Carbohydrate Polymers 229 (2020) 115433

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Oil palm empty fruit bunch-based nanocellulose as a super-adsorbent for T

water remediation
Athanasia Amanda Septevania, , Annisa Rifathinb, Ajeng Arum Saria, Yulianti Samporaa,
⁎

Gita Novi Ariania, Sudiyarmantoa, Dewi Sondaric

a
Research Center for Chemistry, Indonesian Institute of Sciences, Kawasan PUSPIPTEK Serpong, Tangerang Selatan 15314, Indonesia
b
Center of Polymer Technology, Agency for The Assessment and Application of Technology, Kawasan PUSPIPTEK Serpong, Tangerang Selatan 15314, Indonesia
c
Research Center for Biomaterials, Indonesian Institute of Sciences, KM 64 Bogor Street, Cibinong, West Java 16911, Indonesia

ARTICLE INFO ABSTRACT

Keywords: Oil palm empty fruit bunch (EFB)-based nanocellulose (NC) was successfully produced as a super-adsorbent for
Nanocellulose water remediation via sulfuric (NCS) and phosphoric (NCP) acid hydrolysis and functionalized with activated
Adsorbent carbon (AC). The formation of sulfonic groups on the NCS surface could achieve higher remediation capabilities
Heavy metal than that of EFB-NCP. In a very short period, 2 wt.% of the formulated EFB-NCS super-adsorbent showed a
Water remediation
selective and remarkable metal adsorption capability to Pb2+ at 86% efficiency and 24.94 mg/g adsorption
Empty fruit bunches
capacity, which were double compared to those of rice-straw NC, and maintained a similar adsorptive capacity
after second reusability. Conversely, the insignificant improvement in the adsorption capacity of NCS/AC was
attributed to the disturbed surface functionality of micron-size AC. The NCS/AC showed notable organic de-
gradation capability for reducing the chemical oxygen demand (COD) to 93%. All super-adsorbents could
maintain the pH, TDS, sulfate and phosphate contents within the government water quality specifications.

1. Introduction Recently, the interest in the development of cellulose-based ad-

The massive development of petrochemical industries and urbani-
zation via rapid population growth is responsible for the significant
deterioration in water quality due to contamination from heavy metals
and hazardous or toxic chemicals. These contaminants pose a risk to
human health and well-being. This project will develop advanced bio-
based nano-materials for water remediation to provide clean, safe, and
contaminant-free waters. Sustainable and efficient processes that en-
able the mass production of water remediation agents are vital to solve
global water-related challenges. Many studies have developed techni-
ques for water remediation, including electrochemical (Azimi, Azari,
Rezakazemi, & Ansarpour, 2017), physicochemical treatment (Chen
et al., 2018), membrane filtration (Barakat, 2011; Zhang et al., 2019),
and sorption (Kyzas & Kostoglou, 2014; Samiey, Cheng, & Wu, 2014;
Jiang, Zhang, Zhan, & Chen, 2017), photocatalysis (Jiang, Zhang, Zhan,
& Chen, 2019; Jiang, Zhu et al., 2019) as well as biological treatment
(McMullan et al., 2001; Srinivasan & Viraraghavan, 2010) for organic
and heavy metal water remediation. Among these methods, adsorption
is considered the most promising and cost-effective technique due to its
high efficiency, scalable processability, and ease of operation (Kyzas &
Kostoglou, 2014; Srinivasan, 2013; Zhang et al., 2017).
sorbents for water remediation has increased due to their competitive
price, light weight, safe handling, high specific surface area, and affi-
nity for adsorption toward many classes of pollutants (Mahfoudhi &
Boufi, 2017). Further, cellulose has been classified as a non-toxic and
100% biodegradable material with no adverse effect on the environ-
ment and human beings, which is significant with regard to safety
concerns for large-scale applications (Vartiainen et al., 2011). Cellulose
is the most abundant source of bio-polymer on earth. Cellulose can be
found in not only plant sources (wood, cotton, ramie, hemp, straw, and
wheat) but also in non-plant sources such as tunicate (a family of sea
animals known as “sea squirts”), algae, and bacteria (Eichhorn et al.,
2009; Moon, Martini, Nairn, Simonsen, & Youngblood, 2011). Cellulose
has been reported as a valuable and promising candidate for an effec-
tive super-adsorbent (Han, Wang, & Li, 2017; Jiang, Zhu et al., 2019;
Kim, Kim, Kim, Harbottle, & Lee, 2017; Liu et al., 2016; Rui-Hong et al.,
2016) due to its hydrophilicity, ease of chemical surface modification,
(Zhou, Zhang, & Guo, 2005) and its inherent biological abundance and
renewable resources. Most importantly, at the nanoscale level, these
cellulose structures afford unprecedented specific mechanical proper-
ties, highly chemically tunable surface functionality and hydrophilicity
(Eichhorn, 2011; Habibi, Lucia, & Rojas, 2010; Septevani et al., 2018),

