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Procedia - Social and Behavioral Sciences 195 (2015) 2709 – 2716

World Conference on Technology, Innovation and Entrepreneurship

Biosorption of Mn(II) ions from Aqueous Solution by Pleurotus

Spent Mushroom Compost in a Fixed-Bed Column
Ain Nihla Kamarudzamana,*, Tay Chia Chayb, Amnorzahira Amira, Suhaimi Abdul
Taliba
a
Faculty of Civil Engineering, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
b
Faculty of Applied Sciences, Universiti Teknologi MARA (Perlis), 02600 Arau, Perlis, Malaysia

Abstract

The Pleurotus spent mushroom compost have been identified as a low-cost biosorbent for heavy metals removal. The Mn(II) ions
removal from aqueous solution was conducted in a fixed-bed column. The effect of various parameters such as flow rate, bed
height and initial concentration on Mn(II) ions biosorption were investigated. The results of breakthrough time, exhaustion time
as well as the Mn(II) uptake and percentage of removal are highly influenced by the flow rate, bed height and the initial Mn(II)
concentration. The results demonstrated that the breakthrough time and exhaustion time increased with decreases of flow rate and
initial Mn(II) concentration and increased of bed height. The results of EDX confirmed that the Mn(II) ions presence on the
surface of Pleurotus spent mushroom compost after biosorption process and the FTIR identified the carboxyl, hydroxyl and
amide functional groups as the active binding sites for Mn(II) ions biosorption.

©
© 2015
2015TheTheAuthors. Published
Authors. by Elsevier
Published Ltd. Ltd.
by Elsevier This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of Istanbul University.
Peer-review under responsibility of Istanbul Univeristy.

Keywords: Biosorption; Fixed-bed column; Pleurotus spent mushroom compost; Mn(II) removal.

* Corresponding author. Tel.: +6019 3848233; fax: +604 9798636.

E-mail address: [email protected]

1877-0428 © 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of Istanbul Univeristy.
doi:10.1016/j.sbspro.2015.06.379
2710 Ain Nihla Kamarudzaman et al. / Procedia - Social and Behavioral Sciences 195 (2015) 2709 – 2716

1. Introduction

Heavy metals pollution caused by industrial wastewater is a serious environmental issue. Industries such as
electroplating, mining, textile, metal refineries and automotive are the major sources of heavy metals pollution
(Amarasinghe and Williams, 2007). Heavy metals are not biodegradable and tend to accumulate in living organisms.
Exposure to heavy metals posing health hazards if their concentrations exceed allowable limits (Acheampong et al.,
2012). Several techniques have been applied for heavy metals removal from industrial wastewater, including
chemical precipitation, electrochemical, adsorption on activated carbon, ion exchange and membrane filtration
(Anastopoulos et al., 2013; Barakat, 2011). However, these techniques have some limitation such as high operation
and maintenance cost, incomplete metals removal and production of secondary toxic waste (Anastopoulos et al.,
2013). Biosorption has been highlighted as a low-cost alternative technology with possibility for biosorbent
regeneration and metals recovery, high removal efficiency and minimum toxic waste production (Fu and Wang,
2011). The Pleurotus spent mushroom compost is a by-product from Pleurotus mushroom cultivation farm. Due to
the increase in population and consumption, the world demand for mushrooms is projected to grow 15% a year
(Haimid et al., 2013). The high demand from local and global consumers for oyster or Pleurotus mushroom also has
led to increase the production and utilisation of the spent mushroom compost. About 5 kg of spent mushroom
composts per 1 kg mushrooms are generated from mushroom production (Toptas et al., 2014). The spent mushroom
compost has no commercial value and after some use it often disposed to the landfill. Therefore, the disposal of
spent mushroom compost is one of the environmental issues for the mushroom industry. The Pleurotus spent
mushroom compost is made from Pleurotus mycelium, rubber tree sawdust, rice bran, recycled spent mushroom
compost. The rubber tree sawdust contains lignocellulosic enzymes such as cellulose and lignin, both with a capacity
for metal cations binding (Toptas et al., 2014; Süiban et al., 2007). Therefore, the Pleurotus spent mushroom
compost could be considered as a low-cost biosorbent because its easily available in large quantities and
lignocellulosic compositions.

The aims of the study was to investigate the effects of various parameter on Mn(II) ions biosorption including
flow rate, bed height and initial Mn(II) concentration. The study also investigate the characteristics of biosorbent in
order to identify the surface morphology, elemental compositions and functional groups of the Pleurotus spent
mushroom compost.

