Journal of Environmental Sciences 2011, 23(6) 918–922

Kappaphycus alvarezii waste biomass: A potential biosorbent for chromium

ions removal
Oon Lee Kang1 , Nazaruddin Ramli1,∗, Mamot Said1 , Musa Ahmad1 ,
Suhaimi Md Yasir2 , Arbakariya Ariff3

1. School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor,
Malaysia. E-mail: naza@ukm.my
2. School of Sciences and Technology, Universiti Malaysia Sabah, 88400 Kota Kinabalu, Sabah, Malaysia
3. Faculty of Biotechnology and Biomolecular Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia

Received 13 July 2010; revised 26 October 2010; accepted 12 November 2010

Abstract
The Cr(III) sorption experiments onto Kappaphycus alvarezii waste biomass were conducted at different pH values (2–6) under the
conditions of initial metal concentration of 10–50 mg/L and the chemical compositions of Cr-Cu and Cr-Cd. The Cr(III) sorption
capacities were slightly dependent on pH, and the maximum sorption capacity was 0.86 mg/g at pH 3. The sorption capacities
increased with increase in the initial metal concentration, whereas it was suppressed by the presence of Cu(II) and Cd(III) in the
solution. The Cr(III) sorption equilibrium was evaluated using Langmuir, Freundlich and BET isotherms. The sorption mechanisms
were characterised using scanning electron microscopy and Fourier transform infrared spectroscopy. The main mechanisms were ion
exchange coupled with a complexation mechanism. Kappaphycus alvarezii waste biomass represents a potential for Cr(III) ion removal
from aqueous solution.

Key words: biosorption; chromium; Kappaphycus alvarezii

DOI: 10.1016/S1001-0742(10)60498-6
Citation: Kang O L, Ramli N, Said M, Ahmad M, Yasir S M, Ariff A, 2011. Kappaphycus alvarezii waste biomass: A potential
biosorbent for the chromium ions removal. Journal of Environmental Sciences, 23(6): 918–922

Introduction et al., 2010), which are responsible for the interactions

Seaweed biomass is a renewable natural resource and
is available throughout the Asia-Pacific region (Ortiz et
al., 2006). Currently, seaweed biomass is cultivated and
harvested to manufacture hydrocolloids (agar, alginate and
carrageenan) for use in the food and chemical indus-
tries. Apart from these uses, seaweed biomass is utilised
to remove heavy metals from contaminated wastewater
(Hashim and Chu, 2004).
Seaweed biomass derived from species such as Fucus
sp., Padina sp., Palmaria sp., Polysiphonia sp., Pithopho-
ra sp., Sargassum sp. and Ulva sp. have been effective
and reliable to remove Cr(III) ions from contaminated
wastewater (Michalak et al., 2007; Murphy et al., 2008).
Therefore, seaweed biomass is considered to be a cost-
effective and efficient biosorbent to remove Cr(III) ions.
Seaweed biomass possesses a high metal uptake capaci-
ty due to its physicochemical characteristics (Padilha et al.,
2005). Seaweed biomass contains various chemical groups
attached to the cell wall polysaccharides and proteins,
such as amino, carboxyl and hydroxyl groups (Yalçin
with metal cations via complexation, coordination, micro-
precipitation and ion exchange (Yang et al., 2010). Data
show that about 1 million tonnes of seaweed biomass
are collected and extracted to produce 55,000 tonnes of
hydrocolloids (FAO, 2003). Hence, a large amount of
seaweed waste biomass is generated by seaweed pro-
cessing industries, and disposal of this waste biomass is
problematic. Biosorption using seaweed waste biomass
is an innovative technology to minimize seaweed waste
disposal and to add values to seaweed waste biomass.
Biosorption using seaweed biomass can reduce capital cost
by 20%, operational costs by 36% and total treatment costs
by 28%, compared with conventional method (Loukidou et
al., 2004).
In the present work, Cr(III) sorption onto Kappaphycus
alvarezii waste biomass was investigated. Cr(III) sorption
equilibrium was evaluated using Langmuir, Freundlich
and BET isotherm. Cr(III) sorption mechanisms were
elucidated using Fourier transform infrared spectroscopy
spectroscopy (FT-IR) and scanning electron microscopy
(SEM).