⁎
Corresponding author.
E-mail address: athanasia.amanda.septevani@lipi.go.id (A.A. Septevani).

https://doi.org/10.1016/j.carbpol.2019.115433
Received 28 May 2019; Received in revised form 6 September 2019; Accepted 3 October 2019
Available online 04 October 2019
0144-8617/ © 2019 Elsevier Ltd. All rights reserved.
A.A. Septevani, et al.
which lead to a higher adsorption capacity for water remediation for
both organic pollutants (Liu et al., 2015; Suteu, Malutan, & Bilba, 2011)
and heavy metal contaminants (Kardam, Raj, Srivastava, & Srivastava,
2013; Sharma et al., 2018; Suopajärvi, Liimatainen, Karjalainen, Upola,
& Niinimäki, 2015; Zhang et al., 2017).
In this study, the chosen cellulose resource is biomass waste from an
oil palm plantation. Indonesia is the largest producer of palm oil in the
world. A vast amount of solid residue of approximately 43.24 million
tons in the form of empty fruit bunches (EFB) is generated every year
from the palm oil industry. Further, EFB contains approximately
40–43% high cellulose, 22–25% hemicellulose, and approximately
19–21% lignin (Burhani & Septevani, 2018). A high content of cellulose
in EFB can be utilized as a potential resource of nanocellulose (NC).
During the isolation of cellulose from EFB, a by-product in the form of
black-liquor is produced. To develop an integrated bio-refinery pro-
duction that is based on EFB, studies on the synthesis of modified ac-
tivated carbon (AC) from this recycled black liquor sludge-containing
PACI-lignin were successfully conducted in our previous study. This
modified AC showed organic degradation capabilities for the treatment
of peat water and landfill leachate (Sari et al., 2017). The performance
of this AC remains limited for the remediation of organic pollutant,
which negates its significance as a super-adsorbent for various water
contaminants.
Thus, the goal of this study is to demonstrate that EFB can be a
model of potential solid waste biomass to produce functional NC, which
functions as an effective super-adsorbent agent for water remediation.
Comprehensive studies of the capabilities of EFB-NC super-adsorbent
will be investigated in terms of the remediation of heavy metals and
organic pollutants. To develop an integrated production of bio-refinery-
based material, the functionalization between EFB-NC and the pre-
viously obtained black-liquor sludge-based AC will also be investigated.
Because AC offered the capability of removing organic contaminants
(Sari et al., 2017), the performance of EFB-NC/AC nanocomposites is
expected to achieve higher super-adsorbent activities for both heavy
metal and organic pollutants. Schematic integrated production of EFB
super-adsorbent is illustrated in Figure S1 in the Supplementary Data.
2. Methodology
2.1. Materials
Oil palm EFB was obtained from PT Perkebunan Nusantara I,
Sumatera Utara, Indonesia. Technical grade sodium hydroxide was
purchased for the alkaline pre-treatment process. Sulfuric acid 98% and
phosphoric acid 85% were purchased from Merck for the acid hydro-
lysis. AC was obtained from RC-Chemistry LIPI following the reported
process of the black liquor sludge of pre-treated process for EFB (Sari
et al., 2017).
2.2. Methods
2.2.1. Isolation of NC using acid hydrolysis
Prior to the acid hydrolysis, the pre-treatment process of EFB, in-
cluding copping, grinding and oven drying, was performed to produce
dried fine-size fiber of EFB. This pre-treated EFB was further processed
to produce high-content cellulose-based EFB and its co-product in the
form of lignin rich black liquor by a chemical explosion that employs an
alkaline process with 10% wt. NaOH at 150 °C and a pressure of 4 bar
for 30 min. This pre-treated EFB cellulose was further hydrolyzed using
two types of acids: H2SO4 36% with a solid/liquid ratio of 1:80 and
H3PO4 62% with a solid/liquid ratio of 1:185 according to our pre-
viously reported studies (Septevani, Evans, Martin, & Annamalai, 2018;
Septevani, Evans, Annamalai, & Martin, 2017). The obtained NC was
then neutralized by simultaneous centrifugation and dialysis. The lignin
rich-black liquor from the pre-treatment was further processed into
activated carbon via the process of coagulation, carbonization and
2
Carbohydrate Polymers 229 (2020) 115433
activation (Sari et al., 2017). The obtained NC and AC were further
synthesized into super-adsorbent.
2.2.2. Synthesis of NC- and/or NC/AC-based super-adsorbent
