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ISSN: 2229-6646

IJSTM, Vol. 2 Issue 4, December 2011


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CHARACTERIZATION OF BANANA AND ORANGE PEELS:


BIOSORPTION MECHANISM
Suantak Kamsonlian*, S. Suresh1*, C.B. Majumder and S. Chand
Department of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee-247 667, Uttarakhand,
India
1
Department of Chemical Engineering, Maulana Azad National Institute of Technology Bhopal, Bhopal-462 051,
India
*
Corresponding Email: sureshpecchem@gmail.com (SS), shoncool@gmail.com (SK)

Abstract- Banana and orange peels can provide an efficient and cost-effective biosorbents for
dyes, metals and organic pollutants removal from industrial water/wastewaters. Energy
dispersive Atomic X-ray (EDAX), Spectrometry Scanning electron microscopy (SEM),
Fourier transformation infrared (FTIR) and thermogravimetric (TGA) analysis were used to
characterize the surface of biosorbent. A better understanding of the chemistry behind these
interactions can help in the preparation of commercial biosorbents using waste banana and
orange peels. EDAX showed the presence of carbon, oxygen, sodium, aluminium, calcium,
Magnesium, potassium, sodium, silica and other minor elements on the surface of peels. FTIR
spectrometric results confirm that aliphatic group, carboxylic acid group etc on the surface of
peels. The TG traces showed the loss of moisture and the evolution of some light weight
molecules including water.
Key words Biosorbents, peels, EDAX and SEM analysis, FTIR spectrometry, TGA analysis

1. Introduction
Orange (Citrus sp.) is one of the citrus that
are abundant in India and orange residue is a
by-product of fruit industries that is mainly
used as animal feed. Banana (Musa sp.) peel
is an abundant and low cost agricultural
waste residue and is easily available in large
quantities. Achak et al. [2009] investigated
the efficiency of banana peel as a biosorbent
for removal of phenolic compounds from
Olive mill wastewaters. Orange residue, like
other citrus fruit residue, is composed of peel
and pulp (the fraction screened from the
juice). Orange peel is largely composed of
cellulose, pectin (galacturonic acid),
hemicellulose, lignin, chlorophyll pigments
and other low molecular weight compounds,
including limonene. Dominant components
of these fractions are respectively pectin,
cellulose, hemicellulose, lipid, some nitrogen
compound and almost 3% ash content
[Kefford and Chandler, 1970]. Pectic
substances are the predominant type of
polysaccharide identified for the cell walls of

orange residue. Due to the carboxyl


functions of galacturonic acid, pectic
substances are known to strongly bind metal
cations in aqueous solution [Khormaei et al.,
2007]. The organic compounds of fruit peel
are mainly cellulose, hemicellulose, pectin
substances, chlorophyll pigments, and other
low molecular weight compounds [Xiaomin
et al., 2007]. The pectin substances, which
account for more than 40 % of the dry
matter, are complex heteropolysaccharides
containing galacturonic acid, arabinose,
galactose, and rhamnose as the major sugar
constituents [Reddad et al., 2002]. Due to the
carboxyl functions of galacturonic acid,
pectin substances are known to strongly bind
metal cations in aqueous solution [Saeed et
al., 2005].
Owing to the high cost and difficult
procurement of activated carbon, efforts are
being directed towards finding efficient and
low-cost materials. Numerous approaches
have been studied for the development of
low-cost adsorbents for the removal of

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organic and organic pollutants from water
and wastewater. Fruits and their products can
serve as a major role for wastewater
treatment. The use of peel not only would
provide a less costly adsorbent in contrast to
activated carbon or synthetic ion exchangers
but is also easily available and will save the
environment from the abovementioned
pollution. Many sorbents based on low cost
agricultural by-products had been used for
dye sorption from wastewater, which
included banana pith [Namasivayam and
Kanchana,
1992],
orange
peel
[Namasivayam et al., 1996], tea waste
[Kamsonlian et al., 2011]wheat straw
[Robinson et al., 2002], sawdust [Garg et al.,
2004], powdered waste sludge [Serpil and
Fikret, 2006], wheat shells [Bulut et al.,
2007], wheat bran [Sulak et al., 2006] and
hen feathers [Mittal et al., 2007].
Polymerized onion skin with formaldehyde
[Kumar and Dara, 1981], waste wool
[Friedman and Nasri, 1973; Friedman and
Waiss, 1972], peanut skin [Randall et al.,
1975; Randall et al., 1978], modified barks
[Randall et al., 1976; Kumar and Dara,
1980], barks [Gharaibeh et al., 1998], barley
straw [Ajmal et al., 1998] have been studied.
Removal of nickel by adsorption using solid
residue form olive mill products [Guangju et
al., 1986], Mangifera indica seed shell
[Donali et al., 1992] have been reported.
Biosorption, the sorption of pollutants using
biological material, has emerged as a costeffective alternative to this problem, as it
utilizes cheap or even waste materials to
remove heavy metal ions. Citrus fruit waste
material has proved its potential as an
efficient lead biosorbent [Volesky, 1990;
Annadurai et al., 2003]. Some of biosorption
studied in literatures were shown here below.
Thirumavalavan et al. [2010] and Li et al.
[2007] was demonstrated to convert solid
fruit peel residue into an effective adsorbent
for the adsorption of metal ions and
compared the activity with activated carbon.
Lemon peel, orange peel, and banana peel as
adsorbents for the removal of various metal
ions such as Cu(II), Ni(II), Zn(II), Pb(II), and
Cd(II). All these adsorbents were