* Corresponding author. E-mail: naza@ukm.my

No. 6 Kappaphycus alvarezii waste biomass: A potential biosorbent for chromium ions removal 919

1 Experiment using initial Cr(III) concentration varied from 10 to 50

1.1 Seaweed waste biomass preparation
Kappaphycus alvarezii waste biomass was prepared in
the laboratory using a common industrial process. The
seaweed biomass was extracted with aqueous solution at
60°C for 6 hr. Then, the seaweed waste biomass was
separated from the aqueous solution containing the hydro-
colloids materials using filter paper (Whatman No. 2). The
seaweed waste biomass was washed with distilled water
and dried at 60°C for 24 hr. The dried seaweed waste
biomass was ground in a blender and stored in a desiccator.
1.2 Metal solution preparation
The stock Cu(II), Cd(II) and Cr(III) solutions (1000
mg/L) were prepared by dissolving the metal nitrates
(Merck) in deionised water. Cr(III) solutions with different
concentrations and compositions were prepared by diluting
the stock solutions with deionised water. The solution pH
was adjusted to the desired value by using 0.1 mol/L HCl
and 0.1 mol/L NaOH.
1.3 Seaweed waste biomass characterisation
The untreated and Cr(III)-treated seaweed waste
biomass samples were analysed using Fourier transform
infrared spectrometer (FT-IR) (GX, PerkinElmer, USA).
The seaweed waste biomass samples were encapsulated in
KBr at a ratio of 1:100. The infrared spectroscopy (IR)
spectra were collected using a PerkinElmer spectrometer
within the range 400–4000 cm−1 .
The untreated and Cr(III)-treated seaweed waste
biomass samples were examined using scanning electron
microskop (SEM) (SUPRA 55VP, ZEISS). The seaweed
waste biomass samples were coated with gold under vacu-
um.
1.4 Sorption isotherm experiment
mg/L.
Batch experiments were carried using binary systems
containing Cr(III) and a divalent metal cation (Cu2+ or
Cd2+ ) to determine the effect of co-existing ions.
2 Results and discussion
2.1 FT-IR analysis
The untreated and Cr(III)-treated seaweed waste
biomass samples were analysed using Fourier transform
infrared spectroscopy (FT-IR) (Fig. 1). The untreated sea-
weed waste biomass spectrum presented six predominant
peaks: 3430 cm−1 (–OH and –NH stretching), 2930 cm−1
(–CH3 stretching), 1642 cm−1 (–COO stretching), 1385
cm−1 (–CH3 bending), 1264 cm−1 (–C–O–C stretching)
and 1053 cm−1 (–C–O stretching). The FT-IR results were
similar to those reported in the literature for other brown
seaweed biomass, such as Gracilaria sp., Bifurcaria sp.,
Laminaria sp., Padina sp., Sargassum sp. and Ulva sp.
(Freitas et al., 2008; Sheng et al., 2004).
Table 1 displays the main vibrational wavenumber cor-
respond to functional groups that potentially interacted
with Cr(III). The spectrum of the Cr(III)-treated seaweed
waste biomass revealed a few changes in the frequencies,
suggesting that these functional groups are involved in
Cr(III) sorption.
The absorption peak around 1642 cm−1 (–COO group)
shifted to 1647 cm−1 ; and the peak at 3430 cm−1
(–NH group) shifted to 3423 cm−1 , suggesting that amino
and carboxyl groups are involved in Cr(III) uptake. A
new peak appeared around 1720 cm−1 after contact with
the Cr(III) solution, indicating that –C–O groups were
Unloaded biomass Cr(III) loaded biomass
100
Transmitance (%)