2. Methodology

2.1. Biosorbent Materials

The Pleurotus spent mushroom compost sample was obtained from a mushroom production farm at Muar, Johor,
Malaysia. The sample was autoclaved (Hirayama HVE-50) at 121°C, under pressure of 18 psi for 15 minutes and
kept in an oven at 60ºC for 48 hours. The dried sample was ground into powder and sieved to the particle size less
than 710 ȝm. Afterward, it was rinsed with ultrapure water and dried in an oven at 60ºC.

2.2. Chemicals and Reagents

All the chemicals and reagents used in the study were of analytical grade. The stock solution of Mn(II) 1000
mg/L was prepared by dissolving Manganese(II) Nitrate Tetrahydrate (Mn(NO3)2.4H2O) with ultrapure water. The
stock solution was further diluted to the desired concentration with ultrapure water (Millipore, USA).

2.3. Fixed Bed Column Biosorption Studies

A glass column with 1 cm internal diameter was packed with a known quantity of Pleurotus spent mushroom
compost. In order to provide a uniform inlet flow, a layer of glass beads was placed at the top of the packed
biosorbent. The experiments were conducted by pumping Mn(II) solution through the column in down-flow mode
using a peristaltic pump (Cole Parmer, Model 77200-60, USA). All experiments were conducted at room
 Ain Nihla Kamarudzaman et al. / Procedia - Social and Behavioral Sciences 195 (2015) 2709 – 2716 2711

temperature and optimum pH 6 (Kamarudzaman et. al, 2014). The effect of various parameter such as flow rates (1,
10 and 20 mL/min), bed height (10, 20 and 30 cm) and initial Mn(II) ions concentrations (10, 50 and 100 mg/L)
have been investigated. The column is considered to be essentially exhausted when the effluent concentration
reaches 90% of initial concentration and the breakthrough point is 1 mg/L (Standard B, EQA 1974). The effluent
samples were periodically collected from the column outlet by a fraction collector (Gilson, FC 204, USA). The
effluent samples were later analysed using Inductively Coupled Plasma Atomic Emission Spectroscopy (Perkin
Elmer, 7300DV). The instrument was calibrated before each use with multi elements standard solutions.

2.4. Biosorbent Characterization

The surface morphology and elemental compositions of Pleurotus spent mushroom compost was investigated
using a Environmental Scanning Electron Microscopy (ESEM)(Quanta 450 FEG) and Energy Dispersive X-ray
(JEOL JSM-6701F), respectively. Fourier Transform Infrared Spectroscopy (FTIR) (Perkin Elmer, Spectrum One)
analysis was also conducted in order to identify the functional groups responsible for Mn(II) ions biosorption by the
Pleurotus spent mushroom compost.

3. Results and Discussions

3.1. Effect of Flow rate

The effect of flow rate on the Mn(II) ions biosorption by Pleurotus spent mushroom compost in a fixed-bed
column was studied and the breakthrough curves are shown in Fig. 1. The flow rates were varied to 1, 10 and 20
mL/min, while, the bed height and initial Mn(II) concentration were kept constant at 20 cm and 50 mg/L,
respectively. The results shows that the column breakthrough time and exhaustion time were reduced from 117 to
2.7 minutes and 261 to 18.9 minutes respectively, when the flow rate increased from 1 to 20 mL/min. In addition,
the Mn(II) ions percentage removal also reduced from 68.81 to 47.65% as the flow rate increased. At higher flow
rate, it was observed that the breakthrough curves of Mn(II) became steeper which indicating a shorter mass transfer
zone (Vimala et al., 2011). This also resulted less Mn(II) uptake and percentage removal. These results are also in
agreement with the findings reported in literatures (Khalilnezhad et al., 2014; Simate and Ndlovu, 2014). Reduction
in metal uptake at higher flow rate was due to inadequate residence time of the metal ions in the column. Therefore,
the contact time between Mn(II) ions and the biosorbent was reduced and Mn(II) ions did not have enough time to
diffuse into the pores of the biosorbent and leaving the column before equilibrium was achieved. However, at a
lower flow rate the residence time of the metal ions in the column was increased, thus the Mn(II) ions had more time
to contact with biosorbent in the column. In addition, allowed enough time for Mn(II) ions to diffuse into the pores
of biosorbent through intra-particle diffusion (Ahamad and Jawed, 2012). Therefore, lower flow rate was resulted in
higher Mn(II) ions removal in the column.

