Journal of Environmental Management 184 (2016) 229e239

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Journal of Environmental Management

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Research article

An efficient and economical treatment for batik textile wastewater

containing high levels of silicate and organic pollutants using a
sequential process of acidification, magnesium oxide, and palm shell-
based activated carbon application
Payam Moradi Birgani a, Navid Ranjbar a, Rosniah Che Abdullah a, Kien Tiek Wong b,
Gooyong Lee a, Shaliza Ibrahim a, Chulhwan Park c, Yeomin Yoon d, Min Jang a, b, *
a
Department of Civil Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur, 50603, Malaysia
b
Department of Environmental Engineering, Kwangwoon University, 20 Kwangwoon-Ro, Nowon-Gu, Seoul, 01897, Republic of Korea
c
Department of Chemical Engineering, Kwangwoon University, 20 Kwangwoon-Ro, Nowon-Gu, Seoul, 01897, Republic of Korea
d
Department of Civil and Environmental Engineering, University of South Carolina, Columbia, SC, 29208, USA

a r t i c l e i n f o a b s t r a c t

Article history: Considering the chemical properties of batik effluents, an efficient and economical treatment process
Received 3 April 2016 was established to treat batik wastewater containing not only high levels of Si and chemical oxygen
Received in revised form demand (COD), but also toxic heavy metals. After mixing the effluents obtained from the boiling and
18 September 2016
soaking steps in the batik process, acidification using concentrated hydrochloric acid (conc. HCl) was
Accepted 19 September 2016
Available online 4 October 2016
conducted to polymerize the silicate under acidic conditions. Consequently, sludge was produced and
floated. XRD and FT-IR analyses showed that wax molecules were coordinated by hydrogen bonding with
silica (SiO2). The acidification process removed ~78e95% of COD and ~45e50% of Si, depending on the
Keywords:
Batik
pH. In the next stage, magnesium oxide (MgO) was applied to remove heavy metals completely and
Wastewater almost 90% of the Si in the liquid phase. During this step, about 70% of COD was removed in the hydrogel
Acidification that arose as a consequence of the crosslinking characteristics of the formed nano-composite, such as
Magnesium oxide magnesium silicate or montmorillonite. The hydrogel was composed mainly of waxes with polymeric
Palm-shell activated carbon properties. Then, the remaining Si (~300 mg/L) in the wastewater combined with the effluents from the
Sequential process rinsing steps was further treated using 50 mg/L MgO. As a final step, palm-shell activated carbon (PSAC)
was used to remove the remaining COD to < 50 mg/L at pH 3. Overall, the sequential process of acidi-
fication and MgO/PSAC application developed could serve as an economical and effective treatment
option for treating heavily polluted batik effluents.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction terms of effluent quality, treatment, and hazardous effects (Kant,

The huge amount of waste originating from various
manufacturing processes, such as the oil palm, paddy, rubber, co-
coa, sugar cane, tea, and coconut industries, have jeopardized
various environments in southeast Asian countries. Because these
wastes are produced in industrial quantities, many studies have
been conducted to reduce their adverse environmental effects.
While some traditional textile industries have been studied in
* Corresponding author. Department of Environmental Engineering, Kwangwoon
University, 20 Kwangwoon-Ro, Nowon-Gu, Seoul, 01897, Republic of Korea.
E-mail addresses: minjang@kw.ac.kr, heejaejang@gmail.com (M. Jang).
2011), few studies have been performed on the overall status and
treatment of batik wastewater. Most batik industries are relatively
small family-based facilities that do not have wastewater treatment
units. Due to their sporadic locations, it is difficult to establish
centralized large-scale treatment systems.
Batik is one of the oldest cottage textile industries in Malaysia.
Over 1000 batik factories are scattered mainly throughout Kelantan
and Terengganu on the east coast of Malaysia (Rashidi et al., 2013;
Redzuan and Aref, 2009). A major problem related to the batik in-
dustry is the discharge of wastewater produced during the soaking,
boiling, and rinsing steps without proper treatment. This problem
involves large volumes of water and chemicals such as waxes, dyes,

