Microchemical Journal 113 (2014) 5963

Contents lists available at ScienceDirect

Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Characterization of water bamboo husk biosorbents and their application

in heavy metal ion trapping
Hillary B. Asberry a, Chung-Yih Kuo b, Chin-Hau Gung c, Eric D. Conte a,, Shing-Yi Suen c,d,
a
Department of Chemistry, Western Kentucky University, Bowling Green, KY 42101, USA
b
Department of Public Health, Chung Shan Medical University, Taichung 402, Taiwan
c
Department of Chemical Engineering, National Chung Hsing University, Taichung 402, Taiwan
d
Center of Nanoscience and Nanotechnology, National Chung Hsing University, Taichung 402, Taiwan

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

Article history: The use of plant-based biosorbents for removing environmental pollutants from water is gaining widespread at-
Received 12 October 2013 tention. In this paper, the 45250 m biosorbents were prepared from the husks of water bamboo (Zizania
Received in revised form 18 November 2013 caduciora Turcz.), with a pore size distribution of 5.713.8 nm and surface area of 1.87 m2/g. These water bam-
Accepted 18 November 2013
boo husk particles contained OH and COOH groups and had a zero point of charge between pH 2 and 3. An opti-
Available online 27 November 2013
mal negative charge on particle surface was achieved at pH 5. Moreover, their cation exchange capacity was
Keywords:
about 1.3 meq/g. When trapping metal ions at pH 5, the prepared biosorbents exhibited strong afnity to
Water bamboo husk Cu2+, Cr3+, Pb2+, and Fe3+. Adsorption isotherms and breakthrough studies were generated for Fe3+ (stronger
Biosorbent afnity) and Ni2+ (weaker afnity), and the interpretation of results indicated that the water bamboo husk par-
Heavy metal ions ticles are well suited to trap these ions at low concentrations. Also, column trapping of metal ions (breakthrough
Adsorption isotherm volume: 75 bed volume for Ni2+ and 90 bed volume for Fe3+) proved much more efcient than static adsorption.
Breakthrough curve 2013 Elsevier B.V. All rights reserved.

1. Introduction It is essential to remove these heavy metal ions from industrial

Heavy metal ions are usually released into streams as waste prod-
ucts from industries such as mining operations, metal plating facilities,
tanneries, etc. [1,2]. Heavy metals from these polluted streams can
then enter into the surrounding soil, surface water, and groundwater.
When the polluted water is consumed by living organisms, the toxic
heavy metals can accumulate and cause harm [3]. Some commonly ex-
pelled heavy metals are nickel (Ni) and copper (Cu). Nickel can be
discharged into the environment from silver renery, storage battery,
electroplating, and zinc base casting industries. The toxicity of nickel
has been documented to cause cancers of nose, lung and throat [4] as
well as other conditions such as gastrointestinal distress, pulmonary -
brosis, and skin dermatitis [5]. Many of the copper ions released into the
environment are a consequence of metal cleaning and plating baths,
paper board mills, wood-pulp production, and fertilizer industries.
When the body intakes an excessive amount of copper, it accumulates
in the liver and can result in cirrhosis [2,6]. Copper poisoning has also
been correlated with various conditions such as hemochromatosis and
gastrointestinal catarrh. Moreover, copper is harmful to aquatic species
even in trace amounts [7].
Corresponding author. Tel.: +1 270 7456019; fax: +1 270 7456293.
Correspondence to: S.-Y. Suen, Department of Chemical Engineering, National Chung
Hsing University, Taichung 402, Taiwan. Tel.: +886 4 22852590; fax: +886 4 22854734.
E-mail addresses: eric.conte@wku.edu (E.D. Conte), sysuen@nchu.edu.tw (S.-Y. Suen).
sources before they enter the environment. Common removal processes
include chemical precipitation, ion exchange, adsorption, membrane l-
tration, electrochemical ltration, etc. [1,2,8], among which adsorption
is considered a simple and efcient method. Many natural biosorbents
that are inexpensive and region-specic agricultural wastes are now
being used popularly and gaining widespread attention [2,9]. Plant
waste biosorbents that demonstrated the ability to adsorb heavy
metal ions are pomegranate peel [1], gooseberry fruit [2], banana peel
[10], peanut hull [11], Ponkan mandarin peel [12], papaya wood [13],
almond husk [14], sunower leaves [15], wheat shell [16], and so on.
In Taiwan, the husks of water bamboo (Zizania caduciora Turcz.)
are one of the major agricultural wastes. Water bamboos grow best dur-
ing the summer when the climate in Taiwan is warm, humid, and sunny.
Their husk wastes are readily available, free of expense, and eco-
friendly. To reuse water bamboo husk wastes in special applications
has become an important issue in Taiwan. In a previous literature [17],
the bers obtained from water bamboo husks were characterized
by nuclear magnetic resonance, elemental analysis, pyrolysis, and ther-
mal techniques, which had veried their applicability in pulping and
composite materials. In the present study, water bamboo husks would
be utilized to prepare the biosorbent particles for trapping heavy
metal ions from water. To the best of our knowledge, the use of water
bamboo husks as biosorbent material has not been reported before. In
this paper, the characterization of water bamboo husk particles and
their potential on the removal of heavy metal ions would be systemati-
cally investigated.