The neutral NC emulsion was varied at the concentration of 0.3–3%
wt. in water for further homogenization using Ultra-Turrax Heidolph
DIAX 600 at 20,000 rpm for 40 min. The NC was then cast on a poly-
styrene Petri dish in a controlled room with a maximum humidity of
50%. The dried NC-based super-adsorbent that was obtained from
sulfuric acid was denoted as NCS, while the nanocellulose-based super-
adsorbent obtained from phosphoric acid was denoted as NCP. For the
NC/AC formulation, 0.5% of AC was added to the NC emulsion by a
homogenization and drying process that was applied to the NC only.
The obtained dried super-adsorbent was named NCSx/NCPx and/or
NCSx/AC05 or NCPx/AC05,
where x corresponds to the percentage of NC (03, 05, 1, 2, and 3
refer to 0.3% wt., 0.5% wt., 1% wt., 2% wt. and 3% wt., respectively)
2.2.3. Characterization of obtained NC or NC/AC super-adsorbent
The morphology of the obtained NC for both NCS and NCP after
neutralization was investigated using transmission electron microscopy.
The NC suspension was spotted onto a gold glider grid G400 G and then
stained with 2% aqueous uranyl acetate. The prepared samples were
analyzed in a JEOL JEM 1010 (JEOL, Japan) at 80 kV. The morphology
of the NCS/NCP and/or NC/AC-based super-adsorbent were char-
acterized by scanning electron microscopy (SEM). The element map-
ping was analyzed with backscattered electron microscopy (BSE) with
energy-dispersive X-ray (EDX) spectroscopy using the Hitachi SU3500
operated at 3 kV in the Research Center for Physic LIPI.
The adsorption efficiency and capacity of the Pb2+, Cd2+, and Cr3+
solution by EFB-NC were determined by the following experiments.
Metal solution at an initial concentration of approximately 30 ppm was
prepared and subsequently mixed with a NC or NC/AC super-adsorbent
at a fixed concentration of 0.01 g in 10 ml metal solution for only 3 min.
After mixing, a floc appeared and precipitated at the bottom of the
vessel. The non-flocculated solution was then filtered and character-
ized. The concentration of the metal solution of the initial metal and
that of the metal after treatment were analyzed by graphite furnace
atomic absorption spectroscopy (GF-AAS), GBC Scientific Equipment.
The adsorption efficiency and adsorption capacity were calculated
based on the following equation:
% efficiency =
Co Ci
x 100 %
Co (1)
V
Adsorption capacity (Qe ) = Co Ci
W (2)
where Co = initial concentration of metal in solution (mg/l)
Ci = concentration of metal mixing with NC super-adsorbent (mg/l)
V = volume of solution (l)
W = weight of the NC-super-adsorbent (g)
To understand the metal remediation mechanism, the flocculated
part at the bottom of the flask after mixing was dried and characterized
by the Tensor 27 with Hyperion 2000 Fourier-transform infrared
spectroscopy (FTIR) spectrometer. The samples were grounded with
KBr powder and pressed into transparent pellets. The sample was
measured using a transmission method between wavelengths that
ranged from 4000 cm−1 to 400 cm−1.
To investigate the remediation capacity of EFB-NC for organic pol-
lutant and the effect of acid hydrolysis on the treated water, the total
dissolved solids (TDS), chemical oxygen demand (COD) and pH level
were analyzed. For these characterizations, a control sample was ob-
tained from the Cisadane River, Indonesia, where the efficiency of each
parameter was calculated based on the difference in the COD, TDS, and
pH of the control sample before and after mixing with the EFB-NC. The
COD concentration was measured based on the SNI 6989.2-2009
A.A. Septevani, et al.
protocol. The TDS and pH were measured by the Benchtop Multi-
parameter Consort C3030 T pH/EC/TDS meter. To investigate the
reusability behaviors of the obtained NC adsorbent, the adsorption-
desorption process was conducted according to reported protocol using
an acid solution (Kardam et al., 2013; Kong, Ren, Wang, & Chen, 2014).
The metal ion was desorbed from EFB-NC super-adsorbent by applying
1 M HCl solution followed by neutralization with 1 M sodium hydroxide
and distilled water. The regenerated super-adsorbent was re-used for
the adsorption-desorption process for three cycles, and the adsorption
capacity and efficiency were calculated according to Eq. (1) and (2).
3. Results and discussion
3.1. Synthesis of NC super-adsorbent from EFB
Lignocellulose is a complex carbohydrate polymer that primarily
consists of three major components; cellulose, hemicellulose and lignin.
