Chemical Engineering Journal 270 (2015) 244271

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Review

Agricultural waste peels as versatile biomass for water purication A

review
Amit Bhatnagar a,, Mika Sillanp b, Anna Witek-Krowiak c
a
Department of Environmental Science, University of Eastern Finland, P.O. Box 1627, Kuopio FI-70211, Finland
b
Laboratory of Green Chemistry, LUT Savo Sustainable Technologies, Lappeenranta University of Technology, Sammonkatu 12, FI-50130 Mikkeli, Finland
c
Division of Chemical Engineering, Department of Chemistry, Wrocaw University of Technology, Norwida 4/6, 50-373 Wrocaw, Poland

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Application of agricultural waste

peels based biosorbents in water
treatment has been reviewed.
 Sorption capacities of waste peels
biosorbents for pollutants have been
reviewed.
 Future research needs in this eld
have been proposed.

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

Article history: Agricultural waste peels have been recognized as an ecological burden for the society. However, waste
Received 3 November 2014 peels, as lignocellulosic biomass-rich materials, have stimulated new gateways for the production of
Received in revised form 22 January 2015 renewable, low cost and sustainable adsorbents for water treatment applications. This review compiles
Accepted 24 January 2015
the work conducted by various researchers over the last few decades on the use of various agricultural
Available online 11 February 2015
waste peels as adsorbents for the water and wastewater treatment. In this review, adsorption capacities
for organic and inorganic pollutants by different peel-based adsorbents are summarized. Wherever appli-
Keywords:
cable, different modication methods, which have been employed to develop modied peel-based adsor-
Fruit peels
Vegetable peels
bents, have also been presented to highlight and discuss the key advancements on the preparation of
Adsorbents novel adsorbents using agricultural waste peels. Adsorption mechanisms responsible for pollutants
Water treatment removal by peel-based adsorbents have also been discussed. Finally, conclusions have been drawn from
Metals the literature reviewed. The paper also discusses the future research needs in the area of biosorbent
Dyes development utilizing agricultural waste peels for application in water treatment.
2015 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
2. Agricultural waste peels as adsorbents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
2.1. Citrus waste peels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
2.1.1. Orange peel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246

Corresponding author. Tel.: +358 503696419.

E-mail addresses: amit.bhatnagar@uef., dr.amit10@gmail.com (A. Bhatnagar).

http://dx.doi.org/10.1016/j.cej.2015.01.135
1385-8947/ 2015 Elsevier B.V. All rights reserved.
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271 245

2.1.2. Pomelo peel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253

2.1.3. Grapefruit peel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
2.1.4. Lemon peels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
2.2. Banana peel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
2.3. Cassava peel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
2.4. Jackfruit peel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
2.5. Pomegranate peel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
2.6. Garlic peel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
2.7. Miscellaneous peels as adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
3. Desorption and regeneration/reuse studies with peel-based adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4. Continuous biosorption studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
5. Real wastewater treatment with peel-based adsorbents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
6. Concluding remarks and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268

