Accepted Manuscript

Title: Adsorption of cesium from aqueous solution by raw

and concentrated nitric acid −modified bamboo charcoal
Authors: Shahjalal Khandaker, Takahiro Kuba, Seiya
Kamida, Yuji Uchikawa

PII: S2213-3437(17)30065-9
DOI: http://dx.doi.org/doi:10.1016/j.jece.2017.02.014
Reference: JECE 1480
To appear in:

Received date: 8-11-2016

Revised date: 12-1-2017

Accepted date: 7-2-2017

Please cite this article as: Shahjalal Khandaker, Takahiro Kuba, Seiya Kamida, Yuji
Uchikawa, Adsorption of cesium from aqueous solution by raw and concentrated
nitric acid −modified bamboo charcoal, Journal of Environmental Chemical
Engineering http://dx.doi.org/10.1016/j.jece.2017.02.014

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 1

Adsorption of cesium from aqueous solution by raw and concentrated nitric acid
- modified bamboo charcoal

Corresponding Author: Shahjalal Khandaker

Corresponding Author's E-mail address: s.khandaker@duet.ac.bd Corresponding
Author's affiliation and address: Department of Urban and Environmental
Engineering, Graduate School of Engineering, Kyushu University, 744 Motooka,
Nishi-ku, Fukuoka, 819-0395, Japan.
Corresponding Author's other contact information:
Cell: +81-080-90644253, Fax: 092-802-3423
First Author: Shahjalal Khandaker
Order of Authors: Shahjalal Khandaker, Takahiro Kuba, Seiya Kamida, Yuji Uchikawa
Authors's affiliation and address:
Takahiro Kuba, Department of Urban and Environmental Engineering, Graduate School
of Engineering, Kyushu University, Japan.
Seiya Kamida, Department of Urban and Environmental Engineering, Graduate School
of Engineering, Kyushu University, Japan.
Yuji Uchikawa, Department of Urban and Environmental Engineering, Graduate School
of Engineering, Kyushu University, Japan.

Abstract
The study is conducted to explore the potential of bamboo charcoal (BC) as an adsorbent to
remove cesium from aqueous solution. Low temperature carbonized BC (500°C) is prepared
and the surface of the BC is modified with 70% concentrated boiling nitric acid (BC-AC).
Specific surface area, field emission scanning electron microscope (FESEM), fourier
transform infra-red (FTIR) spectroscopy, and point of zero charge (pH pzc) of BC and BC-AC
have been investigated in this study. The results demonstrate that BC-AC is enriched with
oxygen-containing functional groups but its porous structure and surface
 2

area are decreased when compared with the raw BC. Optimum cesium adsorption
conditions onto BC and BC-AC have been determined by investigating the contact time,
pH of solution, adsorbent dosage and initial solution concentration in batch adsorption
process. It has been observed that maximum cesium adsorption capacity is 0.17 and 45.87
mg/g for BC and BC-AC, respectively. It has also been observed that almost 100%
cesium could be removed from water at up to 400 mg/L concentrated cesium solution by
BC-AC whereas the removal capacity of cesium by BC is very poor. The experimental
adsorption data of both BC and BC-AC follows the pseudo-second-order kinetic. The
Freundlich adsorption equilibrium isotherm data is more appropriate than the Langmuir
isotherm for adsorption of cesium by BC. However, adsorption isotherm data for BC-AC
is a better fit with Langmuir isotherm than the Freundlich isotherm model. Furthermore,
the separations factor (RL) and the surface coverage (θ) for Langmuir isotherm confirms
that the proposed adsorption process is the most suitable for BC-AC. This study suggests
that BC-AC could be effectively used for the removal of cesium from environmental
water.
Keywords: Bamboo charcoal, surface modification, cesium, adsorption isotherm,
kinetic study.
1. Introduction
Removal of cesium from the environment has engrossed the concern of researchers all
over the world after the gigantic nuclear power plant disaster at Fukushima, Japan in
2011 which released a huge amount of radioactive materials into the water, soil, and air.
135
It is recognized that some isotopes of cesium such as Cs (t1/2=3,000,000 years) and
137
Cs (t1/2=30.17 years) have the long half-life. They are potentially hazardous for human
health as well as the terrestrial ecosystems due to their high solubility. Accumulating with
137
food and water, cesium metal especially Cs can be introduced into human body and
causes thyroid cancer and many other physical problems [1]. Therefore, the safe
discharge limit of cesium concentration in effluent should be taken under consideration
before discharging to the environment.
Hence, over the last few decades, considerable efforts have been employed to develop an
improved and sustainable process for the removal of cesium from contaminated water. In
general, several techniques have been widely applied for the removal of cesium from
 3