Cellulose and hemicellulose are associated with lignin; thus, to increase
the accessibility over the hydrolytic agent during the production of
nanocellulose, lignin and hemicellulose are required to be removed
and/or reduced from the cellulose structure. The delignification process
is an important step prior to the synthesis of nanocellulose via acid
hydrolysis. The component analysis before and after the delignification
process of the EFB biomass is represented in Table S1 in the
Supplementary Data.
Acid hydrolysis is known as an effective method for the decon-
struction of cellulose on the nano-scale. During hydrolysis, the strong
acid will aggressively attack the disordered (amorphous) region, while
the ordered (crystalline) region, which has a more stable and higher
resistance, is not affected.
Fig. 1 shows that the cellulose obtained from sulfuric acid hydrolysis
(NCS) after delignification was shorter and better dispersed and had a
more uniform nano-size than that of NCP. Rod-like NC was obtained
from the strong acid hydrolysis of the delignified EFB cellulose
(Fig. 1A). The diameter of the obtained NCS was approximately
9.6 ± 2.5 nm, and the length of the obtained NCS was
123.3 ± 15.3 nm. The long-entangled nanofiber cellulose obtained
from the phosphoric acid hydrolysis had a diameter of 12.5 ± 2.6 nm
and a length that exceeded 500 nm (Fig. 1B). Measuring the length of
the nanofibers was difficult because the fibers were long and entangled
with each other with a random in-plane orientation; thus, the end
points were not distinct. As predicted, a stronger acid level had a no-
ticeable effect on reducing the size of NC, and thus, the aspect ratio of
NCS (at 13.7) was lower than that of NCP (greater than 50). Sulfuric
acid is known as a very strong hydrolytic agent that offers NC with a
short and uniform nano size compared to other acid hydrolysis (Brinchi,
Cotana, Fortunati, & Kenny, 2013). Moreover, sulfuric acid is more
aggressive in attacking amorphous regions than other strong acids, such
as hydrochloric acid (Hamad & Hu, 2010; Yu et al., 2013), and mild
Fig. 1. Microscopy images of: A. TEM of NCS; B. TEM of NCP; C. SEM of AC.
3
Carbohydrate Polymers 229 (2020) 115433
acids, such as phosphoric acid. Residual sulfate groups (SO42−) caused
CNC to have a negative surface charge, which renders the CNC dis-
persible in water (Beck-Candanedo, 2005; Hamad & Hu, 2010; Moon
et al., 2011). This negative charge of sulfonyl will enhance the heavy
metal capabilities, as noted in the following discussion.
The surface morphologies of NCS and NCP after drying are shown in
Fig. 2. NCP has a rougher surface area and agglomerate than NCS. The
agglomerated fiber of the NCP structure was very distinct because the
long entangled individual fiber was obtained from mild acid hydrolysis;
a micron-sized agglomeration was observed after the drying process (in
Fig. 2B). The structures of the long entangled nano-fibers were orga-
nized in a looser network and had a weaker inter-connection surface in
the matrix of the super-adsorbent. Conversely, a denser surface with a
smaller pore size of the interconnected individual NC was distinctively
observed in the NCS sample (refer to Fig. 2A) compared to the surface
morphology of NCP (Fig. 2B). A shorter and more uniform NCS provides
a well-organized and interconnected hydrogen bonding of the super-
adsorbent matrix. We hypothesize that these distinguished inter-
connected networks between NCS and NCP may affect the adsorbent
efficiency for metal removal and organic pollutant remediation.
For the nanocomposite NC/AC, the presence of AC in the matrix of
both NCS and NCP (Fig. 2C and Fig. 2D, respectively) showed disturbed
surface morphologies of the NC matrixes. A micron-size of AC (Fig. 1C)
was responsible for the fracture-structure morphology of the resulting
nanocomposites and created a looser embedded network between AC
and NCS or between AC and NCP.
3.2. Effect of simultaneous surface modification of NC adsorbent on metal
removal
The metals adsorption efficiency of EFB-NC in removing Pb2+, Cd2+
and Cr3+ is shown in Fig. 3. The removal efficiency was enhanced with
the increase in the percentage ratio of NC in the matrixes of NCS/NCP
with 1% of NCP and 2% of NCS. The functionalization of AC on EFB-NC
did not improve the metal adsorption, which confirmed that the micron
size of AC disturbed the network structure of nano-scale cellulose as
