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Journal of Purity, Utility Reaction and Environment
Removal of Heavy Metals and Colour
Industrial Wastewater by Novel Composite
Adso
rbent of Alginate and Mangrove B
Coated by Chitosan
Rana Jaafar Jawada
, Mohd Halim Shah Ismail
Izhar Siajam
Department of chemical and Environmental Engineering, Faculty of
Engineering, Universiti Putra Malaysia,43400 UPM Serdang,
Selangor, Malaysia
a
ranajaafarjawad@yahoo.com,
c
shamizhar@upm.edu.com
ISSN (Online):2232-1179
I
ISSN (Print):2314-8101
ABSTRACT
This study was about the preparation of novel adsorbent
Mangrove beads Coated by Chitosan (AMCC), characterized by Fourier Transform Infrared
Spectroscopy (FTIR), Scanning Electron Microscope (SEM) and swelling studies to prove the
successful coating by Chitosan,
respectively,
and then applied to remove Zinc (Zn
Mill Effluent (POME) using batch adsorption studies by two parameters pH and adsorbent dosage. As a
result, th
e characterization analyses revealed that the coating by Chitosan has a great influence on the
adsorbent (i.e. more function groups, rougher surface, and highly resistant for acid and base solution).
In addition, the maximum removal percentage for (AMCC) w
% of Mn2+
, and (55.66) % of colour
Keywords:
Alginate; Mangrove; Chitosan; Heavy metals; colour; Adsorption
Journal of Purity, Utility Reaction and Environment
Vol.5 No.5, October 2016,
1
Removal of Heavy Metals and Colour
from
Industrial Wastewater by Novel Composite
rbent of Alginate and Mangrove B
eads
Coated by Chitosan
, Mohd Halim Shah Ismail
b, Shamsul
Izhar Siajam
c
Department of chemical and Environmental Engineering, Faculty of
Engineering, Universiti Putra Malaysia,43400 UPM Serdang,
Selangor, Malaysia
ranajaafarjawad@yahoo.com,
bmshalim@upm.edu.com,
shamizhar@upm.edu.com
Received:
Accepted:
Published online:
© 2012 Design for
Scientific Renaissance All rights reserved
This study was about the preparation of novel adsorbent
which is
a composite of Alginate and
Mangrove beads Coated by Chitosan (AMCC), characterized by Fourier Transform Infrared
Spectroscopy (FTIR), Scanning Electron Microscope (SEM) and swelling studies to prove the
successful coating by Chitosan,
to discover the surf
ace morphology, and the crystalline of the beads
and then applied to remove Zinc (Zn
2+), Manganese (Mn2+
), and colour from Palm Oil
Mill Effluent (POME) using batch adsorption studies by two parameters pH and adsorbent dosage. As a
e characterization analyses revealed that the coating by Chitosan has a great influence on the
adsorbent (i.e. more function groups, rougher surface, and highly resistant for acid and base solution).
In addition, the maximum removal percentage for (AMCC) was found to be (75.48) % of Zn
, and (55.66) % of colour
and was achieved at pH 3.
Alginate; Mangrove; Chitosan; Heavy metals; colour; Adsorption
1
18-129
Article Info
Received:
25thMay 2015
Accepted:
1st June 2015
Published online:
1st October 2016
Scientific Renaissance All rights reserved
a composite of Alginate and
Mangrove beads Coated by Chitosan (AMCC), characterized by Fourier Transform Infrared
Spectroscopy (FTIR), Scanning Electron Microscope (SEM) and swelling studies to prove the
ace morphology, and the crystalline of the beads
), and colour from Palm Oil
Mill Effluent (POME) using batch adsorption studies by two parameters pH and adsorbent dosage. As a
e characterization analyses revealed that the coating by Chitosan has a great influence on the
adsorbent (i.e. more function groups, rougher surface, and highly resistant for acid and base solution).
as found to be (75.48) % of Zn
2+, (59.29)
Alginate; Mangrove; Chitosan; Heavy metals; colour; Adsorption
.