1. Introduction reactive groups (hydroxyl, acetamido or amino functions) in poly-

The water quality has severely deteriorated globally in last few
decades, mainly due to the anthropogenic activities, population
growth, unplanned urbanization, rapid industrialization and
unskilled utilization of natural water resources. The main sources
of water pollution include discharge of untreated sanitary and tox-
ic industrial wastes, dumping of industrial efuent, and runoff
from agricultural elds besides others. In recent years, various tox-
ic chemicals/compounds (e.g., micropollutants, personal care prod-
ucts, endocrine disrupting compounds, pesticides, inorganic anions
etc.) have been detected at dangerous levels in drinking waters in
many parts of the world and a variety of health risks to human
beings due to water pollution have been reported in literature.
Keeping the view of serious health problems to human beings
due to elevated concentration of toxic pollutants, there is an urgent
need for developing robust, economically feasible and environ-
mentally friendly processes to remove them from water and to
safeguard the health of affected populations.
A variety of treatment technologies are available with varying
degree of success to control/minimize water pollution [1]. Howev-
er, the shortcomings of most of these methods are high operational
and maintenance costs, generation of toxic sludge and complicated
procedure involved in the treatment. Comparatively, adsorption
process is considered a better alternative in water treatment
because of convenience, ease of operation and simplicity of design
[2]. Further, this process can remove/minimize different type of
pollutants and thus, it has a wider applicability in water pollution
control. Activated carbon is undoubtedly considered as universal
adsorbent for efuent treatment and is commonly used for the
removal of various pollutants from water. However, its widespread
use in wastewater treatment is sometimes restricted due to its
higher cost. A large variety of low-cost adsorbents have been
examined for their ability to remove various types of pollutants
from water and wastewater and have been reviewed extensively
[38]. In general, an adsorbent can be assumed as low cost if it
requires little processing, is abundant in nature, or is a by-product
or waste material from the industry. It has been found that various
low-cost adsorbents developed from different origins show little or
poor adsorption potential for the removal of aquatic pollutants as
compared to commercial activated carbon. Therefore, the search
to develop efcient sorbents is still going on.
In past few years, numerous approaches have been studied for
the development of cheaper and more effective adsorbents con-
taining natural biopolymers. These biopolymers represent an inter-
esting and attractive alternative as adsorbents because of their
particular structure, physico-chemical characteristics, chemical
stability, high reactivity and excellent selectivity toward aromatic
compounds and metals, resulting from the presence of chemical
mer chains. Various bio-based/biopolymer materials have been
examined for the removal of diverse type of pollutants from water.
Agricultural waste materials are economic and eco-friendly due to
their unique chemical composition, and their availability in abun-
dance, renewable nature and low cost make them viable option for
aquatic pollutants remediation. Agricultural by-products usually
are composed of lignin and cellulose as major constituents and
may also include other polar functional groups of lignin, which
include alcohols, aldehydes, ketones, carboxylic, phenolic, and
ether groups. These groups have ability to bind aquatic pollutants
through different binding mechanisms. Among several agricultural
wastes that have been studied as biosorbents for water treatment,
waste peels from fruits and vegetables are of great importance
since most of the peels are discarded as waste and nd no applica-
tion anywhere, which sometimes pose serious disposal problems.
Being a renewable resource and an agro-industrial waste, waste
peels are, therefore, a promising resource for environmental tech-
nology if applied in the treatment of water and wastewaters.
Although many review articles have been published so far dis-
cussing the importance of low-cost adsorbents and/or biosorbents
in water pollution control, but many of them are generally either
adsorbate-specic (metals, dyes, phenols, etc.) or adsorbent-specif-
ic. There is only a recent review article available summarizing the
published literature (after 2010) on the use of agricultural peels for
dye adsorption only (adsorbate specic) [9]. However, to the best
of authors knowledge, no other review is yet available discussing
the usefulness of various agricultural waste peels as adsorbents
for the removal of variety of aquatic pollutants. Therefore, the pre-
sent review focuses on the valorization approach of different agri-
cultural peels (fruits and vegetables) as adsorbents for the removal
of diverse aquatic pollutants (metals, dyes, phenolic compounds,
inorganic anions, radionuclides etc.) from water and wastewater.
For information pertaining to detailed experimental methodology
and conditions, readers are referred to the full articles listed in
the references.
2. Agricultural waste peels as adsorbents
Fruit and vegetable peels consist of the highest percentage of
wastes in most kitchen garbage bins. Furthermore, in fruit and veg-
etable industries, it is common that some waste is generated dur-
ing processing (selecting, sorting, boiling processes). Processing of
fruits and vegetables produces different types of waste including a
solid waste of peel/skin. Many of the fruits and vegetables skins
(peels) are discarded in the garbage or fed to livestock. Fruits and
vegetables wastes and by-products, which are formed in great
amounts during industrial processing, represent a serious problem,
as they exert an inuence on environment and need to be managed
246 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
Fig. 1. Record of the number of publications in indexed journals containing the keyword peels and adsorbents between 2000 and 2014. (Source: Scopus, searched on 06
January, 2015).
and/or utilized. On the other hand, they are very rich in bioactive
components, which are considered to have a benecial effect on
health [10]. Since last decade, efforts have been made to improve
methods and ways of reusing fruits and vegetables wastes. One
of the important ways is to valorize the biocomponents in by-prod-
ucts from fruit and vegetable industries. Plant waste is prone to
microbial spoilage; therefore drying is necessary before further
exploitation. Till now, agro industrial waste often is utilized as feed
or fertilizer. They are high value products and their recovery will
be economically attractive [10]. Some novel value-added products
from fruit and vegetable wastes which have developed in recent
years include essential oils, polyphenolic compounds, edible oils,
pigments, food additives, anti-carcinogenic compounds, dietary
bres, enzymes, bio-ethanol, bio-degradable plastic and other mis-
cellaneous products.
Agricultural waste peels are natural, eco-friendly and economic
sources of adsorbents, which can be used in the removal of diverse
types of aquatic pollutants and also reduce pollution. Being a
renewable resource, agricultural waste peels are, therefore, a
promising resource for environmental technology if applied in
the treatment of water and wastewaters. As a matter of fact, pub-
lications related to peel-based adsorbents in indexed journals have
been growing rapidly, especially in past few years, indicating a
growing interest of the scientic community in this research eld
(Fig. 1).
2.1. Citrus waste peels
Citrus production and consumption worldwide has increased
tremendously over the past few decades. Statistical data from the
Food and Agriculture Organization of the United Nations (FAO-
STAT) reveals that the world production of citrus fruits in 2010
was over 100 million tons [11]. A large amount of citrus waste is
generated by the consumption of these fruits, which may be as
high as 50% of the fruit weight. Up to now, the majority of citrus
wastes are still deposited or disposed of simply by burning or used
as raw material for active substance extraction and animal feed
manufacturing, leading to serious environmental pollution and
great wastage of resources. Therefore, it is highly desirable to
develop green and economical ways to deal with citrus wastes,
as well as to utilize the wastes to produce staple or value-added
products such as adsorbents.
2.1.1. Orange peel
Orange peel is discarded in the orange-juice and soft-drink
industries all over the world. Accumulation of orange waste in
the orange industries has resulted in two important problems
which are land space occupation and pollution with phenolic com-
pounds due to dumping of this waste. Orange peel is mostly com-
posed of cellulose, pectin, hemi-cellulose, lignin, chlorophyll
pigments and other low molecular weight hydro-carbons which
contain many hydroxyl functional groups thus making it a poten-
tial sorbent for many pollutants. Since the orange peel is available
free of cost from orange processing industries, many researchers
have investigated its potential as sorbent for various aquatic pollu-
tants removal. The ability of fruit peel of orange to remove Zn, Ni,
Cu, Pb and Cr from aqueous solution by adsorption was studied
[12]. The adsorption was in the order of Ni(II) > Cu(II) > Pb(II) > Z-
n(II) > Cr(II). The adsorption of Ni(II) was pH dependent and max-
imum removal occurred at pH 6. Desorption was possible with
0.05 M HCl and was found to be 95.83% in column and 76% in batch
process, respectively. The spent adsorbent was regenerated and
recycled thrice. The removal and recovery was also done in waste-
water and was found to be 89% and 93.33%, respectively. Orange
peel modied with different chemical reagents as biosorbents
were used to remove cadmium ion from aqueous solution [13].
First crude dried orange peel was ground in ball mill to obtain
smaller particles of approximate size between 0.1 and 0.2 mm
which were used in the experiments. Its average pore diameter
was 30.5 and specic surface area was 128.7 m2 g1. Effects of
different chemical modications including washing, alkali saponi-
cation, cross-linking temperature and concentration of cross-link-
ing reagent on the biosorbent properties were investigated. It was
concluded that cadmium ion could be removed by 0.6SCA80
(orange peel modied with 0.6 mol/L citric acid under 80 C after
alkali saponication) biosorbent effectively and quickly. For
0.6SCA80, the maximum capacity of cadmium was 0.90 mol/kg,
the optimum pH value was 6, the reaction balance was established
after a shaking time of 120 min and the optimum solid/liquid ratio
was 4.3 g/L. The desorption rate of cadmium was 94% with
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
Fig. 2. Mechanism of alkaline modication. Reprinted with permission from Elsevier from Ref. [14].
Fig. 3. Mechanism of acid oxidation after saponication. Reprinted with permission from Elsevier from Ref. [14].
0.15 mol/L HCl solution. The preparation of chemically modied
orange peel cellulose adsorbents and its biosorption behaviors of
Co(II), Ni(II), Zn(II) and Cd(II) have been studied [14]. The elemen-
tal analysis of raw orange peel showed that it is composed of 42.2%
carbon, 5.4% hydrogen, 51.4% oxygen and 1.0% nitrogen. Effects of
different chemical modications including different alkalis saponi-
cation (NaOH, NH4OH, and Ca(OH)2) and different acids (C6H6-
O7.H2O, H2C2O4, and H3PO4) modication after saponication
with NaOH (SNa) on the adsorbent properties were investigated.
Fourier transform infrared spectroscopy (FTIR) spectra showed that
there were different functional groups in adsorbents, which were
able to react with metal ions in aqueous solution. The maximum
adsorption capacities of Ni(II), Co(II), Zn(II) and Cd(II) for SPA
(orange peel modied with phosphoric acid after SNa), SCA (orange
peel modied with citric acid after SNa) and SOA (orange peel
modied with oxalic acid after SNa) were obtained as 1.28, 1.23,
1.21 and 1.13 mol/kg and have increased by 95%, 178%, 60% and
130% compared to raw orange peel, respectively. The reaction
mechanism, suggested by the authors, was ion exchange mechan-
ism between Na+ or NH+4 or Ca2+ and the bivalent metal ions, as
shown in Fig. 2.
Furthermore, mechanism of acid oxidation after saponication
involved the production of acid anhydride. The reactive anhydride
was combined with cellulose hydroxyl groups so as to form an
ester linkage and introduce carboxyl groups to the cellulose. The
authors proposed that enhanced metal ions adsorption might be
attributed to the generation of COOH groups and the adsorption
process can be expressed as Fig. 3.
Natural, formaldehyde-treated and copolymer-grafted orange
peels (COP) were evaluated as adsorbents to remove lead ions from
aqueous solutions [15]. The proposed mechanism, involved during
copolymerization of acrylamide and methacrylic acid and (b) graft-
ing reaction of COP onto natural biomass (NB), is shown in Fig. 4.
The optimum pH for lead adsorption was found to be 5. The
adsorption process was fast, reaching 99% of sorbent capacity in
10 min for the natural and treated biomasses and 20 min for the
grafted material. In the continuous test with the treated biomass,
the capacity at complete exhaustion was 46.61 mg/g for an initial
concentration of 150 mg/L. FT-IR spectra revealed that the func-
tional groups responsible for metal biosorption were the OH,
COOH and NH2 groups on the surface. The chemically modied
orange peel (OP) was prepared from hydrolysis of the grafted
copolymer, which was synthesized by interaction of methyl
acrylate (MA) with cross-linking orange peel [16]. Fig. 5 shows
247
the proposed grafting mechanism of OP with MA using ceric
ammonium nitrate as initiator.
The presence of poly (acrylic acid) on the biomass surface was
veried by infrared spectroscopy (IR), scanning electron micro-
scopy (SEM) and thermogravimetry (TG). The modied biomass
was found to exhibit high adsorption capacity and fast adsorption
rate for Cu(II) ions. From Langmuir isotherm, the adsorption capa-
city for Cu(II) was found to be 289.0 mg/g, which was about 6.5
times higher than that of the unmodied biomass. The adsorbent
was used to remove Cu(II) from electroplating wastewater and
was found suitable for repeated use for more than four cycles.
The adsorption behavior of Cu2+ and Cd2+ on mercapto-acetic acid
modied orange peel was investigated [17]. The chemical treat-
ment involved pretreatment of orange peel with NaOH solution;
followed by leaching with mercapto-acetic acid (C2H4O2S) in order
to convert its abundant hydroxyl groups into mercapto groups
which have a high afnity for metal ions, thereby enhancing its
adsorption capacity according to the reaction shown below:
ROH HOOCCH2 SH ROOCCH2 SH nH2 O
The results of element analysis of C and S on infrared CS
analyzer showed that after chemical modication, C% decreased
from 43.24% to 36.94%, and S% increased from 0.12% to 0.19%,
which means that some hydro-carbons were removed and sulfur
atom was chemically bonded and/or physically adhered to the sur-
face of OP. Maximum adsorption capacities of Cu2+ and Cd2+ on the
mercapto-acetic acid modied orange peel were found to be 70.67
and 136.05 mg/g, respectively. Adsorptiondesorption studies
showed that the mercapto-acetic acid modied orange peel could
be used for more than ve cycles. Orange peel (OP) was used as
raw material to prepare two novel adsorbents: MgOP (Mg2+ type
orange peel adsorbent) and KOP (K+ type orange peel adsorbent)
[18]. In the preparation of different orange peel adsorbents, etha-
nol was rst used to discolor the orange peel and remove some
polarity organic compounds. NaOH was utilized to further remove
hemi-cellulose, pigment and other low molecular weight com-
pounds, and also to convert COOCH3 on orange peel surface to
COO by hydrolyzation, thereby increasing the amount of car-
boxylic group. Meanwhile, NaOH, MgCl2 and KCl all can be used
to exchange H+ type of carboxylic groups to Na+, Mg2+ or K+ type
in order to increase ion-exchange ability. Moreover, MgCl2 can
immobilize some COO in the form of (COO)2Mg to reduce
unnecessary loss of useful functional groups with water washing.
FTIR analysis revealed that some functional groups (COOH and
248 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
Fig. 4. (a) Copolymerization of acrylamide and methacrylic acid and (b) grafting reaction of COP onto natural biomass (NB). Reprinted with permission from Elsevier from Ref.
[15].
OH) were successfully modied by chemical treatment. Langmuir
model provided the best correlation for the adsorption of Cu2+ by
both MgOP and KOP, and the mono-layer adsorption capacity for
Cu2+ removal by MgOP and KOP were 40.37 and 59.77 mg/g,
respectively. The adsorbed amounts of Cu2+ increased with the
increase in contact time and reached equilibrium within 20 min.
Thermodynamic studies showed the spontaneous and exothermic
nature of the adsorption of Cu2+ by MgOP and KOP. Orange peel
biosorbent containing the extractant Cyanex 272 was prepared
by the method of solidliquid grinding and studied in removing
Pb(II) from aqueous solution [19]. Orange peel (OP) biosorbents
were characterized by various analytical techniques, which con-
rmed that carboxylic groups were introduced into the orange peel
by chemical modication [citric acid (CO), saponication and citric
acid (SCO)] and that Cyanex 272 was successfully immobilized on
the orange peel (272OP, 272CO, and 272SCO). In addition, Cyanex
272 played an important role in the adsorption process, i.e., the
maximum adsorption capacity was improved, with the order of
the adsorption capacities being 272SCO (1.30 mol/kg) > SCO
(1.26 mol/kg) > 272CO (1.20 mol/kg) > 272OP (1.02 mol/kg) > CO
(0.62 mol/kg), and the equilibrium time was shortened from 60
to 40 min for 272SCO. Adsorption of Pb(II) was found to be strongly
dependent on pH, with the optimum pH range being 5.05.8 for all
adsorbents, and the removal rate of Pb(II) by 272SCO could be as
high as 100%. The optimum solid/liquid ratio was 3.7 g/L for an ini-
tial Pb(II) concentration of 0.002 mol/L. The optimum desorption
agent was found to be 0.1 mol/L HCl. The adsorption capacity of
272SCO declined slightly after being recycled six times. After the
sixth cycle, the adsorption rate of Pb(II) onto 272SCO was still
89.61%.
Orange peel (OP) was modied by KCl to prepare a novel orange
peel adsorbent named as KOP [20]. The adsorption behaviors of
KOP for ve heavy metals (Cu2+, Cd2+, Pb2+, Zn2+, Ni2+) were stud-
ied. The equilibrium was achieved in 20 min and kinetic data of
ve heavy metal ions were tted to pseudo-second-order model.
The maximum adsorption capacities for Cu2+, Cd2+, Pb2+, Zn2+ and
Ni2+ were calculated as 59.77, 125.63, 141.84, 45.29 and
49.14 mg/g, respectively. Recycle and reuse experiments indicated
that KOP could be used for more than ten cycles. Sulfured orange
peel (MOP) was used as adsorbent to investigate its adsorption
behaviors of Pb2+ and Zn2+ from aqueous solutions [21]. The max-
imum Langmuir adsorption capacities for Pb2+ and Zn2+ removal by
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
Fig. 5. Proposed mechanism of graft copolymerization of MA on OP using ceric ammonium nitrate initiator. (Cell-OH, Hemicell-OH and Gala-OH represent cellulose,
hemicellulose and galacturonic acid a hydroxyl group respectively and Lign-phOH represents a phenolic hydroxyl group on lignin). Reprinted with permission from Elsevier
from Ref. [16].
MOP were evaluated as 164 and 80 mg/g, respectively. The sul-
fured orange peel can adsorb metal ions through ion exchange,
or complexation, or by a combination of both processes. Authors
further explained that in a cation exchange mechanism, H+ will
be released from the SH, OH and COOH bonds from MOP,
meanwhile metal ion will be adsorbed onto the active sites of
the adsorbent. The possible reactions, proposed by the authors,
are shown blow:
2ROH M2 RO2 M 2H
2RCOOH M2 RCOO2 M 2H
2ROOCCH2 SH M2 ROOCCH2 SH2 M 2H
Authors suggested that in a complexation mechanism, four sul-
fur atoms will complex with one divalent metal ion, which can be
shown as follows:
249
A binary mixture of Pb2+ and Zn2+ was studied by using a packed
column, suggesting that effective mutual separation and pre-con-
centration of Pb2+ away from Zn2+ using MOP could be satisfactory
achieved.
Orange peel powder (OPP) was successfully modied into a
novel magnetic nano-adsorbent (MNPOPP) by co-precipitating it
with Fe3O4 nanoparticles (MNP) for cadmium ion removal from
aqueous solutions [22]. The BET surface area of OPP, MNP and
MNPOPP was found to be 47.03, 76.32 and 65.19 m2g1 respec-
tively. Authors pointed out that although MNPOPP had a lower
surface area than MNP, its adsorption capacity was higher which
indicates that the multiple functional groups on MNPOPP played
an important role in the enhancement of the adsorption capacity.
Characterization of MNPOPP by FTIR, SEM, XRD, TEM and VSM
also revealed the covalent binding of hydroxyl groups of MNP with
the carboxyl groups of OPP, and further conrmed its physico-che-
mical properties favorable for metal binding. Results of the study
revealed a faster kinetics and efciency of MNPOPP in comparison
to those of MNP and OPP and further conrmed a complexation
and ion exchange mechanism to be operative in metal binding. It
was discussed by the authors that at pH > pHpzc, FeOH and
FeO(C@O)(OH)n are the dominant species in MNP and MNP
OPP respectively. Such deprotonated species undergo electrostatic
attraction for Cd2+ that result in the formation of metalligand
250 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
Fig. 6. Preparation of metal-loaded orange peel gels. Reprinted with permission from Elsevier from Ref. [23].
magnetic composite complexes which caused enhanced adsorp-
tion. Authors suggested that complexation and ion exchange
appear to be the principle mechanism of the adsorption as revealed
by:
FeOH Cd
2
! FeOCd H for MNP
2
HOC@OMOHn Cd ! HOC@OMOCdn and 3.22 mg/g for the dyes congo red, procion orange and rho-
nH for OPP
2
FeOC@OOHn Cd ! FeOC@OOCdn 12.0, 11.0 and 11.0, respectively. The effectiveness of orange peel
nH for MNPOPP
The adsorption equilibrium data obeyed the Langmuir model
and the kinetic data were well described by the pseudo-second-
order model. Langmuir adsorption plot showed maximum Cd2+
removal capacity of 76.92 mg/g by MNPOPP at optimal conditions
and thermodynamic studies revealed the feasibility of the process.
Pseudo-second-order model was determined as the best t model.
Column studies with a breakthrough capacity of 55.38 mg/g as well
as 82% Cd2+ removal from an electroplating efuent simulated was-
tewater revealed the practical utility of the developed adsorbent.
Orange peel was chemically modied and loaded with Zr(IV), La(III),
Ce(III) and/or Fe(III) (Fig. 6) and its adsorption behavior was exam-
ined for Mo(VI) [23]. The maximum adsorption capacity for molyb-
denum was in the order, Zr(IV)-SOW (1.13 mol/kg) > La(III)-SOW
(1.07 mol/kg) > Fe(III)-SOW (0.90 mol/kg) > Ce(III)-SOW (0.88 mol/
kg) at the same experimental condition. The removal of As(III) from
contaminated water by orange peel (OP) was studied [24]. At the
optimum treatment conditions of pH (7), temperature (30 C), con-
tact time (90 min) and adsorbent dosage (4 g), OP biomass was
found to be effective for the removal of As(III) with 82.45% sorption
efciency at a concentration of 50 mg/L As(III), and thus uptake
capacity was 1.18 mg As(III)/g of biomass.
The adsorption of metals (Cu2+, Zn2+, Co2+, Ni2+, Pb2+) from syn-
thetic solutions using the acid-, alkali-, and water-treated orange
peels was studied [25]. The adsorption capacity was found to be
7.75 (Pb2+), 6.02 (Ni2+), 5.25 (Zn2+), 3.65 (Cu2+), and 1.82 mg/g
(Co2+) using orange peel. The adsorption of dyes such as congo
red, procion orange and rhodamine B by waste orange peel was
examined at different concentrations of dyes, adsorbent dosage,
agitation time and pH [26]. The adsorption capacity was 22.4, 1.3
damine B, respectively. The adsorption was maximum at pH 5.0,
3.0 and 3.0 for congo red, procion orange and rhodamine B, respec-
tively. The optimum pH for desorption of congo red, procion
orange and rhodamine B from the dye-loaded adsorbent was
in adsorbing Acid violet 17 from aqueous solutions has been stud-
ied as a function of agitation time, adsorbent dosage, initial dye
concentration and pH [27]. The adsorption followed both Langmuir
and Freundlich isotherms. The adsorption capacity was found to be
19.88 mg/g at initial pH 6.3. The equilibrium was achieved in
80 min for different initial dyes concentration. A maximum
removal of 87% was obtained at pH 2.0 for an adsorbent dose of
600 mg/50 mL of 10 mg/L dye concentration. Adsorption increased
with increase in pH. Maximum desorption of 60% was achieved in
water medium at pH 10.0. The removal of textile dyes (Direct Red
23 (DR23) and Direct Red 80 (DR80)) from aqueous solutions by
orange peel was investigated [28]. The adsorption capacity was
found to be 10.72 and 21.05 mg/g at initial pH 2. The results indi-
cated that acidic pH supported the adsorption of both dyes on the
adsorbent. Orange peel with concentrations of 8 and 4 g/L showed
adsorption efciencies of about 92 and 91% for DR23 and DR80,
respectively. Maximum desorption of 97.7% for DR23 and 93% for
DR80 were achieved in aqueous solution at pH 2. The potential
use of activated carbon prepared from orange peel for the removal
of direct blue-86 (DB-86) dye from simulated wastewater was
examined [29]. Optimum pH value for dye adsorption was deter-
mined as 2.0. Maximum dye was sequestered within 30 min after
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271 251

Fig. 7. Chemical modication of peel waste and proposed mechanism of adsorption/desorption of uoride. Reprinted with permission from Taylor & Francis from Ref. [36].

the beginning for every experiment. The adsorption of DB-86 fol-
lowed a pseudo-second-order rate equation and tted well with
Langmuir, Tempkin and DubininRadushkevich (DR) models bet-
ter than Freundlich and RedlichPeterson models. The maximum
removal of DB-86 was obtained at pH 2 as 92% for adsorbent dose
of 6 g/L and 100 mg/L initial dye concentration at room tem-
perature. The maximum adsorption capacity obtained from Lang-
muir model was 33.78 mg/g. The removal of textile dyes from
articial textile dye efuent by activated carbons developed from
orange peel was examined [30]. Direct Yellow 12 (DY-12) was used
as the model compound due to its wide range of applications and
high stability in the environment. The maximum removal was 96%
for 125 mg/L of DY-12 concentration at 5 g/L carbon concentration.
The results indicated that acidic pH (1.5) supported the adsorption
of DY-12 on activated carbon developed from orange peel. The
maximum adsorption capacity calculated from the Langmuir iso-
therm model was 75.76 mg/g. Activated carbon developed from
orange peels was used for the removal of Direct Navy Blue 106
(DNB-106) from wastewater [31]. The maximum adsorption capa-
city was 107.53 mg/g for 150 mg/L of DNB-106 concentration and
2 g/L carbon concentration. Adsorption of the reactive gray BF-2R
dye from an aqueous solution using orange peel as adsorbent
was investigated in batch mode [32]. Characterizing the orange
peel using the BET method, surface area of 2.14 m2 g1 with a pore
volume of 4.8714 cm3 g1 a pore size of 9.24 was obtained.
Experiments characterizing the chemical and physical properties
of the adsorbent found that orange peel is a microporous material
with a pHzpc (point of zero charge) 3.9 and containing carboxylic
and sulfonic groups. The greatest adsorption capacity was obtained
using a 23 factorial design for 0.25 g of adsorbent, particle size
<0.419 mm and at 300 rpm.
The adsorption of naphthalene from aqueous solution onto
unripe orange peel has been investigated [33]. Results of the batch
adsorption experiment showed that equilibrium adsorption was
252 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271