http://dx.doi.org/10.1016/j.jenvman.2016.09.066
0301-4797/© 2016 Elsevier Ltd. All rights reserved.
230 P.M. Birgani et al. / Journal of Environmental Management 184 (2016) 229e239
and fixing agents like silicate, resulting in a high pH, chemical ox-
ygen demand (CODCr), total suspended solids (TSS), and heavy
metals (Arumai Dhas, 2008; Ghoreishi and Haghighi, 2003; Khalik
et al., 2015). Because the presence of various chemicals in the ef-
fluents could threaten aquatic organisms due to their toxicities and
non-biodegradability, it is more difficult to treat the water because
of the complexity of the pollutants (Carmen and Daniela, 2012;
Forgacs et al., 2004; Noor Syuhadah and Rohasliney, 2011; Rai
et al., 2005). In the batik process, the three major sequential
steps, soaking, boiling, and rinsing, which each have their own
contaminants, lead to the complexity of wastewater treatment. In
particular, wastewaters from the boiling and soaking steps have
large amounts of COD, silicate, and heavy metals. Thus, an appro-
priate treatment is needed to remediate the effluents in compliance
with local standards and regulations (Noor Syuhadah and
Rohasliney, 2011; Saidah Malihah, 2010).
Currently, the major conventional methods for treating textile
dye wastewater are physical and chemical treatments, because
biological treatments are difficult to operate and usually require a
long retention time, nor are they applicable for toxic heavy metal-
containing wastewater (Aouni et al., 2009). Treatment using
membrane filtration can reclaim water and chemicals, especially
nano-filtration (NF) and reverse osmosis (RO); however, these are
quite expensive and have significant fouling problems (i.e., RO) (Lau
and Ismail, 2009). Moreover, ultrafiltration (UF) cannot be reused if
the wastewater contains a high concentration of salt from the
dyeing process (Babu et al., 1995). Electro-kinetic coagulation is
feasible, but is also expensive in terms of energy costs and gener-
ates a high volume of sludge (Robinson et al., 2001). Activated
carbon is economically attractive, but the removal efficiencies of
dyes and other organic substances are fairly high only for a low
range of concentrations (Carmen and Daniela, 2012). Photocatalysis
have been studied on the remediation of textile wastewater
(Cardoso et al., 2016; Soni et al., 2016; Souza et al., 2016), repre-
senting that organic dyes have been removed effectively.
Nevertheless, conventional technologies mentioned above
could not be applied effectively to the batik wastewater that con-
tains not only organic dyes, but also high contents of silica, wax and
heavy metals. Accordingly, there is a continuous need for new
technologies to treat batik wastewaters containing high levels of
silicate, organic pollutants (i.e. wax), and heavy metals in an
economical and effective manner.
In this study, for the first time, a sequential treatment method
was developed through understanding the characteristics of batik
wastewaters. The method developed consists primarily of three
sequential steps. The first is to induce the polymerization of silicate
via acidification using concentrated hydrochloric acid (conc. HCl).
The resulting polymerized silica (SiO2) could be coordinated with
oxygenated groups of wax, the major organic pollutant in batik
wastewater. In the second step, magnesium oxide (MgO) is applied
to remove the remaining wax, silicate, and heavy metals. In the
final step, palm shell-based activated carbon (PSAC) is used to
remove the remaining organic fraction from the water. The main
objectives of this study were to characterize actual batik effluents,
to examine the feasibility of a sequential process of acidification
and MgO/PSAC application for remediating wastewaters, and to
determine the treatment mechanism.
2. Materials and methods
2.1. Materials
Actual batik wastewater was collected from the Dagang Batikraf
factory located in Kelantan, Malaysia. The sequence of batik and
wastewater production is shown in Fig. 1A. Wastewater samples
were collected from four points in the batik process: soaking,
boiling, and two rinsing steps. All collected samples were preserved
at 4
C prior to batch testing. Conc. HCl (37%, R&M) and powdered
MgO (99%, R&M) were used for acidification and further water
treatment. Granular-sized palm shell-based activated carbon
(PSAC, 18  35 mesh-size, avg. size 0.707 mm) was obtained from
Bravo Green Sdn Bhd, Kuching, Malaysia, and used as an absorbent
to remove the remaining CODCr. The pHPZC of PSAC was measured
as described in the supporting information (SI).
2.2. Treatment process
Fig. 1B shows a schematic of the overall sequential treatment
process. First, wastewaters obtained at the soaking and boiling
steps in the batik process were mixed at a ratio of 70 mL boiling to
1000 mL soaking wastewaters. This ratio was the same as the
production of wastewater on-site and elsewhere for batik produc-
tion. Mixed wastewaters were kept for use in this research. After
preparing mixed wastewater, conc. HCl was gradually added to
adjust the solution pH to a predetermined pH (1, 2, or 3). During the
addition of HCl, the mixture was stirred at ~30e50 rpm for
approximately 15 min. Sludge was formed instantly, floating on the
surface of the solution. The acidified suspension was kept calm
until complete separation of the sludge from the liquid. The floating
sludge was removed by filtration, and the remaining liquid phase
(phase 1 liquid) was analyzed for heavy metals and COD, and then
used for the next step. The sludge was also characterized using X-
ray diffraction (XRD) and Fourier transform infrared spectroscopy
(FTIR). Among the pH conditions tested, the optimum pH was
chosen based on the removal of COD and heavy metals. The phase 1
liquid was further treated by the addition of different amounts of
MgO (500, 750, 1000, or 1500 mg/L). The suspension was stirred at
50 rpm for 20 min and filtered to separate the liquid and solid
(hydrogel) using 0.45 mm-pore filter paper prior to heavy metal and
COD analyses. Because a hydrogel was produced during the appli-
cation of MgO into the phase 1 liquid, the volumes were measured
at the initial stage, after filtration, and after drying at 105
C. The
filtrate of the phase 1 liquid and two rinsing waters were mixed
with a ratio of effluent rates and designated the phase 2 liquid that
was further treated to remove the remaining Si with MgO at lower
concentrations (20, 50, 75, or 100 mg/L). After adding MgO into the
phase 2 liquid, the suspension was stirred for 20 min and filtered
with 0.45 mm-pore filter paper. The filtrate was designated the
phase 3 liquid and treated with PSAC to remove color and COD in
the final stage. The phase 3 liquid was treated with different
amounts of 18  35 mesh-sized PSAC (5, 10, 15, or 20 mg/L) for 8 h
without pH adjustment or at pH 3. All operational temperatures
were 27 ± 1
C. Kinetic tests were also conducted using 15 g/L PSAC
with an initial concentration of COD (322 mg/L) at 40 rpm for
predetermined times (2, 4, 6, 8, and 10 h). Adsorption isotherms of
COD were examined using the Langmuir and Freundlich models,
while kinetic data were fitted with a pseudo second-order kinetic
equation due to the chemisorption of organic dye on the pore
surface of PSAC (Ho and McKay, 1998; Plazinski et al., 2013). All
isotherms and kinetic models are described in the SI.
2.3. Analytical methods
Heavy metals in all samples were measured using inductively
coupled plasma atomic emission spectroscopy (ICP-AES, Perkin
Elmer model OPTIMA 8300). COD (potassium dichromate (K2Cr2O7)
method) was measured by the APHA method (5220 closed reflux,
titrimetric standard method). XRD analysis (Empyrean Panalytical,
the Netherlands) was used to characterize the qualification of
inorganic matter in the sludges obtained at different pHs and the
 P.M. Birgani et al. / Journal of Environmental Management 184 (2016) 229e239
Fig. 1. (A) Sequence of batik and wastewater production, (B) scheme of sequential treatment (PSAC: palm-shell based activated carbon).
hydrogel, which was a by-product obtained by MgO application.
The XRD device was equipped with monochromatic Cu Ka radiation
(l ¼ 1.54056 Å) operated at 45 kV and 40 mA, with a step size of
0.026
and a scanning rate of 0.1
s1 in the 2q range of 10e80
. FTIR
analysis was also carried out using a Perkin Elmer System series
2000 spectrophotometer in the frequency range of 450e4000 cm1
to identify organic functional groups in the sludge and hydrogel.
For elemental analyses of the sludge and hydrogel, an energy
dispersive spectrometer at 15 kV (EDS), embedded in the Phenom
ProX system scanning electron microscope (SEM), was used. To
evaluate the major elemental concentrations in the hydrogel, EDS
was performed for five single points and the average value
analyzed. Moreover, to observe the physical characteristics of the
solid phase, a Dino-Lite digital microscope was used at
10e50  and 200  magnification.
3. Results
3.1. Characterization of batik wastewater
Samples were taken from different stages of the batik process
(soaking, boiling, and rinsing). The concentrations of heavy metals
and COD in each sample were compared with national regulatory
values of EQA 1974, for Environmental Quality (Industrial Effluents)
Regulation 2009, under the Fifth Schedule for Standards A and B
(Department of Environment, 2010) (Table 1), and for COD under
the Seventh Schedule (Regulation 12) (Khalik et al., 2015).
The wastewaters of each step had different contents of heavy
metals and COD as well as flow rates. For example, ~500 L/day is
released from the soaking step while ~35 L/day is discharged at the
boiling step. After applying sodium silicate as a color stabilizer,
soaking and boiling wastewaters had very high pHs (11.3 and 12.1)
231
and dissolved heavy metals, far above the current regulatory limits.
In the soaking step, Si was especially high (8965 mg/L); moreover,
Fe (3 mg/L) and Cu (0.29 mg/L) were higher than in Standard A. The
concentration of Al (12 mg/L) in the soaking step was also high,
coming from the silicate, while other heavy metals were from the