reflected by the fracture-structure morphologies of NCS and NCP (refer
to Fig. 2) and a reduction in the active metal adsorption site, which
yielded a lower heavy metal performance. The optimum dose for heavy
metals removal is 2% of NCS with removal efficiencies of 80%, 9%, and
8% for Pb2+, Cd2+, and Cr3+, respectively. The notion that the ad-
sorption capacity toward Pb2+ is substantially higher than those of
other metals was attributed to the lower hydration energy of Pb2+
compared to those of other metals, which increased the ion interaction
toward the activated sites of super-adsorbent (Zhang et al., 2017).
During acid hydrolysis, the deconstruction of cellulose into nano-
cellulose will cause the simultaneous formation of sulfate groups on the
surface of NC (Septevani, Annamalai, & Martin, 2017). This simulta-
neously sulfonated surface modification on EFB-NC may enhance the
A.A. Septevani, et al.
Fig. 2. SEM images of selected EFB-NC of A. NCS; B. NCP; C. NCS/AC; D. NCP/AC.
heavy metal adsorption capacity. The sulfonated NC has a higher ability
of heavy metals adsorption, specifically for Pb2+ removal, than phos-
phoric NC because sulfonated NC possess a large number of binding
sites due to the high surface area of nanofibrils (Fig. 2). Previous studies
have investigated that the ionization degree of sulfonic groups was
relatively higher than that of other ionic groups, including, carboxyl- or
hydroxyl- active groups (Dong, Zhang, Pang, Liu, & Zhang, 2013;
Suopajärvi et al., 2015). Zhang et al. (2017) conducted a further sul-
fonation reaction on the NC back-bond, which revealed an increase in
the number of binding sites and accessibility of fibrils and an increase in
the diffusion of Pb2+ to active adsorption sites. The presence of a sul-
fonated active site influenced the heavy metal adsorption, which was
analogue to the effectiveness of the sulfonated sites on the surface NCS
due to acid hydrolysis in this experiment toward Pb2+ adsorption al-
though no further sulfonation reaction was applied. Another possible
mechanism is attributed to the electrostatic interaction between inter-
intra active adjacent hydroxyl groups on the origin surface of super-
adsorbent and the positive charge of the metal ions. Both mechanisms
can simultaneously occur because both active groups were present on
the surface of NCS. The possible mechanism due to the electrostatic
interaction between the positively charged metal ion and the negatively
charged ionic attachment on the surface of NC is represented in Fig. 4.
3.3. FTIR spectra analysis
The optimum metal binding sites attributed to the effectiveness of
ionic attachment on the surface of NC can be further investigated using
FTIR. Sulfonated attachment on NCS was greater than the phosphoric
surface modification of NCP. As shown in Fig. 5B, several new peaks at
4
Carbohydrate Polymers 229 (2020) 115433
1163 (S]O stretching) and 615 (SO2 scissoring) cm−1 are clearly ob-
served for NCS2 compared to those for raw EFB, which contributes to
the sulfonate group (Chieng, Lee, Ibrahim, Loo, & Then, 2017; Lambert,
Shurvell, Lightner, & Cooks, 1987). The results indicated that the sul-
fonate group successfully attached to the NC structure. In terms of the
presence of the phosphate group in NCP (Fig. 5A), although a new peak
of the vibrations band of P]O occurred at 1283 cm−1, the vibrations
band of PeOeC at 915 – 1055 cm−1 was not distinct (only observed in
shoulder form) (Chieng et al., 2017; Petreus et al., 2014). This finding
may indicate minor phosphate group functionalization on the surface of
the NCP structure.
The effectiveness of heavy metal adsorption of NCS and NCP can
also be explained by comparing NCS and NCP before and after heavy
metal adsorption treatment. The occurrence of interactions between NC
and metal ions can be explained based on the FTIR spectra shifting
peak. For example, the interaction between carboxylated-NC and Cd2+
was observed by the COO− stretching peak shifting from 1581 to
1630 cm-1 (Sharma et al., 2018). In agreement with the previous study,
two active sites of heavy metal ions—the origin inter-intra hydroxyl
group for both NCS and NCP; and sulfonyl and phosphoryl ion sites for
NCS and NCP—are observed in this study. In the case of the hydroxyl
group, both the NCS sample and the NCP sample exhibited OH spectra
shifting. The initial OH stretching peak of the NCS adsorbent shifted
from 3416 cm-1 to 3449 cm-1 after treatment. Similarly, the NCP OH