0026-265X/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.microc.2013.11.011
60 H.B. Asberry et al. / Microchemical Journal 113 (2014) 5963

2. Experimental

2.1. Materials

The outer husks of water bamboo were the wastes of local markets
in Taichung, Taiwan. Solutions of Ni2+ and Fe3+ were made with deion-
ized water using reagent grade salts (NiSO46H2O and FeCl36H2O, both
purity 99%) from SHOWA. The pH was adjusted to 5 with 0.1 M sodium
hydroxide and nitric acid (SHOWA) using a Istek Model 720P pH meter.
Moreover, a mixture of multiple ions adopted in this study was the ICP
Multi Element Standard Solution IV from Merck (USA). Each ion con-
centration was 1000 10 mg/L. This solution was diluted and its pH
was adjusted to 5 prior to use.

2.2. Preparation and characterization of water bamboo husk particles

Water bamboo husk was cut into small pieces (about 1 cm), washed
with deionized water, and then dried in an oven at 60 C for 24 h. An in-
dustrial grinder (RT-02A, Rong Tsong Precision Technology, Taiwan)
was adopted to grind the chopped husks into powders for 1 min,
which was repeated 3 times. The resulting particles were rinsed
with deionized water and dried in the oven at 60 C for 24 h. Particles
ranging from 45 to 250 m were obtained using a Retsch sieving
machine (Mesh no. 60 (250 m) and no. 325 (45 m), Germany).
For decoloration, the water bamboo husk particles were placed in
1 L of fresh deionized water and washed with an ultrasonic cleaner
for 30 min, which was repeated 3 times in sequential. The particles
were then immersed in 1 L of fresh deionized water and heated at
50 C for 24 h. Finally, the particles were ltered from the solution,
and dried in the oven at 60 C for 24 h. The photos for pristine
water bamboo husk, chopped pieces, and the prepared particles are
shown in Fig. 1.
The functional groups on water bamboo husk particles were char-
acterized using a FTIR spectroscopy (FT-720, Horiba, Japan). The
spectrum was obtained with 650 cumulative scans from 4 to
4000 cm 1. The pore size distribution and surface area of water
bamboo husk particles were measured by a Micromeritics BET
(ASAP 2010, USA). Prior to measurement, the particles were
degassed at 120 C, under vacuum for 24 h. In addition, the pH at Fig. 1. Photos of pristine water bamboo husk, chopped pieces, and the prepared particles.
zero point of charge (pHzpc) for water bamboo husk particles (2 mg
in 10 mL of water for 10 min) was determined with a zeta potential
meter (Zetasizer Nano-ZS, Malvern, USA).
The procedures for ion exchange capacity (IEC) measurement were diluted to t within calibration range. The adsorbed metal ion capacity
as follows. 50 mg of water bamboo husk particles were soaked in was calculated using the difference between the nal and initial
20 mL of 0.1 M HCl solution and shaken at 100 rpm and room temper- concentrations.
ature for 24 h. The acid was poured out and the particles were washed In the batch desorption experiment, the water bamboo husk parti-
with 50 mL of deionized water for 3 h to remove the traces of acid. After cles loaded with metal ions (c0 = 10 mg/L) were immersed in 50 mL
the removal of deionized water, 20 mL of 0.01 M NaOH was added and of desorption solution for 1 and 3 h at room temperature and with shak-
the particles were immersed in NaOH solution for 24 h. The IEC was de- ing at 100 rpm. Two desorption solutions were tested: 0.1 M HNO3
termined from the alkalinity reduction in NaOH solution by back titra- (pH 1.8) and 0.01 M EDTA. The desorbed metal ion amount was evalu-
tion using 0.01 M HCl as IEC (meq/g) = MO,NaOH ME,NaOH, where ated by multiplying the metal ion concentration in desorption solution
MO,NaOH and ME,NaOH are the moles of NaOH before and after the equili- by the solution volume.
bration, respectively.