waste stream including precipitation, solvent extraction, membrane filtration, ion

exchange, and adsorption [2-4]. However, the drawbacks of these processes that they are
costly and inappropriate for large scale application of cesium removal [5]. Nevertheless,
among these processes, adsorption is one of the very promising processes for removal of
cesium in terms of high removal efficiency, process simplicity, applicability at low
concentrations, cost effectiveness, and abundance of various adsorbents, scope of batch
and continuous process application [6].

Although in previous years, different types of natural clay minerals such as zeolite,
betonies, montmorillonite, sericite, laterite, Turkish clays, cocoanut shell, coal, chitosan,
and walnut shell etc. have been studied for this purpose. These materials are not suitable
for widespread applications due to poor adsorption capacity and high cost [7-11]. For
example, Brown et al. [12] reported that the cesium removal efficiency of activated
carbon and zeolite were 0-10% and 40-70%, respectively. Moreover, in the recent years,
several synthetic and synthetic-polymer composite adsorbents have been developed for
cesium removal such as poly (acrylic acid-co-benzo-18-crown-6 acrylamide) hydrogel
[13], PVA (polyvinyl alcohol)-alginate encapsulated Prussian blue-graphene oxide
hydrogel beads [14], dibenzo-18-crown-6 ether immobilized mesoporous silica [15],
potassium titanium hexacyanoferrate [16], zeolite−polymer composite fiber [17],
strontium/yttrium tungstate and molybdate nanoparticles [44]. However, the preparation
and commercial application of these adsorbents is a little bit complicated and is not
efficient for water contaminated with a wide range of cesium concentration. Therefore,
further research is needed to introduce some renewable and low-cost biosorbents for the
removal of cesium in order to overcome the challenges.
Bamboo is one of the naturally abundant and inexpensive renewable bio-resources and
mostly found in south-east Asian countries. Recently, bamboo charcoal has attracted a great
deal of attention as bio-adsorbent due to its exclusive micro porous structure and 4 to 10
times larger surface area than those in wood charcoal [18]. The excellent adsorption
capability of bamboo charcoal for removal of different substance, including heavy metal is
already established [19]. In order to increase the adsorption performance, bamboo charcoal is
physically and chemically modified with different reagents. Generally, strong
 4

oxidizers such as KMnO4, HNO3, H2SO4 and H2O2 are commonly used in surface
modifications of activated carbons. Acidic modification of activated carbon introduces
surface oxygen as well as acidic functional groups on the surface of the adsorbents
which led to enhanced ion exchange capability in adsorption process with different metal
cations [20].
To the best of our knowledge, until now, no studies have been conducted for the removal
of cesium ions using bamboo charcoal although undoubtedly it is a potential adsorbent.
Therefore, in the present study, we attempt for the first time to explore the adsorption
capability of cesium from aqueous solution under several experimental conditions using
raw and concentrated nitric acid-modified bamboo charcoal along with the analysis of
their physiochemical characteristics.
2. Materials and methods
2.1Materials
Mosso bamboo (Phyllostachys pubescens) was used to prepare bamboo charcoal in this
study which was collected from the forest located near the Ito campus of Kyushu
University, Japan. All reagents and chemicals used in this experiment were of analytical
grade purity and purchased from Wako Pure Chemical Industries Ltd, Japan. Ultrapure
water (Elix Millipore, Japan) was used throughout the experiments. All working solutions
were newly prepared with ultrapure water before experiments.
2.2 Preparation of bamboo charcoal
Sufficiently dry bamboo was cut into approximately cubic size (12X8X5 mm) and boiled for
6 hours (2 hrs X3) with distilled water and dried at 110 ˚C overnight. Carbonization was
performed following the procedure mentioned by Sakuma et. al [21]. Briefly, BC was
burned at 500 ˚C for 3 hours with heating rate of 5 ˚C/min and nitrogen flow of
0.150 m3/min in a muffle furnace (Yamato FP32, Japan). BC was crushed by ball mills machine (Mixer
Mill MM 400, RETSCH, Japan) and sieved at 75 microns. This raw bamboo charcoal was termed as BC.
Moreover, the percentage of the yield of the BC was also calculated using the following formula.
ℎ ℎ