rul et al., 2009; Merzouk
reactive dyes (Allegre et al., 2006; Ertug
et al., 2009; Wang et al., 2011). COD (3950 mg/L) was also 79
times higher than in the current Regulation A (50 mg/L). The con-
centrations of Si (320.5 mg/L) and Al (4.08 mg/L) in the boiling
wastewater were lower than those at soaking; however, levels of
other heavy metals, such as Fe, Cu, Zn, and Pb, were higher. This is
because the loss of water through steaming and boiling may
slightly increase the metal concentration, as these metals accu-
mulate and deposit with boiling (Adam et al., 2013; Santhi et al.,
2008).
The detected Pb (0.57 mg/L) in boiling wastewater was also
much higher than in Standard B. Importantly, COD (~13,600 mg/L)
was much higher at the boiling step than the other wastewaters
due to the addition of wax (about 272 times higher than Standard A
(50 mg/L)). There were two rinsing steps, producing 250 and 500 L/
day. In the rinsing steps, most metal concentrations decreased. This
trend was also observed for Si and COD. Overall, the contaminated
loadings of Si and COD were heavily concentrated in the boiling and
soaking wastewaters (98.2% and 95.2%, respectively). Thus, in this
treatment scheme, the wastewaters loaded with high levels of Si
and organic pollutants were treated separately by a sequence of
acidification and MgO.
3.2. Acidification
When mixed wastewater was subjected to conc. HCl, sludge
started to form instantly at pH 4. Upon reaching a lower pH (1e3),
232 P.M. Birgani et al. / Journal of Environmental Management 184 (2016) 229e239

Table 1
Heavy metals and COD contents in wastewater samples at different steps.