119
Journal of Purity, Utility Reaction and EnvironmentVol.5 No.5, October 2016, 118-129
1. Introduction
Water pollution is one of the most critical problems faced in this present world. In fact,
industrialization has caused major damages due to the huge amount of wastewater generated
from factories that contain many toxic wastes, such as heavy metals and colour. Heavy metals
are non-biodegradable, toxic, and bio-accumulate in aquatic living organisms and can transfer
to human through the food chain and cause many diseases such as cancer, brain and lung
damages (Bernard & Jimoh, 2013; Shaker, 2015), and the presence of colour in water bodies
led to prevent the sunlight entrance and will subsequently have an effect on photosynthesis,
and also some colour compounds react with metal ions and create toxic materials (Bello et al.,
2013). Hence, the wastewater must be treated before being discharged to water sources to
minimize all pollutants to the permissible limits. Worldwide, palm oil is considered the most
effective oil among the other kinds of oilseeds. As a sequence of producing this oil, an
enormous amount of effluent was discharged known as Palm Oil Mill Effluent (POME),POME
is a thick brown liquid, contains many heavy metals such as Lead, Zinc, Cadmium,
Manganese, Iron, Copper, and Chromium (Idris, Jamal, & Alam, 2012; Ohimain, Seiyaboh,
Izah, Oghenegueke, & Perewarebo, 2012; Shavandi, Haddadian, Ismail, Abdullah, & Abidin,
2012), it also contains organic components which are pectin, lignin, carotene, and phenolic,
these components are responsible of the colour of POME (Bello et al., 2013). Among the many
methods that have been used to treat industrial wastewater including POME, the adsorption
method has been considered as one of the best technologies because it has been found
sufficient in removing pollutants even at low concentrations, easy to handle, and economical
(Fadzil et al., 2016; Xueying Li et al., 2015). Thus, this method has been considered as an
excellent process for removal organic and inorganic pollutants (Husin et al., 2011).
In the recent years, many studies have attempted to discover new, eco-friendly, and economical
materials, which could function sufficiently as adsorbents to solve the toxic waste problems
generated by factories, and some of these adsorbents had been made from natural substances,
wastes of agriculture or by-product of the industrials (Abas et al., 2013), such as using mango
stone and cocoa pod waste to remove Cd2+ and Pb2+ (Olu-owolabi et al., 2012),banana peel to
remove Cu2+ (Hossain et al., 2012), maize stalks to adsorb Mn2+, Cd 2+, and Zn 2+ (Jagung,
2011), orange peels skin to adsorb Cr and Zn (Ekpete et al., 2010), orange peel & neem leaf
powder to remove methylene blue dye (Khatod, 2013), and watermelon shell to remove Cu
(Banerjee et al., 2012). On the other hand, limited studies had been performed to find natural
adsorbent to treat POME. Therefore, this study prepared novel types of adsorbentto treat
POME in the shape of beads, because the beads are considered as the superior form of
biopolymer adsorbent for heavy metals removal in wastewater and also to prevent many
problems occurred when using the powder as an adsorbent. Mangrove bark is an agricultural
waste, a by-product of the charcoal factory, which contains lignin, cellulose, and
hemicelluloses (Asadpour et al., 2014),these substances are excellent in adsorption because of
their structure contains the functional groups (carboxylic, phenolic, and hydroxyl)(Rozaini et
al., 2010). Mangrove barkis abundant, therefore, using it will help to solve the waste disposal
problem and it can be convertedinto useful materials. Nevertheless, the mangrove bark need to
be modified to improve the capacity of adsorption (M Emin Argun & Dursun, 2007; Asadpour
et al., 2014; Seey & Kassim, 2012). Na-alginate is a biopolymer can be obtained from the
brown algae, and the alginate has the ability to dissolve in water, andform gel when in contact
with calcium salt (Yang et al., 2011). Na-alginate include 1, 4–linked β-D-mannuronate (M)
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Journal of Purity, Utility Reaction and EnvironmentVol.5 No.5, October 2016, 118-129
and α–L-guluronate (G)residues (Gazori et al., 2009). Furthermore, Alginate contains
carboxylate groups (Bée et al., 2011) and hydroxyl groups (Kleinübing et al., 2011) these
groups can function well in heavy metals removal in the treatment of wastewater. Moreover,
the alginate is an eco-friendly, cost–effective, and biodegradable material(NiŃa et al., 2007).
Chitosan is a natural polymer that can be obtained from shrimps and other crustacean via base
treatment of chitin. Interestingly, there is plenty of chitin on this planet as it takes the second
place after cellulose (El-Hefian et al., 2010). Chitosan consist of β (1→4)–linked 2-acetamido-
2-deoxy-β-D-glucopyranose and 2-amino-2deoxy-β-D-glucopyranose (Holme et al., 2008).
Chitosan possesses great features, for example, non-allergenic, non-toxic, biodegradable, and
has the ability to flocculate and regenerate (Ahmad et al., 2004; Saifuddin & Dinara, 2011).
