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Materials Today: Proceedings 5 (2018) 16675–16683 www.materialstoday.com/proceedings

SCICON 2016

Green adsorbents from solid wastes for water purification

application
S. Thambiraja G. Sharmilab and D. Ravi Shankarana,*
a
National Centre for Nanoscience and Nanotechnology, University of Madras, Chennai, India.
b
Department of Nanoscience and Technology, Bharathiar University, Coimbatore, India.

Abstract

We developed a green adsorbent material from orange fruit peel for the removal of dyes from polluted water. The conversion of
orange peels into green adsorbent was done by direct sunlight without using any chemical treatment. The adsorption study was
carried with three different dyes namely, brilliant green, methyl violet, and solochrome black. Different concentrations of the dye
solutions were prepared and evaluated for adsorption characteristics. The properties of the orange fruit peel and its interaction
with dyes have been characterized by various analytical techniques. The UV-vis, Fourier transform infrared spectroscopy and
visible color change results suggest that orange peels were effective toward removal of dyes from water. This method provides a
simple, green and low-cost strategy for water purification.

© 2017 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of International Conference on Advanced Materials (SCICON ‘16).

Keywords:Orange fruit peels; solid waste; green conversion; water purification; green adsorbent.

1. Introduction

Solid waste management is one of the major challenges faced by many countries around the global [1]. Many
industries including textile, paint, leather, printing, dyestuff, paper and plastic releases the pollutants such as organic
dyes, heavy metal ions, pesticides, food and pharmaceuticals wastes into the aquatic environment, which cause
major health problem to the living organisms and environment [2-9]. Removal of organic dyes from pollutant water
is highly important as the quality of the water is mainly influenced by color. Even, a small amount of dye is visible
and undesirable as they are highly toxic and carcinogenic [5, 10-12].

* Corresponding author. Tel.: +91- 9487974004

E-mail address: dravishankaran@hotmail.com; dravishankaran@unom.ac.in.

2214-7853© 2017 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of International Conference on Advanced Materials(SCICON ‘16).
16676 Thambiraj et al. / Materials Today: Proceedings 5 (2018) 16675–16683

Most of the organic pollutants including dye are more stable, non-biodegradable and small in size and hence it is
difficult to remove them from contaminating water [13]. There are many water purification methods including
chemical coagulation, precipitation, photodegradation, membrane separation, activated sludge, flocculation, and ion
exchange have been used to eliminate pollutant from contaminated water [2, 4, 14, 15]. The demand for the
development of simple and efficient method for the removal of harmful chemicals and dyes from pollutant water is
ever growing. When compared to the conventional methods the use of green adsorbent for water purification is
highly advantageous because of its readily availability, low-cost, high efficiency and environmental friendliness [5].
The natural green adsorbent such as orange peel, banana peel, rice husk, sugarcane bagasse, tea waste, avocado peel,
hamimelon peel, dragon fruit peels and other peels have been used for the extraction of heavy metal ions and organic
dyes from contaminating water [2, 9, 16-24].
One of the major areas of application of fruit peel wastes is water purification. The solid wastes can be utilized as
green adsorbents for the removal of toxic components such as heavy metals, dyes and pesticides from the
contaminated water [25]. The multifunctional characteristics of the fruit peel wastes for adsorption of pollutant from
water is facilitated by combination process, involving complexation, ion exchange and electrostatic interactions [26].
Orange fruit peel waste is one of the most abundant natural materials and most geographically diverse bio-waste
residues on earth and the huge remnants have never been utilized in an effective manner [27]. Orange peels waste
are composed of carbohydrates including fructose, glucose, sucrose, and cellulose [28]. The porous orange fruit peel
surface is hydrophilic in nature, which could be a good green adsorbent material for the removal of organic dye from
contaminated water. It was reported that, the adsorption behaviour enhanced after carbonization and activation of the
fruit peel surfaces [29, 30].
In this context, we aimed to develop a green adsorbent material from fruit peel wastes for water purification
application. Here, green adsorbent of orange peels was selected because of its low-cost, ready availability, stability,
processing method and potential stability to extract various pollutants. Orange fruit peel contains polar functional
groups such as –OH, -NH2 and – COOH on the surface. The characterization of the green adsorbent for dye
adsorption was studied by UV-visible spectroscopy and SEM. The results suggest that the green adsorbent of orange
peel is simple, low-cost and highly effective natural adsorbent for water purification.

2. Experimental Section

2.1. Materials

Orange fruits (Citrus sinensis – Rutaceae family) were collected from the local market in Chennai and orange was
peeled out and dried in the sunlight. Solochrome black and brilliant green dyes were purchased from Merck
chemicals, Mumbai, India. Methyl violet dye was procured from Hi-Media chemicals, Mumbai, India. All dyes were
used without any further purification. Millipore water was used for the preparation of stock solutions by dissolving
appropriate amounts of corresponding dyes in water.

