1051-Article Text-3401-1-10-20200311
1051-Article Text-3401-1-10-20200311
1051-Article Text-3401-1-10-20200311
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International Journal of Natural Sciences
ISSN 2519-5549 (online)
Vol. 2, Issue 1, No. 1, pp 1 - 17, 2020 www.iprjb.org
Abstract
Purpose: In the present study, removal of cobalt (II) from aqueous solutions by using
dried roots of water hyacinth has been investigated.
Methodology: The removal of cobalt was examined as a function of initial
concentration of cobalt, pH, weight of roots and contact time. Ten different
concentrations from 10µg.ml-1 to 100 µg.ml-1 were used. The obtained results are
applied for Langmuir, Freundlich and Timken isotherms.
Findings: The results indicated that the removal of cobalt depend on concentration of
cobalt, weight of roots, pH and very rapid. Comparing the regressions and error values
of the used isotherms indicated that the removal of cobalt by water hyacinth roots
follows a Langmuir isotherm better than Freundlich and Timken isotherms. Langmuir
dimensionless constant indicated that the removal of cobalt by water hyacinth roots is
favorable.
Unique contribution to theory, practice and policy: This investigation indicated a new
material successfully removes cobalt (II) from aqueous solutions. And can be used for
removing 60Co from aqueous solutions that might be released into the environment from
radioactive waste.
Key words: Cobalt, removal, Water hyacinth roots, Langmuir isotherm
1.0 INTRODUCTION
The transition metal, cobalt has molecular mass of 58.93 u, and atomic weight 27 and
belonging to group 8B of the periodic table. The most important cobalt ores are Linneite
(Co3S4), erythrite (Co3(AsO4)2.8H2O), Safflorite (CoAs2), and cobaltite (CoAsS).
Cobalt has great hardness and being resistant to high temperatures, so it is used in the
manufacture of many alloys (iron, nickel, and aluminum), electroplating, surface
coatings, in the ceramics industry and chemical industry as a catalyst (Ivanova, et al,
2006 & Lee, 1999). These applications produce various liquid and solid wastes and
could be a source of contamination for water and soils by cobalt. Pulmonary fibrosis,
respiratory sensitization, bronchitis, asthma, and emphysema are diseases resulted from
entrance of cobalt into human body (Lombaert, et al, 2008). So, removal of cobalt from
liquid wastes containing cobalt is very important.
There are several treatment techniques such as precipitation, oxidation/ reduction, ion-
exchange, membrane filtration, electrochemical reduction, and adsorption (Keskinkan,
et al, 2003). Adsorption process is highly economical and removes contaminants even
at trace levels. The use of this technique in wastewater treatment due its simplicity, low
cost of operation and wide end use has been reported before (Naeem et al, 2007).
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International Journal of Natural Sciences
ISSN 2519-5549 (online)
Vol. 2, Issue 1, No. 1, pp 1 - 17, 2020 www.iprjb.org
Experimental studies showed that water hyacinth has been successfully used for
removing many elements from aqueous solution such as Cd (O'Keeffe, et al, 1984,
Hasan, et al,2007, Nir, et al, 1990, Sadhna, et al, 1994, and Lu, et al, 2004), Hg
(Chattopadhyay, et al, 2012, Lenka, et al, 1990, Panda, et al, 1988, and Tabbada, et al,
1990), Zn (Akicin, et al, 1993, Hasan, et al,2007 and Lu, et al, 2004), Cu (Lee &
Hardy,1987 and Swain, et al, 2014), Pb (Akicin, et al, 1994, Pereira, et al, 2014 and
Win, et al, 2003), Ni (Hussain, et al, 2010 and Turnquist, et al,1990), As (Alvarado, et
al, 2008, Low and Lee 1990 and Snyder, 2006), Fe (Win, et al, 2002), REEs (Chua,
1998) and mixture from 137Cs and 60Co (Saleh, 2012).
Water hyacinth (Eichhornia crassipes) used as a scavenger of heavy metal pollutants
in the lake Chivero and its associated rivers in Zimbabwe. (Zaranyika & Ndapwadza,
1995). Water hyacinth is a good tool for water monitoring (Ismail, et al, 1996), a
powerful bio-accumulator for uranium in the River Nile (Aly, et al,2004) and a good
tool for monitoring the environmental impact of industrial facilities on the River Nile
(Aly, et al, 2009). Water hyacinth (Eichhornia crassipes) plants acted as an efficient
adsorbent for phosphorus and nitrogen from swine waste water (Chen, et al,2010) and
being able to grow and clean up extremely polluted environment such as leachates
(Akinbile, 2012). Also, water hyacinth was able to remove cyanide from aqueous
solution and could be useful in treating cyanide effluents from small scale gold mines
(Ebel, et al, 2007).