Table 1 and water molecule that may be available in the coordination

Chemical composition of orange peel adsorbent by X-ray uores- sphere could also be contributing to the ligand-exchange reactions
cence analysis. Reprinted with permission from Braz. J. Chem. Eng.
from Ref. [43].
with uoride ion. Maximum uoride removal (5.605 mg/g) was
achieved at adsorbent dose of 7.0 g/L, pH 6.0, and a contact time
Characteristics Values of 50 min. The reuse study of the adsorbent resulted in retention
CaO 1.42% of 83% capacity in eighth cycle. Desorption studies showed that
K2O 0.18% the uoride can easily be desorbed by using 0.1 N NaOH solution.
SO3 0.14%
MgO 0.12%
The chemical composition of the orange peel adsorbent as deter-
Fe2O3 0.11% mined by X-ray uorescence is shown in Table 1.
SiO2 0.08% Activated carbon from orange (Citrus sinensis) peel was devel-
P2O5 0.05% oped by H3PO4 acid activation by Fernandez et al. [37] and its abil-
BaO 0.02%
ity as an adsorbent was examined for the removal of two
SrO 0.01%
Al2O3 0.01% representative basic dyes (methylene blue and rhodamine B) from
NiO 0.01% single and binary dyes solutions in batch and continuous modes.
WO3 Not detected The orange peel-based activated carbon presented a high specic
ZnO Not detected surface area (1090 m2/g), predominance of mesopores and acidic
Mn Not detected
character. The prepared adsorbent showed a high adsorption capa-
Organic matter 97.83%
city for both dyes in batch and dynamic modes. Breakthrough
curves obtained from single-dye solutions exhibited a better
attained in 180 min. The adsorption capacity of the unripe orange removal performance for rhodamine B. Adsorption capacity at
peel for an initial 100 mg/L of naphthalene was maximum at an exhaustion time for this dye was 11% higher than for methylene
optimum pH of 6, with an orange peel loading of 7.5 g. Orange peel blue. The adsorption of toluidine blue (TB), a basic dye, onto orange
was also utilized as low-cost adsorbent to remove carbofuran from peel waste (OPW) was investigated by La et al. [38]. The maxi-
aqueous solution [34]. The maximum monolayer adsorption capa- mum monolayer adsorption capacity by Langmuir model was
city was found to be 84.49 mg/g at 30 C. Orange peel was also uti- reported as 314.3 mg/g. A continuous increase in the sorption
lized as low-cost adsorbent to remove furadan from aqueous capacity of OPW occurred in the pH range of 2.73.6 (60% at pH
solution by adsorption [35]. Both Langmuir and Freundlich models 3.5). This increase in dye removal, as pH increased, was explained
tted the adsorption data quite reasonably (R2 > 0.98) and the in terms of PZC of the adsorbent (PZC = 3.6). At pH > PZC, the adsor-
maximum adsorption capacity was 161.29 mg/g. The ability of zir- bent is negatively charged and the adsorbate are positively
conium(IV)-loaded carboxylated orange peel (ZCOP) to remove the charged. Such a situation enhanced the electrostatic attraction
uoride ion from drinking water was examined [36]. The authors between the cationic dye and the negatively charged adsorbent
proposed a mechanism of uoride adsorption and desorption on surface. Authors proposed the following reactions to occur at the
ZCOP (Fig. 7) in which uoride removal by ZCOP could occur due solid/liquid interface:
to the exchange between the water coordinated with the adsor- OPW H ! OPWH
bent and uoride. Authors also pointed out that the use of zirconi-
um ion, in particular, preferred as a material of choice due to the OPW H TB ! OPWH TB
fact that the tetravalent zirconium in its hydrated form can gener- electrostatic repulsion in acid medium
ate tetranuclear ions as well as octanuclear species with abundant
hydroxyl ions and water molecules that can take part in ligand OPW OH ! OPWOH
substitution reactions with uoride ion. Further, the hydroxyl ion