2.3. Batch adsorption/desorption experiment 2.4. Column adsorption experiment

The adsorption capacity was studied for metal ion solution at pH 5
and room temperature in batch process. In this experiment, 250 mg of
water bamboo husk particles were placed in a 100 mL wide-mouth
vial and immersed in 50 mL of the metal ion solution, shaking on the
TKS OS 701 orbital shaker (Japan) at 100 rpm. Adsorption equilibrium
was reached after 3 h of contact time. Then, the solution was ltered
to remove the sorbent particles. The metal ion concentration was
analyzed using either a PerkinElmer AA3300 Flame Atomic Adsorption
Spectrometer (USA) for a single metal ion or a Horiba ULTIMA2
ICP (Japan) for a mixture of metal ions. Some of the samples were
250 mg of water bamboo husk particles were carefully packed in
a glass column with length of 30 cm and inner diameter of 1 cm
(Adjusta chrom). The bed height was 1.4 cm. Thus, the bed volume
was about 1.1 mL. A metal ion solution of 10 mg/L was fed into the
column using a HPLC pump (Waters 600 controller/600 system
pump, USA) in up-ow direction. The ow rate was 1 mL/min, and
the pressure drop was about 2332 psi. The fractions of column
efuent were collected at 10 mL in each vial. The metal ion concen-
tration in each fraction was determined by the Flame Atomic Absorp-
tion Spectrometer.
 H.B. Asberry et al. / Microchemical Journal 113 (2014) 5963 61