3.2. Effect of Bed Height

The breakthrough curves of Mn(II) ions biosorption by Pleurotus spent mushroom compost at different bed
heights are presented in Fig. 2. The flow rate and initial Mn(II) concentration were kept constant at 1 mL/min and 50
mg/L, respectively. The bed heights were varied to 10, 20 and 30 cm which equivalent to 1.4424, 2.8848, and
4.3272 g of biosorbent, respectively. The results shows that the Mn(II) ions percentage removal increased from
63.84 to 74.25% with increasing the bed height. In addition, the breakthrough time and the exhaustion time were
increased from 63 to 207 minutes and 153 to 378 minutes, respectively, with increase the bed height from 10 to 30
cm. As the bed height increased, both the breakthrough and exhaustion time were delayed, simultaneously improved
the column performance. Whereas, as the bed height reduced, the breakthrough and exhaustion became faster and
declined the column performance. The column performance was increased with bed height because more biosorbent
were packed in the column which provided greater biosorption sites for Mn(II) ions, longer residence time of Mn(II)
ions in the column and thus provided better intra-particle phenomena (Kundu and Gupta, 2007; Yahaya et al., 2011).
2712 Ain Nihla Kamarudzaman et al. / Procedia - Social and Behavioral Sciences 195 (2015) 2709 – 2716

3.3. Effect of Initial Concentration

The breakthrough curves of Mn(II) ions biosorption by Pleurotus spent mushroom compost at different initial
concentrations (10, 50 and 100 mg/L) are depicted in Fig. 3. The flow rate and bed height were held constant at 1
mL/min and 30 cm, respectively. The curves demonstrated that the breakthrough time as well as the exhaustion time
decreased from 990 to 99 minutes and 1602 to 198 minutes, respectively, with increasing the initial Mn(II)
concentration from 10 to 100 mg/L. As the initial concentration increased, the breakthrough curves were steeper and
the breakthrough occurred faster. In addition, higher initial Mn(II) concentration also faster the exhaustion of the
bed column. The results also in agreement with the findings reported by others researcher (Acheampong et al., 2012;
Chowdhury et al., 2012). Therefore, by decreasing the initial Mn(II) concentration, the breakthrough time and the
exhaustion time of the column can be extended, thereby also increased the volume of Mn(II) solution that can be
treated. However, the biosorption capacity increased from 2.892 to 3.341 mg/g with increasing the initial Mn(II)
concentration. This was due to higher concentration gradient caused the diffusion coefficient increased and leading
faster transportion of metals ion (Long et al., 2013).

1
0 .9
0 .8
0 .7
1 m l/m in (in scale 1 /1 0 )
in 0 .6
/Ct 1 0 m l/m in
u
o
0 .5
C
0 .4 2 0 m l/m in
0 .3
L in ear (B reak th ro u g h P o in t)
0 .2
L in ear (E x ha u stio n P o in t)
0 .1
0
0 20 40 60 80 100
T im e (M in )

Fig. 1. Breakthrough curves for Mn(II) ions biosorption onto Pleurotus spent mushroom compost at different flow rates (Experimental condition:
bed height = 20 cm, initial Mn(II) concentration = 50 mg/L).

1
0.9
0.8
0.7
0.6 10 cm
n
i
C
/t 0.5 20 cm
u
o
C 0.4
30 cm
0.3
Linear (Breakthrough point)
0.2
0.1 Linear (Exhaustion point)

0
0 100 200 300 400 500 600 700 800
Time (Min)
Fig. 2. Breakthrough curves for Mn(II) ions biosorption onto Pleurotus spent mushroom compost at different bed heights (Experimental
condition: flow rate = 1 mL/min, initial Mn(II) concentration = 50 mg/L).
 Ain Nihla Kamarudzaman et al. / Procedia - Social and Behavioral Sciences 195 (2015) 2709 – 2716 2713

0.9

0.8

0.7

n
i
0.6
/Ct
u
o
0.5
C 10 mg/L
0.4
50 mg/L
0.3
100 mg/L
0.2 Linear (Breakthrough point)
0.1 Linear (Exhaustion point)

0
0 500 1000 1500 2000 2500
Time (Min)
Fig. 3. Breakthrough curves for Mn(II) ions biosorption onto Pleurotus spent mushroom compost at different initial concentrations (Experimental
condition: flow rate = 1 mL/min, bed height = 30 cm).

3.4. Biosorbent Characterization

The ESEM micrographs of the Pleurotus spent mushroom compost before and after Mn(II) ions biosorption are
presented in Fig. 4. While, the EDX spectra of Pleurotus spent mushroom compost before and after Mn(II) ions
biosorption are presented in Fig. 5. Before biosorption, the Pleurotus spent mushroom compost have a rough and
porous structure as shown in Fig. 4(a). These porous structures were contributed to the metal ions biosorption
because its increased the surface area of biosorbent. However, after Mn(III) ions biosorption, some of porous
structure cannot be observed and it created a smooth surface. Based on the EDX analysis, the raw of Pleurotus spent
mushroom compost constituted elements such as carbon, oxygen, calcium and silica. However, after the Mn(II) ions
biosorption, the EDX analysis has detected peaks of Mn(II) element appears on the surface of Pleurotus spent
mushroom compost and indicated that the Mn(II) was adsorbed onto the biosorbent surface.