2.2. Methods

2.2.1. Preparation of adsorbent from fruit peel by green method

The orange fruits was purchased in local market (in Chennai) were washed thoroughly with tap water,
peeled the outer layer and cut into small pieces of around 1-2 cm in size. The sliced orange fruit peels were washed
with tap water followed by deionized water for several time to remove any external dirt and dried in sunlight for 5
days. The dried peels were used as adsorbent for water purification. Fig.1. shows the schematic representation of the
dye removal from aqueous solution with the orange peel based green adsorbent.
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Fig.1. Schematic representation of dye removal using orange fruit peel

2.2.2. Preparation of dye solutions and adsorption studies

Different dye solutions were prepared and evaluated for adsorption studies using orange fruit peel. Dried orange
peel (Adsorbent - 0.5 g) was added to (10 mL) of different dye solutions at different concentrations (1mM, 3mM and
5mM). The adsorption studies were carried out at room temperature. The residual concentrations of solution were
analyzed after predetermined intervals of time. The initial concentrations of dye solutions were tested at 2, 5 and 10
mL and the experiments were carried out at room temperature for different time intervals from 0 to 30 h. Initial and
final dye concentrations in water were characterized by FT-IR and UV-visible spectroscopy.

2.3. Characterization Techniques

2.3.1. Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FT-IR) was performed by using a Thermo Scientific & Co., (Id
3, USA). FT-IR spectrometer simultaneously collected spectral data in a wide spectral range of 4000-400 cm-1 with 2
cm-1 spectral resolution at 16 scans. This study is used to analyze the various functional groups present in the orange
peel.

2.3.2. UV-Visible spectroscopy

UV-visible absorption of different dye solutions were recorded on Agilent diodaris spectrophotometer,
(Cary-8453, India). The sample solution was diluted with millipore water and sonicated for 10 minutes. The samples
were analyzed using standard quartz cuvettes in a spectral range of 200-800 nm at room temperature.
16678 Thambiraj et al. / Materials Today: Proceedings 5 (2018) 16675–16683

2.3.3. Scanning electron Microscope

The structural and morphological features of the orange peel were investigated by Scanning electron
microscope (SEM) (Hitachi SN-3400N-Japan) equipped with EDAX analysis, in the secondary electron mode.
Samples for SEM analysis were prepared by air-drying the adsorbed orange peels and the raw orange peels. SEM
operating in variable pressure (VP) mode and 20kV accelerating voltage was used for studying the surface
morphology of the orange peel. Elemental analysis of the dried orange fruit peel was studied before and after the
adsorption using EDX analysis.

3. Result and Discussion

Over the years, the concept of waste to wealth is growing rapidly on the management of solid waste. The
use of solid waste based natural green adsorbent for water purification is gaining a great interest [9]. The green
adsorbent material was evaluated for adsorption of the different dye solutions such as brilliant green (BG), methyl
violet (MV) and solochrome black (SB). The adsorption study was carried out by varying time, agitation speed,
particle size, concentration of adsorbate and adsorbent. The efficiency of adsorption various with the changes in
different parameters.

3.1. Green adsorbent from orange peel

The adsorption studies were carried out using different dyes solutions (solochrome black, methyl violet and
brilliant green). Fig.2 shows the photographic images of the adsorption behaviour of orange peel adsorbent. Fig.2 (a)
shows the dried orange peel. Fig.2 (b, c and d) shows the adsorption process of SB, MV and BG, respectively, by
the orange fruit peel. After adding the adsorbent, the color variation of the dye solutions was investigated at different
time intervals (6, 12, 18, 24 and 30 h).

Fig.2. Photographic images of the adsorption of dyes by the orange peel at different time intervals. (a) Orange peel;
(b) adsorption of solochrome black dye; (c) adsorption of methyl violet dye; and (d) adsorption of brilliant green
dye.
3.2. Surface functional group of orange peel

The functional groups on the orange peel with and without adsorbed dyes were studied by FT-IR
spectrophotometer (Fig. 3). The broad band observed at 3200−3650 cm−1 is attributed to the O-H stretching
vibration of orange peel [26]. The sharp peaks observed at 2928, 2921 and 2926 cm−1 corresponds to C-H stretching
frequency of the natural peels. The strong absorption peak appears at 1754 cm−1 is attributed to the C=O stretching
frequency of esters or carboxylic acid is present in the orange peel [26]. The band at 1680 cm-1 corresponds to the -
 Thambiraj et al. / Materials Today: Proceedings 5 (2018) 16675–16683 16679

C=C stretching vibration of an aromatic rings present in the orange peel. The absorption peak at 1330- 1200 cm-1
corresponds to the C-H stretching vibration of angular deformation plane in the aromatic ring. The weak absorption
band at 1250-1000 cm-1 is ascribed to the axial C-O bond in the phenolic group present in the orange peel [9].

After dye adsorption of orange peel, the peak positions of 3400, 3213, 2926 and 1613 cm−1 were shifted to 3446,
3236, 2906, 1622 cm−1. This indicates that OH, C-H-C, C=C, C=O frequency of carbonyl group could be involved
in the adsorption of orange peel [31]. There are no significant peak differences in the spectra observed the orange
peel after adsorption of SB dye. But, MV and BG dye adsorbed orange peels peak showed a slight difference. FT-IR
spectra clearly indicate that the orange fruit peel adsorbs dyes from the contaminated water.

