VNL 21603
VNL 21603
VNL 21603
Jute fibers were grafted with acrylic acid by using the in water with higher quantities can damage of the central
direct gamma irradiation technique, which used as an nervous system and chromosomes and can cause the chest
adsorbent substrate for the toxic heavy metal ions
such as Hg21 and Pb21 from their aqueous solutions.
pain [4]. Because of increased environmental awareness,
The structure and crystallinity of the grafted jute fibers the development of cost-effective methods for the
were characterized by using Fourier-transform infrared removal of lead and mercury from aqueous solutions has
spectroscopy and X-ray diffraction, respectively. The gained great importance. Different techniques were used
effect of pH range of the metal ion solutions, contact to remove the undesirable dissolved heavy metal ions
time, and the adsorption kinetics of the adsorption
process were investigated. The effect of the initial con- from aqueous solutions. The conventional techniques such
centration of dissolved metal ions and the adsorption as chemical precipitation, ion exchange, reverse osmosis,
isotherm for both Langmuir and Freundlich adsorption membrane separation, and electrochemical treatment pro-
models were also investigated. From the results, it can cesses [5–7], although, these techniques are often costly
be concluded that the adsorption process obeys the
or ineffective, especially in removing heavy metal ions at
second-order kinetic reaction and follows the Lang-
muir adsorption isotherm model, while, about 86 and low Concentrations [8], whereas the adsorption methods
80% of Pb21 and Hg21, respectively, were adsorbed at are more effective for removing the undesirable heavy
pH 5 and 6 after a contact time of 60 min. J. VINYL metals without producing unwanted by-products. Different
ADDIT. TECHNOL., 00:000–000, 2017. V
C 2017 Society of Plas-
materials such as activated carbon [9], carboxylated cellu-
tics Engineers
lose nanocrystals [10], fly ash [11], soy protein hollow
microspheres [12], sawdust [13], polyrhodanine-
encapsulated magnetic nanoparticles [14], and chitosan
INTRODUCTION entrapped CM-cellulose hydrogels [7], were used as
adsorbents. Moreover, the grafted substrates with poly(a-
Heavy metal pollution can cause serious environmental crylic acid) have a characteristic chelating ability toward
problems as a result of their toxicity and carcinogenic different divalent metal ions [15, 16].
effects on the natural environment and its accumulation The irradiation technique is known to be an effective
in living organisms [1]. The toxicity of heavy metals technique for changing the properties of matters. The
might be caused by blocking essential functional groups graft copolymerization by using the direct irradiation
of biomolecules and by disrupting the integrity of bio-
technique was used over the past decades for polymer
membranes [2]. Mercury and lead are from the most
treatments, in which, new side chains could be introduced
famous toxic heavy metals, which are responsible for the
to the polymer backbone by covalent bonding [17–19]. In
water pollution from industrial effluents.
this regard, the radiation was used to induce the graft
Mercury pollution usually comes from different indus-
copolymerization process to produce high performance
tries such as chloroalkali, paint, pharmaceutical, pulp, and
chemically active polymer materials for adsorption and
paper. Lead pollution comes as a result of the batteries’
separation processes. For example, the grafting process
storage and plating industries [3]. The increase in lead
with poly (acrylic acid), which acts as a chelating poly-
concentrations in the drinking water can affect the mental
mer, has a considerable attention in the separation of
development of children and can increase the blood pres-
heavy metals due to its ability to form chelates [15].
sure in adults. On the other hand, the presence of mercury
Jute is one of the most affordable natural fibers and is
the second to cotton in amount produced and variety of
Correspondence to: M. S. Hassan; e-mail: [email protected]
DOI 10.1002/vnl.21603
its raw material extracted from vegetable fibers. Jute
Published online in Wiley Online Library (wileyonlinelibrary.com). fibers are lignocelluloses natural fibers, composed mainly
C 2017 Society of Plastics Engineers
V of cellulose, hemicellulose (82–85%), and lignin [20]. It
tends to level off as a result of homopolymer formation These findings prove the introduction of PAAc grafted
of PAAc [26]. chains onto the backbone of jute fibers [27].
FIG. 2. FTIR spectra of ungrafted jute and Jute-g-PAAc fibers. FIG. 3. XRD patterns of ungrafted jute and Jute-g-PAAc fibers.