(a) (b)

Fig. 4. ESEM micrograph of Pleurotus spent mushroom compost at 500x magnification (a) Before biosorption; (b) After Mn(II) ions biosorption.
2714 Ain Nihla Kamarudzaman et al. / Procedia - Social and Behavioral Sciences 195 (2015) 2709 – 2716

(a) (b) 3600

2400
3300
2200
3000
2000
2700
1800
2400
1600

OKa M nLl M nLa

2100

CKa
1400
C ounts

Counts
CKa

1200 1800

1000 1500
OKa

1200

CaKa
800
SiK a

SiKa
C aK a

900

CaK b

M nKa
M nK b
C aK b
600
400 600
200 300
0 0
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
keV keV

Fig. 5. EDX spectra of Pleurotus spent mushroom compost (a) Before biosorption; (b) After Mn(II) ions biosorption.

The FTIR technique was used to identify the functional groups presence before and after Mn(II) ions biosorption,
and the results are shown in Fig. 6. Several wavenumber were identified from the raw of Pleurotus spent mushroom
compost. The wavenumber of 3328 cm-1 corresponded to the O–H stretch bonds of hydroxyl groups and the N–H
stretch of secondary amines (Ma et al., 2013; Kurniawan et al., 2011; Jin and Bai, 2002). The wavenumber of 1633
cmí1 attributed to N-H bending and C=O stretching in amides or the asymmetric and symmetric COO- of
deprotonated carboxylate functional groups of cellulose (Xiao-jing et al., 2014; Zakaria et al., 2009). The peak at
1319 cmí1 attributed to C-O stretching of COOH or C–N amides (Tay, 2012; Blázquez et al., 2012). The peak at
1237 cmí1 represents stretching of C–O groups from carboxylic acids, C–N stretching and N–H bends (Blázquez et
al., 2012). The peak at 1032 cm-1 corresponded to the -OH groups (cellulosic compounds) or phosphate group in the
biosorbent (Xiao-jing et al., 2014). However, the FTIR spectra had some changes after Mn(II) ions biosorption. The
wavenumber at 3328 cm-1 shifts to 3323 cmí1. Also, the wavenumbers at 1633 cm-1 shifts to 1736 cm-1 and at 1237
cm-1 shifts to 1233 cm-1. Therefore, by comparing the wavenumbers before and after Mn(II) ions biosorption, it
suggested that the functional groups of carboxyl, hydroxyl and amide may contributed to the Mn(II) ions
biosorption.

(a)

(b)
%T

Fig. 6. FTIR spectra for Pleurotus spent mushroom compost biosorbent (a) Before biosorption; (b) After Mn(II) ions biosorption.
 Ain Nihla Kamarudzaman et al. / Procedia - Social and Behavioral Sciences 195 (2015) 2709 – 2716 2715

4. Conclusion

Mn(II) ions biosorption studies using Pleurotus spent mushroom compost have been successfully performed in a
fixed-bed column. Column performance are strongly influenced by the variation of flow rate, bed height and initial
metal concentration. Mn(II) ions biosorption in fixed-bed column were achieved better performance at a flow rate of
1 mL/min, bed height of 30 cm and initial Mn(II) concentration of 10 mg/L. As a result, under these optimum
conditions the breakthrough time and exhaustion time were obtained at 16.5 hours and 26.7 hours, respectively.
Furthermore, when the breakthrough time and exhaustion time were extended, simultaneously the uptake and the
percentage removal of Mn(II) were increased. The study also revealed the surface morphology, elemental
compositions and functional groups of Pleurotus spent mushroom compost via ESEM, EDX and FTIR analysis. The
FTIR spectra suggested the carboxyl, hydroxyl and amide were the potential functional groups that may involved in
the Mn(II) biosorption. As conclusion, the Pleurotus spent mushroom compost has the potential as biosorbent for
the removal of Mn(II) ions from aqueous solution. For research improvement, the further study will focus on
investigating the mechanisms that may be involved during biosorption process.

Acknowledgements

We are grateful for the university resources provided by Universiti Teknologi MARA, Malaysia. Special
acknowledge to the Ministry of Education (MOE), Malaysia for granting us financial support under the Long Term
Research Grant (LRGS) (203/PKT/6720004).

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