Furthermore, chitosan is well-known as a perfect adsorbent for removing heavy metals and
colour (Narayanan & Dhamodharan, 2015) because it contains effective functional groups,
which are amino and hydroxyl (Igberase et al., 2014; Liu & Zhang, 2015), the application of
chitosan helps to convert waste materials (shell waste of crustacean) into valuable materials
(Ahmad et al., 2004).
The purpose of this study is to prepare novel adsorbent AMCC beads from materials that are
natural, eco-friendly, with sufficient functional groups, and well-known of their ability to
adsorb pollutants from wastewater. These beads were characterized by using FTIR, SEM and
swelling studies, then the removal of Zn2+, Mn2+, and colour by AMCC was explored under
batch adsorption studies.
2. Experimental
2.1. Materials
POME sample was collected from Palm Oil Mill in Seri Ulu Langat, Malaysia. Mangrove
barkwas collected from charcoal factory in Malaysia, while chitosan powder was obtained
from a local manufactory in Malaysia. The other chemicals (Na-alginate, Sodium Hydroxide,
Acetic Acid, Hydrochloric Acid, and Calcium Chloride) were purchased from R & M
Chemicals.
2.2. Preparation of adsorbent
Mangrove bark had been washed with distilled water to remove all dirt. After that, the bark
was left to dry at room temperature, ground by using an electric blender to rough powder, and
sieved with a 250 micron mesh size sieve to obtain fine powder, the fine powder of mangrove
bark was base modified by NaOH, due to the fact that NaOH is the best agent used to obtain
additional active surfaces, as well as to stop the elution of tannin (Mehmet et al., 2006).In
order to perform this modification; (12) g of the mangrove bark Powder was added to (500) ml
of (0.1) M of NaOH solution, stirred for (2) hrs at (125) r.p.m. and after that, the treated bark
powder was washed for a number of times with distilled water to remove the excess of NaOH
until the pH reached between 6.5 and 7. Later, the bark was filtered and dried in oven at 63ᵒc
for 24 hrs. In order to prepare the mixture of Alginate and Mangrove bark (AM), (5) g of Na-
alginate was dissolved in (200) ml of distilled water, then continuously stirred for (24) hrs. at
(125) r.p.m. After that, (2.5) g of the treated mangrove was added to the Na-alginate mixture
and was left to mix till it obtained a homogenous mixture. In addition, by using a syringe pump
device to form the beads via dropping technique, (10) ml of the AM mixture was taken by the
syringe, and then, the AM mixture was dropped wise into CaCl2 solution. The distance
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Journal of Purity, Utility Reaction and EnvironmentVol.5 No.5, October 2016, 118-129
between the syringe and the CaCl2 surface was set to (18) cm in order to obtain spherical
shape, due to the fact that the distance is a very important factor to obtain the spherical
shape(Su et al., 1989). The beads were washed with distilled water to remove the excess of
CaCl2, left to dry in room temperature, and then coated by chitosan solution which was
prepared by adding (7.5)g of Chitosan powder to (250) ml (0.2%) of acetic acid solution, and
the solution was stirred for (3) hrs. at (45-50)ᵒc to obtain viscous gel (Popuri et al., 2009).
Furthermore, in order to ensure that all bubbles were taken out from the solution, the solution
was inserted into an Ultra sonic device for (10) min and it was kept overnight. Next, to do the
coating, (40) g of the beads were immersed in (250) ml of chitosan solution with slow stirring
at (45-50) ᵒc for an hour. After that, the beads were removed from the chitosan solution and
immersed into (250)ml of (0.1)M NaOH for an hour to be neutralized with excess acetic acid
(Popuri et al., 2009).Next, the AMCC were washed with distilled water to remove any excess
sodium hydroxide, then, left to dry in room temperature, and kept in a glass container. Fig. 1
(a, b) illustrates the images of beads before and after the coating respectively.
Fig. 1. Image of: (a) Beads before the coating, (b) Beads after the coating (AMCC)
2.3. Characterization of adsorbent
2.3.1 Fourier Transform Infrared Spectroscopy (FTIR)
FTIR was used to determine the surface functional groups in beads before and after the
coating, as the spectra were measured from (4000 to 600) cm-1.
2.3.2 Scanning Electron Microscopy (SEM)
SEM was used to determine the surface morphology of beads before and after the coating,
where the beads were coated with gold (Au) before the analysis to magnify the electron
transmission.