Fig. 8. Proposed mechanism of adsorption of TB on OPW. Reprinted with permission from Taylor & Francis from Ref. [38].
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
OPW OH TB ! OPWOH TB
electrostatic repulsion in basic medium
Authors proposed a mechanism for the biosorption of the TB
onto OPW, based on the basis of the FTIR spectrum and active site
analysis (Fig. 8).
Besides these, several other researchers also examined orange
peels as adsorbents for different aquatic pollutants removal [39
44].
2.1.2. Pomelo peel
Pomelo has more peel and segment membrane than most other
citrus fruits, generating a signicant quantity of pomelo waste.
Pomelo peel as biosorbent using the zinc chloride activating
method was used in laboratory to test its capability of removing
Pb2+ from wastewater [45]. The optimal conditions for the adsorp-
tion were found to be: 5.36.5 initial pH of the wastewater, 1.5 h of
exposure duration, 10 g/L adsorbent dosage, 100 mg/L of initial
Pb2+ concentration of wastewater at 30 C. Under the given
experimental parameters, the adsorbent could remove more than
90% of Pb2+ from the wastewater. The removal of copper (Cu2+)
from aqueous solution by adsorption on pomelo peel (PP) and
depectinated pomelo peel (DPP) were studied [46]. Factors affect-
ing adsorption such as initial pH, initial concentration, contact time
and temperature were investigated. It was found that the highest
Cu2+ adsorption capacity for PP and DPP were 19.7 mg/g and
21.1 mg/g at the following conditions: pH: 4, initial concentration:
125 mg/L, temperature: 25 C and equilibrium time: about 60 min.
Pomelo peel was also studied as adsorbent to treat the simulated
dye wastewater with methylene blue [47]. The results showed that
the removal rate of 140 mg/L methylene blue solution with 100 mL
could reach more than 83% under the optimum conditions, which
were as follows: 0.4 g pomelo peels powder, reaction temperature:
30 C, pH 8 and oscillating time: 60 min. Theoretical saturation
adsorptive capacity of pomelo peel was 133 mg/g at 30 C.
The removal of Reactive Blue 114 dye from aqueous solutions
was also studied by using pomelo peels [48]. The surface area
and average pore radius were 0.034 m2/g and 1.3  103 lm,
respectively, as measured using the BET (Brunauer Emmett Teller)
method with nitrogen gas. Maximum adsorption capacity was
obtained as 16 mg/g at pH 2 and 303 K solution temperature. The
adsorption process was observed to be reaching equilibrium after
about 90 min.
Fig. 9. Proposed ion exchange mechanism between a proton of grapefruit peel waste and crystal violet dye. Reprinted with permission from Elsevier from Ref. [56].
253
Activated carbon produced from pomelo peels (PPAC) was test-
ed for its effectiveness in the removal of malachite green (MG) dye
from aqueous solution [49]. Results of proximate analyses of PPAC
showed that moisture (9%), ash (8.2%) and volatile matter (11.4%)
contents were low however, the xed carbon content (71.4%)
was satisfactory. Ultimate analysis showed high percentage of ele-
mental carbon (75.8%), low hydrogen (2.95%) and nitrogen (1.53%)
contents and an insignicant value for sulfur (0.32%). The surface
area of PPAC was found to be 1357.21 m2/g. The average pore dia-
meter of the prepared sample was found to be 2.72 nm. Dye
removal was pH dependent, resulting in 95.06% removal at pH
8.0. Quantum chemical studies suggested that the cationic MG
dye possessed minimal molecular size at planar geometry coupled
with high-electrostatic interaction thereby, enhancing the adsorp-
tion at high pH. Langmuir isotherm tted the adsorption data rea-
sonably well with maximum monolayer adsorption capacity of
178.43 mg/g. Regeneration efciency of spent PPAC was studied
using 0.2 M HCl, and the efciency was found to be in the range
of 92.7196.35% after four cycles. Besides these, several other
researchers also examined pomelo peels as adsorbents for the
removal of different aquatic pollutants [5055].
2.1.3. Grapefruit peel
Grapefruit is cultivated in all tropical and subtropical regions of
the world, with approximately 4 million metric tons annual pro-
duction. Thus, a lot of grapefruit peel (GFP) is available throughout
the world. GFP contains several water soluble and insoluble mono-
mers and polymers. The water soluble fraction contains glucose,
fructose, sucrose and some xylose, while pectin, cellulose, hemicel-
lulose and lignin constitute between 50% and 70% of the insoluble
fraction. These polymers are rich in carboxyl and hydroxyl func-
tional groups, which may bind pollutants in aqueous solution
[56]. The sorption of crystal violet (CV) dye by grapefruit peel
(GFP) was examined [56]. Sorption equilibrium reached rapidly
with 96% CV removal in 60 min. The equilibrium process was well
described by the Langmuir isotherm model, with maximum sorp-
tion capacity of 254.16 mg/g. The GFP was regenerated using 1 M
NaOH, with up to 98.25% recovery of CV and could be reused as
a dye sorbent in repeated cycles. Authors proposed that the sorp-
tion of CV by GFP occurs via an ion exchange mechanism between
the negatively charged groups present in the cell wall of GFP and
the cationic dye molecule. The proposed mechanism of sorption
of CV by GFP is shown in Fig. 9.
254 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
Response surface methodology (RSM) was utilized to optimize
the best adsorbent conditions on malachite green in wastewater
by the activated carbon which was prepared from grapefruit peel
with potassium hydroxide activation [57]. Built on single-factor
experiment, adsorbent dosage, pH, initial MG concentration and
temperature were chosen as inuencing factors during adsorption.
The experimental mathematical model was arranged according to
central composite design (CCD). The results showed that the best
conditions were pH 9, initial MG concentration of 2000 mg/L, 1 g/
L dosage of adsorbent and 40 C. The cadmium binding mechanism
for native and protonated grapefruit peels was also investigated
[58]. Potentiometric titrations revealed two main acidic sites with
pKa values around 4 and 11, which were carboxyl and hydroxyl
groups, respectively. Metal binding by protonated peels was higher
than by native peels, which was explained due the competition
between naturally present cations with cadmium for the same
binding sites. The maximum capacity, reached at Cd2+ concentra-
tion in solution above 150 mg/L, was 1.7 meq/g for native and
2.2 meq/g for protonated peels. Ion exchange was suggested as
the main mechanism by authors during metal binding: for native
peels, the amount of ions such as Ca2+ released was equal to the
amount of cadmium bound; for protonated peels, protons were
exchanged against Cd2+. Esterication of carboxyl groups with
acidic methanol or propylene oxide reduced Cd2+ binding by 80%,
demonstrating that Cd2+ binds to carboxyl groups. Blocking amine
and hydroxyl groups by formaldehyde reduced binding by 3050%
compared with native and protonated peels, demonstrating that
these groups contributed to the metal binding.
The adsorbent was prepared from grapefruit peel by activation
(GPA) with ZnCl2 and employed to remove Pb(II) from wastewater
[59]. The affecting factors on the adsorption of Pb(II) from aqueous
solution with GPA, such as solution pH, contact time, GPA dosage,
initial Pb(II) concentration, and reaction temperature were investi-
gated. The results showed that the factors mentioned above had
remarkably inuence on adsorption of Pb(II) ions onto GPA. The
suitable conditions for the adsorption were, solution pH: 5.36.5;
contact time: 1.5 h; GPA dosage: 10 g/L; initial Pb(II) ion concen-
tration: 100 mg/L; temperature: 30 C. Under the suitable condi-
tions, the removal rate of Pb(II) was more than 90% and the
sorption capacity of GPA for Pb(II) was 12.73 mg/g. The urani-
um(VI) biosorption by grapefruit peel was studied from aqueous
solutions [60]. The equilibrium process was well described by the
Langmuir, RedlichPeterson and KobleCorrigan isotherm models,
with maximum sorption capacity of 140.79 mg/g at 298 K. The nat-
ure of biomassuranium (VI) interactions was evaluated by FTIR
analysis, which showed the participation of COOH, OH and NH2
groups in the biosorption process. Authors proposed that the
mechanism of uranium(VI) biosorption on GFP might be based
on ion exchange and the pattern of uranium(VI) biosorption onto
GFP was attributable to the active groups and bonds present on
them. Functional groups such as COOH and OH of cellulose can
react with uranium(VI) to form complexes by releasing protons.
The reactive anhydride combines with cellulosic hydroxyl groups
to form an ester linkage and introduce carboxyl groups into the
Fig. 10. Proposed ion exchange mechanism between a proton of GFP and uranium(VI) ion. Reprinted with permission from Springer from Ref. [60].
cellulose. At pH above 5.0, the carboxylic groups are deprotonated
and negatively charged carboxylate ligands (COO) bind the
positively charged uranium(VI) molecules. This conrms that the
biosorption of uranium(VI) by GFP was an ion exchange mechan-
ism between the negatively charged groups present in the cell wall
of GFP and the uranium(VI) cations which was represented by
Fig. 10.
Natural grapefruit peel (GFP) exhibited good efcacy to adsorb
uranium(VI) [61]. Through the xed-bed column technique,
adsorption characteristics of uranium(VI) was observed at different
ow rate, bed depth, inuent uranium(VI) concentration and parti-
cle size of adsorbent. The results showed that adsorption reached
saturation faster with increasing the ow rate and inuent urani-
um(VI) concentration. The data were tted to the Thomas model,
the Yan model, the Clark model and the mass transfer model by
nonlinear regressive analysis. When the ow rate was 8.0 mL/
min and the inuent concentration of uranium(VI) was 90 mg/L,
the maximum adsorption quantity reached 104.1 mg/g according
to the Thomas model. The bed depth service time model was
applied to predict the service times with other ow rate and initial
concentration. The theoretical breakthrough curve was compared
with experimental breakthrough curve prole in the dynamic pro-
cess. The results showed that the Yan model was better for the
description of breakthrough curves at the experimental conditions
than the Thomas and the Clark models. The saturated column was
regenerated by 0.05 mol/L HCl solution and GFP could be reused in
uranium(VI) removal.
The biosorption of cadmium and nickel onto grapefruit peel
from aqueous solution has been investigated using batch tech-
nique [62]. The maximum uptakes of Cd(II) and Ni(II) by grapefruit
peel were found to be 42.09 and 46.13 mg/g, respectively. Authors
suggested that the main sorption mechanism was ion exchange
due to the release of cations and protons from the biosorbent dur-
ing sorption of Cd(II) and Ni(II) ions. FTIR analysis demonstrated
that carboxyl and hydroxyl groups were involved in the biosorp-
tion of metal ions. The recovery of the Cd(II) and Ni(II) from grape-
fruit peel was found to be more than 97% using 0.1 M HCl.
2.1.4. Lemon peels
India is the largest producer of lemon in the world (an average
of 1.5 million tons of lemon production per year). Lemon is of agro-
nomic importance because the lemons are consumed as an ingre-
dient in cooking, as garnish, and as juice in lemonade,
carbonated beverages, and other drinks. To make better use of this
cheap and abundant agricultural waste, lemon peel after juice
extraction, can be utilized as an inexpensive adsorbent for aquatic
pollutants.
The adsorption potential of lemon peel was examined as an
adsorbent for the removal of two anionic dyes, Methyl orange
(MO) and Congo red (CR) from aqueous solutions [63]. The adsorp-
tion capacities of lemon peel adsorbent for dyes were found to be
50.3 and 34.5 mg/g for MO and CR, respectively. Batch adsorption
studies were conducted to remove cutting oil from wastewater
using activated lemon peels [64]. The effect of various important
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
parameters, namely, pH, dose of adsorbent, contact time, mixing
speed, and initial oil concentration, and their optimum conditions
for maximum sorption efciency were studied and results indicat-
ed that adsorbent dosage of 5 g/L, contact time of 70 min, mixing
rate of 4550 revolutions/min, and pH of 2 provided maximum
oil removal efciency . The feasibility of lemon peel waste was
studied for the removal of cobalt ions from aqueous solutions
[65]. The maximum adsorption capacity of lemon peel adsorbent
for cobalt removal was ca. 22 mg/g. Adsorption of Azure A dye in
aqueous solution on commercial activated carbon (CAC) and
indigenously prepared activated carbon from orange peel (OPC)
and lemon peel (LPC) carbon have been studied [66]. Extent of
dye removal increased with decrease in the initial concentration
of the dye and particle size of the adsorbent and also increased
with increase in contact time, amount of absorbent used and the
initial pH of the solution. The biomass Citrus limetta fruit peels
was examined for its potential for Pb2+ ions [67]. Cold alkali treat-
ment resulted in increased uptake of Pb2+ owing to de-esterica-
tion of the galacturonic acid present in the biomass. Carboxylate
groups in the biomass played an important role in Pb2+ binding
as demonstrated by selective blocking experiments, as well as by
FT-IR spectroscopy. A higher uptake of metal ions was found with
increasing pH, increasing initial metal-ion concentration, and
decreasing biomass concentration. Ion exchange was identied to
be the dominant mechanism. Pb2+ binds with the carboxylic
groups of galacturonic acid chain, forming a stable gel. The Lang-
muir sorption capacity of 630 mg/g was reported which was found
much higher than the capacities of most biosorbents and compara-
ble to those of synthetic ion-exchange resins. The kinetics, equilib-
rium and thermodynamics of cadmium removal using lemon peel
and green coconut shell powder have been investigated in batch
reactor [68]. Under the optimum conditions and with 50 mg/L of
initial concentration, the % removal of Cd using lemon peel was
80.8%. The maximum adsorption capacity obtained from the Lang-
muir isotherm for cadmium ion removal using lemon peel has been
found to be as 11.24 mg/g. Besides these, several other researchers
also examined citrus fruits peels or lemon peels as adsorbents for
different aquatic pollutants removal [6975].
2.2. Banana peel
Banana, Musa spp, is a worldwide consumed tropical fruit and
comprises several varieties. Banana peel is the main residue, corre-
sponding to 3040% (w/w), and has been mainly used in compost-
ing, animal feeding, and the production of proteins, ethanol,
methane, pectin, and enzymes [76]. Cellulose, hemicellulose, pect-
in, chlorophyll, and other low molecular weight species are its
main constituents. The banana peel presents a high adsorption
capacity for metals and organic compounds, and this aspect is pri-
marily due to the presence of the hydroxyl and carboxyl groups of
the pectin. The adsorption of lead(II) and cadmium(II) on peels of
banana has been studied in batch mode [77]. Maximum adsorption
capacity of banana peels from Langmuir isotherm indicated that
1 g of banana peels can adsorb 5.71 mg of cadmium and 2.18 mg
of lead. Untreated banana peels (UTBPs), alkali-hydrolyzed banana
peels (AlBPs), acid-hydrolyzed banana peels (AcBPs), and bleached
banana peels (BBPs) were used as adsorbents separately for the
removal of Cr(VI) and Mn(II) from aqueous solution during batch
experiments [78]. The maximum removal capacities for Cr(VI)
were: UTBP (45%), AlBP (87%), AcBP, (67%) and BBP (40%). While
for Mn(II), the maximum removal capacities of theses adsorbents
were: UTBP (51%), AlBP (90%), AcBP (74%) and BBP (67%) at opti-
mum conditions. The maximum removal of Cr(VI) and Mn(II)
was obtained at initial concentration of 3 mg/L, adsorbent dose of
4 g/L, pH 6, and contact time of 60 min. It was noted that the metal
ions removal capacity of these adsorbents was AlBP > AcB-
255
P > UTBP > BBP, which indicated that chemical treatment of banana
peels enhanced the biosorption of metal ions. The adsorption of
metals (Cu2+, Zn2+, Co2+, Ni2+, Pb2+) from synthetic solutions using
the acid-, alkali-, and water-treated banana peels was investigated
[25]. The adsorption capacity was found to be 7.97 (Pb2+), 6.88
(Ni2+), 5.80 (Zn2+), 4.75 (Cu2+), and 2.55 mg/g (Co2+) using banana
peel. The potential application of banana peel as a biosorbent for
removing phenolic compounds from olive mill wastewaters was
also investigated [79]. Chemical and physical properties of banana
peel are shown in Table 2. The banana peel showed a high adsorp-
tion capacity of phenolic compounds (689 mg/g). The adsorption
process was very fast, and it reached equilibrium in 3 h of contact
time. The equilibrium solid-phase concentration of phenols
decreased with increasing adsorbent (banana peel) concentration
was mainly attributed to the unsaturation of the adsorption sites
through the adsorption process. Desorption experiments showed
chemisorptive interactions between the natural phenolic and the
adsorption sites on the banana peel.
Removal of a basic dye, methylene blue, from an aqueous solu-
tion was studied by biosorption on banana peels waste [80]. The
biosorbent was chemically modied with caustic soda (NaOH).
The maximum values of adsorption capacities for activated banana
peel (ABP) was 19.671 mg/g and 18.647 mg/g for natural banana
peel (NBP) at pH 48, 20 C. The adsorptive behavior of Acid Blue
25 (AB25) dye on the banana peel was studied [81]. Analysis of
the acidbase properties of the biomass provided the number of
weak acid groups, that was found to be 0.288(7) mmol/g for mod-
ied banana peel in 0.1 M KNO3. An uptake capacity value of
0.215(13) mmol/g was obtained by tting the batch experiments
data to sorption isotherms. The application of banana peel for the
remediation of heavy metals (Pb, Zn and Cr) was examined [82].
The adsorbent activated with 0.5 M H2SO4 showed the highest per-
centage removal of chromium ion (88.9%) at pH 6. It was found
that particle size had no effect on the removal of zinc ion and it
was also reported that the removal efciency of lead and chromi-
um ion decreased with increase in contact time and particle size.
Authors also reported that untreated banana peel waste increased
the biochemical oxygen demand (BOD) and chemical oxygen
demand (COD) values of wastewater.
Atrazine removal from water by treated banana peels was stud-
ied [83]. Batch experiments demonstrated that 15 g/L adsorbent
dosage removed 9099% of atrazine from 1 to 150 ppm aqueous
solutions. The removal was both pH and temperature dependent
with the most atrazine removed between pH 7 and 8.2 and
increased with increasing temperature. Equilibrium data tted
well to the Langmuir and Redlich-Peterson models with a maxi-
mum adsorption capacity of 14 mg/g. The feasibility of using
Table 2
Chemical and physical properties of banana peel used in the
experiments. Reprinted with permission from Elsevier from Ref.
[79].
Parameters Data
Moisture content (%) 13.55
Volatile matter (%) 86.44
Ash (%) 3.85
C content (%) 31.79
O content (%) 42.87
K content (%) 14.86
Na content (%) 1.33
Si content (%) 1.48
Al content (%) 1.05
Cl content (%) 3.22
pH 6.60
Particle size <1
256 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
banana peel for the removal of pesticides atrazine and ametryne
from river and treated waters has been demonstrated [76]. The
conditions for removal of these pesticides in a laboratory scale
were optimized as sample volume = 50 mL, banana mass = 3.0 g,
stirring time = 40 min, and no pH adjustment necessary. The sorp-
tion potential of ametryne by the banana peel was considered to be
high as the KF(sor) (Freundlich parameter) value was estimated as
54.1 lg/g which corresponds to 75.3% of the applied ametryne
amount. A moderate sorption potential was estimated for atrazine
[KF(sor) = 35.8 lg/g], corresponding to 59.8% of the applied atrazine
amount. Besides these, several other researchers also examined the
potential of banana peels as adsorbents for different aquatic pollu-
tants removal [8491].
2.3. Cassava peel
Cassava is known as one of the most important agricultural
commodities in many countries (e.g., Indonesia, Nigeria etc.). Cas-
sava is used as raw material for the production of cassava starches
and traditional foods and cakes. Its leaves can be utilized as vegeta-
bles or natural medicine since it contains high amounts of protein
and other bioactive compounds, and its wood is often used as re-