Dead whole water hyacinth plant powder removed Cr (VI) from aqueous solutions
(Gude & Das, 2008) and dead water hyacinth whole plant powder (chemically treated)
removed of Zn (II), Cd (II), and Cr (VI) from single, bi, tri – metal systems (Saraswat
& Rai, 2010) and Methylene blue (El-Khaiary, 2007 & El-Khaiary, et al, 2009) from
aqueous solutions. Dried water hyacinth roots have ability to remove Cr (III) (Low &
Lee, 1997), Cr (VI) (Mohanty et al, 2006 and Sarker, et al, 2010), Cu (Low et al, 1994
and Zheng, et al,2009), As (Al Rmalli et al, 2005 and Govindaswamy, et al 2011), La
(Aly et al, 2013), Eu (Kelley, 1999), Th (Aly et al, 2014) and U (Bhainsa & D'Souza,
2001, Shawky, et al, 2005 and Sadeek, et al, 2014) from aqueous solutions. Also, water
hyacinth roots (chemically treated) were used in removal of U (Sadeek et al, 2014 and
Abd El-Mageed, et al, 2017), and water hyacinth shoot removed Cr and Cu from
aqueous solutions (Sarkar, et al, 2017).
Water hyacinth ash removed Ni (Hussain, et al, 2010) and Phenol (Uddin, et al 2007)
from aqueous solutions. Cd (II) was removed from aqueous solutions using activated
carbon prepared from water hyacinth (Singh & Verma, 2017). Cu was removed from
aqueous solution by cellulose xanthogenate prepared from raw fiber of water hyacinth
(Tan, et al., 2007). Magnetic graphene oxide polypyrrole composite synthesized from
water hyacinth roots removed Th from aqueous solutions (Gado, 2018). Ethanol extract
of water hyacinth roots effective in the removal of As from treated organs rat and may
be effective in the removal of As from patients of chronic arsenic poisoning (Quayum,
2007).
No previous published data about removal of cobalt (II) by dried water hyacinth roots,
so this work studies the removal of Co (II) from aqueous solution by water hyacinth
roots under various experimental conditions such as pH, concentration of Co (II),
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International Journal of Natural Sciences
ISSN 2519-5549 (online)
Vol. 2, Issue 1, No. 1, pp 1 - 17, 2020 www.iprjb.org
contact time, and weight of roots. The obtained data has been analyzed in terms of
Langmuir, Freundlich and Timken isotherms. This study is a model for removing 60Co
from aqueous solutions that might be released into the environment from radioactive
waste.
Where, Coi and Coe are the concentrations of cobalt in the initial and equilibrium
solution, respectively.
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International Journal of Natural Sciences
ISSN 2519-5549 (online)
Vol. 2, Issue 1, No. 1, pp 1 - 17, 2020 www.iprjb.org
Cobalt concentration, pH of the solution, shaking time and weight of water hyacinth
roots were studied to investigate the removal process of cobalt from aqueous systems
by water hyacinth roots.
Effect of pH of solution
In this study the removal of cobalt by water hyacinth roots was investigated in the pH
range from 2 to 8 because cobalt precipitated at pH > 8 as a result of formation of a
cobalt hydroxide precipitate (Demirbas, 2003). According to our pervious study on the
prepared water hyacinth roots, the roots have isoelectric point at 7.53 (Aly, et al, 2013).
So, the roots surface has a positive charge in the pH range 2-7 and has a negative charge
at pH8.
Changing the pH of the solution will change; 1- The degree of protonation or
deprotonation of the functional groups of the roots such as carboxylates which will
affect the removal process (El-Khaiary, 2007 & El-Khaiary, et al, 2009). 2- The types
and ratios of cobalt chemical species such as Co+2 and Co (OH) + which may have
different reactivity towards the roots (Kim & Lee 2001, Netzer & Hughes 1984 and
Rengaraj & Moon 2002). All of these factors effect on the removal of cobalt by water
hyacinth roots.