%= × 100%
ℎ ℎ

2. 3 Surface modification
 5

BC was chemically modified by concentrated (70%) nitric acid. 10 g of dried BC was

allowed to boil at 120 ˚C in 100 ml HNO3 (solid liquid ratio=1:10) for 6 h in a hot plate
and washed with ultrapure water carefully using a vacuum filter for several times until
the pH was unchanged. The pH of the washed water was about 5.0-6.0. Modified BC was
dried in an air circulated oven at 110 ˚C for 12 h and this was named as BC-AC. Sample
was stored into a desiccator for further experiments.
2. 4 Characterization methods
Different physical and chemical characterization techniques that were employed for the
samples are stated below.
2.4.1 Surface area and porosity analysis
The specific surface area, pore volume and average pore size were estimated based on the
nitrogen adsorption-desorption isotherms at −196 °C (77 K) by using BELSORP-mini II,
Japan according to the BET (Brunauer, Emmett and Teller) method [22]. Prior to the
measurement, samples were out gassed at 110 ˚C for 3 h in the presence of nitrogen (N2)
gas flow.

2.4.2 Field emission scanning electron microscope (FESEM)

The surface morphology and porous structure were analyzed using an ultra-high
resolution field emission scanning electronic microscope (UHR FE-SEM, Model:
SU8000, HITACHI, Japan). All images were taken at accelerating the voltage of 1.0 kV.
2.4.3 Fourier transform infra-red (FTIR) spectroscopy analysis
The qualitative analysis of surface functional groups of BC and BC-AC was carried out
using FTIR (FT/IR-620, JASCO, Japan) in potassium bromide (KBr) pellet method.
Oven dried samples were mixed with KBr in the ratio of 1:100 and ground to make
fine homogenous powder and compressed to prepare pellets for spectrophotometer
-1
analysis. The spectra were recorded from 4000 to 400 cm .
2.4.4 Determination of the point of zero charge (pHpzc)
The pHpzc of samples was determined following the pH drift method described by Yang et.
al. [23]. Shortly, a solution of 0.005 M CaCl2 was boiled to remove dissolved CO2 and
then cooled to room temperature. The pH was adjusted to 2.0, 4.0, 6.0, 8.0, 10.0 and 12.0
by adding 0.1M NaOH or HCl. 60 mg of samples was added into 20 ml of the pH-
 6

adjusted solution and equilibrated for 24 h in a reciprocating shaker at room temperature.

Afterward, the suspension was filtered, and then solid residue was separated. The final
pH was measured and plotted against the initial pH. The pH at which the curve crosses
the pH initial = pH final line is considered as pHPZC.

2.5 Batch adsorption study

2.5.1 Preparation of solution
133
1000 mg/L stock solution of Cs was prepared by dissolving non-radioactive ( Cs)
CsCl (FW: 168.36 g) into ultrapure water for the sake of safety. Stock solution was used
to prepare required concentration of cesium by appropriate dilution.
2.5.2 Adsorption experiments
All batch experiments were conducted on a reciprocating shaker (EYELA Multi shaker
MMS–3010, Japan) at 20 ˚C, with a rotating speed of 140 rpm. Adsorbate and adsorbent
ratio was maintained 1:100 (0.3 g adsorbent in 30 ml cesium solution except adsorption
kinetic study). Each experiment was triplicated to check the reproducibility, and the
average value was considered for data analysis. The first experiment was performed to
find out the equilibrium contact time (adsorption kinetic). 1.5 g of BC added into a flask
containing 150 ml (100 mg/L concentrated) cesium solution and supernatants were
withdrawn using a syringe (about 5 ml) at predetermined time intervals up to 6 h. The
function of pH on adsorption was investigated in the second experiment by varying the
pH of initial cesium solution from 2.0 to 12.0 using 0.1M HCl or NaOH during the
equilibrium adsorption time. In the third experiment, the effect of adsorbent dose (0.1 g,
0.2 g, 0.3 g, 0.4 g and 0.5 g) was investigated with 100 mg/L cesium solution at
maximum adsorption pH and equilibrium contact time. The fourth experiment was
carried out to study the adsorption isotherm by varying the initial concentrations of
cesium solution (20 mg/L, 50 mg/L, 100 mg/L, 200 mg/L, 400 mg/L, 600 mg/L, and 800
mg/L) at the previous conditions.
After the adsorption period, the solution was filtered through 0.45 µm membrane filter by
syringes and then the filtrates were preserved for analysis. Initial and final concentration
 7

of cesium solution after adsorption was analyzed by atomic adsorption

spectrophotometer (AAS, AA-7000, SHIMADZU, Japan).
2.5.3 Calculation of removal percentage and adsorption ability
The removal percentage of cesium and the amount of cesium adsorbed per unit weight of adsorbent
(mg/g) were calculated from the following equations:
(C0−Ct)
(1)
R% = × 100