spectra shifted from 3440 cm-1 to 3435 cm-1.
In the case of the sulfonyl and phosphoryl ion sites for NCS and NCP,
a distinct shift of the spectra peak indicated different adsorption ca-
pacities for these two adsorbents. For the NCS sample, the spectra peaks
that correspond to the sulfate group were slightly shifted. For example,
A.A. Septevani, et al.
Fig. 3. Metal adsorption of EFB-based modified nanocellulose of: A. NCP and B.
NCS.
the initial S]O stretching peak of the NCS sample before Pb2+ ex-
posure was shifted from 1163 cm−1 to 1170 cm−1 of NCS after treat-
ment. The untreated NCS sample of the SO2 scissoring peak of 615 cm-1
also shifted to 621 cm-1, which indicated the occurrence interaction
between sulfonic ions and Pb2+ ions. Conversely, no spectra shift was
observed in the P]O peak of the sample after adsorption, which in-
dicates no significant heavy metal adsorption site on the sample of NCP.
This finding is consistent with the agglomerated morphology (Fig. 2)
which reveals looser and weaker binding sites of negatively charged
phosphoric ions as a function of lower heavy metal removal perfor-
mance of NCP compared to the case of NCS (Fig. 3).
3.4. Effect of initial metal concentration and contact time on heavy metal
removal
As previously explained, NCS possessed a higher heavy metal ion
adsorption for Pb2+ compared to that of NCP. In this study, the effect of
the initial metal concentration was investigated for Pb2+ adsorption
using optimum NCS2 adsorbent in the range of 1–100 ppm.
Fig. 4. Schematic of possible electrostatic interaction on the surface of adsorbent.
5
Carbohydrate Polymers 229 (2020) 115433
Fig. 6A shows that the adsorption capabilities of Pb2+ increased
with an increase in the initial metal concentration to 30 ppm, after
which the adsorption capacity remained constant. However, the op-
timum adsorption efficiency was achieved when the initial metal con-
centration was 30 ppm and the efficiency was 80%. As previously re-
ported by Dong et al. (2013); (Sharma et al., 2018), the increasing
initial metal ion concentration accelerated the diffusion of metal ion
onto the adsorbent to the optimum point, in which the adsorptive
capabilities of the active binding sites on the NC adsorbent attained the
saturation point. After the saturation point was achieved, the adsorp-
tion capacity remained constant while the adsorption efficiency gra-
dually reduced.
The contact time has an important role in the adsorption me-
chanism. The capabilities of the metal ion uptake in terms of the ad-
sorption efficiency and capacity were measured as a function of contact
time to investigate the optimum adsorption time. EFB-NCS2 super-ad-
sorbent at an initial Pb2+ ion concentration of 30 ppm was selected for
this study at the adsorption contact time from 30 to 300 s.
Fig. 6B shows that the increasing contact time gradually increased
the capability of EFB-NC to adsorb the metal ion. For short contact
times, the adsorption gradually increased due to the presence of active
sites of sulfonated NC on the surface of adsorbents. At the maximum
adsorption (150 s), the capabilities of Pb2+ removal attained 86% of
adsorption efficiency, while the adsorption capacity was 30.45 mg/g.
After equilibrium (180 s), a significant lead desorption occurred in
which the lead was released into the solution. The pH of the treated
solution decreased from 7 to 3 due to lead-sulfonic acid desorption from
the adsorbent surface. A similar Pb2+ desorption mechanism for the
additional contact time of exposure of sulfonated wheat nanocellulose
was observed by Suopajärvi et al. (2015).
3.5. Adsorption isotherm of NC super-adsorbent
In this study, Langmuir and Freundlich isotherm models were em-
ployed to understand the adsorption interaction between the adsorbent
(NCS2) and sorbed species (Pb2+) based on the steady state of ad-
sorption equilibrium. The Langmuir isotherm model describes a type of
monolayer adsorption with a uniform distribution of active sites, while
the Freundlich model is associated with multi-layer adsorption with
heterogeneous surface absorptive energies (Zhang et al., 2017).
The Langmuir model is expressed as
1 1 1 1
= +
Qe QM QM . KL Ce (3)
where KL is the Langmuir constant and QM is the amount of ad-
sorbed material at the saturation point.
The Freundlich model is expressed as
1
Ln Qe = Ln Ce + lnKF
n (4)
A.A. Septevani, et al. Carbohydrate Polymers 229 (2020) 115433