3. Results and discussion 5

3.1. Properties of water bamboo husk particles 0

The particle diameter of the water bamboo husk sorbents prepared -5

in this study ranged from 45 to 250 m. The BET measurement gave a

pore size distribution of 5.713.8 nm for these particles, which is close
to that of Ponkan mandarin peel particles (313 nm) [12] but slightly
larger than banana peel particles (1.05 nm) [10]. The specic surface
area of water bamboo husk particles, also determined by BET,
was found to be 1.87 m2/g. This result is near those for banana peel
(2 m2/g) [10] and Pu-erh tea powder (40 mesh, 1.71 m2/g) [18]. Never-
theless, it is much smaller than that reported for Ponkan mandarin
peel (119.3 m2/g) [12] and much larger than pine cone powders
(0.0993 m2/g (raw pine cone) and 0.122 m2/g (acid-treated pine
cone)) [19]. The pore size and surface area of biosorbents vary with
the agricultural material adopted. Water bamboo husk provides the
properties similar to most of the plant wastes studied in the literature.
To identify the functional groups on water bamboo husk particles,
their FTIR spectrum was recorded and the result is presented in Fig. 2.
The spectrum is very similar to the results of other biosorbents. The
broad band at 3420 cm1 was mainly ascribed to the OH group, where-
as the band at 2920 cm1 was assigned to the aliphatic CH groups
[2,1012,1821]. Moreover, the peaks at 1710 and 1640 cm1 were at-
tributed to the CO bond of carboxylic acids [2,1012,1821]. The above
FTIR results indicate that water bamboo husk particles contain OH and
COOH groups. Accordingly, positively-charged heavy metal ions would
be able to bind with these active groups under appropriate pH condi-
tions, via charge interaction, and adsorbed onto the water bamboo
husk particles.
The pHzpc of water bamboo husk particles was determined by
zeta potential at the range of pH 26. As illustrated in Fig. 3, the zeta po-
tential was positive (0.56 mV) at pH 2 but switched to negative at pH 3
(5.78 mV). Accordingly, the pHzpc value of water bamboo husk parti-
cles should be between 2 and 3, which is slightly lower than those re-
ported for Pu-erh tea powder (pHzpc = 3.6) [18] and tea waste
(pHzpc = 4.3) [21]. The zeta potential of water bamboo husk continued
to decrease with increasing pH and then remained stable at pH 6.
An optimal negative charge on particle surface was achieved at pH 5
( 26.40 mV). It is also worthy to note that the weakly acidic COOH
groups are usually the main sites on plant waste sorbents for the uptake
of cationic substances [10,22]. The pKa of COOH group is about 3.55.5
so that a majority of carboxyl groups are deprotonated at pH values in
this range, resulting in more negatively-charged sites [22]. Our zeta po-
tential results are in good agreement with the above explanation.
zeta potential
-10
-15
-20
-25
-30
1 2 3 4 5 6
pH
Fig. 3. Zeta potential results of water bamboo husk particles.
Moreover, pH 5 is also the optimal value for trapping metal ions by
Ponkan mandarin peel particles [12]. Subsequently, in the following ad-
sorption processes, the solution pH was xed at 5 in order to adsorb
plenty of positively-charged metal ions.
3.2. Batch adsorption results
In batch process, 250 mg of water bamboo husk particles were
employed to adsorb heavy metal ions from a 50-mL mixture (23 kinds
of metal ions) with a concentration of 5 mg/L for each single ion
(prepared by diluting the standard solution) at pH 5 and room temper-
ature. In this case apparent equilibrium was established within 3 h of
contact time. The adsorption of water bamboo husk particles was
more favorable to seven metal ions in a competitive circumstance and
their adsorption results are shown in Fig. 4. The other 16 metal ions ex-
hibited negligible adsorption. In Fig. 4, ions having a strong afnity to
water bamboo husk biosorbent included Cu2+, Cr3+, Pb2+, and Fe3+.
The adsorption percentage ranged from 15.5% (Ni2+) to 99.8% (Fe3+).
Ni2 + and Fe3 + were thus selected for the subsequent investigations
on static and dynamic adsorption.
The adsorption isotherms of Ni2+ and Fe3+ are presented in Fig. 5
(solid symbols, red color), along with the extent of adsorption (open

