigation of the contamination potential of
industrial wastes on Borkena River was successfully
accomplished in differential pulse anodic stripping
Voltammetry on glassy carbon electrode. Based on the
findings, Borkena River water gets polluted highly due to
toxic metals Pb and Cd when it reaches Kombolcha. The
quality of the river water is not safe for domestic use.
The largest contributor of the pollutants Pb and Cd was
Kombolcha steel products industry. Kombolcha brewery
and Kombolcha textile factory was the second and third
in their lead content, however, there are other factories
which were not included in this work and may cause
pollution. Such unregulated discharge of toxic metal
containing waste effluents should be ceased to avoid
farther pollution. Furthermore, the current effect of the
contamination of Borkena River on human and aquatic
life should be subject to full investigation. Finally this
work is not complete and exhausted. But, it lights
awareness and can be used as a foot step for full
investigation of environmental pollution.
Reference
1- W. A. Bott, Stripping Voltammetry: Principles
Discussion and Applications, West Lafay. 12 (1993)
141-146.
2- S.Yilmaz, M. Sadikoglu, G. Saglikoglu1 S. Yagmur,
and G. Saglikoglu, Determination of Ascorbic Acid
in Tablet Dosage Forms and Some Fruit Juices by
DPV, Int. J. Electochem. 4 (2009) 288 294.
3- M. Jonathan Bruce, Volltammetric Analysis of Zinc,
Cadmium, Lead and Copper in Marine waters,
Meterohom Uk Ltd Water and waste water Asia, J.
Electrochem. 6 (2005) 242-248.
4- P. Sharma, and S. Songara, Voltammetric Trace
Determination of Sub -µg level Chlorate in Natural
Water, Chemical Techn., 15 (2008) 504-506.
5- P. Sonthalia, E. McGaw. and Greg M. Swain, Metal
ion analysis in contaminated water samples using
anodic striping Voltammetry and nanocrytaline
Diamond thin-film Electrode, Analytica. Chemica.
Acta .,522 (2004) 35-44.
6- A. Stephen, Heavy metal Analysis of liquid waste and
Sediments from the Aliaga Petrochemical Plant,
Aliaga Izmir Publication, 1996, 10-97.
7- V. Sychra, I. Lang, and G. Sebor, Analysis of
petroleum and petroleum products by atomic
absorption spectroscopy and related techniques, Prog.
J of Ana. Chem. 4 (1981) 341-426.
8- W. Mertz, Accumulation of trace elements by
Biological Matrix. Sci. 213 (1981) 1332 1338.
9- M. Tomar, Quality Assessment of Water and Waste
Water, Lewis Publisher New York, 1999, 23-90.
10- M. H. Matloob, Determination of Cadmium, Lead,
Copper and Zinc in Yemeni Khat by anodic Stripping
Voltammetric, Eastern Mediterranean Health J., 901
(2001) 1-8.
11- T. Mathialagan and T. Viraraghavan, Adsorption of
cadmium from aqueous solutions by perlite J.
Hazardous Materials, 94 (2002) 291-303.
12- M.O. Akinola, K.L. Njoku, and B.E. Keifo,
Determination of Lead, Cadmium and Chromium in
the Tissue of an Economically Important Plant Grown
Around a Textile Industry at Ibeshe, Ikorodu Area of
Lagos State, Nigeria , Advances in Environmental
Biology. 2 (2008) 25-30.
13- Saad A Al-Jlil, Saudi Arabian clays for lead removal
in wastewater in
wastewater, J.App. Clay Science 42 (2009) 671-
674.
14- A. Hassan, and J. A. Mayouf, Comparative studies of
the determination of Divalent Cd, Pb and Cu in the
Boiling Medical herbs by Striping Voltammetry and
by Atomic absorption spectrometry, American J. of
appl. sci., 6 (2009) 594-600.
15- I. Ali, C. K. Jain, Pollution Potential of Toxic metals
in the Yamuna River at Delhi, India, J. Enviro.
Hydro. 9 (2001) 1-8.
16- UNICEF, Hand book on Water Quality, Chemical
contamination of water, VCH Publisher, UK, 2007,
pp.19-32.
17- D. T. Sawyer, Electrochemistry for Chemists 2
nd
Edn., Interscience publication , Wiley, 1995, PP. 20
75.
18- P. H. Rieger, Electrochemistry 2
nd
Edn. Thomson
Publication, New York, 1994, pp. 200-30.
19- F. W. Fifield, and D. Kealey, Principle and Practice
of Analytical Chemistry 4
th
Edn., VCH
Publications, New York, 1995, pp. 243-251.
20- I. Rubinstein, Physical Electrochemistry Principles,
Methods and Applications, Marcel Dekker
Publications, New York, 1995, PP. 4-24.
21- Paulo, J.S. Barberria and N. R. Stradiotto,
Simultaneous determination of trace amount of zinc,
lead and copper in rum by anodic stripping
Volttammetry Talanta., 44 (1997) 185-188.
22- G. Somer, U. Unal and F.Edebiyat, A new and direct
method for the trace element determination in
cauliflower by differential pulse polarography, J.
Science Talanta, 62 (2004) 323-328.
23- D. S. Stef, I.Gergen, and M. Harmanescu ,
Determination of the microelements content of some
medical herbs, J. of Agroalimentary Processes and
Techno.,15 (2009) 163-167.
24- A. Massadeh, F. Alali and Q. Jaradat, Determination
of Copper and Zinc in different brands of Cigaratetes
in Jordan, Acta Chim. Slov., 50 (2003) 375-381.
Journal of Environmental Treatment Techniques 2015, Volume 3, Issue 2, Pages: 118-125
125
25- S.A. Khan, L. Khan N. Akhtar, Comparative
assessment of Heavy metals in Euphorbia helioscopia
L, Pak. J. Weed J. Sci. Res., 14 (2008) 91-100.
26- A. Rejendran, V. Narayanan and I. Gnanavel Study
on the Analysis of Trace Elements in Aloe Vera and
in its Biological Importance, J. Appl. Sci. Res.
3(2007) 1476-1478.
27- D. A. Skoog, Fundamentals of Analytical Chemistry
8
th
Edn, UK Publications, D. M. West, F. J Holler,
2001,150-208.