C0

qt =
(C 0−C t)V

(2)
m

Where 0 and (mg/L) are the initial and final concentrations of cesium in the solution at time t, respectively. R is the cesium removal
percentage, V is the volume of the cesium solution (L), and m is the mass of the adsorbent used in the adsorption experiment (g).

2.6 Adsorption kinetic study

To understand the mechanisms of adsorption kinetic, pseudo-first-order and pseudo-
second-order kinetic models were applied as is stated below.
2.6.1 Pseudo-first-order equation
The rate constant for adsorption process can be calculated by using pseudo-first-order equation [4]:
K1
(3)
log(qe − qt) = logqe − ( )t
2.303

Where, and are the amount of cesium adsorbed (mg/g) at equilibrium and at time t, respectively. K1 is the rate constant of adsorption (min-1).
The values of the first-order rate constant ( 1 ) and theoretically can be calculated from the slope and the intercept of the plot of log( − )
versus t, respectively.

2.6.2 Pseudo-second-order equation

The pseudo-second-order kinetic model can be represented by the following equation
[24]:
t 1 1 (4)
= 2 + t

q Kq q
t 2 e e

Where the theoretical equilibrium adsorption capacity (mg/g) and the pseudo-second-order rate constant 2 (g/mg.min) can be measured from the slope and the intercept of

plot versus t, respectively.

 8

2.7 Adsorption isotherm study

Currently, Langmuir and Freundlich isotherms are commonly used among the several
adsorption isotherms. The equilibrium data that was obtained from cesium adsorption on
BC and BC-AC was analyzed by these adsorption isotherm models.
2.7.1 Langmuir`s isotherm
The linear form of Langmuir`s adsorption isotherm model is written below:
C
e
= 1
+ 1
(5)
C
e
q
mK
qe qm

Where (mg/g) and (L/mg) are the Langmuir constant related to the maximum amount of
cesium adsorption and energy of sorption, respectively. is the amount of adsorbed cesium
(mg/g) and is and concentration of cesium in solution (mg/L) at equilibrium time.
The separation factor (RL) is an important dimensionless parameter indicating the favorability of
the adsorption. It is based on the Langmuir equation and is also calculated following this equation [25,
26].
1 (6)
RL =

(1+ KLCo)

C0 represents the different initial concentrations of cesium solution in the adsorption

isotherm experiments.
The value of indicates the isotherm to be either unfavorable (RL > 1), linear (RL = 1), favorable (0< RL < 1) or irreversible (RL = 0).

Another factor, surface coverage (θ) can also assist to comprehend the characteristics of
the adsorption process. The equation is shown below [27].
K C
θ = L i 1+KLCi

Where
θ is the surface coverage.
is the Langmuir constant Ci
(7)

is the different initial concentration of cesium and

2.7. 2 Freundlich isotherm
The linearized form of Freundlich isotherm can be determined as follows [28].
1 (8)
logq e = logK F + logC e
n
 9

Where (L/mg) and n are the Freundlich constants that are related to adsorption capacity and adsorption intensity, respectively. The linear plot of log
versus is used to calculate the Freundlich constants.