Fig 1 shows the effect of pH on the removal of cobalt by water hyacinth roots. The
effect of pH on the removal of cobalt was investigated in the range of 2-8. 0.1 g of roots
were equilibrated in 20 ml of 50 µg.ml-1 cobalt solution and shaken for 90 min at 25
°C. This illustrates that the amount of removed cobalt increased until pH 8, the results
of the experiments showed that the removed cobalt depends on the pH of the solution.
The highest cobalt removal yield (86.9 %) was achieved at pH 8.0.
The effect of pH on removal of cobalt indicates three stages of increment. Elevated
increment by changing the pH of solution from 2 to 3 the removal increases from 10.8
% to 70.22 % respectively, i.e. the removal becomes 6.5 times from its value at pH 2.
The second stage from pH 3 to pH 5 the removal increases from 70.22 % to 82.96 %
respectively, i.e. the removal becomes1.18 times from its value at pH 3. And in this
stage the increase in the removal is constant (6.3%) by increasing the pH of the solution
from 3 to 4 and from 4 to 5. The last stage from pH 5 to pH 8 the removal increased
very slowly from 82.96% at pH 5 to 86.9% at pH 8.
At pH 2 the removal of cobalt is low (10.8 %) as a result of competition of H+ ions with
the cobalt ions. Increasing the pH (2-8) of the solution enhance removal of cobalt. That
may be attributed to increasing pH of the solution enhance the negative charge groups
of the water hyacinth roots then the chemical species of cobalt such as Co+2 and Co
(OH)+ can be easily removed by the water hyacinth roots (Netzer & Hughes, 1984;
Rengaraj & Moon, 2002; Kim & Lee, 2001).
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International Journal of Natural Sciences
ISSN 2519-5549 (online)
Vol. 2, Issue 1, No. 1, pp 1 - 17, 2020 www.iprjb.org
100
80
Removal %
60
40
20
0
2 3 4 5 6 7 8
PH
95
90
85
80
Removal %
75
70
65
60
55
50
0.02 0.04 0.06 0.08 0.10
weight of roots
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International Journal of Natural Sciences
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Vol. 2, Issue 1, No. 1, pp 1 - 17, 2020 www.iprjb.org
100
80
Removal %
60
40
20
0 20 40 60 80 100
1400
1200
1000
qe(µg)
800
600
400
200
0 20 40 60 80 100
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Vol. 2, Issue 1, No. 1, pp 1 - 17, 2020 www.iprjb.org
95
90
85
80
75
Removal %
70
65
60
55
50
45
40
35
30
0 20 40 60 80 100
Time (min)
Where Coeq is the concentration of solute in the solution phase at equilibrium (mg L-1),
y is the amount of solute removed per unit weight of sorbent (mg g-1), b and a are
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3.0
2.5
2.0
Coeq/y (g/L)
Y=A+B*X
R SD N P
------------------------------------------------------------
0.5
0.99741 0.05549 10 <0.0001
------------------------------------------------------------
0.0
0 5 10 15 20 25 30 35 40
Coeq (mg/L)
Figure 6: Langmuir removal isotherm b = 0.13 L g-1L g-1,Qms= 15.8 mg g-1 and
R2 = 0.997
(Co = (10-100) μg mL-1, pH= 6, V= 20 mL, t =90 min, wt. = 0.1 g, and T = 25ºC)
The data were expressed as the amount of cobalt removed per unit weight of sorbent
(Coeq / y) versus the cobalt concentration in the solution at equilibrium (Coeq). These
data conformed to the Langmuir equation (Equation 2) where the values of b and Qms
were calculated to be 0.13 L g-1 and 15.8 mg g-1 respectively. Also, removal of La (Aly,
et al, 2013), Th (Aly, et al, 2014), U (Shawky, et al, 2005) and Cu by water hyacinth
roots fits Langmuir isotherm (Zheng, et al, 2009).
The Langmuir model assumes that the energy of adsorption is the same for all surface
sites and doesn’t depend on the degree of coverage, indicating monolayer adsorption of
the adsorbate, and finite numbers of identical sites. Fitting of Langmuir model is
suggesting the occurrence of binding to the biomass with homogenous surface energy
with no interaction between the removed metals. Schneider, et al, (2001) stated that
Langmuir fit may be evidence to ion exchange mechanism.
In order to predict the favorability of the adsorption process, the essential feature of
Langmuir model can be expressed in terms of a dimensionless constant factor “RL”
given as following.