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characterized by FT-IR, BET, and SEM
(Explanation is given in the result and
discussion part).
Ajmal et al. [2000]
reported solid residue of orange fruit peel
and convert it to an adsorbent that has a large
surface area and thus great potential to
adsorb harmful contaminants, such as heavy
metals from aqueous solutions and industrial
waste at relatively low cost compared with
other available adsorbents. Biswas et al.
[2009] reported Zr(IV) and Fe(III) ions were
loaded onto an orange waste precursor to
prepare a metal-loaded orange waste gel for
the adsorptive removal and recovery of
antimony (III and V) from an aqueous
environment.
Feng et al. [2009] An adsorbent, the
chemically modified orange peel, was
prepared from hydrolysis of the grafted
copolymer, which was synthesized by
interaction of methyl acrylate with crosslinking orange peel. The presence of poly
(acrylic acid) on the biomass surface was
verified by FTIR, SEM and TGA
(Explanation is given in the result and
discussion part). Ghimire et al.[2003]
worked on the chemically modified
cellulose and orange waste were by means
of phosphorylation. The chemically
modified gels were further loaded with
iron(III) in order to create a suitable
chelating environment for arsenate and
arsenite removal. Preparation of adsorption
gel for metal ions from orange wastes by
simple chemical modification by Dhakal et
al. [2005]. Two types of adsorption gels,
Ca2+ and H+ gels, were prepared by
saponifying orange juice residues with
calcium hydroxide and its subsequent acid
treatment, respectively. Both gels were
adequately stable against dissolution in
aquatic environment. The Ca2+ form gel
was effective for the complete and selective
removal of Pb(II), Cu(II) and Fe(III)
compared with other divalent metal ions.
The removal of heavy metal ions Cr (VI)
and Zn (II) from aqueous solution using the
skin of orange peel Ekpete et al. [2010].
Lai et al. [2010] have conducted the
experiments orange peel cellulose, banana

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peel cellulose, orange peel cellulose


immobilized Ca-alginate beads and banana
peel cellulose immobilized Ca-alginate
beads for the adsorptive removal of Cu2+,
Pb2+, and Zn2+ from an aqueous solution
was tested. Liang et al. [2010] Mg2+ and
K+ type orange peel adsorbent for removal
of Cu2+. FTIR and SEM were used to
characterize the adsorbents. Lu et al. [2009]
reported orange peel cellulose bio-sorbents
has been specifically prepared by different
chemical modifications to understand the
mechanism of copper adsorption from
chloride solutions. The different biosorbents and raw orange peels were
characterized using elemental analysis and
FTIR. Li et al. [2008] have prepared the
chemically modified orange peel cellulose
adsorbents and its biosorption behaviors of
Co(II), Ni(II), Zn(II) and Cd(II) have been
studied. Effects of different chemical
modifications on the adsorbent properties
including different alkalis saponification
(NaOH, NH4OH, and Ca(OH)2) and
different acids (C6H6O7H2O, H2C2O4, and
H3PO4) modification after saponification
with NaOH were investigated. The FTIR
spectra showed that there are different
functional groups in adsorbents, which are
able to react with metal ions in aqueous
solution.
The purpose of this work is to investigate
the surface texture and other properties like
SEM, EDAX, FTIR and TGA on the
surface of banana and orange peels to
confirm the biosorption mechanism studies.
2. Material and methods
Biomass preparation: Fruit peel of banana
and orange peels was collected from the
fruit stall located in the campus of Indian
Institute of Technology, Roorkee, India.
The fruit peels were dried, crushed and
washed thoroughly with double distilled
water to remove the adhering dirt and
finally dried in an air oven at 100105 oC
for 24 h. After drying the bio-sorbents was
sieved through 150-mesh size and analysis
as such.