3. Results and discussion

3.1 Evaluation of surface characteristics
3.1.1 Carbon yield, porosity and surface area analysis
Physical characteristics including porosity, surface area and pore size distribution are
considered as essential characteristics of bamboo charcoal for adsorption
performance. Results for the carbon yield, BET surface area, total pore volume and
pore size distribution of BC and BC-AC are listed in Table 1.
The carbon yield of the BC was found to be 30.8%. The surface area and total pore
2 3 2 3
volume of BC declined from 312.5 m /g and 0.1518 cm /g to 2.3 m /g and 0.0079 cm /g
in BC-AC, respectively. However, the average pore size increased remarkably, from 1.94
nm to 13.96 nm. The results reveal that BET surface area and total pore volume reduced
significantly due to the nitric acid oxidation. Several studies demonstrated that the boiling
nitric acid treatment could dissolve some permitted inorganic components of adsorbents
and produce oxygen containing functional groups which may have led to the blockage of
pore opening [29, 30]. Moreover, some large molecules of residual humic-type sticky
compounds that were produced during the oxidation process and adhered onto the surface
of the modified BC. This may have caused the narrowing of pore volume. Other factors
such as electrostatic repulsion of surface probe molecules (nitrogen), erosion of carbon
by nitric acid etc. could be responsible for the reduction of pore volume. On the other
hand, corrosive nitric acid may have destroyed the micropores (< 2 nm) of the modified
BC. Therefore, the surface area decreased significantly but the mesopore (2-50 nm) or
macropore (> 50 nm) were not damaged severely. Ultimately, micropores were changed
into mesopores or macropores in the nitric acid oxidation process. This may have been
the reason for the increase of the pore opening in the modified BC [45].
3.1.2 FESEM observations
The FESEM images of BC and modified BC illustrated their morphology and these are
shown in Fig. 1(a, b). It can be clearly observed that the surface of the BC was highly
porous nature. However, in modified BC, exterior porous structure almost disappeared
 10

and pores were clogged. Moreover, the changing of the surface structure of the modified
BC already proved by the surface porosity analysis.
3.1.3 FTIR analysis
The FTIR spectral analysis is important to recognize the functional groups which are
accountable for adsorption. The comparison of FTIR spectra for BC and BC-AC was
illustrated in Fig. 2. Compared with the FTIR spectrum of BC, there are some peaks that
were transferred, extricated, and new peaks appeared on the surface of the modified BC.
-1
The spectra for –OH (hydroxyl groups) in the region of 3413.39 and 3667.94 cm on BC
were slightly shifted on BC-AC and simultaneously, the same type of functional groups
-1
were introduced at 3856.93 and 2481.94 cm [31]. This bond is important to amplify the
-1
cesium adsorption capacity of adsorbents. The signals created at about 1711.61 cm and
-1
1611.31 cm were considered for the newly formed carboxylic acid, aldehyde, and
ketone (C=O) groups which might have had a dominating influence on adsorption of
cesium. In general, acidic functional groups on the surface could improve the ion
exchange capacity of adsorbents during adsorption process.
-1
However, in finger print region (below 1000 cm ), some minor peaks for alkene (C-H)
bending were shifted where the adsorption process cannot be clearly assigned for a
particular vibration because of their complex interacting vibration systems [32]. The
relevance elucidation of a shift in the spectra, depletion, and disappearance of peaks may
be changing their surface chemistry due to the oxidation of BC with concentrated nitric
acid.

3.1.4 The point of zero charge (pHPZC)

The point of zero charge is one of the physical parameters that depend on the chemical
and electrical potential of the functional groups of the solid particles surface. Fig. 3
shows the effect of pH on the point of zero charge of raw and modified BC, respectively.
The pHpzc of raw BC and modified BC were 10.20 and 2.10, respectively. The extremely
low pHpzc on BC-AC might be due to the deposition of a large amount of acidic
functional groups on the surface during oxidation. As a consequence, surface acidity
increased on BC-AC and that led to increase the anionic properties. This characteristic of
 11

BC-AC could improve the anion exchange capability with cesium cation during the
adsorption process.
3.2 Adsorption studies for cesium
3.2.1 Effect of contact time
The equilibrium contact times for BC and BC-AC were shown in Fig. 4. The adsorption
reached its maximum capacity within a short time period. For BC-AC, although cesium
adsorption stabilized within short time period, the equilibrium contact time was
considered to be 2.0 h. The short equilibrium time of BC-AC indicates that its surface
was strongly anionic in nature and could greatly reduce the application time. On the
other hand, the equilibrium contact time for BC was considered to be 5.0 h. After the
equilibrium time, the adsorption of cesium by BC and BC-AC was 1.93 mg/g (19.43 %)
and 9.11 mg/g (90.97%), respectively for 100 mg/L concentrated cesium solution.
The fast adsorption at the beginning stage might be due to the higher concentration
gradient between the adsorbate in aqueous solution and adsorbate in adsorbent as there
must be increased available vacant sites in the initial stage [33]. Further experiments were
conducted maintaining the equilibrium time of the respective adsorbents and the data
obtained from the effect of contact time was further used to investigate the kinetic of
cesium adsorption.
3.2.2 Effect of pH
The initial pH of the solution is one of the important dominating factors for the
adsorption process of cesium and other heavy metals because of its effect on the
adsorbent surface charge and the degree of protonation [34]. Fig. 5 shows that the
adsorption of cesium strongly depends on the pH of the adsorbate solution. The
maximum amount of adsorption was found at the pH value of 12.0 for BC and 4.0 and
above for BC-AC.
It was observed that for BC-AC, the cesium adsorption accelerated when the pH value
increased from 2.0 to 4.0. The further increase of initial pH up to 12.0 in solution did not
enhance the cesium adsorption which indicates that it reached the maximum uptake at
pH 4.0. This is perhaps due to the fact that the surface of this adsorbent contained highly
negative charges for the presence of several oxygen containing functional groups such as
carboxylic, aldehyde, ketone, hydroxyl etc. The existence of these anionic groups on
 12