wood for cooking. Cassava starch processing produces a large
amount of solid wastes (cassava peels), and direct discharge of the-
se solid wastes causes environmental problems. Utilization of cas-
sava peels as precursor for activated carbon with a high surface
area has been demonstrated by various researchers. Activated car-
bons were prepared from waste cassava peel by employing physi-
cal and chemical methods and their efciency was tested in the
removal of dyes and metal ions from aqueous solution [92]. Both
adsorbents were found efcient for dyes and metal ions, however,
the material impregnated with H3PO4 showed higher efciency
than the heat treated materials. Sorption of arsenic from aqueous
solution was carried out using polyvinyl pyrrolidone (PVP) K25
coated cassava peel carbon (PVPCC) [93]. In batch studies, the
adsorption was dependent on initial As(V) concentration and
adsorbent dosage. The adsorption was higher in batch mode when
compared to the column mode studies. The IR studies conrmed
the presence of PVP K25 and As(V) on the adsorbent. The XRD stud-
ies revealed that the nature of adsorbent was amorphous before
and after the As(V) adsorption process. The 32% of As(V) desorption
from spent adsorbent was possible at pH 11 using NaOH as des-
orbing agent.
The modication studies of cassava peel waste with nitric acid
and mercaptoacetic acid has been reported [94]. The modied bio-
mass was used as adsorbent of single and multiple metal ions
Pb(II), Cu(II) and Cd(II). Adsorption capacities of metal ions
adsorbed were optimum at pH around 4 and 5. From thermody-
namic data, the adsorption capacities for metal ions Pb(II), Cu(II)
and Cd(II) on biomass modied by 1.0 M mercaptoacetic acid were
higher than on biomass modied by 0.5 M mercaptoacetic acid and
on biomass activated by HNO3, with the order of the adsorption
capacities for each metal ion as follow; Pb(II) > Cu(II) > Cd(II). In
the multiple metal adsorption study, Pb(II) ion competitions
toward adsorbent were higher than Cu(II) and Cd(II) ions on bio-
mass modied by mercaptoacetic acid and activated by HNO3.
The ability of activated carbon from cassava peels to remove Cu(II)
and Pb(II) from hospital wastewater was investigated [95]. The
study showed that pH 8 was the best for the sorption of both metal
ions onto the biosorbent. The time-dependent experiments for the
metal ions showed that the binding of the metal ions to the bio-
mass was rapid and occurred within 20120 min. Sorption efcien-
cy was found to increase with a rise in adsorbent dosage and it
increased from 12% to 73% for Pb(II) and 26% to 79% for Cu(II) when
the adsorbent dose increased from 2 to 12 g. An increase in tem-
perature led to an increase in sorption for both metal ions. The
Langmuir model showed that the biomass had a higher sorption
capacity for Cu(II) than Pb(II) (5.80 mg/g for Pb(II) and 8.00 mg/g
for Cu(II)). The uptake of methyl red, an azo dye from aqueous
solution onto NaOH-activated cassava peels carbon in a xed-bed
column was studied [96]. Optimum adsorption capacity of
206.08 mg/g was obtained at carbon bed height of 20 cm, inlet con-
centration of 200 mg/L and ow rate of 13.3 mL/min. The maxi-
mum removal of 78.62% was obtained for inlet concentration of
50 mg/L, carbon bed height of 30 cm and ow rate of 13.3 mL/
min. The ability of cassava peel to remove Cu(II) from aqueous
solution was also evaluated and a maximum adsorption capacity
of 41.77 mg/g was reported [97]. The feasibility of cassava peel
waste for Ni sorption was also evaluated [98]. Sips model demon-
strated the best tting with the maximum uptake capacity for
Ni(II) ions as 57 mg/g (0.971 mmol/g) at pH 4.5.
2.4. Jackfruit peel
Jackfruit (Artocarpus heterophyllus L.) is specie of tree of the
mulberry family (Moraceae) and is widely grown in Thailand,
Indonesia, Myanmar, India, Philippines and Malaysia. Jackfruits
usually reach 1025 kg in weight at maturity however, the large
sized jackfruits, sometimes, weight as much as 50 kg. Jackfruit peel
wastes have no economic value and in fact often create a serious
problem of disposal for local environments. Thus, utilizing jackfruit
peel as a low-cost adsorbent would increase its economic value,
will help to reduce the cost of waste disposal, besides this, the
problem of environmental pollution also can be reduced
considerably.
Treatment of jackfruit peel with sulfuric acid produced a car-
bonaceous product (JPC) which was used to study its efciency
as an adsorbent for the removal of Cd(II) from aqueous solution
[99]. Physical and chemical characteristics of JPC are summarized
in Table 3. The removal of Cd(II) ions increased from 13.1% to
98.7% with increase in pH from 2.0 to 5.0 and thereafter remained
quantitative (98.799.4%) over the pH range of 5.010.0. After per-
forming adsorption experiments with 40 mg/L of Cd(II) solution
and 0.7 g/L of JPC dose, the exhausted carbon loaded with Cd(II)
was separated and gently washed with distilled water to remove
any unadsorbed Cd(II) ions. The Cd(II) laden carbons were agitated
with 100 ml of different strengths of HCl (0.010.1 M) for 1 h and
the Cd(II) ions desorbed into the solution. A complete recovery of
the adsorbed Cd(II) ions was achieved using HCl at concentration
as low as 0.01 M.
Table 3
Physico-chemical characteristics of JPC. Reprinted with permis-
sion from Elsevier from Ref. [99].
Parameters Data
pH 7.24
Moisture content (%) 16.27
Bulk density (g/ml) 0.72
Ash content (%) 4.99
Water soluble matter (%) 1.32
Acid soluble matter (%) 9.30
Decolourising power, mg/g 46.50
Ion exchange capacity, meq./g 0.93
Surface area, m2/g 123.17
Iron content (%) 0.07
Ash analysis (%)
SiO2 16.0
Na2O 4.03
K2O 0.72
MgO 33.8
CaO 16.6
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
The feasibility of using jackfruit peel (JFP) for the adsorption of
methylene blue was examined [100]. Batch adsorption studies were
conducted to evaluate the effects of contact time, initial concentra-
tion (35400 mg/L), pH (211), and adsorbent dose (0.051.20 g)
on the removal of dye at 30 C. The experimental data tted well
with the type 2 Langmuir model with a maximum adsorption capa-
city of 285.71 mg/g. The potential of jackfruit peel waste for remov-
ing Rhodamine dye from aqueous solution was studied [101]. The
adsorption isotherm were studied by carrying out a series of experi-
ments at different adsorbent dosages (1.0, 2.0, 3.0 g/L), tem-
peratures (30, 40 and 60 C) and pH (4.95, 8.14, 9.74),
respectively. The monolayer adsorption capacity was determined
to be 4.3611.98 mg/g. The effectiveness of an adsorbent prepared
from jackfruit peel for the removal of phenol, 2-chlorophenol,
4-chlorophenol, 2,4-dichlorophenol from aqueous solutions
was investigated [102]. It was found that after mercerization
treatment of peel, the proportion of C and H were decreased. The
adsorption equilibrium was reached in 5 h. The order of removal
was: 2,4-dichlorophenol > 4-chlorophenol > 2-chlorophenol > phe-
nol. The maximum sorption capacities for phenol, 2-chlorophenol,
4-chlorophenol, and 2,4-dichlorophenol were found to be
144.9 mg/g, 243.9 mg/g, 277.7 mg/g, and 400.0 mg/g, respectively.
The removal of phenols was most effective at lower pH.
2.5. Pomegranate peel
Punica granatum L. (Punicaceae), commonly called pomegra-
nate, is one of the most popular fruits in the world due to its pleas-
ant taste, high nutritional value, and many medical features.
Pomegranate fruits are widely consumed fresh and in processed
forms as juice, jams and wine. The pomegranate peel, a by-product
from juice industry, constitutes 5% to 15% of its total weight. Pome-
granate peel is composed of several constituents, including
polyphenols, ellagic tannis and gallic and ellagic acids. Pomegra-
nate peel is discarded as waste residue that can be used as a low
cost and renewable source of biosorbent. Removal of lead(II) and
copper(II) from aqueous solutions was studied using pomegranate
peel (raw), activated carbon prepared from pomegranate peel
(AC1) and activated carbon prepared from chemically treated
pomegranate peel (AC2 and AC3) [103]. The optimum pH required
for maximum adsorption was found to be 5.6 and 5.8, for lead and
copper, respectively. Equilibrium was achieved in 2 h. The feasi-
bility of pomegranate peel waste for the removal of nickel from
water was also examined [104]. The maximum sorption capacity
of pomegranate peel adsorbent for nickel removal was found to
be ca. 52 mg/g.
The pomegranate peel was also tested for Cu(II), Ni(II), Cd(II),
Zn(II) and Cr(VI) ions [105]. The maximum adsorption was
observed for Cu(II) ions, followed by Zn(II), Cd(II), Ni(II) and Cr(VI)
ions. Attempts were made using batch and column methods to
desorb Cu(II), Ni(II), Zn(II), Cd(II) and Cr(VI) ions from synthetic
wastewater as well as from wastewater derived from electroplat-
ing activities. The breakthrough capacities of Cu(II), Ni(II), Zn(II),
Cd(II) and Cr(VI) ions were 6, 2, 2, 2 and 0 mg/g, respectively, when
a mixture of these metal ions was treated. The adsorbent was uti-
lized to recover Cr(VI) ions from electroplating wastewater. The
use of activated carbons prepared from pomegranate peel for the
removal of direct blue 106 dye from aqueous solution was investi-
gated [106]. Removal of dye was pH dependent and the maximum
removal was attained at pH 2. The equilibrium adsorption was
achieved in 120 min. The adsorption potential of pomegranate peel
was studied for the removal of 2,4-dichlorophenol (2,4-DCP) from
aqueous solutions [107]. The adsorption capacity of pomegranate
peel adsorbent for 2,4-DCP was found to be 65.7 mg/g. Pomegra-
nate peel carbon was also tested for its ability to adsorb iron(II)
ions from solutions [108]. The maximum adsorption potential of
257
pomegranate peel activated carbon for iron(II) was found to be
18.52 mg/g (calculated by Langmuir model) at pH 6.0 and 1 g L1
of biosorbent concentration at 29 C.
2.6. Garlic peel
Garlic peel, an agricultural and easily available waste, could
be an alternative for wastewater treatment processes. Due to
the high consumption of garlic, massive amounts of peels are
disposed, causing a severe problem in the community. The viabi-
lity of garlic peel (GP) to remove Pb2+, Cu2+, and Ni2+ was
evaluated [109]. The results showed that the adsorption process
could attain equilibrium within 20 min. GP had remarkable high-
er adsorption afnity for Pb2+ than Cu2+ and Ni2+ with the max-
imum adsorption capacity of 209 mg/g. The adsorption efciency
and uptake capacity of one metal ion were reduced by the pres-
ence of the other metal ion. The adsorption mechanism was sup-
posed to be ion exchange between Ca2+ of GP with heavy metal
ions in the solution. Native garlic peel and mercerized garlic peel
as adsorbents for the removal of Pb2+ has been studied [110]. For
determination of major components of native garlic peel and
mercerized garlic peel, the elemental analysis was carried out,
and the results are shown in Table 4.
The adsorption capacity of garlic peel after mercerization was
increased 2.1 times and up to 109.05 mg/g. FT-IR and scanning
electron microscopy (SEM) results indicated that mercerized garlic
peel offered more little pores acted as adsorption sites than native
garlic peel and had lower polymerization and crystalline and more
accessible functional hydroxyl groups, which resulted in higher
adsorption capacity than native garlic peel. The FT-IR and X-ray
photoelectron spectroscopy analyses of both garlic peels before
and after loading with Pb2+ further illustrated that lead was
adsorbed on the peels through chelation between Pb2+ and O atom
that existed on the surface of garlic peels. The potential of garlic
peel (GP) was also evaluated to remove methylene blue (MB) from
aqueous solution in a batch process [111]. Experiments were car-
ried out as a function of contact time, initial concentration (25
200 mg/L), pH (412) and temperature (303, 313 and 323 K). The
maximum monolayer adsorption capacities were found to be
82.64, 123.45, and 142.86 mg/g at 303, 313, and 323 K, respective-
ly. The efciency and performance of garlic peel (GP) adsorbent for
the removal of Direct Red 12B (DR12B) from wastewater was
investigated [112]. More than 99% removal efciency was obtained
within 25 min at adsorbent dose of 0.2 g per 50 mL for initial dye
concentration of 50 mg/L. The maximum DR12B sorption capacity
of the sorbent was found to be 37.96 mg/g. The optimization study
of phenol adsorption onto garlic peel (GP) was also conducted by
Muthamilselvi et al. [113]. The optimum conditions for maximum
removal of phenol from an aqueous solution of 50 mg L1 were
found as follows: pH: 2, adsorbent dosage: 2.1 g L1, contact time:
7 h, and agitation speed: 135 rpm. The results from the study
demonstrated that more than 80% phenol removal was possible
at the above-mentioned optimum conditions. The maximum
adsorption capacity was calculated as 14.49 mg/g (determined
from the Langmuir isotherm).
Table 4
The percentages of main elements in garlic peels by element analysis. Reprinted with
permission from Springer from Ref. [110].
Material C (%) N (%) O (%) H (%) S (%)
Native garlic peel 37.01 1.04 47.71 4.22 0.81
Mercerized garlic peel 36.01 1.47 48.79 4.11 1.02
258 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
2.7. Miscellaneous peels as adsorbents
The removal of mercury ions by Egyptian mandarin peel was
investigated [114]. Three different adsorbents were prepared, the
rst adsorbent was the raw peel (MP), the second one was pre-
treated mandarin peel with NaOH (MNa), and the third one was
carbonized mandarin peel (MC). The maximum monolayer adsorp-
tion capacities were found to be 19.01, 23.26, and 34.84 mg/g for
MP, MNa, and MC, respectively. Potato peel charcoal (PPC) was
investigated as an adsorbent for Cu(II) removal from aqueous solu-
tions [115]. One gram of PPC was found enough to remove 99.8% of
copper(II) from an aqueous solution of 150 mg/L (100 ml) at pH 6.0
with a shaking time of 20 min. An adsorption capacity of
0.3877 mg/g was reported for Cu(II) by PPC. The biosorption ability
of potato peels was also investigated for the removal of Pb(II),
Cd(II) and Zn(II) from aqueous solutions [116]. The adsorption of
metal ions was found to be strongly inuenced by pH, contact time,
initial metal ion concentration and temperature, while adsorbent
particle size had no effect. The percentage removals were 92%,
75% and 42% for Pb(II), Cd(II) and Zn(II), respectively at initial metal
ion concentration of 100 mg/L and at room temperature. The
removal followed the order of Pb(II) > Cd(II) > Zn(II). The adsorp-
tion of methylene blue was studied from aqueous solutions using
waste potato peels [117]. After one hour, the maximum adsorption
capacity was determined as 33.87 mg/g at pH 8. Potato peels were
also used to produce samples of carbons after (i) pyrolysis or (ii)
hydrothermal treatment by Kyzas and Deliyanni [118]. After acti-
vation with KOH and modication with oxidation agents, the
resulting materials were used for the removal of two drug com-
pounds (dorzolamide and pramipexole) from synthetic aqueous
efuents. The FTIR spectroscopy conrmed that the major adsorp-
tion interaction between drug molecules and carbon-network was
pp stacking. An adsorption capacity of 5266 mg/g was reported
by prepared adsorbents. The feasibility of the biosorption of two
acid dyes (Acid Blue 113 and Acid Black 1) from aqueous solution
using biomass prepared from potato peel waste was examined
[119] and satisfactory results were found.
Chemically (with 0.1 M nitric acid for 1 h, followed by soaking
in methanol for 1 h) and thermally (thermal treatment in a closed
mufe furnace) treated watermelon peels (TWMP) have been uti-
lized for the removal of methyl parathion (MP) pesticide from
water [120]. The surface area of untreated watermelon peels
(UTWMP) was found to be 15.1 m2g1, while after treatment, sur-
face area of adsorbent was increased and found to be 23.4 m2g1.
Maximum adsorption (99 1%) was achieved for (0.38
3.80)  104 mol dm3 of MP solution, using 0.1 g of adsorbent in
20 ml of solution for 60 min agitation time at pH 6. The maximum
adsorption capacity of pesticide was determined as
24.3 1.6 lmol/g by TWMP. Melon (Cucumis melo L.) peel was uti-
lized for the removal of cadmium from aqueous phase [121]. Max-
imum monolayer sorption capacity of 81.97 mg/g was reported by
the researchers for Cd(II) by melon peel. Modied watermelon peel
adsorbent was also used for the removal of Pb(II) [122]. The
dynamic adsorption of methylene blue (MB) by melon peel (MP)
was studied in packed bed columns by Djelloul and Hamdaoui
[123]. The Langmuir model was found to t the adsorption iso-
therm data well with a maximum adsorption capacity of
333.33 mg/g at 25 C. The obtained results showed that both
breakthrough and exhaustion times decreased with the increase
in the initial dye concentration, as constant binding sites were
available for adsorption. The mass of the adsorbent forming the
homogenous xed bed was proportional to the dye-sorbed quanti-
ty and as a result both breakthrough and exhaustion times
decreased with the increase in the initial dye concentration. For a
given initial dye concentration, the lower the ow rate was, the
higher were the breakthrough and exhaustion times. This ow rate
dependence was accounted for by the fact that for lower value of
ow rate, the contact time was longer and hence the interaction
between the dye and the adsorbent was also greater.
The yellow passion fruit peel was used as an alternative adsor-
bent for the removal of methylene blue (MB) from aqueous solu-
tions without any pre-treatment [124]. The optimum pH for the
adsorption of MB was in the range 710 and the shaking contact
time necessary for equilibrium was 50 h. The maximum adsorption
capacity after 50 h of contact time at pH 9.0 and temperature 25 C
was found to be 0.0068 mmol/g of adsorbent. The ability of ponkan
peel to remove Pb(II) ions from aqueous solution by adsorption
was studied [125]. The specic surface area and pore volume of
ponkan peel waste obtained by BET method were 115.3 m2g1
and 0.30 cm3g1, respectively. The pore diameter found by BJH
method was 5 nm, characteristic of mesoporous materials. The
optimal pH for maximum adsorption capacity was 5.0. The
biosorption was relatively quick, about 60 min. Based on the Lang-
muir-type isotherms, the maximum uptake capacity of lead ions on
ponkan peel was 112.1 mg/g. The uptake of hexavalent chromium
from aqueous solutions by mosambi (C. limetta) peel was examined
[126]. Maximum uptake of hexavalent chromium from con-
taminated water was 250 mg/g at pH 2.0 and 40 C. FTIR spec-
troscopy revealed the involvement of OH, NH, C@O, and CO
groups in chromium binding on the cell surfaces.
The potential of mango peel waste (MPW) as an adsorbent to
remove Cu2+, Ni2+, and Zn2+ from constituted metal solutions and
real electroplating industry wastewater was reported [127]. The
adsorption process was found to be pH dependent, while the max-
imum adsorption was observed to occur at pH 5 to 6. The equilib-
rium was established within 60 min. Maximum adsorption of the
heavy metal ions at equilibrium was 46.09, 39.75, and 28.21 mg/
g for Cu2+, Ni2+, and Zn2+, respectively. Release of alkali and alkaline
earth metal cations (Na+, K+, Ca2+, Mg2+) and protons (H+) from
MPW, during the uptake of Cu2+, Ni2+, and Zn2+, and EDX analysis
of MPW, before and after the metal sorption process, revealed that
ion exchange was the main mechanism of sorption. FTIR analysis
showed that carboxyl and hydroxyl functional groups were
involved in the sorption of Cu2+, Ni2+, and Zn2+. The adsorption
potential of lychee (Litchi chinensis) peel waste was studied for
the removal of Acid Blue 25 dye from aqueous solutions [128].
An adsorption capacity of ca. 200 mg/g was found for Acid Blue
25 dye by lychee peel waste adsorbent. Fruit peel of Litchi also
showed remarkable adsorption capacity toward Cr(VI) ions [129].
The adsorption of Cr(VI) was maximum at pH 2. An adsorption
capacity of 101.10 mg/g was found for Cr(VI) by lychee peel waste
adsorbent. The breakthrough and exhaustive capacities were found
Table 5
Physico-chemical characteristics of GPP. Reprinted with permis-
sion from Springer from Ref. [135].
Physical properties GPP
Specic surface area (m2/g) 316.20
Specic pore volume (cm3/g) 0.2717
Average pore diameter () 34.95
Bulk density (g/cm3) 0.672
Proximate analysis (wt.%)
Moisture 9.39
Volatile matter 14.25
Fixed carbon 70.67
Ash content 5.69
Ultimate analysis (%)
C 61.74
H 1.37
N 5.63
S 9.33
O 21.93
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271 259