Samples ICP (mg L1) COD (mg L1) pH Flowrate (L day1)

Pb Fe Cu Zn Al Mn Mg Ca Cr Si

Standard A 0.1 1 0.2 2 10 0.2 ND ND 0.2 ND 50 6e9 e

Standard B 0.5 5 1 2 15 1 ND ND 1 ND 250 5.5e9

After soaking 0.04 3.0 0.29 0.29 12 0.02 0.97 4.23 0.08 8965 3950 11.3 500
After boiling 0.57 3.71 0.5 0.39 4.08 0.02 0.89 7.27 0.08 320.5 13,600 12.1 35
Rinse 1 0.03 0.61 0.11 0.52 1.02 ND 1.71 6.13 0.06 226.3 428 7.6 250
Rinse 2 0.01 0.26 0.18 0.08 0.58 ND 0.92 4.32 0.06 49.95 34 6.4 500

more flocs occurred and floated on the surface of the water. The 100 5000
formation of flocs was minimal with pH 4. Table 2 shows heavy Si
metal concentrations in the mixed wastewater and phase 1 liquid
80 4000

Concentration (mg L )
after acidification. Before acidification, Si and COD concentrations

-1
were 8400 and 4915 mg/L, respectively; these values reduced to COD

Removal (%)
minimums of 4315 and 230 mg/L, respectively, at pH 3. Fig. 2 shows
60 3000
the removal percentages and remaining concentrations of Si and
COD in the phase 1 liquid obtained by acidification followed by Si
filtration. As can be seen, the removal percentages for Si and COD 40 2000
increased from 45 to 50% and 78e95%, respectively, as the pH
increased from 1 to 3. Thus, it can be concluded that the sludge
formed consisted mostly of Si and organic molecules. As observed 20 COD 1000
in Table 2, the concentrations of most heavy metals after acidifi-
cation were higher than in the initial mixture. Especially, under all 0 0
acidic conditions, Pb, Fe, Cu, and Al levels were higher than Stan- 0.5 1.0 1.5 2.0 2.5 3.0 3.5
dard A. This might be because heavy metals complexed by dye
pH
molecules were converted to more soluble forms by the acidic
condition (Hahn and Klute, 1988). The lowest amount of Si Fig. 2. Si and COD concentrations in phase 1 liquid and their removal percentages
(4315 mg/L) and significant reduction of COD were obtained at pH according to pH, initial concentrations of COD (4915 mg/L) and Si (8400 mg/L).
3. Because acidification at pH 3 resulted in the optimum removal in
this stage, further processes were conducted based on this pH
condition. Sludge characterization using XRD, SEM-EDS, and FTIR peaks assigned to SiO2 were clearly higher, indicating a more
was conducted to investigate the removal mechanism of Si and crystallized phase of Si.
COD. Organic substances in the sludge were investigated by FTIR. As
observed in Fig. 3B, the small bands at 500e1000 cm1 indicated
SieO vibrations (Royer et al., 2010). The absorption band at
3.3. Sludge characterization
822 cm1 is related to the symmetric stretching of SieOeSi groups
(Royer et al., 2009). Moreover, other bands for silica were observed
XRD analysis was conducted to observe the crystalline phase of
at 967 and 1080 cm1, attributable to SieOH stretching and
the sludge obtained after acidification at each pH. To prepare the
SieOeSi asymmetric stretching vibrations, respectively. These Si
XRD sample, filtered sludge was dried in an oven at 105
C for 3 h
peaks were due to the sodium silicate used in the soaking step. The
and ground. Fig. 3A shows XRD patterns of sludges at different pHs.
absorption bands at 1461 and 1386 cm1 were attributed to the
The results revealed that the sludge remaining after acidification
CeH scissoring vibration (Panwar et al., 2015) and CeH symmetric
consisted of major crystalline phases of NaCl and SiO2. As discussed
deformation mode, respectively. The characteristic peak of car-
in Section 3.2, this result is consistent with the Si removal after
boxylic groups (C]O stretch) can also be observed at the intense
acidification. The XRD patterns were consistent with NaCl (JCPDF
peak of 1694 cm1 (Chen et al., 2002; Lucic et al., 2014). The FTIR
file: 01-075-0306), similar to the findings of Kiel et al. (Kiel et al.,
spectrum also revealed that the bands related to the structure
2012), and SiO2 (JCPDF file: 01-075-1544). As can be seen, the
detected at 2851 and 2920 cm1 were associated with symmetric
variation in pH did not cause marked changes in the crystalline
and asymmetric stretching of CH2 (Ranjbar et al., 2015; Royer et al.,
phase of the sludge. However, as the pH increased, the intensities of

Table 2
Concentrations of heavy metals and COD in the mixture of boiling and soaking wastewaters as well as after acidification followed by filtration at pH 1, 2 or 3.

ICP (mg/L) COD (mg/L)

Pb Fe Cu Zn Al Mn Mg Ca Cr Si

Standard A 0.1 1 0.2 1 10 0.2 ND ND 0.2 ND 50

Standard B 0.5 5 1 1 15 1 ND ND 1 ND 100

Mixed wastewater 0.1 3 0.3 0.3 11 ND 1 4.4 0.1 8400 4915

At pH 1 0.4 4.99 0.49 0.53 14.3 0.06 1.37 7.41 0.09 4535 1152
At pH 2 0.23 4.82 0.44 0.36 14.8 0.06 1.3 5.89 0.09 4547 998
At pH 3 0.25 3.79 0.45 0.35 13.5 0.04 1.16 5.57 0.09 4315 230
 P.M. Birgani et al. / Journal of Environmental Management 184 (2016) 229e239 233

A N S: SiO2
N: NaCl
S N
S N N N
at pH 3
N
N
Intensity

S
S N N N
at pH 2
N

N
S N
S N N
at pH 1

10 20 30 40 50 60 70 80

2 theta

B
at pH 1

at pH 2
Transmission (%)

at pH 3

822
1461
3387 967
2851 1386

2920
1694 1080

4000 3500 3000 2500 2000 1500 1000 500

-1
Frequency (cm )

Fig. 3. (A) XRD and (B) FT-IR measurement of sludge obtained after acidification.