surface makes it favorable to achieve the optimum adsorption at a comparatively lower

pH. This phenomenon is also supported by Huang et. al. [35]. They reported that the
higher adsorption by modified BC at lower solution pH is obviously related to the
changing of surface charge due to the larger number of acidic functional groups. At
higher pH, surface charge was partially neutralized and adsorption did not increase. On
the other hand, for BC, the adsorption of cesium at higher pH clearly indicates that
+
under higher H ion concentration in the solution, cesium ions have to compete with
excessive protons in the adsorbents, causing lower cesium uptake [36]. Moreover, when
pH of the cesium solution increases, the number of protonated adsorption sites decrease
with increasing negative charge on the adsorbent. It is very clear that the higher number
of negative charges on the surface enhances the cationic cesium ion adsorption because
of electrostatic attraction mechanism.
Furthermore, the effect of pH on adsorption can be explained by pHpzc of the adsorbent.
The pHpzc of BC and BC-AC were 10.20 and 2.10 respectively. The surface charge of the
adsorbents was positive when the pH of the adsorbate solution was lower than the pHpzc
value and the pH was above the pHpzc when the surface of the adsorbents became
negative. Therefore, when the pH of the cesium solution reached above the pHpzc value
that led to speeding up of the adsorption of cesium. Therefore, further adsorption
experiments were performed at the pH 5.0 for BC-AC and 12.0 for BC to optimize the
adsorption.
3.2.3 Effect of adsorbent dosage
Adsorption of cesium at different adsorbent doses (0.1-0.5 g adsorbent in 30 ml cesium
solution) was investigated at a constant concentration (100 mg/L) and their respective
optimum pH of cesium solution. Fig. 6 demonstrates that the percentage of cesium uptake
increased from 15.98 to 46.85% for BC. Similarly, adsorption was also increased from
71.37 to 87.15 % for BC-AC with increase adsorbent doses. When the amount of
adsorbent increased in the cesium solution, active sites would be abundant on the surface
areas to attract cesium ions.
However, for BC-AC, the higher amount of adsorbents in the solution, led to increase
larger amounts of surface acidic functional groups in turn to increase the cesium
adsorption through ion exchange mechanism. Similar phenomenon for the effect of
 13

adsorbent dose on adsorption was also observed by other researchers [35, 37].
Nevertheless, the cesium removal percentage did not increase with the same trend with
increasing adsorbent dose. This is maybe one of the reasons of unsaturation of adsorption
sites through adsorption process.
3.2.4 Effect of initial cesium concentration
A wide range of cesium concentration (20 mg/L to 800 mg/L) was used to perform the
adsorption experiment to investigate the effect of initial concentration on adsorption for
BC and BC-AC (Fig. 7). For BC, the removal range was 51.33% to 19.17% whereas for
BC-AC, cesium removal range was 99.94% to 60.47%. The results reveal that almost
100% cesium removal is possible up to 400 mg/L concentrated solution by using modified
BC although above this concentration, cesium removal efficiency gradually decreases. It
+
can be explicated that the modified BC can exchange the Cs in solution with the surface
functional groups (carboxylic acid, aldehyde, ketone etc.) that formed in the surface due
to nitric acid oxidation. Therefore, the adsorption mechanism of modified BC can be
considered as chemisorption which increases the removal efficiency of cesium. However,
the adsorption by BC can be addressed as physisorption as only the surface of BC is
involved with the adsorption process and this adsorption is comparatively very lower than
the chemisorption.
On the other hand, although the percentage of adsorption reduced, the adsorption capacity
increased with increasing initial cesium solution concentration (47.40 mg/g at 800 mg/L
for BC-AC). This is because of the larger driving force at higher initial concentration to
overcome the mass transfer resistance of cesium ion between aqueous and solid phase
[38]. The data obtained from this experiment were further applied to identify the
cesium adsorption isotherms.
3.3 Kinetic studies
Among the several kinetic models, the experimental data obtained from the effect of
contact time (360 min) on adsorption was used to evaluate the mechanism of adsorption
kinetic by pseudo-first-order and pseudo-second-order models. The adsorption of cesium
does not follow the pseudo-first-order kinetic due to the very large variation of the
experimental and calculated values of (data is not demonstrated).
 14