IJSTM, Vol. 2 Issue 4, December 2011


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To understand the morphology of the peels,
the scanning electron microscopy (SEM)
was carried out using a scanning electron
microscope (QUANTA, Model 200 FEG,
Netherland). Samples were gold sputtered
using a sputter coater, (Edwards S150), and
the SEM and the elementary analysis was
done simultaneously using an EDAX
Spectrometry. Textural characteristic of the
peels was determined by nitrogen
adsorption at 77.15 K using an automatic
pulse chemisorption system (Micromeritics
Chemisorb 2720). The BrunauerEmmett
Teller (BET) [Brunauer et al., 1938] surface
area and monolayer pore volume of the
Peels were determined using software
available with the instrument. The
functional groups in the peels were
ascertained using FTIR spectrometer
(Thermo Nicolet, NEXUS, USA) at room
temperature.
Pellet
(pressed-disk)
technique was used for this purpose. The
spectral range was from 4000 to 400 cm-1.
Thermogravimetric analysis (TGA) of the
samples was carried out using a DuPont HiRes TGA 2950, USA. About 10 mg of the
GAC sample was uniformly spread over
the crucible base in all the experimental
runs. Under a heating rate of 10 K/min and
an oxidizing atmosphere (moisture-free air
flowing at a rate of 200 ml/min), the
samples were heated from the ambient
temperature to 1000 oC. The differential
thermal gravimetry (DTG) and differential
thermal analysis (DTA) data were recorded
as a function of sample temperature and
time, using the Pyris diamond software.
3. Results and discussion
The average particle size of peels was
calculated to be 0.89 mm and 0.97mm.
Proximate analysis showed for banana peel
and orange peel: 12.20%, 10.32% moisture,
87.34%, 89.12% volatile matter and
3.3.5%, 3.10% Ash in blank-GAC. Heating
value of banana peel and orange peel were
found to be 3.83 MJ/ kg and 4.23 MJ/ kg,
respectively. The BET surface area of
orange peel and banana peel were found to
be 2.341 m2/g and 1.856 m2/g. Similar

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surface area has obtained in the modified
orange
peel
and
banana
peel
[Thirumavalavan et al., 2010].
3.1. Scanning electron microscopy
(SEM)
Characterization of the banana peel and
orange peel was studied using SEM
micrograph in the Fig. 1(a) and Fig. 1(b). It
showed the morphology behavior of banana
peel and orange peel. This figures showed
that the peels have an irregular and porous
surface.
Similar
structure
and
morphological were observed on the orange
peel [Thirumavalavan et al., 2010].

IJSTM, Vol. 2 Issue 4, December 2011


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peel were as follows: 30.12%,33.22% of
C, 41.81%, 44.12% of O, 15.60%, 13.02%
of K, 1.32%,1.12% of Si, 0.32%,0.4% of
Ca, 2.03%,1.30% of Na, 0.8%,1.34% of
Al, and 2.33%, 3.30% of Mg. Hence the
existence of proteins and polysaccrides
inside the biomass cell cover were
observed.

Figure 2a. EDX analysis of banana peel

Figure1a. SEM of banana peel.

Figure1b. SEM of orange peel


3.2. EDX analysis
EDX analysis of banana peel and orange
peel has been represented in the Fig. 2(1)
and Fig. 2(b). It showed the percentage
weight of chemical compositions available
on the surface of banana peel and orange

Figure 2b. EDX analysis of orange peel


3.3. Fourier transformation infrared
(FTIR)
FTIR spectroscopy method was used to
show the functional groups present on the
surface of the peels. Fig. 3(a) and 3(b)
shows FTIR spectra of the banana peel and
orange peel. As it could be seen from FITR
spectra, many functional groups were
presented on the peels surface. Looking at
the spectra, it shows band shifting and
possible involvement of hydroxyl groups
around the broad peak 3421.57 cm1 and
3422.43 cm1. The peak at 2923.06 cm1
and 2924.75 cm1 is due to CH stretching
vibrations of CH, CH2, and CH3 groups.
Apart from this the major visible change is
the increase in the C-O carboxyl band
1383.45 cm1 and 1236.34 cm1. Changes
in this band usually result from

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complexation of the carboxyl oxygen.