70
100
60
80
50
adsorption %
transmitance %

40 60

30 40

20
20
10
0
0 Ni2+ Zn2+ Cd2+ Cu2+ Cr3+ Pb2+ Fe3+
4000 3000 2000 1000
wavenumber (cm-1) Fig. 4. Batch adsorption performance for seven metal ions at pH 5 and room temperature,
solution volume = 50 mL, particle amount = 250 mg, contact time = 3 h, c0 of each ion
Fig. 2. FTIR spectrum of water bamboo husk particles. in the mixture = 5 mg/L.
62 H.B. Asberry et al. / Microchemical Journal 113 (2014) 5963
10 100
8 80
adsorption %
q (mg/g)
6 Ni2+ 60
4 Fe3+ 40
2 20
Ni2+
Fe3+
0 0
0 50 100 150 200 250 300
ceq (mg/L)
Fig. 5. Adsorption isotherms of Ni2+ and Fe3+ at pH 5 and room temperature, solution
volume = 50 mL, particle amount = 250 mg, contact time = 3 h.
symbols, green color). The well-known Langmuir isotherm model for
homogeneous monolayer adsorption was adopted to analyze the
isotherm data:
qm ceq
q 1
K d ceq
where q is the adsorbed metal ion capacity (mg/g adsorbent), ceq is
the aqueous metal ion concentration at equilibrium (mg/L), q m is
the maximum metal ion adsorption capacity (mg/g), Kd is the equi-
librium dissociation constant (mg/L). The best-t values of the
model parameters estimated from Eq. (1) by nonlinear regression
analyses are: q m = 8.4 mg/g and K d = 72.4 mg/L (R 2 = 0.90) for
Ni2 + ; q m = 4.7 mg/g and K d = 14.6 mg/L (R2 = 0.92) for Fe3 +.
The isotherm simulation results are also shown in Fig. 5 as red lines
(solid line for Ni2 + and dashed line for Fe3 +).
After further calculation, the qm values for the prepared water bamboo
husk particles were 0.143 mmol/g for Ni2+ and 0.084 mmol/g for Fe3+.
Considering the charge number on each metal ion (2 for Ni2+ and 3 for
Fe3+), the saturated adsorption capacity of Ni2+, 0.286 meq/g, is close
to that of Fe3+, 0.252 meq/g. On the other hand, the measured cation ex-
change capacity of water bamboo husk particles was about 1.3 meq/g.
When comparing qm to this value, it reveals that only 20% of the
negatively-charged sites on the particles were occupied by metal ions. Ac-
cordingly, the maximum possible metal ion adsorptivity for the prepared
water bamboo husk biosorbents should be 5 times than the measured
values, i.e. about 40 mg Ni2+/g and 25 mg Fe3+/g, which are comparable
to the maximum adsorption capacities listed in Refs. [22,23].
In addition, an extraordinary and interesting isotherm behavior
happened in Fig. 5: Ni2 + exhibited lower adsorption capacities at
lower concentrations but higher capacities at higher concentrations,
in comparison with Fe3+. An intersection for both isotherms occurred
at ceq 60 mg/L. This explains why Ni2+ revealed a lower adsorption
percentage than Fe3+ at an initial concentration of 5 mg/L as shown
in Fig. 4, although Ni2+ had a larger qm.
On the other hand, the dissociation constant (Kd) for Ni2+ was larger
than that for Fe3+. However, Kd is the reciprocal of the afnity constant.
It indicates that Fe3+ revealed stronger interaction with water bamboo
husk particles than Ni2+, which could be attributed to their difference in
charge number.
Also shown in Fig. 5 is the extent of adsorption versus the equilibri-
um concentration. It is found that the adsorption percentage decreased
drastically with the increasing concentration. Conclusively, water bam-
boo husk particles should be more suitable for the adsorption of low-
concentration heavy metal ions in water in order to attain higher
removal efciency.
3.3. Batch desorption results
Table 1 lists the batch desorption results. Prior to desorption, metal
ions were loaded onto the water bamboo husk particles at the following
conditions: c0 = 10 mg/L, pH 5, room temperature, contact time of 3 h.
Two desorption solutions were tested: 0.1 M HNO3 (pH 1.8) and
0.01 M EDTA. The former condition is to make the water bamboo husk
particles positively-charged by using a pH lower than pHzpc, following
with the release of adsorbed metal ions. The latter is to employ chelators
for catching and removing (through a shift in equilibrium) the metal
ions from the particle surface. The volume of desorption solution was
50 mL, the same as the loading volume. As shown in Table 1, the optimal
desorption condition was 0.1 M HNO3 with a contact time of 3 h. A di-
minished 110% desorption with a shorter contact time (1 h) was ob-
served. Moreover, the desorption efciency of Ni2 + was higher than
Fe3+. This phenomenon is in good agreement with the batch adsorption
results, namely Ni2+ had weaker interaction with water bamboo husk