The comparison of the results including the correlation coefficients, obtained from the
pseudo-second-order kinetic for both BC and BC-AC are presented in Table 2. The
correlation coefficients for BC and BC-AC were 0.999 and 0.963, respectively and also
the experimental value of was comparable with the calculated value (Fig. 8 a and b).
Hence, it can be firmly asserted that, the adsorption process of both BC and BC-AC
followed a pseudo-second-order kinetic model.
3.4 Adsorption isotherm studies
Adsorption isotherms were applied for a wide range of initial concentration of cesium (20
mg/L to 800 mg/L) with a fixed amount of adsorbents (0.3 g) for BC and BC-AC. The
equilibrium data were analyzed using the two popular adsorption isotherms, Freundlich
and Langmuir model (equation 5 and 8) to justify the suitability of isotherm. The
isotherms adsorption parameters are presented in Table 3.

2 2
It is clearly seen that the Freundlich isotherm (R =0.981) is more appropriate than the Langmuir isotherm (R =0.901) for adsorption of

cesium by BC although the both isotherms can be applied to explain the adsorption mechanism. On the other hand, for BC-AC, the higher

2 2
value of regression coefficients (R ＝0.991) suggests that the Langmuir isotherm can be applied instead of Fruendlich isotherm (R =0.867)

to fit the experimental adsorption parameters for the uptake of cesium. The maximum calculated Langmuir isotherm adsorption capacity

was 45.87 mg/g for BC-AC.

The suitability of the adsorption process of BC-AC can be explained by the separation factor according to the Langmuir
isotherm equation. The different values of separation factor (RL) were calculated according to the equation no. 6 and
plotted against the various initial cesium concentrations (Fig. 9). The values of RL ranging from 0 to 1 confirm that the
modified BC is favorable for the adsorption of cesium under the conditions of a wide range of initial concentrations.

The adsorption characteristics of cesium ion onto BC-AC can be further understood by the
surface coverage (θ) which is connected to the Langmuir isotherm. Surface coverage
against initial concentration was plotted in Fig. 10. Initially, the surface coverage increased
promptly with the increase of initial concentration and gradually decreased when the
concentration went beyond 200 mg/L as the value of θ close to 1. This actually indicates
that the surface of the adsorbent closely covered with a monomolecular layer.
 15

Therefore, BC-AC could be used more efficiently to remove cesium ions from aqueous
effluent.
It can be summarized that considering the higher correlation coefficient, the suitable
range of separation factors and surface coverage proved that the cesium adsorption
by BC-AC was a best fit the Langmuir adsorption isotherm equilibrium data.
A number of studies have been conducted to remove cesium from aqueous solution using
the different types of natural adsorbents that were compared with our study (Table 4).
The comparison shows that the outstanding adsorption capacity of nitric acid modified
bamboo charcoal introduced it as a promising bioadsorbent for cesium removal from
aqueous solution.
4. Conclusions
Recent research attention in the development of economical and renewable biomaterials
for removal of hazardous cesium from the contaminated water led us to investigate the
adsorption of cesium by using raw and nitric acid-modified bamboo charcoal. Wide
range of characterization, including surface area measurement, FESEM observation,
FTIR analysis, and pHpzc revealed that a large number of acidic functional groups were
generated on the surface of BC with lower surface area due to the boiling nitric acid
treatment and this significantly enhanced the cesium uptake. The maximum adsorption
capacity was 0.17 mg/g for BC and 45.87 mg/g for BC-AC. The maximum cesium
removal efficiency was almost 100% at up to 400 mg/L concentrated cesium solution
(adsorbent: adsorbate solution=1:100) by BC-AC. This result proved that the modified
BC is applicable at low level to high level cesium contaminated water. The adsorption
isotherm for BC-AC was a better fit for Langmuir isotherm compared to Freundlich
isotherm. The calculated separation factor (RL) was achieved from 0-1.0, which
confirms that the adsorption process was satisfactory for BC-AC. Furthermore,
adsorption mechanism of modified BC can be described properly by pseudo-second-
order kinetic model. The experimental findings suggest that modified bamboo charcoal
could be an ideal biosorbent for cesium removal from water. Practical application of the
bamboo charcoal, according to the developed procedure for large scale cesium
contaminated waters, might be interesting.
 16