Fig.3. FT-IR spectra of a) orange peel; b) orange peel after adsorption of SB dye; c) orange peel after adsorption of
MV dye; d) orange peel after adsorption of BG dye.

3.3. Morphological studies of orange fruit peel

The dried orange peels possess highly porous structure with the combination of small and large size pores on
the surface with the average pore size of ~19 ± 9 µm. The morphology of the dye adsorbed fruit peels shows a
significant change on the surface. After adsorption, the peel surface was partially covered by dye and the
homogeneous surface has been changed to heterogeneous rough surfaces. The fruit peel possesses hydroxyl and
carboxyl groups on the surface, which are responsible for the adsorption of dyes from the water [9].

Fig.4 shows the SEM micrographs of the orange peel before and after the adsorption of dye solutions at 100
µm magnifications. Fig.4 (a) shows the dried orange peel was observed the irregular morphology with an average
pore size of ~19 µm. This image clearly indicates the fruit peel surfaces is highly porous and homogeneous. Fig. 4
(b) shows the SB dye adsorbed orange peel and the porous surface were partially covered by dye. Fig. 4 (c) shows
MV dye adsorbed orange peel. Fig.4 (d) shows the BG dye adsorbed of orange peel and the porous surface was
completely closed with BG dye. This image clearly indicates the orange fruit peel acts as an efficient green
adsorbent for the removal of dyes.
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Fig.4. SEM images of the orange peel before and after adsorption; a) dried orange peel; b) SB dye adsorbed orange
peel; c) MV dye adsorbed orange peel; and d) BG dye adsorbed orange peel.

Elemental composition of different dye adsorbed orange peels was studied by EDX spectroscopy and the
results are shown in fig.5. Fig.5 (a) depicts the dried fruit peel confirms the elements of carbon and oxygen. These
elements indicate the peel surface was conceivably observed the hydroxyl and carboxyl groups of the cellulose
materials. Fig.5 (b) shows the SB dye adsorbed orange peel presents the elements of carbon, oxygen, magnesium
and silicon. Fig. 5 (c) shows the elemental composition of MV dye adsorbed orange peel surface confirms the
various elements of carbon, oxygen and nitrogen. Fig.5 (d) shows the BG dye adsorbed orange peel confirms the
elements of carbon, oxygen, nitrogen and sulphur. This spectrum depicts the BG dye was completely adsorbed on
the fruit peel surface. Comparison of the three dye solutions, SB and MV dyes are partially absorbed on the oranges
peel surfaces but, BG dye was completely adsorbed on the orange fruit peel surface.
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Fig.5. EDS orange peel adsorbed with different dyes; a) dried orange peel; b) SB dye adsorbed peel: c) MV dye
adsorbed orange peel; and d) BG dye adsorbed orange peel.

3.4. UV-Vis study on the absorption of different dyes on orange peel

Fig. 6. UV-Visible spectra of before and after adsorption of dyes at different time intervals; a) adsorption of SB dye,
b) adsorption of MV dye and c) adsorption of BG dye.
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Adsorption of the three different dye solutions was studied by UV-visible absorption spectroscopy. The
dyes solutions were evaluated for the spectral features before and after the interaction with orange peel adsorbent at
different time intervals such as 6h, 12h, 18h, 24h and 30h (Fig. 6). Fig. 6 (a) corresponds to the UV-vis spectra of
SB dye before and after adsorption, which showed an absorption band at 568 nm at 0th hour. After six hours the dye
was partially removed, whereas at 30th hour, a complete removal of dye by the orange peel was observed. Fig.6 (b)
depicts the UV-visible spectra of MV dye before and after interaction with orange peel. Two absorption peaks at
590 nm and 385 nm were observed for MV. On interaction with orange peel, a decrease in the peak intensity
indicates its adsorption. Similar result has been observed for the BG dye. Fig.6 (c) indicates the UV-visible
absorption spectra of before and after adsorption of BG dye solution. It showed absorption peaks at 315, 430 and
645 nm, which deceased on interaction with orange peel. The results indicate the orange peel acts as highly efficient
adsorbent for the removal of dyes from water.

4. Conclusion

The use of orange fruit peel as a potential green adsorbent for the extraction of organic dyes in water was
investigated. The orange peel was converted into dry adsorbent by sunlight without using any chemical treatment.
The adsorption studies at various conditions were carried out with the different dyes such as SB, MV and BG. It was
observed that adsorption efficiency increases with increase in particle mesh size. Uptake capacity of adsorbent
decreased with increase in adsorbent dose. The surface functional groups such as –OH, -NH2 and – COOH are
responsible for the enhanced adsorption properties. The results suggested that orange peel based green adsorbent is
highly effective towards the removal of dyes from pollutant water. Moreover, advantages of the orange fruit peels
such as renewable, low-cost, and non-toxic makes it a highly promising and green adsorbent material for water
purification.

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