Fig. 5. FTIR of selected EFB-NC based on A. phosphoric acid hydrolysis and B. sulfuric acid hydrolysis.

where KF is the relative sorption capacity and n is the capacity of the

sorption process and distribution of active sites.
Based on the linear regression of the correlation coefficient (R2)
(Fig. S2, in the Supplementary Data), the Langmuir isotherm model
shows a better fit (R2 ≈ 1) than the Freundlich model. This best-fit
model suggested that the adsorption process occurred on the surface of
the solid following the monolayer sorption mechanism. Every single
sorption possesses an equivalent homogenous energy distribution and
interaction of adsorption with the sorbed species (Hubbe, Hasan, &
Ducoste, 2011).
Table 1 shows the parameter obtained from the model based on the
Langmuir and Freundlich models. Because the best fit of this study is
based on the Langmuir model, the QM (maximum capacity) of the lead
adsorption using 2 wt. % of CNCs was 24.94 mg/g. Compared to those
of similar studies on the use of sulfonated-based NC as a super-ad-
sorbent, the metal ion uptake capacity in this study was twice as large
as the nanocellulose from rice-straw without further sulfonation
(9.42 mg/g) (Kardam et al., 2013) and similar to that of Pb2+ removal
by the cellulose with a further sulfonation process (capacity of ap-
proximately 21 mg/g) (Dong et al., 2013).
SEM-EDX was also conducted to investigate the elemental mapping
of metal adsorption in the treated adsorbent and understand the ad-
sorption mechanism. Both the elemental mapping/distribution and the
% weight of elements are shown in Fig. 7. The elemental mapping

Table 1
Parameter obtained from Langmuir and Freundlich equations.
Langmuir

Fig. 6. A.) Effect of initial metal ion concentration on adsorption; and B) Effect QM =24.94 mg/g KL = 1.12 L/mg R2 = 0.9998
of contact time on metal ion adsorption at initial Pb2+ of 30 ppm.
Freundlich

nF = 5.56 KF = 4.99 R2 = 0.9936

6
A.A. Septevani, et al. Carbohydrate Polymers 229 (2020) 115433

Fig. 7. SEM-EDX Element Mapping of CNS after Pb adsorption.

Table 2 third cycle adsorption capacities were similar to those of a fresh sul-
COD properties. fonated NC from rice-straw with an adsorption capacity of 9.42 mg/g
Sample Code COD (mg/l) COD reduction (%)
(Kardam et al., 2013). This result suggests the potential of EFB as a
source of super-adsorbent material.
Control 1304.4 –
NCP05 704.44 46.00
3.7. Effect of NC-super-adsorbent on organic pollutant remediation
NCP05_AC05 434.44 66.69
NCP1 524.44 59.80
NCS05 418.89 67.89 To measure the organic pollutant remediation by the NC-based
NCS05_AC05 97.78 92.50 super-adsorbent, the Cisadane River was selected as the control sample.
NCS2 394.44 69.76
Cisadane is one of the most important rivers in Indonesia due to its
contribution to domestic purposes, industrialization and agriculture.
The growth in population and industrialization (more than 1400 com-
shows that the adsorbent matrixes are dominated by carbon (C) and
pany manufacturers) along the river and land development has caused
oxygen (O) as the main element in the NC matrixes. Silica (Si) is also
water pollution and the environmental deterioration of the Cisadane
detected as the source of the NC that is derived from lignocellulose
River. Table 2 shows that the COD concentration of the Cisadane River
sources of EFB that contain silica bodies embedded in fiber (Omar,
was 1304.4 mg/l, which indicates that people who live along the river
Mohammed, & Baharuddin, 2014). Element mapping of heavy metal
are not able to use the river without special treatment of its water.
ion was also detected in the EDS mapping in small amounts, which is
After treatment with NC-super-adsorbents, the COD concentration
expected because the initial amount of Pb2+ was on the scale of ppm.
of the control sample significantly decreased from 46 to 92.5% de-
This SEM-EDS element mapping confirms that the NC-adsorbent ad-
pending on the formulation (refer to Table 2). The maximum removal of
sorbed the heavy metals ion, in which the distribution was considered
COD was obtained using the functionalized NC/AC. SiO2 and Al2O3
to uniformly spread in the adsorbent matrix. This finding reveals the
functional oxidized groups were present on the surface of the AC from
equivalent sorption ability on every sorption site, as reflected by the
the black liquor sludge (Sari et al., 2017). The surface of silica (SiO2)
Langmuir model in the kinetic study (Table 1).
has a high affinity toward organic compounds. The central ion of sili-
cates (Si) has a very strong affinity for electrons; therefore, the oxygen
3.6. Reusability studies of super-adsorbent on metal removal atoms that are bound to the silicon ions have a low basicity, which
causes the silica surface to act as a weak acid (Mohan & Gandhimathi,
A regeneration study was performed using super-adsorbent from 2009). The oxygen atoms on the silica surface are free to react with
NCS2 with an initial lead concentration of 30 ppm. After regeneration water and form surface silanol (SiOH) groups, which reduces the level
with HCl solution followed by neutralization, the spent NCS2 super- of oxygen in treated water that is susceptible to oxidation; this reduc-
adsorbent was re-used for the next adsorption up to three cycles. The tion is a standard measurement in a COD test. The highest COD removal
lead removal capacity of the first cycle with fresh NCS2 adsorbent was was obtained after treatment with sulfonated NC with AC
28.58 mg/g. However, the adsorption capacities of NCS2 deteriorated (NCS05_AC05) with greater than 93% removal.
after regeneration. The regenerated NCS2 adsorbent possessed ad- In terms of pH level, the effect on the use of NCS and/or NCP and
sorption capacities of 10.34 mg/g and 7.80 mg/g after the second and their combination with AC on the final pH of the treated water was nil
third cycles, respectively (refer to Table S2 in the Supplementary Data). (refer to Fig. 8). The pH of all treated water can be maintained at
The deterioration of the adsorption capacity after the second re- 7.5 ± 0.2. However, a slight increase in the TDS level was observed for
covery, which exceeded 50% of the initial capacity, may be attributed the treated water by NC only (NCS and or NCP), and significant increase
to the notion that the super-adsorbent in this study was derived from in the TDS level was observed for the treated water by nanocomposite
easily degradable resources of EFB-NC. Nevertheless, the second and of NCS/AC and/or NCP/AC at 151 mg/l and 159 mg/l, respectively.