2.3.3 Swelling studies
The swelling studies are essential to determine the crystalline nature of the beads (Ngah &
Fatinathan, 2008). In this work the swelling studies were conducted by immersing (3) g of
AMCC beads into (50) ml of different solutions (5% CH3COOH, distilled water, and 0.1 M
NaOH) with pH values (2.5, 6.5 and 11.5) respectively. After that, the solutions were shaken
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Journal of Purity, Utility Reaction and EnvironmentVol.5 No.5, October 2016, 118-129
for (24) hrs with (180) r.p.m. at room temperature. Later, the beads were removed from the
solutions, placed on filter paper to remove the excess solutions and weighted.
The swelling percentage was calculated by using the equation (1).
Swelling%=
x 100 (1)
Where Ws and Wd are the weight of the swollen beads and dry beads respectively.
2.4. Batch Adsorption Studies
The batch adsorption studies were achieved in series of 250 ml glass bottles, each one contain
100 ml of POME, a fixed amount of AMCC were added and agitated at 150 rpm at room
temperature. The effects of two parameters were studied pH and adsorbent dosage. The pH of
POME solution was adjusted by using 0.1 M NaOH and 0.1 M HCl in the range of (3-9). The
effect of dosage was conducted in the range of (2.5-20) g forZn2+ and from (10-50) g forMn2+
and colour. The Zn2+ and Mn2+concentration in POME before and after the treatment were
determined by Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES). To do
the analysis the samples were filtered and acidified by adding concentrated HNO3.
The Removal Percentage and the amount of Zn2+ and Mn2+adsorbed by AMCC was calculated
by equations (2)
Removal % =
× 100 (2)
Where Ci and Ce (mg/L) are the initial and equilibrium concentration of the adsorbate
respectively. While, the colour of POME was determined using a double beam UV
spectrophotometer at 440 nm, different concentration of POME was set by diluting the raw
POME to the range of (10% - 100%), and a absorbance verses POME concentration was plot to
obtain the calibration curve as shown in (Fig. 2), the colour removal of POME after treatment
was computed by the absorbance value.
Fig. 2. Calibration Curve
y = 0.965x + 0.2971
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0% 20% 40% 60% 80% 100% 120%
ABS
Concentration
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Journal of Purity, Utility Reaction and EnvironmentVol.5 No.5, October 2016, 118-129
3. Results and interpretations
3.1. Fourier Transform Infrared Spectroscopy (FTIR)
Fig. 3 (a,b) illustrates the FTIR spectra of beads before and after the coating, it is clear that
most of the basic functional groups existed in both spectra. This means; the coating by chitosan
did not effect on the main functional groups, although the wave number shifted a little after
coating due to interaction with chitosan. On the other hand, three new peaks appeared for
AMCC, whereby two of them (1034.87 and 779.23) cm-1indicated the functional groups
(Amines),which had been evident of coating with chitosan as amines are part of the major
functional groups in chitosan (Ahmad et al., 2005). Meanwhile, the third peak appeared at
(657.16) cm-1, which referred to alkyl halides (Lin-Vien et al., 1991), whereas the wave
numbers (3387.88, 3395.96) in beads before and after the coating respectively exhibited high
concentration of hydroxyl group because of the broad adsorption band (Seey & Kassim, 2012),
whereby the hydroxyl group was found to exist in mangrove bark, alginate, and chitosan.
Moreover, the wave numbers (1642.32 and 1642.59) in beads before and after the coating
indicated the functional group carboxylic acid (Kleinübing et al., 2011; Li et al., 2008;
Socrates, 2004), which had been present in alginate. As a result, the coating has an excellent
influence on the beads, due to the fact that more effective functional groups was added, and
these groups are well-known for their ability of heavy metals adsorption (Argun & Dursun,
2007).
Fig.3. FTIR of: (a) beads before the coating, (b) beads after the coating (AMCC)
3.2. Scanning Electron Microscopy (SEM)
SEM images of beads before and after the coating are shown in Figures 4 (a, b, c, and d). Fig.
4(a) depicts the image of beads before coating, which was in spherical shape (the air-drying
process did not effect on the spherical shape of beads), textured, while its surface morphology
is presented in Fig. 4(b) that revealed irregular and smooth outer surface. On the other hand the
image of beads after coating (AMCC) (Fig. 4(c)) shows that the shape was still spherical after
coating. Besides, contained holes on its surface, as the surface morphology portrayed in Fig.
4(d) displayed irregular and rough surface. This means; the coating has a great effect on the
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Journal of Purity, Utility Reaction and EnvironmentVol.5 No.5, October 2016, 118-129
beads because after the coating the beads exhibited rough and irregular surface with holes,
which led to the increase in the surface area and more diffusion of pores (Rozaini et al., 2010).