80
Cr(III) sorption experiments were conducted in shake
60
flasks. Seaweed waste biomass (0.5 g) was added to a
flask containing 50 mL of Cr(III) solution. The samples 40
2930 1720 1262
were agitated on a rotary shaker at 300 r/min for 3 hr. 20 1647
1642 1232
3423
The samples were filtered using filter paper (Whatman 1385 1053 1062
0
No. 2), and the Cr(III) concentrations were measured 4000 3600 3200 2800 2400 2000 1600 1200 800 400
using an atomic absorption spectrometer (AAnalyst 800, Wavenumber (cm-1)
PerkinElmer, USA). Fig. 1 FT-IR spectra of untreated and Cr(III)-treated Kappaphycus
The Cr(III) sorption capacities were calculated using the alvarezii waste biomass.
following Eq. (1): Table 1 FT-IR vibration wavenumber and corresponding functional
groups observed on Kappaphycus alvarezii waste biomass
Qm = (C0 − Ce ) × V/M (1)
Wave number (cm−1 )
Untreated Cr(III)-treated Functional groups
where, Qm (mg/g) is the amount of metal adsorbed, V (L) biomass biomass
is the volume of the solution, M (g) is the mass of the
biomass, and C 0 (mg/L) and Ce (mg/L) are the initial and 3430 3423 –OH and –NH stretching
2930 2930 –CH3 stretching
equilibrium concentrations of metal ions, respectively. – 1720 –C=O stretching
Batch experiments were carried out at pH ranging from 1642 1647 –COO stretching
2–6 to determine the effect of pH with a handheld pH meter 1385 1385 –CH3 bending
1264 1232 –C–O stretching
provided with a combined glass electrode (Jacques et al.,
1053 1062 –C–O stretching of
2007). alcoholic groups
Effect of initial Cr(III) concentration was investigated
920 Journal of Environmental Sciences 2011, 23(6) 918–922 / Oon Lee Kang et al. Vol. 23

a b

Fig. 2 SEM micrographs of unloaded (a) and Cr(III) loaded (b) Kappaphycus alvarezii waste biomass at a magnification of 2000×.

oxidized by Cr(III) ions to form –C=O groups. However, with H+ and/or other cations (Havelcová et al., 2009;
the adsorption peaks around 2930 and 1385 cm−1 did not Ofomaja and Ho, 2007).
change, indicating that CH groups were not involved in
Cr(III) uptake. 3(−RCOOH) + Cr3+ ←→ (−RCOO)3 Cr + 3H+ (2)
+
The significant changes in the vibrational frequencies 2(−RCOOH) + CrOH 2+
←→ (−RCOO)2 CrOH + 2H
indicate that amino and carbonyl groups bind with Cr(III) (3)
ions through ion exchange and complexation reactions.
3(−RCOOM) + Cr3+ ←→ (−RCOO)3 Cr + 3M+ (4)
2.2 SEM analysis 2(−RCOOM) + CrOH 2+
←→ (−RCOO)2 CrOH + 2M +

The untreated and Cr(III)-treated seaweed waste (5)

biomass samples were analysed using SEM. The SEM
The slight differences in pH indicate that carboxyl
micrograph in Fig. 2a shows that the untreated biomass
groups interact with Cr(III) ions through an ion exchange
sample had an irregular and porous surface, which pro-
(Havelcová et al., 2009). The slight increases in pH sug-
vided a large surface area. The SEM micrograph in Fig.
gest that Cr(III) was retain by the biomass rather than
2b shows the Cr(III)-treated biomass sample with consid-
hydrolyzed and cations exchanged with Cr(III) ions rather
erable differences in surface morphology. The mound-like
than H+ during the sorption process (Blázquez et al.,
structure indicates that Cr(III) replaced light metals on the
2009).
cell wall.
2.3.2 Effect of initial Cr(III) concentration
2.3 Cr(III) sorption experiments
The Cr(III) sorption onto Kappaphycus alvarezii waste
2.3.1 Effect of pH biomass was carried out at initial Cr(III) concentrations
The Cr(III) sorption onto Kappaphycus alvarezii waste of 10–50 mg/L. The Cr(III) sorption capacity increased
biomass was carried out at pH range 2–6 to avoid the with increasing initial metal concentration (Fig. 4), sug-
formation of insoluble Cr(OH)3 , which occurs at pH higher gesting that a higher initial metal concentration provides
than 7. The Cr(III) sorption capacity increased as the pH an important driving force to overcome mass transfer
increased and then dramatically decreased when the pH resistances between the metal sorbent and the sorption
increased beyond the optimum level (Fig. 3). medium (Yalçin et al., 2010).
The Cr(III) sorption capacity was greatest at pH 3, sug- The time course profile indicates that the contact time
gesting that carboxyl groups take part in Cr(III) sorption. had a significant impact on the sorption equilibrium. The
Carboxyl groups dissociate at pH higher than 2.5 and thus Cr(III) sorption reached equilibrium within the first 30 min
were able to coordinate with Cr(III) ions through exchange and remained uniform for 180 min.
10 mg/L 30 mg/L 50 mg/L
Cr (III) sorption capacity (mg/g)