Fig. 11. Possible adsorption mechanism of Cr(VI) (a) and other metal cations (b) binding to the functional groups of the polyphenolic compounds (taking gallic acid as the
example here) in the mangosteen peel gel. Reprinted with permission from Springer from Ref. [136].

to be 30 and 50 mg/g respectively in column operations. The
potential use of activated carbon prepared from the peel of Cucumis
sativa fruit for the removal of malachite green (MG) dye from
simulated wastewater was studied [130]. Optimum pH for dye
adsorption was 6.0. Maximum dye was sequestered within
50 min of the start of every experiment. The maximum removal
(99.86%) of MG was obtained at pH 6 at room temperature. An
adsorption capacity of 36.23 mg/g was found for MG by C. sativa
peel sorbent. Cucumber peels (CP) have also been used as low-cost
adsorbents to remove methylene blue (MB) from aqueous solu-
tions [131]. The monolayer biosorption capacity of 111.11 mg/g
was obtained for CP. Recoveries of MB were achieved by 0.1 M of
various acids. HCl was the most effective desorbent with 93.66%
efciency for desorption of MB from CP. The adsorption of Cd(II)
ions from aqueous solutions by modied Cucumis sativus peel
(CSP) by HCl treatment was investigated by Pandey et al. [132].
The maximum removal efciency was 84.85% for 20 mg/L Cd(II)
ion at pH 5. CSP exhibited monolayer adsorption capacity of
58.14 mg/g at 298 K. The peel of C. sativa fruit for the removal of
crystal violet (CV) dye from simulated wastewater was also inves-
tigated [133]. The maximum removal of CV was obtained at pH 7
as 92.15% for adsorbent dose of 0.2 g/50 mL and 25 mg L1 initial
dye concentration at room temperature. The maximum adsorption
capacity obtained from Langmuir model was 34.24 mg/g.
A viable and cost-effective technology was explored for removal
of heavy metal ions such as Cu2+, Ni2+, Zn2+, Cd2+, and Pb2+ from
260 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
Fig. 12. Scheme of chemical modication mechanism of muskmelon peel by calcium hydroxide. Reprinted with permission from Springer from Ref. [139].
aqueous solution using three fruit peels namely orange peel (OP),
lemon peel (LP), and banana peel (BP) [134]. The surface of the
LP and lemon peel cellulose (LPC) was chemically modied (alkali
saponication, acid treatment (carboxylation), acid treatment (car-
boxylation) after saponication, and cellulose acid treatment (car-
boxylation) after saponication). It was concluded that carboxylic
acid and hydroxyl groups of cellulose played a vital role in binding
the metal ions. The FT-IR spectra of the adsorbents after metal ion
adsorption showed a decrease in the intensity of carboxylic and
hydroxyl group peaks due to coordination with metal ions. LPCACS
(lemon peel cellulose acid carboxylation after saponication)
showed enhanced adsorption capacity among all the adsorbents
due to an increase in the functional groups. Among the ve metals,
Cu2+ and Ni2+ could effectively be adsorbed by the adsorbents. An
adsorption capacity of 70.92344.83 mg/g was found for Cu2+ by
prepared sorbents from peel wastes. The adsorption of MB by
green pea peel (GPP) and acid-treated carbon (GPP-AC) has been
reported [135]. Physico-chemical characteristics of GPP are sum-
marized in Table 5. The adsorption equilibrium data were best
described by the Langmuir isotherm model, with maximum
adsorption capacity of 163.94 mg MB/g GPP at 30 C.
Mangosteen peel after chemical modication using calcium
hydroxide was used to prepare the adsorbent and it exhibited
highly selective adsorption for Cr(VI) over other metal ions such
as Pb2+, Fe3+, Zn2+, Cd2+, and Cr3+ at the pH values of 14 [136].
The maximum adsorption capacity for Cr(VI) at pH 1, 2, 3, and 4
was found to be 2.46, 2.44, 1.99, and 2.14 mol/kg, respectively.
The adsorption mechanism for Cr(VI) on the saponied gel was
veried to follow an esterication reaction coupled with the reduc-
tion of Cr(VI) to Cr(III) in which H+ played a role of promoter.
Authors discussed that the contrast adsorption behavior for Cr(VI)
over the other metal ions can be ascribed to the different uptake
mechanisms, as shown in Fig. 11(a), an esterication reaction fol-
lowed by a reduction of Cr(VI) adsorption mechanism, while an
ion exchange mechanism for the uptake of other metal cations pos-
sibly through at least three kinds of paths as illustrated in
Fig. 11(b).
An adsorbent prepared from C. limetta peel was used to study its
sorption potential on removing Brilliant green dye [137]. A maxi-
mum dye removal of 95% was achieved with an initial concentra-
tion of 10 mg/L. Zirconium loaded apple peels were used to
extract anions such as phosphate, arsenate, arsenite, and chromate
ions from aqueous solutions [138]. Zr treated apple peels showed
efcient adsorption towards AsO 2 (15.64 mg/g), AsO3 4
(15.68 mg/g), Cr2O27 (25.28 mg/g), and PO 3
4 (20.35 mg/g) anions.
The adsorption and desorption studies revealed the adsorption
mechanism involved electrostatic interactions. Arsenate and chro-
mate anions were strongly adsorbed at the pH range from 2 to 6,
while arsenite was extracted efciently between pH 9 and 10. A
cost-effective biosorbent was prepared by a green chemical
modication process from muskmelon peel by saponication with
alkaline solution of Ca(OH)2 and tested its adsorption behavior for
lead ions [139]. Fig. 12 shows the scheme of chemical modication
mechanism of muskmelon peel by calcium hydroxide proposed by
the authors. Results showed that the optimal equilibrium pH range
for 100% adsorption was from pH 4 up to 6.4. Adsorption equilibri-
um was attained within 10 min. The maximum adsorption capa-
city for lead ions was found to be 0.81 mol/kg. Scheme of
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
Fig. 13. Scheme of adsorption mechanism of lead ions on chemically modied muskmelon peel. Reprinted with permission from Springer from Ref. [139].
adsorption mechanism (as proposed by researchers) of lead ions on
chemically modied muskmelon peel is shown in Fig. 13.
The adsorption of methylene blue (MB) and acid orange 7 (AO7)
dye onto Ananas comosus mixed peels and leaves (ACMPL) was
investigated [140]. Highest percentage removal for MB was exhib-
ited at pH 9, which was 95.81%. Meanwhile for AO7, the highest
percentage removal was 31.06% at pH 3. The percentage removal
of MB had reached the equilibrium at dosage 0.5 g while AO7 kept
increasing with the increment of adsorbent dosage. The percentage
removal of MB and AO7 had increased until 2.5 h which was from
72.5% to 86.93% and 19.441% to 36.89% respectively, and reached
equilibrium in 3 h.
The adsorption capacity of activated carbon prepared from
guava fruit peel waste has been studied for congo dye [141]. The
activation process was carried out under microwave radiations in
the presence of KOH. The maximum adsorption capacity for congo
dye was found to be 61.12 and 120.62 mg/g for unactivated and
KOH + microwave heated guava fruit peel. The utilization of ash
gourd (defatted) peel in biosorption of chromium was reported
[142]. The BET surface area of powder was found to be
0.4854 m2/g. In equilibrium studies at pH 1, more than 91% Cr(VI)
was adsorbed on ash gourd peel powder at an adsorbent dosage of
6 g/L for 125 mg/L solution. The sorption capacity of peel for Cr(VI)
in batch studies was 18.7 mg/g. FTIR spectroscopy of samples
before and after adsorption revealed the presence of carboxyl func-
tional group, which played an important role in adsorption of
Cr(VI). The processing of 1000 kg of ash gourd peel was capable
of adsorbing as high as 261.8 g of Cr(VI). Breadnut skin, in both
its unmodied (KS) and base-modied (BM-KS) forms, was inves-
tigated for its potential use as a low-cost adsorbent for the removal
261
of malachite green (MG) [143]. The adsorption capacity was greatly
enhanced when breadnut skin was chemically modied with
NaOH, leading to an adsorption capacity of 353.0 mg/g. Regen-
eration experiments on BM-KS indicated that its adsorption capa-
city was still maintained at >90% even after ve cycles. Peel of
breadnut, Artocarpus camansi, was also investigated for the
removal of methylene blue (MB) [144]. A maximum biosorption
capacity of 409 mg/g was reported for MB by peel of breadnut.
Removal of ultramarine blue dye from aqueous solution using
yam peels waste was investigated by Owamah et al. [145]. Maxi-
mum adsorption was found to occur at pH 10. Maximum adsorp-
tion capacity was obtained as 0.940 mg/g. The adsorption of
malachite green (MG) dye onto rambutan peel-based activated car-
bon (RPAC) was examined by Ahmad and Alrozi [146]. Solution
pH > 8 was proved to be more favorable for adsorption of MG on
the RPAC. Boyd plot revealed that the adsorption of MG on RPAC
was controlled by lm diffusion. The same researchers also used
the rambutan peel based activated carbon (RPAC) for Remazol Bril-
liant Blue R removal [147]. The optimum conditions for RPAC
preparation were obtained by using activation temperature of
789 C, activation time of 1.8 h and impregnation ratio of 3.5,
which resulted in 78.38% of RBBR removal and 18.02% of RPAC
yield. Rambutan (Nephelium lappaceum) peel was also used as the
precursor for preparation of activated carbon by chemical assisted
KOH activation and tested for acid yellow 17 dye adsorption [148].
The maximum monolayer adsorption capacity of dye was found to
be 215.05 mg/g.
Activated carbons were synthesized from durian peel and used
for the removal of lead(II) ions from water [149]. The activated car-
bons were produced with physical activation method using CO2 as
262 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271

Table 6
Uptake capacities of various peel-based adsorbents for metals removal.

Peel/adsorbent type Metal Amount adsorbed References

Citric acid modied orange peel Cd(II) 0.90 mol/kg [13]
Chemically modied orange peel Cu(II) 289.0 mg/g [16]
Mercapto-acetic acid modied orange peel Cu(II) 70.67 mg/g [16]
Mercapto-acetic acid modied orange peel Cd(II) 136.05 mg/g [16]
Mg2+ type orange peel adsorbent Cu(II) 40.37 mg/g [18]
K+ type orange peel adsorbent Cu(II) 59.77 mg/g [18]
KCl modied orange peel Cd(II) 125.63 mg/g [20]
KCl modied orange peel Pb(II) 141.84 mg/g [20]
KCl modied orange peel Zn(II) 45.29 mg/g [20]
KCl modied orange peel Ni(II) 49.14 mg/g [20]
Sulfured orange peel Pb(II) 164 mg/g [21]
Sulfured orange peel Zn(II) 80 mg/g [21]
Orange peel As(III) 1.18 mg/g [24]
Pomelo peel Cu(II) 19.7 mg/g [46]
Depectinated pomelo peel Cu(II) 21.1 mg/g [46]
ZnCl2 activated grapefruit peel Pb(II) 12.73 mg/g [59]
Grapefruit peel Uranium(VI) 140.79 mg/g [60]
Grapefruit peel Uranium(VI) 104.1 mg/g [61]
Banana peel Cd(II) 5.71 mg/g [77]
Banana peel Pb(II) 2.18 mg/g [77]
Activated carbon from cassava peels Cu(II) 8.00 mg/g [95]
Activated carbon from cassava peels Pb(II) 5.80 mg/g [95]
Pomegranate peel Ni(II) 52 mg/g [104]
Pomegranate peel carbon Fe(II) 18.52 mg/g [108]
Mercerized garlic peel Pb(II) 109.05 mg/g [110]
Egyptian mandarin peel (raw) Hg(II) 19.01 mg/g [114]
Egyptian mandarin peel (NaOH treated) Hg(II) 23.26 mg/g [114]
Egyptian mandarin peel (carbonised) Hg(II) 34.84 mg/g [114]
Potato peels Cu(II) 0.3877 mg/g [115]
Ponkan peel Pb(II) 112.1 mg/g [125]
Mosambi (Citrus limetta) peel Cr(VI) 250 mg/g [126]
Mango peel waste Cu2+ 46.09 mg/g [127]
Mango peel waste Ni2+ 39.75 mg/g [127]
Mango peel waste Zn2+ 28.21 mg/g [127]
Litchi peel waste Cr(VI) 101.10 mg/g [129]
Modied Cucumis sativa peel Cd(II) 58.14 mg/g [132]
Zirconium loaded apple peels AsO2 15.64 mg/g [138]
Zirconium loaded apple peels AsO3
4 15.68 mg/g [138]
Zirconium loaded apple peels Cr2O2
7 25.28 mg/g [138]
Muskmelon peel Pb(II) 0.81 mol/kg [139]
Ash gourd peel powder Cr(VI) 18.7 mg/g [142]