2010), respectively. The characteristic absorption bands of the charged soluble silicate species at high pH. When the pH is lowered,
stretching vibrations of hydrogen-bonded O-H groups, which are silicate can be converted to silicic acid by reaction (R1).
involved in hydrogen bonding and thus may also be due to adsor-
bed water molecules, were integrated into a broad peak at Naþ þ HSiO
3 þ HCl þ H2O / Si(OH)4 þ NaCl (R1)
3387 cm1 (Ahmad and Hameed, 2009; Chen et al., 2002; Lu ci
c
et al., 2014). Hydrocarbon and hydroxyl groups are inherent to Second, two silicic acids can react to produce a silicate dimer,
the wax and complex organic dyes. Overall, the XRD and FTIR re- which further polymerizes to form polymerized SiO2.
sults indicate that the sludge is composed mainly of SiO2 and
organic wax and dye molecules. Si(OH)4 þ Si(OH)4 / Si2O(OH)6 þ H2O (R2)

Because waxes consist of long alkyl chains containing primary

3.4. Mechanisms of COD and Si removal by acidification
Based on the analytical results of XRD, FTIR, and ICP, the domain
reaction for sludge production by acidification could be defined as
follows. First, sodium silicate is dissolved to obtain negatively
alcohols and fatty acids, the oxygen molecule of waxes can be co-
ordinated with silanol groups (SieOH) through hydrogen bonding.
Fig. 4 shows the coordination between a typical wax ester and
polymerized SiO2.
234 P.M. Birgani et al. / Journal of Environmental Management 184 (2016) 229e239
Fig. 4. Mechanism of Si polymerization and wax removal as floated sludge by acidification.
3.5. Treatment of remaining heavy metals, Si, and COD by
magnesium oxide
As shown in Section 3.2, about 50% of Si and 98% of COD were
removed by acidification at pH 3. However, heavy metals such as
Pb, Fe, Cu, and Al, exceeding Standard A and high concentrations of
Si and COD, were left in the phase 1 liquid. Thus, there was a need to
treat this polluted acidic water in an effective and economical way.
In this study, various concentrations of MgO were applied not only
to raise the pH, but also to remove organic and inorganic pollutants
in the phase 1 liquid. Fig. 5 shows the changes in pH and concen-
trations of all metal species and COD by the addition of MgO to the
phase 1 liquid. As MgO was added, the initial concentration of Si
(about 4300 mg/L) was reduced considerably to 550 mg/L at
250 mg/L MgO, and decreased linearly to 290 mg/L at 1000 mg/L
MgO. Heavy metals such as Cu, Zn, and Mn were removed
completely by 250 mg/L MgO, whereas most of the Fe and Al was
eliminated by 500 mg/L MgO. The Mg and Ca concentrations
increased by adding 250 mg/L MgO, but dropped again to less than
5 and 10 mg/L, respectively, by increasing the concentration of MgO
above 500 mg/L. As expected, the pH increased gradually from 3 to
7.2 at 250 mg/L MgO and increased further to 8.5 at 750 mg/L MgO.
Generally, MgO has two major functions in removing metals.
First, in the presence of water, MgO is hydrolyzed to Mg(OH)2 that
further dissociates to hydroxyl ions (OH) to increase the pH. Most
metal species are hydrolyzed and precipitate by this action. Thus, to
determine the removal mechanism of heavy metals by the increase
in pH, selective precipitation was interpreted using the Hydra/
Medusa chemical equilibrium-modeling software. Second, MgO
has several properties with regard to the removal of pollutants such
as electrostatic interactions, ion exchange, and complexation.
For the first mechanism, the soluble and solid species of indi-
vidual metals, terms of reaction, and equilibrium constants (log K)
were established for the modeling (Table S1). Fig. S1 shows the
various species of each metal according to pH. At pH 8.2, when
500 mg/L MgO is added, Si participates as MgSiO3 (c) at ~10%, while
it exists predominantly as SiO2 (Cr) at pH < 8.2. The Fe exists pre-
dominantly as Fe2O3 (Cr) at 2.2 < pH < 5, but complexes with Cu
and other metal species as CuFe2O4 (c) and montmorillonite (c)
[(Na,Ca)0.33(Al,Mg)2(Si4O10)(OH)2$nH2O] with a proportion of
0.15e0.2 and 0.85 at pH > 8, respectively. At pH < 3, Al ions exist as
soluble Al3þ, whereas they complex to form Al2Si4O10(OH)2 (c) and
montmorillonite (c) at pH > 4 and pH > 8, respectively. Zn exists as
soluble Zn2þ at pH < 6; however, it precipitates as ZnSiO3 (c) at
pH > 7.5. Similar to Zn, Cu also becomes soluble (Cu2þ) at pH < 5.3,
but complexes to form CuFe2O4 (c) or CuO (c) at pH > 7. Thus, it can
be deduced that metal species were predominantly removed as
solid complexes with the increase in pH by MgO. However, Mg was
largely reduced with 500 mg/L MgO (pH 8.2), where Mg predom-
inantly remained as a soluble species (Mg2þ) at pH < 8, and a solid
complex (MgSiO3) becomes dominant at pH > 9.5. In addition to the
results of Mg, Si was not fully removed even though its precipitated
forms were SiO2 (Cr) and MgSiO3 (c). Thus, the removal mechanism
could not be explained solely with this chemical speciation
modeling.
For the second theory described above, the mechanism could be
explained as follows. MgO has a high pH of zero point charge
(pHZPC, 12.4) (Crittenden et al., 2012; Moussavi and Mahmoudi,
2009). Thus, it has a strong basicity so that Hþ or Mg2þ can be
adsorbed onto the surface of MgOH to form MgOHþ 2 or MgOH-
Mg2þ. As MgO increases, the adsorbed sites increase for eliminating
Mg2þ. This might be the reason for the reduction of Mg at 500 mg/L
MgO. Hypothetically, the pH surrounding the surface of the MgO
could be extremely high to transform SiO2 to silicate (H3SiO 4 ),
which is electrostatically coordinated to MgOHþ 2 (Army, 1989), and
complexed to form magnesium silicate [Mg-O-Si(OH)3].
MgOH þ Hþ(or Mg2þ)þOH / MgOHþ
2 (or
MgOHMg2þ) þ OH (R3)
MgOHþ 
2 þ H3SiO4 / MgOSi(OH)3 þ H2O (R4)
Moreover, COD was constantly reduced from ~1800 mg/L
to ~ 480 mg/L over the entire range of MgO concentrations. Thus,
the major components of COD, waxes and dyes, might be combined
with the solid complex. As a particular phenomenon, a hydrogel
was formed 15e20 min after MgO was added into the phase 1
liquid. Although we did not conduct detailed studies on the phys-
ical properties of the hydrogel, the hydrogel was formed with ~70%
volume ratio at all concentrations of MgO. Because the hydrogel
was mechanically fragile, its volume was reduced to ~20% after
pressurized filtration and further condensed to ~2% after drying in
an oven at 105
C for 2 h. Consisting of three-dimensional polymer
networks and large amounts of water, inorganic/organic nano-
composite hydrogel has been reported using exfoliated clay plate-
lets instead of organic crosslinkers such as N,N-
methylenebisacrylamide (BIS) (Haraguchi, 2007; Haraguchi and
Takehisa, 2002). Especially, water-swellable clay minerals, such as
 P.M. Birgani et al. / Journal of Environmental Management 184 (2016) 229e239 235