Fig.4 SEM of: (a and b) Beads before the coating, (c and d) Beads after the coating
3.3. Swelling Studies
The results obtained from the swelling studies conducted upon AMCC is shown in Figures
5.The highest swelling percentages for AMCC beads was (43.3%) at pH (11.5) of (0.1) M
NaOH, this percentages derived from the undesirable act of carboxyl group (COOH)
(Soleimani et al., 2012). Other than that, the second highest swelling percentage for beads was
(26.3%) at pH (6.5), due to the fact that AMCC beads absorbed distilled water to fill the free
area of the beads until it reached equilibrium (Pasparakis & Bouropoulos, 2006), as well as due
to carboxyl groups ionization of alginate (Ngah & Fatinathan, 2008).
Finally, the AMCC beads had shown no swelling percentage at pH (2.5) of 5% CH3COOH.
This behavior can be explained as at lower pH, the H+ increased and led to protonate the amine
group of chitosan, which further let the chains of polymer to fall apart (Ngah & Fatinathan,
2008). Moreover, the H+ protonated the carboxylate group of alginate; reducing the
a
b
c
d
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Journal of Purity, Utility Reaction and EnvironmentVol.5 No.5, October 2016, 118-129
electrostatic repulsion among these group and further shrank the beads (Pasparakis &
Bouropoulos, 2006).
As a result, AMCC Beads can display good performance in the adsorption process because it
shows highly resistance for acid and base solution, in another word the beads are strong and
not fragile (Pasparakis & Bouropoulos, 2006).
Fig.5. Swelling studies ofAMCC
3.4. Batch Adsorption Studies
3.4.1. The effect of pH
The adsorption process of Zn2+ and Mn2+ by AMCC are remarkably influenced by the pH of
solution, To compute the optimum pH, the pH values of POME solution was ranged from (3-9)
(Fig 6). It is shown that the highest removal Percentage for Zn2+ and Mn2+ were occurred at pH
3, which is the optimum pH for AMCC with maximum removal percentage of 52.9% of Zn2+
and 46.67% of Mn2+, due to the fact that at pH 3,the competition between H+ and Zn2+, Mn2+to
bind with the active sites is not strong, leading to most of active sites occupied byZn2+ and
Mn2+ (Şengil & Özacar, 2008). For colour the optimum value of pH was also chosen to be 3,
because the degradation of most organic materials that causes colour (i.e. carotene, pectin, and
lignin) happened at this pH (Bello et al., 2013).
0
5
10
15
20
25
30
35
40
45
50
CH3COOH H2O NaOH
Swelling %
Swelling solution
AMCC
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Journal of Purity, Utility Reaction and EnvironmentVol.5 No.5, October 2016, 118-129
Fig.6 The effect of pH on the adsorption of Zn2+and Mn2+ by AMCC
3.4.2 The effect of adsorbent dosage
By increasing AMCC dosage, the removal percentage of Zn2+ and colour rapidly increased till
it reached the equilibrium, while for Mn2+the removal percentage gradually increased as
shown in Fig 7, this increasing of removal occurred due to increment of available surface area
and adsorption sites (Deepa & Suresha, 2013), the maximum removal percentage at
equilibrium were 75.48% of Zn2+ at AMCC dosage of 10 g, 59.29 % of Mn2+at AMCC dosage
of 50 g, and 55.66 % of colour at AMCC dosage of 30 g.
Fig.7. The effect of adsorbent dosage on the adsorption of Zn2+, Mn2+ and colour by
AMCC
0
10
20
30
40
50
60
0 2 4 6 8 10
Removal %
pH value
%Zn % Mn
0
10
20
30
40
50
60
70
80
0 10 20 30 40 50 60
Removal %
Dosage (g)
%Zn
% Mn
colour
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Journal of Purity, Utility Reaction and EnvironmentVol.5 No.5, October 2016, 118-129
4. Conclusion
In this research, spherical shape of AMCC adsorbent were prepared by mixing alginate and
base modified mangrove bark to form beads then coated by chitosan. Then later applied for
heavy metals and colour removal from industrial wastewater, and were advantageous from
their effective functional group, rougher surface, and anti-acid and anti-base nature. The
maximum adsorption removal percentage obtained were above 70% of Zn2+, and above 50% of
Mn2+ and colour at pH 3 and at (10, 50, and 30) g ofAMCC dosage respectively.
This research suggested that AMCC is a promising adsorbent for the removal of heavy metals
and colour from industrial wastewater.
Acknowledgement
The authors are grateful to Universiti Putra Malaysia (UPM) for the financial support under
grand (GP-IPS/2015/9453200).
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