1
𝑅𝐿 = 1+𝑏𝑐 (4)
Where b is the binding energy constant from Langmuir equation, and C (mg L-1) is the
initial concentration of the cobalt.
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International Journal of Natural Sciences
ISSN 2519-5549 (online)
Vol. 2, Issue 1, No. 1, pp 1 - 17, 2020 www.iprjb.org
10 0.43859649
20 0.28089888
30 0.20661157
40 0.16339869
50 0.13513514
60 0.11520737
70 0.10040161
80 0.08896797
90 0.0798722
100 0.07246377
The parameter indicates the type of the isotherm to be irreversible if the RL is zero,
“favorable” if 0 < RL< 1, “linear” if RL=1, or “unfavorable” if RL>1. The results listed
in Table 1 indicate that the removal of cobalt is favorable. Also, our previous studies
indicated that the removal of La (Aly, et al, 2013), Th (Aly, et al, 2014) and U (Shawky,
et al, 2005) by water hyacinth roots is favorable.
The Freundlich isotherm model assumes heterogeneous surface energies and / or
different mechanisms in which energy term in Langmuir equation varies as a function
of surface coverage. K and 1/n are Freundlich isotherm constants related to the isotherm
constants related to adsorption capacity and intensity of adsorption. It is assumed that
the stronger binding sites are occupied first and that the binding strength decreases with
the increasing degree of site occupation (Vijayaraghavan, et al, 2009). This model
describes reversible adsorption and is not restricted to the formation of monolayer.
The logarithmic form of the Freundlich equation is:
1
Log𝑦 = Log𝐾 + 𝑛 Log𝐶𝑜𝑒𝑞 (5)
The graphical relation between Log y and Log Coeq, gives a straight line of slope 1/n
and the intercept = log K as presented in figure 6.
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International Journal of Natural Sciences
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The results are confirmed to Freundlich equation and the values of K and n were
calculated as 2.3 and 1.9 respectively. Fitting to Freundlich model suggests the binding
to the roost with different functional groups and / or different mechanisms (El – khaiary,
2007). Also, our previous studies indicated that the removal of La (Aly, et al, 2013),
Th (Aly, et al, 2014) and U (Arafat, et al, 2019) by water hyacinth roots fits freundlich
isotherm.
1.2
1.0
Y=A+B*X
0.8
Parameter Value Error
Log y
---------------------------------------------------
A 0.36633 0.03461
0.6 B 0.52736 0.03305
---------------------------------------------------
R SD N P
0.4
---------------------------------------------------
0.98465 0.05093 10 <0.0001
---------------------------------------------------
0.2
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Log Coeq
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12
10
8
Y=A+B*X
y
0
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Ln Coeq
Figure 8: Timken removal isotherm; B =3.24, A= 1.53 (L g-1), and R2= 0.993
(Co = (10-100) μg mL-1, pH=6, V= 20mL, t =90 min, wt. = 0.1 g, and T = 25ºC)
Comparing the linear regressions and standard deviations for all the studied isotherms
indicated that cobalt is best fitted to Langmuir isotherm. Removal of U (Arafat, et al,
2019), La (Aly, et al, 2013) and Cr (Sarkar, et al, 2010) by water hyacinth roots are
best fitted by Langmuir isotherm, while removal of Th (Aly, et al, 2014) at pH 1 and
pH 5 by water hyacinth roots are best fitted by Langmuir and Freundlich isotherms
respectively.
4.0 CONCLUSION
Cobalt was removed successfully from aqueous solutions by water hyacinth roots. The
experiments showed that the removal of cobalt from aqueous solution is influenced by
some factors such as pH, initial cobalt concentration, contact time and weight of the
roots. The amount of cobalt removed increased from 10.8 % to 86.9 % by increasing
the pH of the solution from 2 to 8 respectively. The removal of cobalt increases from
52.6% to 86.9% by increasing the weight of the roots from 0.02 to 0.1 g respectively.
The removal is more efficient from dilute solutions but the removed amount of cobalt
increased from 182 µg to 1334 µg by increasing the initial cobalt concentration from
10 µg.ml-1 into 100 µg.ml-1 respectively. The removal of cobalt by water hyacinth roots
is best fitted by Langmuir isotherm. The velocity of removal was fast and need only 10
min for the process to equilibrium. Finally, this study presents a cheap and available
biomaterial for the removal of Co and may be used for removal of 60Co from radioactive
wastes.
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