9 2000
8
1500

COD (mg L )
7

-1
6

pH
1000
5
4 500
3
2 0
5000 0.5

4000 0.4

Cu (mg L )
Si (mg L )

-1
-1

3000 0.3

2000 0.2

1000 0.1

0 0.0
4 0.4

3 0.3
Fe (mg L )

Zn (mg L )
-1

-1
2 0.2

1 0.1

0 0.0
20 0.10

0.08
15
Mn (mg L )
-1
Al (mg L )
-1

0.06
10
0.04
5
0.02

0 0.00
25 60

20 50
Mg (mg L )

40
Ca (mg L )
-1

-1

15
30
10
20
5 10
0 0
0 400 800 1200 0 400 800 1200
MgO applied (mg L-1) MgO applied (mg L-1)

Fig. 5. Metal concentrations according to MgO application.

hectorite [Na0.3(Mg,Li)3Si4O10(OH)2] and montmorillonite, have
been known to crosslink and form hydrogels with mixtures of
polymers.
Based on the evidence above, we hypothesized that MgO added
into the phase 1 liquid reacts with the major component (Si) to
form water-swellable magnesium silicate-based mineral solids,
further creating hydrogels with wax compounds. With the addition
of 750 mg/L MgO, the weight ratio of Mg to Si in solids participating
in the hydrogel was 1:4.4, which is similar to the composition of
montmorillonite. Thus, this hydrogel formation appears to be the
main mechanism of COD removal.
The physicochemical properties of the dried hydrogel were
further studied using XRD, FTIR, and SEM-EDS. Fig. 6A shows the
XRD patterns of dried hydrogel obtained with 500 mg/L MgO. There
was no crystalline form of MgO or SiO2, but a broad peak at 20e30

of 2q was present, indicating the amorphous phase of magnesium
silicate. As described in Section 3.3, NaCl was detected due to its
highly crystalline phase. FTIR analysis of the dried hydrogel ob-
tained with 500 mg/L MgO is shown in Fig. 6B. The absorption
bands at 436 and 793 cm1 are associated with Si-O-Si bending
vibration and stretching, respectively (Ranjbar et al., 2015), while
the sharp peak at 1043 cm1 is attributable to the Si-O-Si asym-
metric stretching vibration (Panwar et al., 2015). The broad peak at
3393 cm1 indicates the stretching vibration of O-H (Royer et al.,
2010). As a representative organic moiety for the wax, a C]O
bond stretch was detected at 1635 cm1, confirming the removal of
COD upon formation of the hydrogel (Das et al., 2013).
Fig. 6C shows an image of dried hydrogel obtained by optical
microscopy (Phenom ProX), while Fig. 6D shows an SEM image and
EDS data at position P1 of the dried hydrogel. Reddish spots were
dispersed heterogeneously, indicating that dye was incorporated in
the hydrogel. Commonly used dyes in the batik process are reactive
236 P.M. Birgani et al. / Journal of Environmental Management 184 (2016) 229e239

Fig. 6. (A) XRD pattern of hydrogel and (B) FTIR spectra of the hydrogel, (C) Microscopic and SEM images of hydrogel and (D) EDS of hydrogel.