Acknowledgement
The authors are grateful to Dr. Tsuyohiko Fujigaya, Department of Applied Chemistry,
Graduate School of Engineering, Kyushu University, Japan for his assistance with
surface area measurement. The authors are also indebted to Dr. Midori Watanabe, Central
Analysis Center, Ito campus, Kyushu University, Japan for her cordial support to FTIR
analysis and FESEM image observation.

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 22

Figure captions:
Fig. 1: FESEM image of (a) BC and (b) BC-AC.
Fig. 2: FTIR spectra of BC and BC-AC.
Fig. 3: pHpzc for BC and BC-AC.
Fig. 4: Effect of contact time on cesium adsorption by BC and BC-AC.
Fig. 5: Effect of pH on cesium adsorption by BC and BC-AC.
Fig. 6: Effect of adsorbent dose on cesium removal by BC and BC-AC.
Fig. 7: Effect of initial concentration on removal of cesium by BC and BC-AC.
Fig. 8: Pseudo-second-order kinetic model for adsorption of cesium on (a) BC and (b)
BC-AC.
Fig. 9: Plot of separation factor (RL) against initial concentration on cesium adsorption by
BC-AC.
Fig. 10: Surface coverage for cesium adsorption plot against initial concentration by BC-
AC.

Figures

(a) (b)
Fig. 1: FESEM image of (a) BC and (b) BC-AC
23
24
25
 26

250
50 y = 0.5181x + 14.025
200 R² = 0.9703
40 y = 0.11x + 0.0385
t/qt 150

t/qt (min g/mg)

30 R² = 0.9999
(min
g/mg) 20 100

10 50

0
0
0 50 100 150 200 250 300 350 400
0 50 100 150 200 250 300 350 400
Time, t (min) Time,t (min)

(a) (b)
Fig. 8: Pseudo-second-order kinetic model for adsorption of cesium on (a) BC (b) BC-AC
27
 28

Tables
Table 1: Carbon yield, specific surface area and pore properties of BC and BC-AC.
Parameters BC BC-AC
Carbon yield % 30.8 -
2 312.5 2.3
Specific surface area (m /g)
3 0.1518 0.0079
Pore volume (cm /g)
Average pore diameter(nm) 1.94 13.96
 29

Table 2: Pseudo-second-order adsorption rate constants and calculated and experimental

values.

Adsorbent Experimental K2(g/mg min) Calculated

value ( / ) value(mg/g)
BC 1.927 0.017 1.972 0.963

BC-AC 9.021 0.314 9.090 0.999

 30

Table 3: Langmuir and Freundlich isotherms parameters for the adsorption of cesium
onto BC and BC- AC.
 31

Parameters Adsorbents
BC BC-AC
Experimental value mg/g 14.85 48.00
Langmuir Isotherm (mg/g) 0.172 45.87
(L/mg) 1.652 0.278
2
0.901 0.991
Freundlich Isotherm (mg/g) 0.233 10.56
1 0.6397 0.2628

2
0.981 0.797
 32

Table 4: Comparison of maximum adsorption of cesium ion by BC and BC-AC and other
bioadsorbents found in the literatures.

Adsorbents (mg/g) Reference

Coal and chitosan 3.00 [9]
Chabazite and activated carbon mix 8.19 [39]
Cocoanut shell activated carbon 0.76 [10]
Brewery’s waste biomass 10.10 [40]
Almond shells 12.63 [41]
Laterite 26.58 [11]
Moss 6.00 [42]
NaOH treated moss 17.00 [42]
Pine cone 5.75 [43]
Touene-ethanol extracted pine cone 7.01 [43]
zeolite A 207.47 [46]
A-X zeolite blend 150.15 [47]
Red clay 4.91 [48]
Bamboo Charcoal 0.17 [This study]
Nitric acid-modified bamboo charcoal 45.87 [This study]