the activating agent at 900 C. Prior to the activation process, duri-
an peel was carbonized under either nitrogen atmospheric or
vacuum pyrolysis. The results showed that the activated carbon
synthesized under vacuum pyrolysis had greater BET surface area,
pore volume and lead(II) adsorption capacity than that synthesized
under nitrogen atmospheric pyrolysis. A low-cost activated carbon
was developed from kiwi peel for removing Pb(II) from aqueous
solution [150]. The adsorbent demonstrated remarkable character-
istics such as high surface area (306.18 m2 g1) and large total pore
volume (0.4810 cm3 g1). It was found that the optimum pH for
removing Pb(II) was 6. The maximum adsorption capacity of Pb(II)
adsorbed by kiwi peel-based activated carbon was 158.82 lg g1.
Durian peel (DP) was studied for its ability to remove Basic blue
3 (BB3) from aqueous solutions [151]. The maximum adsorption
capacity of DP for BB3 was found to be 49.50 mg/g. Raphanus sati-
vus peels (RSP) biomass for the adsorptive removal of cadmium(II)
has been studied [152]. The maximum adsorption capacity was
determined to be 19.82 mg/g under the optimum conditions.
Besides these, several other researchers also examined the suit-
ability of different fruits and vegetables waste peels as adsorbents
for the removal of aquatic pollutants [153174]. Tables 6 and 7
represent uptake capacities of various peel-based adsorbents for
metals and organic pollutants removal from water, respectively.
Table 8 compiles the information on adsorption isotherm studies
of different pollutants onto agricultural waste peel-based
adsorbents.
3. Desorption and regeneration/reuse studies with peel-based
adsorbents
Spent (adsorbate saturated or loaded) adsorbents are generally
of no use and are disposed of as wastes. Disposing of spent adsor-
bents could pose problems as some of them could be hazardous
and need to be incinerated while others may be toxic. Apart from
dumping spent adsorbents, another way is to regenerate these
adsorbents for further reuse and to recover adsorbates. In many
cases, the adsorbates may be a resource (e.g., metals and nutrients)
and need to be recovered or concentrated to earn recovery credits.
Regeneration of spent adsorbent and recovery of adsorbate would
make the treatment process economically feasible. It is therefore,
desirable to desorb the adsorbed pollutant and to regenerate the
adsorbent for another cycle of application. A successful desorption
process requires the proper selection of eluents, which strongly
depends on the type of biosorbent and the mechanism of biosorp-
tion. Although desorption studies (in brief) have been mentioned
in previous sections above (in some cases), but more detailed infor-
mation about desorption studies is being discussed herein. Desorp-
tion of metal ions was studied by using different concentrations of
hydrochloric acid by Li et al. [14]. The results showed that
0.05 mol/L HCl was noted to most effectively desorb 87.23% Zn(II)
biosorbed by SCA; The maximum removal percentage of 93.72% for
Cd(II) was realized with 0.15 mol/L HCl from the Cd-loaded SCA;
desorption of Co(II) and Ni(II) from the metal-laden SPA with
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271 263

Table 7
Uptake capacities of various peel-based adsorbents for organic pollutants removal.

Peel/adsorbent type Organic pollutants Amount adsorbed References

Orange peel Congo red 22.4 mg/g [26]
Orange peel Procion orange 1.3 mg/g [26]
Orange peel Rhodamine-B 3.22 mg/g [26]
Orange peel Acid violet 17 19.88 mg/g [27]
Orange peel Direct Red 23 10.72 mg/g [28]
Orange peel Direct Red 80 21.05 mg/g [28]
Activated carbon prepared from orange peel Direct blue-86 33.78 mg/g [29]
Activated carbon prepared from orange peel Direct Yellow 12 75.76 mg/g [30]
Activated carbon prepared from orange peel Direct Navy Blue 106 107.53 mg/g [31]
Orange peel waste Toluidine blue 314.3 mg/g [38]
Pomelo peel Methylene blue 133 mg/g [47]
Pomelo peel Reactive Blue 114 16 mg/g [48]
Activated carbon from pomelo peels Malachite green 178.43 mg/g [49]
Grapefruit peel Crystal violet 254.16 mg/g [56]
Activated banana peel Methylene blue 19.671 mg/g [80]
Natural banana peel Methylene blue 18.647 mg/g [80]
NaOH-activated cassava peels carbon Methyl red 206.08 mg/g [96]
Jackfruit peel Methylene blue 285.713 mg/g [100]
Garlic peel Direct Red 12B 37.96 mg/g [112]
Garlic peel Phenol 14.49 mg/g [113]
Orange peel Carbofuran 84.49 mg/g [34]
Orange peel Furadan 161.29 mg/g [35]
Banana peel Atrazine 14 mg/g [83]
Banana peel Phenolic compounds 689 mg/g [79]
Jack fruit peel Phenol 144.9 mg/g [102]
Jack fruit peel 2-chlorophenol 243.9 mg/g [102]
Jack fruit peel 4-chlorophenol 277.7 mg/g [102]
Jack fruit peel 2,4-dichlorophenol 400.0 mg/g [102]
Potato peels Methylene blue 33.55 mg/g [117]
Melon peel Methylene blue 333.33 mg/g [123]
Yellow passion fruit peel Methylene blue 0.0068 mmol/g [124]
Lychee peel waste Acid Blue 25 200 mg/g [128]
Cucumis sativa fruit peel Malachite green 36.23 mg/g [130]
Cucumber peel Methylene blue 111.11 mg/g [131]
Cucumis sativa peel Crystal violet 32.24 mg/g [133]
Unactivated guava fruit peel Congo dye 61.12 mg/g [141]
KOH + microwave heated guava fruit peel Congo dye 120.62 mg/g [141]
Breadnut skin chemically modied with NaOH Malachite green 353.0 mg/g [143]
Yam peels Ultramarine blue dye 0.940 mg/g [145]
Rambutan peel Acid yellow 17 215.05 mg/g [148]
Durian peel Basic blue 3 49.50 mg/g [151]

0.1 mol/L HCl resulted in 81.06% and 80.11% recovery of these met-
als, respectively.
The variation of adsorption efciencies of Cu2+ and Cd2+ with
respect to the number of adsorptiondesorption cycles were con-
ducted by Sha et al. [17]. It was found that adsorption efciencies
of these two metals remained almost constant with respect to the
number of cycles (more than ve cycles), i.e., the adsorbents could
be reused after elution of metals. Desorption experiments were
also conducted under different concentrations of HCl by L et al.
[19]. The percentages of desorption increased with increasing HCl
concentration (from 0.005 to 0.1 mol L1) and then changed little
and was almost 100% for HCl concentrations from (0.1 to
0.2 mol L1). Therefore, 0.1 mol L1 HCl was regarded as the opti-
mum desorption concentration. The adsorption capacity of the
recycled biosorbent was investigated over six cycles. It was found
that the adsorption capacity of 272SCO had only a small decline
after six cycles. After the sixth cycle, the adsorption rate of Pb(II)
onto 272SCO was still 89.61%. Desorption experiments were car-
ried out with Cd2+ laden MNPOPP in 0.1 M HNO3 and results
showed that approximately 98% of the adsorbed cadmium was
desorbed [22]. In all cycles, desorption was 98.1998.66%. A
4.74% decrease in adsorption efciency occurred after ve con-
secutive cycles of adsorptiondesorption.
Neutral pH water, acetic acid and alkaline water (pH 12) were
used as desorbing agents and 4.7%, 2.5% and 37% desorption of con-
go red occurred, respectively [26]. The desorption of procion
orange increased with an increase in pH from 16% at pH 3.0 to
78% at pH 11.0. Both congo red and procion orange are anionic in
nature and their increased adsorption in an acidic medium and
their increased desorption in an alkaline medium showed that the-
se dyes were held by the adsorbent, most probably by ion
exchange. In the case of rhodamine B, an increase of pH from 3.0
to 11.0 did not show any marked change in the percentage desorp-
tion (1727%). This indicated that ion exchange might not have a
signicant role in the adsorption process. Chemisorption might
be responsible for the dye uptake. In the desorption studies con-
ducted by Arami et al. [28], it was observed that as the desorbing
pH was increased, the percent desorption increased from 37.5%
(pH 2) to 97.7% (pH 12) for DR23 and from 2.2% (pH 2) to 93%
(pH 12) for DR80 at dye concentration of 50 mg/L. The test of reu-
sable capacity of ZCOW was performed with dried ZCOW [36]. The
percentage of adsorption of uoride by ZCOW was found to be
reduced from 97% to 83% following a sequence of 1st to 8th cycle
of operation. It was observed that at low concentration of NaOH
(0.001 M), leaching of uoride from adsorbent was only 4%. How-
ever, with increased concentration of NaOH (0.1 M), leaching of
uoride from adsorbent reached to 91%. Recovery of crystal violet
(CV) from exhausted biomass of grapefruit peel (GFP) and regen-
eration of GFP was tested by using aqueous solution of 1 M NaOH
[56]. It was found that CV desorbed very rapidly, with the maxi-
mum elution achieved in the rst 30 min amounting to 82% des-
orption. The desorption rate after this initial fast phase, however,
264 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271

Table 8
Adsorption isotherm studies of different pollutants onto agricultural waste peel-based sorbents.

Adsorbent Adsorbate Langmuir constants Freundlich constants References

qm b or KL 1/n KF
Crude orange peel (OP) Cd(II) 0.49 mol kg1 0.82 0.26 1.57 [13]
OP washed with iso-propyl alcohol Cd(II) 0.64 mol kg1 0.54 0.32 2.47 [13]
OP modied with citric acid Cd(II) 0.66 mol kg1 0.90 0.25 2.00 [13]
OP modied with alkali saponication Cd(II) 0.85 mol kg1 0.81 0.27 2.85 [13]
0.6SCA80 (Modied with citric Cd(II) 1.00 mol kg1 0.76 0.29 3.71 [13]
acid after alkali saponication)
OP Cd(II) 0.49 mol kg1 0.82 0.26 1.57 [14]
SNa Cd(II) 0.85 mol kg1 0.81 0.27 2.85 [14]
SAm Cd(II) 0.81 mol kg1 0.87 0.26 2.62 [14]
SCa Cd(II) 0.80 mol kg1 0.79 0.28 2.76 [14]
SCA Cd(II) 1.00 mol kg1 0.76 0.29 3.71 [14]
SOA Cd(II) 1.13 mol kg1 0.61 0.37 5.63 [14]
SPA Cd(II) 0.91 mol kg1 0.99 0.28 3.37 [14]
OP Zn(II) 0.76 mol kg1 0.72 0.37 4.21 [14]
SNa Zn(II) 1.17 mol kg1 0.65 0.37 6.28 [14]
SAm Zn(II) 0.97 mol kg1 1.49 0.24 2.98 [14]
SCa Zn(II) 0.96 mol kg1 1.13 0.22 2.59 [14]
SCA Zn(II) 1.21 mol kg1 1.00 0.36 6.44 [14]
SOA Zn(II) 1.05 mol kg1 0.83 0.30 4.20 [14]
SPA Zn(II) 1.02 mol kg1 0.89 0.31 4.12 [14]
OP Ni(II) 0.46 mol kg1 0.62 0.29 1.67 [14]
SNa Ni(II) 0.73 mol kg1 6.89 0.10 1.12 [14]
SAm Ni(II) 0.70 mol kg1 1.48 0.19 1.63 [14]
SCa Ni(II) 0.69 mol kg1 1.09 0.24 2.09 [14]
SCA Ni(II) 1.11 mol kg1 4.34 0.12 1.94 [14]
SOA Ni(II) 1.05 mol kg1 4.90 0.05 1.29 [14]
SPA Ni(II) 1.28 mol kg1 2.01 0.13 3.21 [14]
OP Co(II) 0.63 mol kg1 0.43 0.29 2.00 [14]
SNa Co(II) 0.82 mol kg1 1.19 0.16 1.58 [14]
SAm Co(II) 0.81 mol kg1 0.45 0.34 3.25 [14]
SCa Co(II) 0.78 mol kg1 0.46 0.30 2.63 [14]
SCA Co(II) 0.84 mol kg1 0.76 0.22 2.09 [14]
SOA Co(II) 0.80 mol kg1 1.25 0.14 1.45 [14]
SPA Co(II) 1.23 mol kg1 0.37 0.33 4.65 [14]
OP Cu(II) 44.28 mg/g 0.019 L/mg 0.424 3.67 mg/g [16]
OPAA Cu(II) 289.0 mg/g 0.033 L/mg 0.504 18.93 mg/g [16]
OP Cu(II) 50.94 mg/g 0.0161 L/mg 0.5367 2.2235 mg/g [17]
MOP Cu(II) 70.67 mg/g 0.0549 L/mg 0.3916 8.4840 mg/g [17]
OP Cd(II) 47.60 mg/g 0.0126 L/mg 0.3584 4.1832 mg/g [17]
MOP Cd(II) 136.05 mg/g 0.0742 L/mg 0.2668 30.0649 mg/g [17]
MgOP Cu(II) 40.37 mg/g 0.095 L/mg 0.39 6.296 (mg/g)(mg/L)1/n [18]
KOP Cu(II) 59.77 mg/g 0.067 L/mg 0.33 9.977 (mg/g)(mg/L)1/n [18]
MOP Pb(II) 164 mg/g 0.066 L/mg 0.350 25.29 [21]
OP Pb(II) 90 mg/g 0.035 L/mg 0.428 8.57 [21]
MOP Zn(II) 80 mg/g 0.010 L/mg 0.558 2.41 [21]
OP Zn(II) 25 mg/g 0.022 L/mg 0.405 2.35 [21]
Zr(VI)-SOW Mo(VI) 1.35 mmol/g 1.06 (m3 kmol1) 0.420 1.58 (m3 kg1) [23]
La(III)-SOW Mo(VI) 1.22 mmol/g 1.15 (m3 kmol1) 0.549 2.04 (m3 kg1) [23]
Fe(III)-SOW Mo(VI) 1.10 mmol/g 0.59 (m3 kmol1) 0.431 2.45 (m3 kg1) [23]
Ce(III)-SOW Mo(VI) 0.99 mmol/g 1.80 (m3 kmol1) 0.440 1.86 (m3 kg1) [23]
OP Carbofuran 84.49 mg/g 0.0124 L/mg 0.6167 2.7020 L/mg [34]
ZCOP Fluoride 2.7020 mg/g 1.555 L/mg 0.491 2.226 (mg 1(1/n) L1/n g1) [36]
Pomelo peel Reactive Blue 114 283 K 14.6 mg/g 0.029 L/mg 0.703 1.334 [48]
303 K 16.3 mg/g 0.166 L/mg 0.567 1.395
323 K 13.8 mg/g 0.045 L/mg 0.627 1.552
PPAC Malachite green 303 K 145.78 mg/g 0.0056 L/mg 0.467 31.64 [49]
318 K 164.91 mg/g 0.0062 L/mg 0.459 32.73
333 K 178.43 mg/g 0.0068 L/mg 0.454 32.88
Grapefruit peel Crystal violet 249.68 mg/g 0.131 L/mg 0.446 3.14 [56]
Lemon peel Methyl orange 25 C 61.7 mg/g 8.1  103 (L mol1) [63]
45 C 42.0 mg/g 7.8  103 (L mol1)
Lemon peel Congo red 25 C 42.3 mg/g 9.2  103 (L mol1) [63]
45 C 27.1 mg/g 7.9  103 (L mol1)
Lemon peel Cobalt 25 C 25.64 mg/g 6.68  104 (L mol1) [65]
45 C 14.97 mg/g 3.90  103 (L mol1)
Banana peels Pb(II) 2.18 mg/g 0.11 L/mg 0.490 0.36 [77]
Banana peels Cd(II) 5.71 mg/g 0.04 L/mg 0.775 0.30 [77]
Untreated banana peels Cr(VI) 3.3557 mg/g 0.8533 L/mg 0.3994 1.4631 mg/g [78]
Alkali-hydrolyzed banana peels Cr(VI) 5.1098 mg/g 0.9466 L/mg 0.4672 1.4014 mg/g [78]
Acid-hydrolyzed banana peels Cr(VI) 4.4889 mg/g 0.9429 L/mg 0.4880 1.4983 mg/g [78]
Bleached banana peels Cr(VI) 2.4644 mg/g 0.7505 L/mg 0.2337 1.3597 mg/g [78]
Untreated banana peels Mn(II) 2.8636 mg/g 0.9397 L/mg 0.3844 1.574 mg/g [78]
Alkali-hydrolyzed banana peels Mn(II) 3.6010 mg/g 0.9573 L/mg 0.8431 2.7245 mg/g [78]
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271 265