350 phase after MgO treatment. In fact, compared with the mass per-
centages of Si and Mg in the solid phase, the percentage of Si was
predominant. The main reason for the over-percentage of Si might
300
be due to the strong hydrogen bonding between the Si layer and the
polymer that can form the outer layer of Si (Haraguchi et al., 2005).
250
This also corresponds with the FTIR results.
In the second MgO treatment, the phase 2 liquid (remaining
Si (mg L-1)

200 phase 1 liquid þ rinse water) was further treated with lower con-
centrations of MgO (20e100 mg/L), and by applying 50 mg/L MgO,
150 all the remaining Si was removed (Fig. 7). The molecular ratios of
removed Si to applied MgO for phase 2 liquid were 19.8 and 8.6 at
100 20 and 50 mg/L MgO, respectively, which were comparable to those
(5.8e21.1) for the phase 1 liquid. As proposed above, this indicates
50 that Si is removed not only as precipitates such as SiO2 (Cr) and
MgSiO3 (c), but also by surface complexation. At this stage, a
0 hydrogel was not formed while COD was not effectively removed
0 20 40 60 80 100 (remaining COD was found to be > 300 mg/L). Hence, a hydrogel
-1 formed of organic components (i.e., waxes) was predominantly
MgO applied (mg L )
removed with the first MgO treatment while color remained after
Fig. 7. Si concentration with the application of MgO. the second MgO treatment, suggesting that dye molecules were left
to be treated further.

red, blue, black, and yellow, as shown in Table S2 in the SI. Although
mixed dyes may be used, reactive red seemed to be dominant in
this sample. As observed in the elemental analysis, the Si content
(average of the five points) was 46.5%, while Cl, Na, Mg, and Fe were
also detected in the hydrogel. Thus, the considerable amount of Si
in the hydrogel is consistent with that removed from the liquid
3.6. Removal of the remaining COD using palm shell-based
activated carbon
Previously in the MgO application, polymerizing organic com-
ponents was removed in the hydrogel formed because COD
(~1800 mg/L) was reduced to ~480 mg/L over the entire range of
 P.M. Birgani et al. / Journal of Environmental Management 184 (2016) 229e239 237

MgO concentrations. Therefore, in the phase 3 liquid, dyes may be
left as the dominant organic pollutants. Fig. 8A shows the equili-
brated COD (Ceq) at each concentration of PSAC applied with or
without acidification, while Fig. 8B shows the isotherm data. For
the case without pH adjustment, COD (360 mg/L) dropped to
~100 mg/L as the PSAC concentration increased to 15 g/L. However,
COD increased again with 20 g/L PSAC, with decreased sorption
capacity due to the increase in solution pH caused by the alkaline
properties of PSAC. Thus, this indicates that solution pH may be an
important parameter. When the pH was adjusted to 3, COD became
<50 mg/L at 15 g/L, meeting that of Standard A (Department of
Environment, 2010). At ~100 mg/L Ceq, the sorption capacity at
pH 3 was ~40 mg/g.
Based on these results, a low pH may be favorable for removing
dyes by PSAC. This might have occurred because of the linkage
between the characteristics of reactive dyes and surface charges of
PSAC. Although we did not identify all dissolved dyes, reactive red
dye was dominant. As shown in Table S2, commonly used reactive
dyes in the batik process have high molecular weights
(984.2e1347.1 g/mol), and their most important deprotonated
groups and pKa are the sulfonate groups (eSO 3 ) and 4e6, respec-
tively (Al-Degs et al., 2008; Sun et al., 2013). Thus, the reactive dyes
become negatively charged species when pH > pKa. Due to the
pHPZC (9.8) of basic PSAC (Fig. S2), more positively charged groups
will dominate as the pH decreases. The protonated groups of acti-
vated carbon are mainly carboxylic (eCOeOHþ
2 ), phenolic (eOH2 ),
and chromenic groups (Sun et al., 2013). At the range of pH
(pKa < pH < pHPZC), electrostatic interaction will be the main
mechanism. When pH > pHPZC, electrostatic repulsion can increase
due to negatively charged surfaces and dye molecules. However, as
pH < pKa, hydrogen bonding and p-p stacking between aromatic
rings and the PSAC surface can be proposed as additional mecha-
nisms because the sulfonate group will be protonated as eSO3H
(Al-Degs et al., 2008; Sun et al., 2013). As a result of the isotherm,
PSAC at pH 3 had double the sorption capacity as the pH-
unmodified condition.
At pH 3, kinetic tests were conducted using 15 g/L PSAC. The
kinetic data were used to determine the removal speed of COD and
the rate-controlling step. As a result, COD was reduced from
322 mg/L to <50 mg/L in 8 h (Fig. 8C), complying with Standard B.
Through fitting the data using of a pseudo-second order kinetic
model (see SI), the sorption capacity at equilibrium (~20 mg/g) was
similar to the isotherm result at 15 g/L PSAC, indicating reliable
experiments (Fig. 8D). Furthermore, external (kf) and internal
diffusion coefficients (D), together with the Biot number (BN), were
obtained to determine the rate-controlling step. The external
diffusion coefficient kf (cm/s) was calculated as shown below (Lee
et al., 1999):
Ct A
ln ¼ kf t (1)
C0 V
Where, C0, Ct, A/V, and t are the initial dye concentration, concen-
þ
tration at time t, the external surface area to the total solution
volume, and the adsorption time, respectively. The external surface
area of PSAC used was 151.1 m2/g. The internal diffusion coefficient
(D) can be obtained with the following equation (Urano and
Tachikawa, 1991):