particles than Fe3+. In addition, the effect of desorption solution volume
under the optimal condition was also investigated. With the volume de-
creasing from 50 mL to 30 mL and 10 mL, the metal ion desorption per-
centage was reduced from 99% to 74% and 34% for Ni2+, and from 92% to
65% and 25% for Fe3+, respectively.
In most studies of heavy metal ion adsorption using biosorbents, a
dilute strong acid (e.g. 0.050.1 M HCl and 12 M HNO3) was chosen
as the desorption solution and the related desorption efciency was
high [2,10,13,22]. In the investigation employing gooseberry fruit
for Cu2+ sorption [2], other desorption solutions such as NaCl, Na2SO4,
CH3COOH, and EDTA were also tested. However, 0.1 M HCl still
achieved the best desorption performance (N 80%). Salts, the weak
acid, and the chelating agent were not effective. Furthermore, the de-
sorption solution volume and contact time in most studies are usually
identical to the values for adsorption stage [2,13,22]. In the work of
adopting papaya wood biosorbent for Cu2+, Cd2+, and Zn2+ sorption
[13], shortening the contact time to one half caused a 20% decrease in
desorption. The desorption results obtained in this study are very simi-
lar to the ndings of the above references.
3.4. Breakthrough curves
Fig. 6 illustrates the breakthrough curves of Ni2+ and Fe3+ at a short
column bed of 1.1 mL volume. The ow rate was 1 mL/min and the feed
metal ion concentration was 10 mg/L. When the breakthrough point
was determined as c/c0 = 0.1 (the efuent metal ion concentration
attained one-tenth of the feed concentration), the related breakthrough
volumes were 75 bed volume for Ni2+ and 90 bed volume for Fe3+, re-
spectively. The dynamic adsorption performance of Fe3+ at a low feed
concentration was better than Ni2+, which agrees well with the batch
results in Figs. 4 and 5. In the study using Ponkan peel as adsorbent
[12], the maximum adsorption capacity for Ni2 + was 1.92 mmol/g
and the associated breakthrough volume was 110 bed volume (1 bed
volume = 5 mL and ow rate = 3.5 mL/min). The Ni2+ breakthrough
performance of the water bamboo particles prepared in this study was
comparable to that of Ponkan peel biosorbent.
Comparing to the static adsorption capacities in Fig. 5, the dynamic
capacities of metal ions obtained at breakthrough points in Fig. 6 are
2 fold (for Fe3 +) or 3 fold (for Ni2 +) higher. This phenomenon may
be attributed to the mass transfer effect in packed-bed process which
forced the metal ions to ow through the intraparticle mesopores and
Table 1
Batch desorption results of Ni2+ and Fe3+ using different desorption conditions.
Ni2+ Fe3+
1h 3h 1h 3h
0.1 M HNO3 92.9 0.6% 99.2 0.5% 86.2 1.2% 91.8 1.8%
0.01 M EDTA 92.3 0.7% 93.1 0.2% 61.2 1.1% 72.1 1.1%
 H.B. Asberry et al. / Microchemical Journal 113 (2014) 5963
2+
1.0 Ni
0.8
0.6
c/c0
0.4
0.2
0.0
0 50 100 150 200 250
bed volume
Fig. 6. Breakthrough curves for Ni2+ and Fe3+ adsorption onto the packed bed of water
bamboo husk particles, 1 bed volume = 1.1 mL, particle amount = 250 mg,
c0 = 10 mg/L, pH 5, ow rate = 1 mL/min.
reach the binding sites more readily. Consequently, the utilization
percentage of the binding sites of water bamboo husk particles was
effectively raised by column processes.
4. Conclusions
This study has demonstrated the potential of water bamboo husk as
biosorbent for removing heavy metal ions from water. Water bamboo
husk is easy to obtain in warm areas, especially in Asia, and free of ex-
pense. The related sorbent preparation from this agricultural waste is
simple. In the current study, seven studied metal ions showed afnity
to the prepared water bamboo husk biosorbent, with Cu2 +, Cr3 +,
Pb2+, and Fe3+ having the strongest binding. Metal ions having a higher
afnity to the sorbent (such as Fe3+) were trapped more efciently at
low feed concentrations. The adsorbed metal ions could be efciently
desorbed by a dilute strong acid solution. Moreover, water bamboo
husk particles exhibited a greater metal ion capacity (2 to 3 fold) in a
ow-through column process than a static setup. Based on these nd-
ings, it is reasonable to suggest that water bamboo husk is a biosorbent
suitable for metal ion trapping and may be further applied in solid phase
extraction or other adsorption applications.
Acknowledgments
This work was sponsored by the Ministry of Education of Taiwan
(ATU plan) and the US National Science Foundation (NSF OISE-
0936693).
63
3+
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