appearance as shown in Fig. 4a. After the grafting process 2Jute-g-COO2 1Hg21 ! ½Jute-g-COO2 Hg ðcomplexÞ (4)
with PAAc, thick spongy layers of the graft copolymer
were noticed on the jute surface resulting in the increase
in the diameter of fibers with uniform shape as shown in Effect of pH. The removal (%) of metal ions by the
Fig. 4b, which can enhance the effluent diffusion through adsorbent as a function of pH, using of (0.1 M) as an ini-
the fiber interspaces leading to the increasing of the tial concentration for both metal salts, at a temperature of
adsorption efficiency. 308C, after 60 min of soaking under shaking is repre-
sented in Fig. 5. It is clear that the removal (%) of metal
Adsorption Mechanism of Metal Ions by Jute-g- ions is strongly pH dependent and maximum removal (%)
PAAc. The mechanism of the metal ion adsorption pro- occurs at pH 5 for lead and pH 6 for mercury. The
cesses is not fully understood, but several mechanisms increase of metal ion removal (%) with an increase in the
were suggested for metal ion binding to the grafted poly- pH is due to a decrease in competition between proton
mer chains including ion exchange, complexation, co- and metal ions for the surface sites and by the decrease in
ordination/chelation, electrostatic interactions, acid–base positive surface charge. Meanwhile, the metal ion
interactions, hydrogen bonding, hydrophobic interactions, removal (%) was decreased at low pH values as a result
physisorption, and possibly precipitation. In the case of of the protonation effect and the increasing competition
Jute-g-PAAc, the hydrogen atom in the carboxylic group of protons for the same binding sites that metal ions can
of AAc can be exchanged by metal ion and then the car- bind. A slight decrease in removal (%) observed above
boxyl groups have two lone pair of electrons on the oxy- pH 5 for lead, which may be due to the precipitation of
gen which can form a chelate with metal ion [29]. Two Pb21 as Pb(OH)2. Hence pH experiments at alkaline
carboxyl groups are required to form a chelate with diva- ranges were avoided. The maximum removal (%) of
lent metal ions. The Jute-g-PAAc was used as an adsor- Hg21 observed at higher pH (6) than that of Pb21 may be
bent matrix for some toxic divalent heavy metal ions attributed to the electrostatic attraction between Hg(OH)1
such as Pb21 and Hg21. Previous reports [30] proved that ions and the negatively charged adsorbent surface [31].
the carboxylic groups of AAc act as a strong complexing
agent for the metal ions as shown in Eqs. 3 and 4. This Effect of Contact Time. The effect of contact time on
complex shows a tetrahedral structure (square planar com- the removal (%) of Pb21 and Hg21 by Jute-g-PAAc fibers
plex) as shown in the following scheme. using the initial concentration of (0.1 M) at pH 5 and a
temperature of 308C was studied, and the results are rep-
resented in Fig. 6. It can be seen that the removal (%) of
Pseudo-first-order Pseudo-second-order
kinetic model kinetic model
Metal ions k1 (min21) qe (mg/g) r2 k2 [g/(mg/min)] qe (mg/g) r2
FIG. 7. The pseudo-first- and second-order plots for the adsorption of Pb21 and Hg21 by Jute-g-PAAc.
On the other hand, the results of qe obtained by using Ce =qe 51=b qm 1Ce =qm ; (7)
of the pseudo-first-order model were much lower than that where qe represents the adsorption capacity (mg/g) at
in the case of the pseudo-second-order model, which could equilibrium of metal ions on Jute-g-PAAc, Ce is the metal
be attributed to the inapplicable of the pseudo-first-order ion concentration at equilibrium (M), qm is the monolayer
equation throughout the contact time more than 20–30 min adsorption capacity (mg/g), and b is the Langmuir adsorp-
of the adsorption process [13, 32]. This indicates sharply tion constant (L/mg). Figure 9 shows the Langmuir plot
that the adsorption processes for both Pb21 and Hg21 by of the adsorption of Pb21 and Hg21 by Jute-g-PAAc. The
Jute-g-PAAc obey the pseudo-second-order model. slope and intercept of the plot of Ce/qe versus Ce were
used to determine qm and b as illustrated in Fig. 9. The
Effect of Initial Concentration. The influence of the values of qm, b, and correlation coefficient (r2) are listed
initial metal ions concentrations Co (M) on the amount of in Table 2.
adsorbed Hg21 and Pb21 at equilibrium (qe) by Jute-g- The Freundlich adsorption isotherm assumes that the
PAAc is shown in Fig. 8. It can be seen that the adsorp- adsorption process occurs at specific heterogeneous sys-
tion capacity (mg/g) at equilibrium (qe) increases with tems and is most commonly used for adsorption process,
increasing of the initial concentration of both Pb21 and using
Hg21. This could be attributed to the acceleration of the
metal ions diffusion into the polymeric network, where, ln qe 5ln Kf 11=nln Ce (8)
at high concentration, the driving force increases, which
overcome the mass transfer resistance between solid–liq- where qe represents the adsorption capacity (mg/g) at
uid phases [41]. equilibrium of metal ions on Jute-g-PAAc, Ce (M) is the
metal ion concentration at equilibrium, Kf is Freundlich
Adsorption Isotherms. The adsorption isotherms are constant, and 1/n is the heterogeneity factor. The slopes
important for the discussion of the interaction of the and intercepts of the plot of ln qe versus ln Ce were used
FIG. 9. The Langmuir and Freundlich plots for the adsorption of Pb21 and Hg21 by Jute-g-PAAc.