7
A.A. Septevani, et al.
Fig. 8. pH and TDS properties.
Based on the World Health Organization (WHO) standard for water
quality and control over water pollution, the maximum permitted TDS
and range of pH level are 1000 mg/l and 6–9, respectively. Thus, the
treated water quality after remediation by NCS and NCP and its com-
bination with AC remain within the water quality specifications.
The possibility of sulfate and phosphate release from the adsorbent
to the treated water was also investigated. The sulfate and phosphate
contents between the control water and the treated water were
17.49 mg/l and 21.43 mg/l, respectively, for NCS in the case of sulfate
release, while the increase in phosphate content for the treated water of
NCP ranged from 0.1 mg/l to 0.9 mg/l. The increase in the sulfate
content and phosphate content after adsorption by NCS and NCP re-
mained below the accepted standard values (250 mg/l and 5 mg/l, re-
spectively).
4. Conclusions
EFB-NC functionalized by sulfuric (NCS) and phosphoric (NCP)
surface modification and their combination with AC from EFB black
liquor has been successfully developed and investigated as a model of
an effective adsorbent that can act in heavy metal and organic pollutant
remediation. At only 2 wt.%, the formulated EFB-NCS super-adsorbent
shows a selective and remarkable metal adsorption to Pb2+ with a
maximum efficiency of 86% and an adsorption capacity of 24.94 mg/g
for a very short contact time of 180 s. These values were double those of
rice-straw NC with similar sulfuric acid hydrolysis and similar to that of
Pb2+ removal of cotton-based cellulose with a further sulfonation
process. The higher metal adsorption of EFB-NCS is attributed to a
larger number of binding sites in the high surface area of nanofibrils
(reflected by SEM analysis), effective simultaneous surface modification
of negatively charged sulfate (FTIR), and effective electrostatic inter-
action between active sites on the NCS surface and positively charged
heavy metals. The reusability studies show a deteriorated adsorptive
capacity of NCS after the second cycle; however, the results indicate a
performance that is similar to the performance of fresh sulfonated NC
from rice-straw in a similar study. Although no improvement in the
effect of AC functionalization on heavy metal ion adsorption was ob-
served, a significant organic pollutant performance in reducing COD
after NC/AC treatment to 93% was observed compared to that of the
8
Carbohydrate Polymers 229 (2020) 115433
neat NC super-adsorbent matrices (maximum of 70%). Finally, the pH,
TDS, sulfate and phosphate content of treated water after remediation
by all formulations of NCS and/or NCP and their combination with AC
fall within government water quality specifications.
Acknowledgements
The authors gratefully acknowledges the financial support of
Science and Technology Research Grant-Indonesian Toray Science
Foundation 2017 and Global Research Project of International
Environmental Research Institute 2019. The authors gratefully ac-
knowledge the facilities and scientific and technical assistance of the
Microscopy and Microanalysis of Research Center for Physics-LIPI.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.carbpol.2019.115433.
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