Table 8 (continued)

Adsorbent Adsorbate Langmuir constants Freundlich constants References

qm b or KL 1/n KF
Acid-hydrolyzed banana peels Mn(II) 4.1516 mg/g 0.9940 L/mg 0.7461 2.8800 mg/g [78]
Bleached banana peels Mn(II) 2.7359 mg/g 0.9359 L/mg 0.5328 2.3115 mg/g [78]
Cassava peels Pb(II) 5.80 mg/g 0.30 L/mg 1.52 1.4 [95]
Cassava peels Cu(II) 8.00 mg/g 0.34 L/mg 1.35 1.8 [95]
Jackfruit peel Methylene blue 285.713 mg/g 0.0172 L/mg 0.745 7.067 [100]
Jackfruit peel carbon Phenol 144.9 mg/g 0.0029 L/mg 0.424 6.04 [102]
Jackfruit peel carbon 2-chlorophenol 243.9 mg/g 0.0027 L/mg 0.444 8.64 [102]
Jackfruit peel carbon 4-chlorophenol 277.7 mg/g 0.0025 L/mg 0.461 8.72 [102]
Jackfruit peel carbon 2,4-dichloro-phenol
400.0 mg/g 0.0024 L/mg 0.510 9.00 [102]
Pomegranate peel Ni(II) 25 C 51.8 mg/g 19.3  103 L/mol [104]
45 C 69.4 mg/g 24.0  103 L/mol
Pomegranate peel 2,4-di-chlorophenol 25 C 75.8 mg/g 6.8  103 L/mol [107]
45 C 96.2 mg/g 8.3  103 L/mol
Garlic peel Pb(II) 209 mg/g 0.112 L/mg 0.163 80.85 [109]
Garlic peel Cu(II) 37 mg/g 0.129 L/mg 0.143 16.02 [109]
Garlic peel Ni(II) 32 mg/g 0.564 L/mg 0.123 14.70 [109]
Native garlic peel Pb(II) 51.73 mg/g 0.1303 L/mg [110]
Mercerized garlic peel Pb(II) 109.05 mg/g 0.2320 L/mg [110]
Garlic peel Methylene blue 82.64142.86 mg/g 0.0440.085 L/mg 0.8060.637 6.2977.88 (mg/g(L/mg)1/n) [111]
Raw Egyptian mandarin peel Mercury 19.01 0.028 0.413 2.028 [114]
Chemically treated Egyptian mandarin peel Mercury 23.26 0.059 0.333 4.298 [114]
Carbonized Egyptian mandarin peel Mercury 34.84 0.176 0.256 11.046 [114]
Mosambi peel Cr(VI) 166.66250 mg/g 0.51 L/mg 0.1890.136 2.042.26 [126]
Lychee peel Acid Blue 25 204.3 mg/g 1.57  103 L/mol 2.43 [128]
Kemangsi skin (KS) Malachite green 177.4 mg/g 0.0036 L/mg 0.602 18.84 [143]
Base-modied KS Malachite green 227.0 mg/g 0.0333 L/mg 0.415 [143]

Fig. 14. Fix-bed column of Acid Blue 25 onto HCl-pretreated banana peel with a dye concentration of 0.02 mmol L1, pHin = 1.98, pHout = 1.9 with about 4 g of biosorbent. The
symbol (s) represents experimental points, continuous line represents the tting obtained using the BohartAdams model. Reprinted with permission from American
Chemical Society (ACS) from Ref. [81].

was observed to slow down signicantly until it reached a plateau
after 60 min, indicating equilibrium of the system. The desorption
efciency was 98.25%. The regenerated GFP biomass was again
used for removal of CV and was found to have the efciency of
87% and 81% in the second and the third cycles, respectively. Thiru-
mavalavan et al. [69] reported that the desorption efciency of the
adsorbed metal ions ranged from 95% to 97%. The reusability of the
adsorbents was measured by repeating the metal ion adsorption
desorption cycle 4 to 5 times using the same adsorbents. The rever-
sibility of As(V) adsorption onto PVPCC was studied at different pH
values [93]. The investigation was carried out using spent adsor-
bent used previously. The desorption of arsenate at different pH
showed that maximum desorption occurred at pH 11 with 32%
As(V) removal. The results suggested that NaOH could be appar-
ently effective desorption agent. Another desorption study was
carried out to recover Cd(II) and recycle the adsorbent and treated
water [99]. The Cd(II) laden carbons were agitated with 100 ml of
different strengths of HCl (0.010.1 M) for 1 h and the Cd(II) ions
desorption into the solution was analyzed. A complete recovery
of the adsorbed Cd(II) ions was achieved using HCl with concentra-
tion as low as 0.01 M. Desorption of anionic pollutants (chromate,
arsenate, and arsenite) was studied at different pH (2, 4, 7, 10, and
266 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271

Fig. 15. Breakthrough curves in the adsorption of Pb2+ and Zn2+ on MOP. Reprinted with permission from Elsevier from Ref. [21].

Fig. 16. Breakthrough curves of Pb(II) using TB. Reprinted with permission from Elsevier from Ref. [15].

12) at a constant temperature of 30 C [138]. Minimum desorption 4. Continuous biosorption studies

was observed at acidic pH, but about 90% of pollutants were des-
orbed at pH 12 within 10 min. The BM-KS saturated with MG
dye was either reused directed after air-dry or subjected to various
desorption methods such as thorough washing with water, 0.1 M
HNO3 and 0.1 M NaOH [143]. It was found by authors that for
adsorbent, which was either reused directly without any desorp-
tion or thoroughly washed in water to desorb the dye, both cases
showed that the adsorbent lost its removal efciency by almost
50% after three consecutive cycles of adsorptiondesorption
experiments and was unable to adsorb any more dye thereafter.
Regeneration of adsorbent by acid treatment gave an initial reduc-
tion of approximately 50% removal efciency, but thereafter the
acid-regenerated adsorbent was able to maintain removal efcien-
cy of around 40% even after the fth cycle. Of the three methods
used, treatment with 0.1 M NaOH was the best as the adsorbent
was still able to remove MG even after the fth cycle maintaining
an excellent removal efciency of >90%.
Continuous biosorption studies are of great importance in order
to evaluate the feasibility of biosorption process for real applica-
tions. Packed bed columns reactors have been widely used for the
purpose. However, the main drawback of the published continuous
biosorption studies using agricultural peels-based biosorbents is
that their use is still in the laboratory stage mostly without pilot
studies or commercialization. Some of the important studies are
discussed herein. Guiso et al. [81] reported the column studies of
banana peel for the removal of AB25 dye. The results (Fig. 14) of
the Acid Blue 25 column in continuous operation revealed that
the breakthrough point was reached in 55.5 h with a 1.5 mL/min
ow rate, so that 5 L of dye free efuent was obtained.
Gupta and Nayak used column of prepared adsorbent (magnetic
nanoadsorbent using waste-orange peel powder) for cadmium
removal from aqueous solutions in xed bed column studies
[22]. It was found that rst 2 L of inuent was adsorbed to the tune
 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
Fig. 17. Breakthrough curves of biosorption of crystal violet by grapefruit peel waste in xed-bed continuous-ow column. Reprinted with permission from Elsevier from Ref.
[56].
of 99%. 74% of Cd2+ adsorption took place in the next 26 L inuent
followed by a rapid decrease of adsorption (741.7%) for 820 L.
The column was exhausted and no further adsorption of cadmium
occurred. A breakthrough capacity of 55.38 mg/g was obtained sig-
nifying 55.8% column utilization which was relatively lower than
the batch adsorption capacity (76.92 mg/g). A column packed with
MOP (sulfured orange peel) was used in removing Pb2+ and Zn2+
from aqueous solutions [21]. The breakthrough prole (Fig. 15) of
Pb2+ (10 mg/L) and Zn2+ (100 mg/L) revealed that the breakthrough
of Pb2+ occurred at 220 bed volume (BV) while that of Zn2+ took
place immediately after the feed ow was started. This was
explained because Pb2+ was much more selectively adsorbed than
Zn2+ under pH around 2.0. Packed bed columns of treated biosor-
bent developed from orange peel were used for Pb(II) removal
[15]. Fig. 16 shows the breakthrough curves of Pb(II) as a function
of efuent volume (L). In this work, two initial concentrations were
used to evaluate the performance in the continuous system (150
and 250 mg/L). The exhaustion time of 464 min was found for
Pb/TB (C0 = 150 mg/L) while it was 617 min for Pb/TB
(C0 = 250 mg/L). The column capacities were found to be greater
than their corresponding batch capacities.
Grapefruit peel (GFP) in a xed-bed continuous ow column
was used to remove crystal violet (CV) from aqueous solution
[56]. It was found that the column bioreactor packed with
14 0.56 g GFP had the capacity to treat 61 L and 29 L dye solution
before reaching the breakthrough point for 50 mg/L and 100 mg/L
CV, respectively, and the saturation points were achieved at 83 L
and 45 L (Fig. 17).
5. Real wastewater treatment with peel-based adsorbents
In order to know the practical feasibility, prepared adsorbents
should also be used to treat real industrial efuents, however, only
a few studies have been reported in this regard. The removal of
Cu(II) from electroplating wastewater was studied using prepared
adsorbent by Feng et al. [16]. It was found that quantitative
removal of Cu(II) from 50 ml wastewater sample containing
14.33 mg L1 Cu(II) ions, an adsorbent dose of 0.250 g was suf-
cient for the removal of 97.1% of Cu(II). In connection to the repeat-
ed use of the prepared gel, cycle tests were carried out to recover
molybdenum from real industrial wastewater [23]. This test was
carried out up to nine cycles and a good extent of adsorption as
well as elution was achieved and Mo(VI) recovery was achieved
267
in the range of 93.5599.22% during 19 cycles. The diluted elec-
troplating wastewater was treated with increasing adsorbent dose
(0.21.0 g) for 24 h [129]. It was found that removal of Cr(VI)
increased with increasing adsorbent dose and reached maximum
(100%) at 6.0 g adsorbent dose. Therefore, it was concluded by
authors that 6 g adsorbent was sufcient to remove 100% Cr(VI)
from electroplating wastewater. Local dyeing industry wastewater
(untreated) was collected and treated with C. sativa peel carbon
[130]. The wastewater contained four dyes namely Yellow MR,
Red M5B, Black B, and MG. The pH and optical density of the was-
tewater were 7.35 and 0.9800, respectively. The percentage
removal of wastewater increased with the increasing contact time
and attained equilibrium at 120 min. The percentage removal of
collected wastewater on CCS was 58.97%. The potential of avacado
peel carbon (APC) in reduction of COD and BOD concentration from
coffee processing wastewater was studied [175]. The optimum
operating conditions for getting maximum COD/BOD concentra-
tion reduction from coffee processing efuent with APC were;
treatment time: 70 min, adsorbent dose: 4 g/l00 ml, pH: 7, initial
COD/BOD concentration: 22,000/12,000 mg/L, agitation speed:
600 rpm and adsorbent particle size: 60.25 mm. Authors stated
that residual concentrations of COD and BOD after treatment with
APC under optimum operating conditions were 396 mg/l and
98.4 mg/l respectively and were well within the permissible limits
of world health organization (WHO) standards. Mexerica mandarin
(Citrus nobilis) peel was used for the removal of selected heavy
metals from ten real wastewater samples from battery industries
in Londrina city (Brazil) [159]. Biosorbent represented high
removal efciency toward Cu(II), Cd(II), and Pb(II) removal ratio
for all samples reached over 99.9%.
6. Concluding remarks and future perspectives
In this review, applications of agricultural waste peels biosor-
bents for the removal of diverse type of pollutants from water have
been reviewed based on a substantial number of relevant research
articles published up till now. The use of waste peels based biosor-
bents for removing various pollutants from water and wastewater
offers many attractive features such as the outstanding adsorption
capacity for many pollutants and the fact that these materials are
low-cost, non-toxic and biocompatible. Although the amount of
available literature data for the application of waste peels based
biosorbents in water and wastewater treatment is increasing at a
268 A. Bhatnagar et al. / Chemical Engineering Journal 270 (2015) 244271
tremendous pace, there are still several gaps which need more
attention, such as enhancement of biosorption capacity through
modication of biosorbent, assessment of biosorbents under mul-
ticomponent pollutants, investigation of these materials with real
industrial efuents, recovery of metal ions, regeneration studies,
and continuous ow studies. A notable disadvantage of fruits and
vegetables peels is the release of soluble organic compounds into
water during the treatment process which limits their use in large
scale applications and further research is needed in this regard.
Furthermore, adsorbents can be modied using eco-friendly che-
micals to avoid secondary pollution. As evident in the literature
reviewed in this paper, the chemical modication can increase
the number of active binding sites in the material, thereby, improv-
ing the ion exchange properties and form new functional groups
that favor pollutants uptake. Studies should also be extended to
pilot and full scale using agricultural peel-based adsorbents to
examine their potential in treating real wastewaters, but it would
require a signicant nancial and technological effort to really
scale it up to a large scale. Despite various drawbacks and chal-
lenges that currently exist, a widespread and great progress in this
area can be expected in the future. Overall, agricultural waste peels
based biosorbents offer signicant advantages over currently avail-
able expensive commercially activated carbons for water pollution
control and, in addition, can contribute to an overall waste
minimization strategy.
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