Cr (III) sorption capacity (mg/g)

1.0 3

0.8
2
0.6

0.4
1
0.2

0 0
0 1 2 3 4 5 6 7 0 30 60 90 120 150 180
pH Time (min)
Fig. 3 Effect of pH on Cr(III) sorption onto Kappaphycus alvarezii waste Fig. 4 Effect of initial metal concentration on Cr(III) sorption onto
biomass. Kappaphycus alvarezii waste biomass.
No. 6
Langmuir isotherm
Qm (mg/g) KL (L/mg)
1.8868 0.570
3 Langmuir and Freundlich isotherms, indicating that the
Cr(III) sorption capacity (mg/g)
2
1
0
0 5
Equilibrium concentration (mg/L)
Fig. 5 Cr(III) sorption isotherm.
2.3.3 Effect of binary metal system
Cr(III) sorption onto Kappaphycus alvarezii waste
biomass was conducted using binary systems containing
Cr(III) and a divalent metal (Cu2+ or Cd2+ ). The Cr(III)
sorption capacity in the binary metals system was lower
than that in the single metal systems. The Cr(III) sorption
capacities were 0.83 mg/g in the single metal system,
0.71 mg/g in the presence of Cu(II) and 0.65 mg/g in the
presence of Cd(II). The suppression of Cr(III) sorption
suggests that Cu(II) and Cd(II) compete with Cr(III) for
same binding sites (Wan Ngah and Fatinathan, 2010).
2.3.4 Cr(III) sorption equilibrium study
The Cr(III) sorption isotherm indicates the multilayer
formation during the sorption process (Fig. 5). The Cr(III)
sorption phenomenon was evaluated using Langmuir, Fre-
undlich and BET isotherms as following Eqs. (6), (7), and
(8), respectively.
Qm × KL × C e
Qe =
1 + KL × Ce
Qe = KFCe1/n
KB × Ce × Qm
Qe =
(Cs − Ce ) × [1 + (KB − 1) × ( CCes )]
where, Qe (mg/g) is the equilibrium metal concentration
on the biosorbent, Qm (mg/g) is the maximum metal
uptake, Ce (mg/L) is the equilibrium metals concentration
in the solution, Cs (mg/L) is the saturation concentration,
KB is the BET equilibrium constant, KL (L/mg) is the
Langmuir equilibrium constant, KF (L/g) is the Freundlich
equilibrium constant and n is the Freundlich equilibrium
constant. Table 2 displays the Langmuir, Freundlich and
BET adsorption constants and the regression correlation
coefficients, that were generated from linearised isotherm
plots.
The BET isotherm with correlation coefficient 0.962
better described the Cr(III) sorption process than the
Kappaphycus alvarezii waste biomass: A potential biosorbent for chromium ions removal 921
Table 2 Langmuir, Freundlich and BET isotherm parameters
Freundlich isotherms BET isotherm
R2 KF (L/mg) 1/n R2 Qm (mg/g) KB R2
0.659 5.272 0.463 0.750 1.201 75.726 0.962
macro-porous sorbent contains Cr(III) sorption sites with
strong and weak affinities.
3 Conclusions
The experimental results showed that readily available
Kappaphycus alvarezii waste biomass was able to remove
Cr(III) ions from aqueous solution. The Cr(III) sorption
10 15 20 25 capacity was 0.86 mg/g at pH 3 and increased with
increasing initial metal concentration. The Cr(III) sorption
capacity was suppressed by other cations present in the
solution. The Cr(III) sorption equilibrium was described
well using a BET isotherm. The Cr(III) sorption mecha-
nisms were ion exchange and complexation. Further work
aimed at analysing the sorption and desorption of single
and multiple metals using Kappaphycus alvarezii waste
biomass is in progress.
Acknowledgements
This work was financially supported by a Research
University Grant from UKM-GUP-NBT-08-27-104
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