Similar peaks are observed by Khormaei et
al. [2007] and Lai et al. [2010]
for
biosorption of Copper ions onto sour
orange residue. As shown in Fig. 3(a) and
3(b), a major difference in the region
3853.67 cm1 and 3854.83 cm1 to 3421.57
cm1 and 3422.43 cm-1 were ascribed as
the vibrations of N-H and O-H functional
groups. The weak bands at 2923.06 cm-1
and 2924.75 cm-1 were assigned to the C- H
stretching mode which represents the
aliphatic nature of the peels. The absorption
bands at around 1637.45-1637.65 cm-1 to
1384.45-1438.70 cm-1 were characteristics
of C=C in aromatics rings. Furthermore,
peaks at 1054.40 cm-1 and 1071.46 cm-1
were attributed to Si-O stretching and Si-O
bending indicating of the silica presence.

light weight molecules including water


upto 174 oC and 175 oC for banana peel and
orange peel. The weight loss was 13.4%and
10.2% for banana peel and orange peel.
Higher temperature drying (>100oC) occurs
due to loss of the surface tension bound
water of the particles. Banana peel and
orange peel do not show any endothermic
transition between room temperature and
175 oC, indicating the lack of any
crystalline or other phase changes during
the heating process. The broad peak
observed from the first derivative loss
curve (DTG) may be due to the combustion
of carbon species.
40.00

251Cel
0.246 mg/min
197Cel
0.204 mg/min

64Cel
0.258 mg/min
30.00

0.600

298Cel
0.428 mg/min

200.0
0.400

372Cel
0.149 mg/min

180.0

0.200

303Cel
15.46 uV

20.00

0.000
160.0
-0.200

-42.9 uJ/mg

10.00

50

147 uJ/mg

48

-0.400

140.0

46

-20.00

38

1383.45

1734.98

40

1637.24

28

22

174Cel
86.6%

-1.200

250Cel
72.2%

80.0

310Cel
54.1%

-1.400

-1.600
60.0

400Cel
41.2%

-60.00

-1.800

600Cel
33.0%

499Cel
34.8%

-2.000

40.0

300 0

250 0

200 0

150 0

100 0

100

150

200

250

300
350
Temp Cel

400

450

500

550

600

Figure 4a. TGA-DTA graphs of banana


peel under oxidizing atmosphere.

16
350 0

-2.200
50

18

400 0

100.0

-70.00

20

-0.800

-1.000

99Cel
91.1%

-50.00

3421.57

24

3821.14

3853.67

26

120.0

71Cel
-7.20 uV

-40.00

2923.06

30

24Cel
99.9%

-30.00

1054.40

34

3751.32

%T

36

32

-10.00

TG %

534.42

42

DTA uV

-0.600

44

500

W av enu mber s ( c m- 1)

2339.73

619.25

Figure 3a. FTIR of banana peel.


0.500

1236.34

0.000

10.00

134 uJ/mg

2924.75

3841.10

3854.83

20

120.0

-10.00

25Cel
100.0%

74Cel
-2.82 uV
175Cel
89.8%

-1.500

300Cel
59.1%

225Cel
77.0%

60.0

-30.00

350 0

300 0

250 0

200 0

150 0

100 0

425Cel
33.8%

500

W av enu mber s ( c m- 1)

Figure 3b. FTIR of orange peel.


3.4. Thermo-gravimetric analysis (TGADTA)
Thermogravimetry was used to study the
thermal degradation characteristics of
peels. The TGA, DTA and DTG curves of
the banana peel and orange peel at a
heating rate of 10 K/min are shown in Fig.
4(a) and Fig. 4(b). The TG traces show the
loss of moisture and the evolution of some

-2.000

350Cel
43.1%

10
400 0

-1.000

80.0

3422.43

12

-0.500

100.0

100Cel
93.3%

-20.00

14

140.0

0.00

DTA uV

22

180.0

160.0

1071.46

1438.70
2849.32

24
%T

200.0

20.00

1637.65

3752.25

26

1742.33

28

16

330Cel
0.428 mg/min

67Cel
0.180 mg/min

30

18

210Cel
0.346 mg/min

30.00

-40.00

599Cel 40.0
26.3%

500Cel
28.4%

-2.500
50

100

150

200

250

300
350
Temp Cel

400

450

500

550

600

Figure 4b. TGA-DTA graphs of orange


peel under oxidizing atmosphere.
Conclusions/Summary
Commercial activated carbons generally
cost US$ 2000/tonnes in India. The waste
material used in the generally available at a
very cheap rate US$ 57/tonnes
[Bhatnagar et al., 2010]. Since the cost of

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DTG mg/min

32

TG %

34

DTG mg/min

0.00

ISSN: 2229-6646
final adsorbent prepared from waste fruit
peel is ~10 times less than the cost of
activated carbons, it is reasonable to
conclude that waste peel can be fruitfully
used as low-cost adsorbents for the
treatment of wastewater. Thirumavalavan
et al. [2010] suggested that a cost-effective
and viable technology for effective
elimination of heavy metal ions from
industrial wastewater could be developed
using easily available, familiar, and ecofriendly fruit peels.

Acknowledgement
Authors are deeply acknowledges the
financial support provided by MHRD,
India.
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