400 400
A without acidification C
with acidification
Concentration of CODCr (mg/L)
Concentration of COD (mg/L)

300 300

200 200

100 100
Regulation A for COD (50 mg/L) Regulation A for COD (50 mg/L)

0 0
0 5 10 15 20 0 2 4 6 8 10
Concentration of PSAC applied (g/L) Time (hour)
80 25

B without acidification D
with acidification
20
Langmuir model
60 Freundlich model

15
QEQ (mg/g)

Qt (mg/g)

40
10

20
5

0 0
0 50 100 150 200 0 2 4 6 8 10
CEQ (COD, mg/L) Time (hour)

Fig. 8. (A) COD concentration of activated carbon before and after acidification, (B) isotherm results, Kinetic plot of (C) COD concentration changes and (D) sorption capacities with
time (dot line is the fit of pseudo-second order kinetic model).
238 P.M. Birgani et al. / Journal of Environmental Management 184 (2016) 229e239
" Acknowledgement
 2 !#
qt qt 4pDt
¼  log 1  ¼ (2)
q∞ q∞ 2:3d2
where qt and q∞ are the solute concentration in the solid at time t
and equilibrium, respectively, and d is the mean particle diameter.
The Biot number was calculated using Eq. (3) (Guibal et al.,
1998).
kf d
BN ¼
D References
Where kf, d, and D are the external diffusion coefficient (cm/s),
particle diameter (cm), and internal diffusion coefficient (cm/s),
respectively.
Based on experimental data, the kf and D obtained were
4.4  109 cm/s and 4.09  108 cm2/s, respectively. Khraisheh et al.
assessed the adsorption of reactive dyes by commercially activated
carbon (FS-400), and reported that external and internal diffusion
coefficients for red dye were 7.02  102 cm/s and 1.31  107 cm2/
s, respectively (Khraisheh et al., 2002). Accordingly, the comparison
revealed that the kf in this study was much lower than that
described by Khraisheh et al., although the internal diffusion co-
efficients are comparable. The BN determined (0.008) was also
much lower than that described by Khraisheh et al. (>100). The BN
number denotes the ratio of the diffusion rate across the liquid
layer to the diffusion rate within sorbent pores. When BN is < 1,
external mass transport resistance is the controlling step, while for
BN > 100, surface diffusion is the controlling mechanism (Guibal
et al., 1998; Khraisheh et al., 2002; Kim et al., 2015). Thus, the
rate-controlling step in this study appears to be an external diffu-
sion mechanism. Based on these results, it seems likely that not
only reactive dyes, but also other organic groups such as wax, might
remain to affect the adsorption behavior. In addition, during the
second treatment with MgO, it seems plausible that fine-sized
polymerized products (i.e., colloidal hydrogel) are produced, hin-
dering external diffusion.
4. Conclusions
Considering the chemical properties of batik effluents, an
effective and economical treatment process was developed to treat
batik wastewater containing not only high levels of Si and COD, but
also toxic heavy metals. After mixing the samples obtained from
the boiling and soaking stages, a simple acidification using conc.
HCl was performed to determine the maximum reduction of Si and
COD. This process removed about ~78e95% of COD and ~45e50% of
Si, depending on the pH. In the following stage, MgO was applied to
remove heavy metals completely and ~90% of Si in the liquid phase.
In this step, ~70% of COD was removed as a hydrogel due to the
crosslinking characteristics of the magnesium silicate-based
nanocomposite. The hydrogel was composed mainly of wax,
which exhibits polymeric properties. Then, the remaining Si
(~300 mg/L) in the wastewater was further treated using 50 mg/L
MgO. As a final step, PSAC was used to remove the remaining COD
to <50 mg/L at pH 3. Overall, this is the first reported sequential
process of acidification and MgO/PSAC application that could
represent an economical and effective treatment option for treating
heavily polluted batik effluents. In addition to this effective treat-
ment, it would be interesting to explore the potential application of
the hydrogel by-products not only for synthesizing porous cement
composites (Rutkevicius et al., 2012, 2015), but also for remediating
oil spills (Sokker et al., 2011; Zolfaghari et al., 2005).
This project was funded by the UM Centre for Innovation and
Commercialization (UMCIC, RU019C-2014E).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jenvman.2016.09.066.
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